US3868251A - Organic photoconductive composition containing chlorinated paraffin - Google Patents

Organic photoconductive composition containing chlorinated paraffin Download PDF

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Publication number
US3868251A
US3868251A US381746A US38174673A US3868251A US 3868251 A US3868251 A US 3868251A US 381746 A US381746 A US 381746A US 38174673 A US38174673 A US 38174673A US 3868251 A US3868251 A US 3868251A
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chlorinated paraffin
weight
parts
poly
photoconductive composition
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Expired - Lifetime
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US381746A
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English (en)
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Shoichi Matsumoto
Kazuyoshi Saito
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Toshiba Corp
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Tokyo Shibaura Electric Co Ltd
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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 or 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
    • 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 or 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
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers

Definitions

  • An organic photosensitive material for use in electrophotography which consists essentially of a polymeric organic photoconductor, examples of which include poly-N-vinylcarbazole, chargetransfer molecular complexes such as poly-N- vinylcarbazole-tetrachloro-p-benzoquinone and poly- N-vinylcarbazole-tetracyanoquinodimethane, poly-N- vinylcarbazole derivatives such as nitrated poly-N- vinylcarbazole, polyvinylanthracene, and polyacenaphthylene; and monomeric organic photoconductors such -as anthracene, pyrazoline, oxazole, triazole and hydrazone.
  • polymeric organic photoconductor examples of which include poly-N-vinylcarbazole, chargetransfer molecular complexes such as poly-N- vinylcarbazole-tetrachloro-p-benzoquinone and poly- N-vin
  • This type of organic photosensitive material has many advantages over known inorganic photosensitive material consisting essentially of selenium or zinc oxide, etc. in easy sensitization, transparency, good film formation,high flexibility, light weight, and low manufacturing cost. Hence there is a growing interest in its practical applications.
  • an object of this invention to provide an organic photoconductive composition for use in electrophotography which can always perform a pre determined function without deterioration in characteristics due to the fatigue caused when used repeatedly in an electrophotographic copying, such as a toner or a charge transfer copying and when used as a photosensitive material for a photosensitive paper.
  • a photoconductive composition for use in electrophotography comprising 100 parts by weight of an organic photoconductor and to 50 parts by weight of chlori nated paraffin.
  • FIGS. 1 and 2 show characteristic curves of built-up voltage vs charge time for a photosensitive plate con-' sisting of an organic photoconductor for use in electrophotography to explain the characteristics of the photoconductor.
  • the organic photoconductive composition of this invention can be prepared by mixing 100 parts by weight of organic photoconductor, about 0.1 to 20 parts by weight of chemical sensitizer, about 0.02 to 4 parts by weight of optical sensitizer and 20 to 50 parts by weight of chlorinated paraffin.
  • composition may be dissolved in a suitable solvent such as chlorobenzene, toluene, benzene, methylene chloride or the like and uniformly stirred to form a photosensitive material.
  • a suitable solvent such as chlorobenzene, toluene, benzene, methylene chloride or the like and uniformly stirred to form a photosensitive material.
  • Organic photoconductor which has been found to be suitable for the composition of the invention is, for example, poly-N-vinylcarbazole, charge-transfer molecular complexes such as poly-N-vinylcarbazoletetrachloro-p-benzoquinone or poly-N-vinylcarbazoletetracyanoquinodimethane, poly-N-vinylcarzole derivatives such as nitrated poly-N-vinylcarbazole, polyvinylanthracene, polyacenaphthylene, anthracene, pyrazoline, oxazole, triazole, or hydrazone.
  • a chemical sensitizer and/or an optical sensitizer may be added to these photoconductors.
  • Various kinds of additives may also be added to improve other properties of the photosensitive material.
  • a suitable polymer such as polymethylmethacrylate, polycarbonate, cellulose nitrate or cellulose acetate is preferably added as a binder to provide film formation.
  • chlorinated paraffin Prefered examples of chlorinated paraffin are Adekacizer-E-4l0, Adekacizer-E-450, Adekacizer-E-480, Adekacizer-E-SOO, Adekacizer-E-52O (trade names of chlorinated paraffins manufactured by Adeka-Argus Chemical Co., Ltd., containing 41 to 52% by weight of chlorine); Enpara K-45, Enpara K-SO, Enpara K-65 (trade names of chlorinated paraffins produced by Ajinomoto Kabushiki Kaisha, containing 40 to 65% by weight of chlorine); and Monocizer-W-40, Monocizer- W-45, Monocizer-W-SO (trade names of chlorinated paraffins by Dainippon Ink and Chemicals, Inc.)
  • chlorinated paraffins contain about eight to 18 carbon atoms, in either liquid or solid state depending on the chlorine content. Taking into account the compatibility with the organic photoconductor, chlorinated paraffin in liquid state containing 40 to 65% by weight of chlorine is most preferred. A mixture of two or more kinds of chlorinated paraffin may also be used.
  • the amounts of chlorinated paraffin to be mixed with the organic photoconductor should be within the range of 20 to parts by weight against 100 parts by weight of the organic photoconductor. This is because the addition of chlorinated paraffin not exceeding 20 parts by weight cannot prevent the occurrence of fatigue failure or deterioration, while the addition of chlorinated paraffin exceeding 50 parts by weight causes a marked reduction in photosensitivity and a considerable decrease in the built-up voltage, although the occurrence of fatigue failure or deterioration may be prevented effec tively. It has been experimentally confirmed that the addition of chlorinated paraffin exceeding the upper and lower limits were unsuitable for practical applications to photoconductors for use in electrophotography.
  • the organic photoconductive composition for electrophotography obtained by mixing an organic photoconductor with a predetermined amount of chlorinated paraffin can prevent or suppress the occurrence of fatigue failure or deterioration, thus performing the desired functions in use as a photosensitive material.
  • chlorinated paraffin Although the operating mechanism of chlorinated paraffin is unknown, it has been found that a photosensitive material containing an organic photoconductor as a main component will suffer in practice negligibly little fatigue failure or deterioration due to electric charge or light exposure by adding chlorinated paraffin. Even when repeatedly used as a photosensitive material for a toner or a charge transfer copying the composition of the invention can always perform a predetermined function as a photosensitive material. Even when applied to a photosensitive paper, it can obtain a clear image without causing a reduction in its image density due to room-light exposure fatigue failure or deterioration.
  • EXAMPLE 1 A charge-transfer reaction was carried out between poly-N-vinylcarbazole and tetr'achloro-p-benzoquinone in a weight ratio of 121.27 to obtain a charge-transfer molecular complex.
  • Adekacizer-E-4l0 was added to each part at the rate indicated in Table l with respect to 100 parts of the charge-transfer molecular complex.
  • the Adekacizer-E-4l0 is a trade name of chlorinated paraffin manufactured by Adeka- Argus Chemical Co., Ltd., containing 41% by weight of chlorine.
  • Each solution was coated on aluminium plate substrates to form, when the solution is dried, seven photosensitive plate samples having a film thickness ranging between 5 and 6 [.trn.
  • Table 1 Amount of chlorinated Fatigue index (7:) due to FIG. 1 shows the results of measuring the electrophotographic characteristic curves of Sample 1 by a paper analyzer (rotation-speed ofa sample turntable: 13 rpm; corona charging voltage: -5,000V: light source tungsten-filament lamp; illumination: 9 lux.).
  • the curves (a), (b) and (c) in FIG. 1 indicate the results obtained when light of 0, 1,000 and 4,000 lux.sec., respectively, are irradiated over the surface of the sample prior to measurement. It is clear from FIG 1 that a sample with no addition of chlorinated paraffin suffered much fatigue (deterioration in initial built-up voltage and reduction in saturation voltage).
  • the fatigue index due to light exposure is defined by (1 0 val 0x 10 where V built-up voltage of a sample subjected to light exposure of 4,000 lux.sec. prior to measurement, and V built-up voltage of a sample when subjected to no previous light exposure.
  • Example 2 The process of Example I was essentially repeated except that Adakacizer-E-4l0 was replaced with AdekaciZer-ESZO (trade name of chlorinated paraffin manufactured by Adeka-Argus Chemical Co., Ltd., containing 52% by weight of chlorine). Samples 8 to 14 having the compositions shown in Table 2 were thus obtained.
  • the fatigue index due to light exposure is defined by 0 VRIVO) X loo EXAMPLE 3
  • a mixture of 100 parts of poly-N-vinylcarbazole, parts of 2, 4, 7-trinitrofluorenone (a chemical sensitizer), and 30 parts of Enpara K-45 (trade name of chlorinated paraffin produced by Ajinomoto Kabushiki Kaisha, containing 45% by weight of chlorine) was dissolved in 1,800 parts of tetrahydrofuran to prepare a photosensitive solution.
  • the surface of an aluminium plate support was coated with this solution and then dried to produce a sample of photosensitive plate.
  • the fatigue indexes of the sample due to light exposure were measured as in Example 1.
  • Related results were 2% in l min. and 0% in 3 min., whereas the corresponding fatigue indexes in a control experiment with no addition of chlorinated paraffin were 33% (l min.) and (3 min.).
  • Example 4 The process of Example 3 was substantially repeated except that poly-N-vinylcarbazole was replaced with polyacenaphthylcne.
  • the measured fatigue indexes of the sample due to light exposure were 1% 1 minute later and 2% 3 minutes later.
  • a photoconductive composition for use in electrophotography comprising 100 parts by weight of an organic photoconductor and 20 to 50 parts by weight of chlorinated paraffin will suffer practically no fatigue failure or deterioration due to electric charge or light exposure. Accordingly, the composition of the invention will always display a predetermined function, even when repeatedly used as a photosensitive material in a toner or a charge transfer copying.
  • a photoconductive composition for use in electrophotography comprising parts by weight of an organic photoconductor and 20 to 50 parts by weight of chlorinated paraffin wherein said chlorinated paraffin contains 40 to 65% by weight of chlorine and wherein said chlorinated paraffin contains eight to 18 carbon atoms.
  • a photoconductive composition for use in electrophotography comprising 100 parts by weight of an organic photoconductor and 20 to 50 parts by weight of chlorinated paraffin wherein said chlorinated paraffin contains 40 to 65% by weight of chlorine and wherein said chlorinated paraffin contains eight to 18 carbon atoms, wherein said organic photoconductor is one member selected from the group consisting of poly-N- vinylcarbazole, charge-transfer molecular complexes. poly-N-vinylcarbazole derivatives, polyvinylanthracene, polyacenaphthylene, anthracene, pyrazoline, oxazole, triazole and hydrazone.
  • the photoconductive composition according to claim 2 wherein said charge-transfer molecular complex is selected from the group consisting of poly-N- vinylcarbzaole-tetrachloro-p-benzoquinone and poly- N-vinylcarbazole-tetracyanoquinodimethane.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)
US381746A 1972-07-28 1973-07-23 Organic photoconductive composition containing chlorinated paraffin Expired - Lifetime US3868251A (en)

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JP47075131A JPS4934327A (fr) 1972-07-28 1972-07-28

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5545499A (en) * 1995-07-07 1996-08-13 Lexmark International, Inc. Electrophotographic photoconductor having improved cycling stability and oil resistance

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5076513U (fr) * 1973-11-16 1975-07-03
JPS53129013U (fr) * 1977-03-22 1978-10-13

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3287114A (en) * 1961-07-24 1966-11-22 Azoplate Corp Process for the sensitization of photoconductors
US3533787A (en) * 1967-07-31 1970-10-13 Eastman Kodak Co Photoconductive elements containing polymeric binders of nuclear substituted vinyl haloarylates
US3652269A (en) * 1968-08-27 1972-03-28 Eastman Kodak Co Photoconductive elements containing halogenated polyethylene binders
US3718463A (en) * 1971-06-22 1973-02-27 Monsanto Co Photoconductive coating compositions using a poly(vinyl-halobenzal)binder

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3287114A (en) * 1961-07-24 1966-11-22 Azoplate Corp Process for the sensitization of photoconductors
US3533787A (en) * 1967-07-31 1970-10-13 Eastman Kodak Co Photoconductive elements containing polymeric binders of nuclear substituted vinyl haloarylates
US3652269A (en) * 1968-08-27 1972-03-28 Eastman Kodak Co Photoconductive elements containing halogenated polyethylene binders
US3718463A (en) * 1971-06-22 1973-02-27 Monsanto Co Photoconductive coating compositions using a poly(vinyl-halobenzal)binder

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5545499A (en) * 1995-07-07 1996-08-13 Lexmark International, Inc. Electrophotographic photoconductor having improved cycling stability and oil resistance

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