US3717461A - Removal of protective resin layer by liquid developer in electrophotographic imaging - Google Patents

Removal of protective resin layer by liquid developer in electrophotographic imaging Download PDF

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Publication number
US3717461A
US3717461A US00115141A US3717461DA US3717461A US 3717461 A US3717461 A US 3717461A US 00115141 A US00115141 A US 00115141A US 3717461D A US3717461D A US 3717461DA US 3717461 A US3717461 A US 3717461A
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United States
Prior art keywords
protective layer
liquid
resin
polar
electrophotographic
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
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US00115141A
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English (en)
Inventor
S Honjo
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Publication of US3717461A publication Critical patent/US3717461A/en
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Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G13/00Electrographic processes using a charge pattern
    • G03G13/22Processes involving a combination of more than one step according to groups G03G13/02 - G03G13/20
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14Inert intermediate or cover layers for charge-receiving layers
    • G03G5/147Cover layers
    • G03G5/14708Cover layers comprising organic material
    • G03G5/14713Macromolecular material
    • G03G5/14717Macromolecular material obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G5/14734Polymers comprising at least one carboxyl radical, e.g. polyacrylic acid, polycrotonic acid, polymaleic acid; Derivatives thereof, e.g. their esters, salts, anhydrides, nitriles, amides
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14Inert intermediate or cover layers for charge-receiving layers
    • G03G5/147Cover layers
    • G03G5/14708Cover layers comprising organic material
    • G03G5/14713Macromolecular material
    • G03G5/14717Macromolecular material obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G5/14743Polymers derived from conjugated double bonds containing monomers, e.g. polybutadiene; Rubbers
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14Inert intermediate or cover layers for charge-receiving layers
    • G03G5/147Cover layers
    • G03G5/14708Cover layers comprising organic material
    • G03G5/14713Macromolecular material
    • G03G5/14747Macromolecular material obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G5/14752Polyesters
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14Inert intermediate or cover layers for charge-receiving layers
    • G03G5/147Cover layers
    • G03G5/14708Cover layers comprising organic material
    • G03G5/14713Macromolecular material
    • G03G5/14747Macromolecular material obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G5/1476Other polycondensates comprising oxygen atoms in the main chain; Phenol resins
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/12Developers with toner particles in liquid developer mixtures

Definitions

  • an insulative protective layer consisting mainly of a non-polar resin.
  • the protective layer may be dissolved with the nonpolar electrically insulating liquid either prior to or during the development of the latent image with the non-polar electrically insulating liquid. If the protective layer is dissolved during the development step, the carrier liquid of the liquid developer is the non-polar, electrically insulating liquid.
  • An electrophotographic coating is generally susceptible to mechanical damage in the course of manufacture storage and processing.
  • Such susceptjbility is reduced by forming overlying the photoconductive coating a protective top coating which can be removed by dissolving away into an insulating liquid prior to or during liquid development.
  • the electrophotographic sensitive material to which the present invention is directed is produced by coating a flexible base with a photoconductive insulative layer made of a mixture comprising a resinous binder and a photoconductive substance. While the flexibility of base offers many advantages, and this sensitive materials of such type are now used abundantly in copying documents, flexible sensitive materials are defective in that the surface is highly susceptible to mechanical damage because of extremely high volume content of photoconductive substance in the sensitive layer.
  • the object of the present invention is to provide an electrophotographic process which makes such shortcomings difficult to occur.
  • This invention relates to an electrophotographic process characterized by forming an electrostatic latent image on an electrophotographic light sensitive material obtained by providing a photoconductive insulative layer on a flexible base and further forming thereon an insulative protective layer consisting mainly of resin and dissolving said protective layer prior to or during the step of developing operation using a liquid developer which is prepared by having electrically charged particles dispersed in an insulating liquid.
  • the aforementioned insulative protective layer is intended to provide mechanical protection for the sensitive layer, it is formed on the sensitive layer subsequently to or, where a special coating method is used, simultaneously with the formation of the sensitive layer on the base.
  • the thickness of this layer should be above 0.2a but should not exceed 5;.
  • Resins for use in this layer have only to satisfy the requirement that they should be soluble in a carrier liquid used for the liquid developer or in an insulative prebath which is applied to the sensitive material prior to the step of liquid development and that they should own a suitable degree of electric insulation.
  • styrene-modified alkyd resin non-drying oil-modified alkyd resin, long oil type epoxyester resin, polybutylrnethacrylete, homopolymer of alkyl ester of acrylic acid or methacrylic acid containing more than 5 carbon atoms in its alkyl group and copolymer mainly consisting of said ester styrene-butylmetyacrylate copolymer, styrene-butadiene copolymer, silicone resins and compatible combinations thereof. Since treating baths are generally made mainly of liquids which are nonpolar and have low dissolving power, the resins to be used in the protective layer are naturally limited to those of nonpolar type.
  • binder for use in the sensitive layer examples include alkyd resins cured with isocyanate compounds, epoxyester resin, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate and ethyl acrylate methyl methacrylate copolymer.
  • alkyd resins cured with isocyanate compounds epoxyester resin
  • vinyl chloride-vinyl acetate copolymer vinyl chloride-vinyl acetate copolymer
  • polyvinyl acetate and ethyl acrylate methyl methacrylate copolymer it is unacceptable to use formulations which permit a hardening catalyst or a hardening agent to diffuse into the protective layer after the step of coating and also cure the protective layer.
  • successful over-coating of a protective layer can be accomplished without affecting the sensitive layer by a resin solution for the protective layer by use of a solvent having the composition similar to that of a bath which is later used for dissolving the protective layer.
  • the sensitive layer with the protective layer coated thereon is subjected to corona charging and image exposure. Then the sensitive material is placed in a prebath capable of dissolving the protective layer immediately before the developing procedure.
  • the electrostatic charge given by corona charging is considered to have penetrated through the thin thickness of the protective layer and reached the upper surface of the photoconductive layer, for a satisfactory image is obtained by subjecting the latent image to ordinary liquid development method after such treatment.
  • the protective layer Prior to electrostatic charging, the protective layer is dissolved with an insulative treating bath and the sensitive material which is still wet to image exposure and then development.
  • the sensitive material is electrically charged by an ordinary method and then it is subjected to image development with a liquid developer which comprises electrically charged particles in a carrier liquid capable of dissolving the protective layer.
  • the resin which forms the protective layer dissolves into the carrier liquid. Consequently, the electrophoretic characteristics are affected gradually by the dissolved resin and the viscosity of the developer increases in particular.
  • This modified process can be exercised within the range in which the viscosity of the liquid is tolerable for the treatment.
  • the presence of the protective layer serves to reduce markedly the chance of the sensitive layer being directly damaged by external forces.
  • the possibility of the finally produced image suffering from defects can be reduced to a great extent.
  • the resin which is one component of the protective layer gradually undergoes dissolution and is contaminated into the bath used for dissolving it. Consequently, the viscosity of the bath increases and electric insulation will be affected. if the bath has its electric resistance degraded excessively, the latent image is destroyed or attenuated rapidly in the case of a) or a sufficiently high potential cannot be achieved in the subsequent charging. Therefore, the resin for use in the protective layer must be of such type that, when dissolved in the bath, it will not lower the resistivity of the treating bath. Among alkyd resins, those of long oil length are preferable in this sense. Since a small portion of the resin for the protective layer contaminates via the dissolving bath into the liquid developer the resin is desired to exert no adverse affect upon the developing agent.
  • this invention can also be applied to any electrophotographic processes utilizing electrostatic latent images other than Carlson Process, such as Kalman process, processes based on photovoltaic effect and Thermo-xerographic Process.
  • EXAMPLE 1 With a suitable quantity of butyl acetate, 100 parts of photoconductive zinc oxide, 20 parts of styrenemodified aklyd resin varnish (nonvolatile content 50 percent) and 14 parts of polyisocyanate compound (nonvolatile content '75 percent) were mixed. The mixture was spread to a dry thickness of 7 u on an art paper which had been treated to possess a suitable electroconductivity. This sensitive material was allowed to stand overnight in a thermostated drying vessel kept at 50C. Then the material had its surface coated with toluene solution of polybutyl methacrylate to form a protective layer. The coated amount was 1.2 g/m on dry base.
  • the sensitive paper thus prepared was subjected to dark adaptation.
  • One sheet of this sensitive paper was negatively charged and exposed to light from an optically positive image and immersed in a liquid developer comprising black toner particles of positive polarity dispersed in kerosene as carrier liquid.
  • a liquid developer comprising black toner particles of positive polarity dispersed in kerosene as carrier liquid.
  • polybutyl methacrylate on the surface was dissolved into the liquid developing agent to give rise to a clear positive image.
  • the sensitive paper was first submerged in cyclohexane so as to allow polybutyl methacrylate layer to be removed by dissolution.
  • This treatment could be accomplished by manual operation or by using an automatic device provided with means to direct a strong flow of liquid against the surface of the sensitive paper and to squeeze the liquid.
  • EXAMPLE 2 With toluene, parts of photoconductive zinc oxide, 40 parts of varnish made from epoxyester of dehydrated castor oil fatty acid (nonvolatile component 50 percent) and 0.1 part of cobalt naphthenate were blended. The mixture was spread to a dry thickness of 10 p. on a sheet of bond paper which had been with an electroconductive polymer. The sheet of paper thus obtained was allowed to harden in a thermostat kept at 40 C. for 15 hours.
  • Pliolite S7 styrene-butadiene copolymer made by Goodyear Tire & Rubber Co. in the US.
  • Pliolite S7 styrene-butadiene copolymer made by Goodyear Tire & Rubber Co. in the US.
  • the coating weights are shown in the following table.
  • the sensitive paper Prior to electrostatic charging, the sensitive paper was wetted on its surface with kerosene to swell the surface layer. It was immediately charged electrically through the exposure to negative corona. After the subsequent image exposure the paper was subjected to development in a liquid developer using kerosene as the carrier liquid. Better results were obtained on areas coated with Pliolite of smaller film thicknesses.
  • Example 2 The procedure of Example 2 was followed, except Pliolite 8-7 was substituted by polybutyl methacrylate. In this case, there was obtained on image of high density free from the edge effect even with the sensitive paper using a protective layer as thick as l .5 u.
  • An electrophotographic process which comprises forming an electrostatic latent image on an electrophotographic sensitive member comprising a flexible support bearing thereon a photoconductive insulating layer insoluble or only sparingly soluble in a nonpolar treatment bath and further thereon an insulative protective layer consisting mainly of a non-polar resin, and dissolving said protective layer with said treatment bath; and developing said latent image with a liquid developer which comprises an electrically insulating carrier liquid and an electrically charged toner dispersed in said carrier liquid.
  • said insulative protective layer consisting mainly of styrene-modified alkyd resin, non-drying oil-modified alkyd resin, long oil type epoxyester resin, polybutyl methacrylate, homopolymers of alkyl ester of acrylic acid or methacrylic acid containing more than 5 carbon atoms in its alkyl group and copolymer mainly consisting of said ester, styrene-butylmethacrylate copolymer, styrene-butadiene copolymer or silicone resin.
  • An electrophotographic process which comprises forming an electrostatic latent image on an electrophotographic sensitive member comprising a flexible support bearing thereon a photoconductive insulative layer insoluble or only sparingly soluble in a nonpolar, electrically insulating carrier liquid and further thereon an insulative protective layer consisting mainly of a non-polar resin, and dissolving said protective layer during the step of development of said latent image with a liquid developer which comprises said non-polar, electrically insulating carrier liquid and an electrically charged toner dispersed in said carrier liquid.
  • said insulative protective layer is selected from the group consisting mainly of styrenemodified alkyd resin, non-drying oil-modified alkyd resin, long oil type epoxyester resin, polybutyl methacrylate, homopolymers of alkyl ester of acrylic acid or methacrylic acid containing more than 5 carbon atoms in its alkyl group and copolymer mainly consisting of said ester, styrene-butylmethacrylate copolymer,

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Dry Development In Electrophotography (AREA)
  • Wet Developing In Electrophotography (AREA)
US00115141A 1970-02-12 1971-02-12 Removal of protective resin layer by liquid developer in electrophotographic imaging Expired - Lifetime US3717461A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP45012192A JPS5023301B1 (enrdf_load_stackoverflow) 1970-02-12 1970-02-12

Publications (1)

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US3717461A true US3717461A (en) 1973-02-20

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Country Status (8)

Country Link
US (1) US3717461A (enrdf_load_stackoverflow)
JP (1) JPS5023301B1 (enrdf_load_stackoverflow)
BE (1) BE762808A (enrdf_load_stackoverflow)
CA (1) CA929016A (enrdf_load_stackoverflow)
DE (1) DE2106720A1 (enrdf_load_stackoverflow)
FR (1) FR2078511A5 (enrdf_load_stackoverflow)
GB (1) GB1326300A (enrdf_load_stackoverflow)
NL (1) NL7101822A (enrdf_load_stackoverflow)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3856548A (en) * 1973-01-05 1974-12-24 Xerox Corp Strippable overcoating for improved xerographic plates
US3907559A (en) * 1969-10-03 1975-09-23 Xerox Corp Imaging process employing friction charging in the presence of an electrically insulating developer liquid
US3933667A (en) * 1972-03-11 1976-01-20 Kabushiki Kaisha Ricoh Double dispersion acrylate or methacrylate wet developer
US3954640A (en) * 1973-06-27 1976-05-04 Xerox Corporation Electrostatic printing inks
US3971658A (en) * 1973-03-14 1976-07-27 Xerox Corporation Imaging process employing friction charging in the presence of an electrically insulating liquid
US4005437A (en) * 1975-04-18 1977-01-25 Rca Corporation Method of recording information in which the electron beam sensitive material contains 4,4'-bis(3-diazo-3-4-oxo-1-naphthalene sulfonyloxy)benzil
US4011078A (en) * 1972-01-14 1977-03-08 Xerox Corporation Photosensitive member and method of imaging

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2907674A (en) * 1955-12-29 1959-10-06 Commw Of Australia Process for developing electrostatic image with liquid developer
US3102026A (en) * 1957-12-24 1963-08-27 Metcalfe Kenneth Archibald Electrophotographic reflex and contact printing
US3120446A (en) * 1961-02-01 1964-02-04 Xerox Corp Method of transferring a developed solid particulate image
US3192043A (en) * 1960-10-07 1965-06-29 Commw Of Australia Method for developing and fixing electrostatic images in initially partially cured base elements
US3251688A (en) * 1962-07-02 1966-05-17 Xerox Corp Liquid transfer development
US3372027A (en) * 1964-05-15 1968-03-05 Xerox Corp Xerographic liquid development
US3434832A (en) * 1964-10-30 1969-03-25 Xerox Corp Xerographic plate comprising a protective coating of a resin mixed with a metallic stearate
US3551313A (en) * 1968-09-03 1970-12-29 Xerox Corp Image contrast control in photoelectrophoretic imaging

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2907674A (en) * 1955-12-29 1959-10-06 Commw Of Australia Process for developing electrostatic image with liquid developer
US3102026A (en) * 1957-12-24 1963-08-27 Metcalfe Kenneth Archibald Electrophotographic reflex and contact printing
US3192043A (en) * 1960-10-07 1965-06-29 Commw Of Australia Method for developing and fixing electrostatic images in initially partially cured base elements
US3120446A (en) * 1961-02-01 1964-02-04 Xerox Corp Method of transferring a developed solid particulate image
US3251688A (en) * 1962-07-02 1966-05-17 Xerox Corp Liquid transfer development
US3372027A (en) * 1964-05-15 1968-03-05 Xerox Corp Xerographic liquid development
US3434832A (en) * 1964-10-30 1969-03-25 Xerox Corp Xerographic plate comprising a protective coating of a resin mixed with a metallic stearate
US3551313A (en) * 1968-09-03 1970-12-29 Xerox Corp Image contrast control in photoelectrophoretic imaging

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3907559A (en) * 1969-10-03 1975-09-23 Xerox Corp Imaging process employing friction charging in the presence of an electrically insulating developer liquid
US4011078A (en) * 1972-01-14 1977-03-08 Xerox Corporation Photosensitive member and method of imaging
US3933667A (en) * 1972-03-11 1976-01-20 Kabushiki Kaisha Ricoh Double dispersion acrylate or methacrylate wet developer
US3856548A (en) * 1973-01-05 1974-12-24 Xerox Corp Strippable overcoating for improved xerographic plates
US3971658A (en) * 1973-03-14 1976-07-27 Xerox Corporation Imaging process employing friction charging in the presence of an electrically insulating liquid
US3954640A (en) * 1973-06-27 1976-05-04 Xerox Corporation Electrostatic printing inks
US4005437A (en) * 1975-04-18 1977-01-25 Rca Corporation Method of recording information in which the electron beam sensitive material contains 4,4'-bis(3-diazo-3-4-oxo-1-naphthalene sulfonyloxy)benzil
US4065306A (en) * 1975-04-18 1977-12-27 Rca Corporation Electron beam recording media containing 4,4'-bis(3-diazo-3,4-dihydro-4-oxo-1-naphthalene-sulfonyloxy)benzil

Also Published As

Publication number Publication date
JPS5023301B1 (enrdf_load_stackoverflow) 1975-08-06
FR2078511A5 (enrdf_load_stackoverflow) 1971-11-05
DE2106720A1 (de) 1971-08-26
GB1326300A (en) 1973-08-08
NL7101822A (enrdf_load_stackoverflow) 1971-08-16
BE762808A (fr) 1971-07-16
CA929016A (en) 1973-06-26

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