US3867140A - Organic photoconductor-(mononitro-2-aza-fluorenylidene)malononitrile charge transfer complex - Google Patents

Organic photoconductor-(mononitro-2-aza-fluorenylidene)malononitrile charge transfer complex Download PDF

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Publication number
US3867140A
US3867140A US326563A US32656373A US3867140A US 3867140 A US3867140 A US 3867140A US 326563 A US326563 A US 326563A US 32656373 A US32656373 A US 32656373A US 3867140 A US3867140 A US 3867140A
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Prior art keywords
malononitrile
aza
fluorenylidene
mononitro
charge transfer
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Expired - Lifetime
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US326563A
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English (en)
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Mitsuru Hashimoto
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Ricoh Co Ltd
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Ricoh Co Ltd
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Priority to US05/537,405 priority Critical patent/US3974167A/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
    • G03G5/0624—Heterocyclic compounds containing one hetero ring
    • G03G5/0635—Heterocyclic compounds containing one hetero ring being six-membered
    • G03G5/0637—Heterocyclic compounds containing one hetero ring being six-membered containing one hetero atom

Definitions

  • ABSTRACT Photosensitive material for use in electrophotography which is a charge transfer complex comprising (mononitro-2-aza-9-fluoreny1idene) malononitrile and an organic photoconductor.
  • the present invention relates to novel compositions suitable for use in electrophotography.
  • Electrophotography is an art which usefully combines photoconductivity with electrostatic phenomena.
  • a wide variety of inorganic substances as selenium, zinc oride, and the like have heretofore been employed as photoconductors.
  • organic photoconductive substances such as poly-N-vinyl carbazole and others have attracted wide attention. They are of particular interest because of their advantageous properties with respect to cost of production, transparency of product film, ease of film forming, etc.
  • their wide adoption has been impeded because they are generally inferior to inorganic substances in sensitivity and exhibit only marginal sensitivities in the visible region of the spectra. This problem has been somewhat alleviated by the use of various sensitizing substances.
  • Another problem which has retarded the adoption of organic photoconductors is that it is difficult to preserve them.
  • One object of the present invention is to provide organic photoconductive compositions which manifest useful sensitivity in the visible region of the spectrum.
  • Another object of the present invention is to provide organic photoconductive compositions which are superior in film transparency, film formability, preservability, etc.
  • a principal feature of the invention is the provision of a charge transfer complex comprising a novel (mononitro-Z-aza- 9-fluorenylidene) malononitrile electron acceptor and any known organic photoconductive electron donor.
  • the above mentioned charge transfer complex comprising (mononitro-Z-aza-9-fluorenylidene) malononitrile as the acceptor and various organic, photoconductive donors comprise the photoconductive compositions of the present invention.
  • the compositions display panchromatic sensitivity and are useful with actinic light in the visible region of the spectrum. Their utility can be enhanced however by the addition of known sensitizers such as Rhodamine B, Rose Bengal, fluorescein and the like.
  • Preparation of electrophotographic compositions of the present invention can be easily effected by: mixing (mononitro-2-aza-9-fluorenylidene) malononitrile, the acceptor, with the selected donor in the weight ratio of from 1:100 to 1501100; adding such additives as may be desired such as binders, additional sensitizers and other conventional additives to the resulting mixture; dissolving the mixture in an appropriate inert, organic solvent such as dioxane, tetrahydrofuran, etc.; subsequently coating the thus obtained solution on an appropriate substrate.
  • Suitable binders include, for example, novolak, acrylic resins and others of the type conventionally employed.
  • Suitable substrates include, for example, aluminum plates, polyester films with a vacuum deposited aluminum layer, paper treated for conductivity, etc. The final product is dried.
  • a composition of the invention may contain added binder in the range of about 5 to 50 parts by weight relative to the total weight of the mixture, and additional sensitizers such as fluorescein in the weight range of about 0.001 to 0.0] parts by weight based on the weight of the donor.
  • additional sensitizers such as fluorescein in the weight range of about 0.001 to 0.0] parts by weight based on the weight of the donor.
  • Typical donors which may be employed in this invention include condensation polycyclic compounds such as pyrene, perylene, anthracene, etc., phenothiazine,
  • the (mononitro-2aza-9-fluorenylidene) malononitrile for use in the present invention can be synthesized by the following procedure:
  • the photosensitive compositions of this invention comprising a charge transfer complex containing (mononitro-2-aza-9-fluorenylidene) malononitrile and an organic photoconductive donor as the principal components are sensitive in the visible region of the spectrum, have satisfactory preservability and reproducibility, and. are further applicable to the transfer process. When deposited on an electrically conductive substrate they form excellent electrophotographic plates.
  • EXAMPLE 1 A solution obtained by dissolving 64 mg of poly-N- vinyl carbazole, 91 mg of (7-nitro-2-aza-9- fluorenylidene) malononitrile and 100mg of diphenyl chloride in 10 g of tetrahydrofuran is coated by means ofa doctor blade having wet gaps of 200p, on an aluminum coated Mylar film and dried to produce an electrophotographic plate having a photosensitive film layer about 10 microns thick.
  • the thus prepared plate is charged by means of corona discharge (-6KV), exposed to light by means of an apparatus equipped with a tungsten lamp capable of producing an intensity ofillumination on the sensitive surface of the plate of 3 luxes and measured for its surface potential, whereby the time required for decreasing said potential to half (hereinafter referred to as exposure time required for half decay) is measured. It was found that the exposure time required for half decay is about 4 seconds.
  • EXAMPLE 2 A solution is prepared by dissolving 900 mg of poly- N-viny1-3-bromocarbazole, 91 mg of (7-nitro-2-aza-9- fluorenylidene) malononitrile and mg of diphenyl chloride in 15 g of tetrahydrofuran. When this composition is treated in the same manner as the compositions of Example 1 it is found that the exposure time required for half decay is about 3.5 seconds.
  • EXAMPLE 3 A sensitive material is prepared in the same way as in Example 1 except for increasing the amount of (7- nitro-2-aza-9-fluorenylidene) malononitrile to 910 mg from 91 mg as employed in Example 1. The exposure time required for half decay of this sensitive material is about 1.5 seconds.
  • EXAMPLE 4 A sensitive material is prepared in the same way as in Example 2 except for increasing the amount of (7- nitro-2-aza-9-fluorenylidene) malononitrile to 910 mg from 91 mg as employed in Example l. The exposure time required for half decay of this sensitive material is about 1.4 seconds.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Other In-Based Heterocyclic Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
US326563A 1972-01-24 1973-01-24 Organic photoconductor-(mononitro-2-aza-fluorenylidene)malononitrile charge transfer complex Expired - Lifetime US3867140A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US05/537,405 US3974167A (en) 1972-01-24 1974-12-30 (7-Nitro-2-aza-9-fluorenylidene) malononitrile

Applications Claiming Priority (1)

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JP47009293A JPS4949506B2 (US07696358-20100413-C00002.png) 1972-01-24 1972-01-24

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US05/537,405 Division US3974167A (en) 1972-01-24 1974-12-30 (7-Nitro-2-aza-9-fluorenylidene) malononitrile

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US (1) US3867140A (US07696358-20100413-C00002.png)
JP (1) JPS4949506B2 (US07696358-20100413-C00002.png)
DE (1) DE2302625C3 (US07696358-20100413-C00002.png)
FR (1) FR2169211B1 (US07696358-20100413-C00002.png)
GB (1) GB1416232A (US07696358-20100413-C00002.png)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3974167A (en) * 1972-01-24 1976-08-10 Ricoh Co., Ltd. (7-Nitro-2-aza-9-fluorenylidene) malononitrile
US4056391A (en) * 1975-09-22 1977-11-01 Xerox Corporation Method for enhancing solid solution stability of electron acceptor molecules and electrophotographic compositions
US4063947A (en) * 1975-10-29 1977-12-20 Xerox Corporation Photoconductive insulating films comprising fluorenone-substituted oligomers
US4474865A (en) * 1983-08-08 1984-10-02 Xerox Corporation Layered photoresponsive devices
KR100457523B1 (ko) * 2002-06-07 2004-11-17 삼성전자주식회사 단층형 전자사진 감광체
CN104035294A (zh) * 2013-03-07 2014-09-10 佳能株式会社 电子照相感光构件、电子照相设备、处理盒和稠合多环芳香族化合物
US20140255836A1 (en) * 2013-03-07 2014-09-11 Canon Kabushiki Kaisha Electrophotographic photosensitive member, and electrophotographic apparatus and process cartridge each including the electrophotographic photosensitive member

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2964000B1 (en) * 2002-12-19 2022-10-05 Signify Holding B.V. Led driver

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2980535A (en) * 1954-01-05 1961-04-18 Feldmuhle Papier Und Zellstoff Light sensitive layers of synthetic materials
US3244516A (en) * 1959-04-09 1966-04-05 Azoplate Corp Electrophotographic mateiral and process
US3252794A (en) * 1956-11-14 1966-05-24 Agfa Ag Photoconductive layers and process for electrophotography
US3301676A (en) * 1963-10-12 1967-01-31 Azoplate Corp Process and material for the production of electrophotographic images
US3307940A (en) * 1959-05-30 1967-03-07 Azoplate Corp Electrophotographic process employing photoconductive polymers
US3484237A (en) * 1966-06-13 1969-12-16 Ibm Organic photoconductive compositions and their use in electrophotographic processes
US3485625A (en) * 1966-06-09 1969-12-23 Eastman Kodak Co Photoconductive elements containing 2,3,4,5-tetraaryl pyrrole
US3556785A (en) * 1968-02-23 1971-01-19 Addressograph Multigraph Sensitizers for organic photoconductor comprising orazolone and butenolide derivatives of of fluorenone
US3583869A (en) * 1967-03-24 1971-06-08 Ricoh Kk Electrophotographic copying paper containing poly-n-vinyl-3-azo carbazole
US3595648A (en) * 1967-03-23 1971-07-27 Ricoh Kk Poly-n-vinyl-3-nitro carbazole photoconductive material
US3674473A (en) * 1970-10-06 1972-07-04 Addressograph Multigraph Cumulene containing photoconductive binder elements for use in electrophotography
US3677752A (en) * 1969-09-02 1972-07-18 Eastman Kodak Co Bis(dialkylaminoaryl)ethylene photoconductors
US3752668A (en) * 1967-10-30 1973-08-14 Addressograph Multigraph Organic photoconductive members comprising dicyanomethylene substituted fluorene sensitizers
US3796572A (en) * 1971-12-27 1974-03-12 Ricoh Kk Electrophotographic light-sensitive material

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2980535A (en) * 1954-01-05 1961-04-18 Feldmuhle Papier Und Zellstoff Light sensitive layers of synthetic materials
US3252794A (en) * 1956-11-14 1966-05-24 Agfa Ag Photoconductive layers and process for electrophotography
US3244516A (en) * 1959-04-09 1966-04-05 Azoplate Corp Electrophotographic mateiral and process
US3307940A (en) * 1959-05-30 1967-03-07 Azoplate Corp Electrophotographic process employing photoconductive polymers
US3301676A (en) * 1963-10-12 1967-01-31 Azoplate Corp Process and material for the production of electrophotographic images
US3485625A (en) * 1966-06-09 1969-12-23 Eastman Kodak Co Photoconductive elements containing 2,3,4,5-tetraaryl pyrrole
US3484237A (en) * 1966-06-13 1969-12-16 Ibm Organic photoconductive compositions and their use in electrophotographic processes
US3595648A (en) * 1967-03-23 1971-07-27 Ricoh Kk Poly-n-vinyl-3-nitro carbazole photoconductive material
US3583869A (en) * 1967-03-24 1971-06-08 Ricoh Kk Electrophotographic copying paper containing poly-n-vinyl-3-azo carbazole
US3752668A (en) * 1967-10-30 1973-08-14 Addressograph Multigraph Organic photoconductive members comprising dicyanomethylene substituted fluorene sensitizers
US3556785A (en) * 1968-02-23 1971-01-19 Addressograph Multigraph Sensitizers for organic photoconductor comprising orazolone and butenolide derivatives of of fluorenone
US3677752A (en) * 1969-09-02 1972-07-18 Eastman Kodak Co Bis(dialkylaminoaryl)ethylene photoconductors
US3674473A (en) * 1970-10-06 1972-07-04 Addressograph Multigraph Cumulene containing photoconductive binder elements for use in electrophotography
US3796572A (en) * 1971-12-27 1974-03-12 Ricoh Kk Electrophotographic light-sensitive material

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3974167A (en) * 1972-01-24 1976-08-10 Ricoh Co., Ltd. (7-Nitro-2-aza-9-fluorenylidene) malononitrile
US4056391A (en) * 1975-09-22 1977-11-01 Xerox Corporation Method for enhancing solid solution stability of electron acceptor molecules and electrophotographic compositions
US4063947A (en) * 1975-10-29 1977-12-20 Xerox Corporation Photoconductive insulating films comprising fluorenone-substituted oligomers
US4474865A (en) * 1983-08-08 1984-10-02 Xerox Corporation Layered photoresponsive devices
KR100457523B1 (ko) * 2002-06-07 2004-11-17 삼성전자주식회사 단층형 전자사진 감광체
CN104035294A (zh) * 2013-03-07 2014-09-10 佳能株式会社 电子照相感光构件、电子照相设备、处理盒和稠合多环芳香族化合物
US20140255836A1 (en) * 2013-03-07 2014-09-11 Canon Kabushiki Kaisha Electrophotographic photosensitive member, and electrophotographic apparatus and process cartridge each including the electrophotographic photosensitive member
US9316931B2 (en) * 2013-03-07 2016-04-19 Canon Kabushiki Kaisha Electrophotographic photosensitive member, electrophotographic apparatus, process cartridge, and condensed polycyclic aromatic compound
CN104035294B (zh) * 2013-03-07 2017-09-22 佳能株式会社 电子照相感光构件、电子照相设备、处理盒和稠合多环芳香族化合物

Also Published As

Publication number Publication date
DE2302625C3 (de) 1975-11-27
FR2169211A1 (US07696358-20100413-C00002.png) 1973-09-07
DE2302625B2 (de) 1975-04-17
JPS4878935A (US07696358-20100413-C00002.png) 1973-10-23
DE2302625A1 (de) 1973-07-26
JPS4949506B2 (US07696358-20100413-C00002.png) 1974-12-27
GB1416232A (en) 1975-12-03
FR2169211B1 (US07696358-20100413-C00002.png) 1979-01-12

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