Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G17/00—Electrographic processes using patterns other than charge patterns, e.g. an electric conductivity pattern; Processes involving a migration, e.g. photoelectrophoresis, photoelectrosolography; Processes involving a selective transfer, e.g. electrophoto-adhesive processes; Apparatus essentially involving a single such process
  • G03G17/02—Electrographic processes using patterns other than charge patterns, e.g. an electric conductivity pattern; Processes involving a migration, e.g. photoelectrophoresis, photoelectrosolography; Processes involving a selective transfer, e.g. electrophoto-adhesive processes; Apparatus essentially involving a single such process with electrolytic development
• • 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
  • G03G5/0503—Inert supplements
  • G03G5/0507—Inorganic compounds
• • 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
  • G03G5/0503—Inert supplements
  • G03G5/051—Organic non-macromolecular compounds
  • G03G5/0514—Organic non-macromolecular compounds not comprising cyclic groups

Definitions

• Photoconductography forms a complete image at one time or at least a non-uniform part of an image as distinguished from facsimile which at any one moment produces only a uniform dot.
• the present invention is applicable to all forms of photoconductography and cross reference is made to the following series of applications filed July 28, 1960, illustrating various types of photoconductography in which this invention can be applied:
• a coating of zinc oxide in a suitable resinous binder is applied on a conductive substrate such as aluminum foil. Any metal support of high conductivity can be used as the conductive substrate. Another useful substrate is NESA glass.
• the coating is then moistened. using an electrolyte, herein referred to as the developer, which may be a manganese nitrate-silver nitrate solution as described in application Serial No. 45,945 above. It has been desirable to increase the speed, gamma, and D' and we have found that increases in these values have been obtained by incorporating amines in the resinous photoconductographic coatings containing zinc oxide.
• the coatings produced have improved image quality, higher image densities at lower exposures at line copy reproduction, and improved tone quality and definition in continuous-tone reproduction.
• One object of this invention is to increase the speed, gamma, and D' in zinc oxide resinous photoconductographic coatings. Another object is to produce improved image quality, higher image densities at lower exposures at line copy reproduction, and improved tone quality and definition in continuous-tone reproduction. A further object is to provide a method for improving the quality of photoconductographic coatings by incorporating amines in the resinous binders used in such coatings.
• An additional object is to provide an improved photoconductographic recording material.
• the above objects are obtained by incorporating 0.01 to 4.0% by weight of an ammonium or amine compound in the zinc oxide resinous coating based on the zinc oxide content.
• the ammonium or amine compounds useful in our invention are those found in two groups.
• the second group is R N+X- where the Rs may be the same or different and include R being 1 to 22 carbon alkyl groups derived from fatty acids, i.e., saturated and unsaturated straight chain groups, and X is a halogen such as chlorine or bromine.
• Various resinous binders may be used as carriers for the zinc oxide but we prefer to use a mixture of a styrenebutadiene copolymer, a silicone polymer, and a hydro carbon polymer derived from the deep cracking of petroleum.
• the styrene-butadiene resin maybe one of those well known in the art; see Zwicker, Ind. Eng. Chem., 44, 774-786, especially pages 778-779, and Bovey et al., Emulsion Polymerization, interscience Publishers, Inc., N.Y., 1955, pages 4067.
• butadiene-styrene resins useful in our invention are those in which butadiene and styrene are polymerized in a ratio of butadiene to styrene of 60:40 to 20:80, although the preferred ratio is from 45:55 to 30:70.
• the silicone may be an organo polysiloxane resin having the following general formula:
• x is an integer from 6 to 40
• R is a methyl or phenyl radical, so chosen that both radicals on any given silicon atom are identical and the molar ratio of methyl to phenyl radicals varies from 4:1 to 1:4.
• Higher molecular weight polysiloxanes are operable for use in this invention as long as they are sufiiciently compatible with the styrene-butadiene resin to permit coating.
• the silicone resins may be obtained by the catalytic equilibration procedure disclosed in chapter 6 of E. G. Rochows Introduction to the Chemistry of the Silicones, John Wiley & Sons, Inc., New York, second edition, 1951. Mixtures of dichlorodiphenylsilane and dichlorodimethylsilane are treated with the appropriate quantity of water to hydrolyze the above chlorosilaues with concurrent polymerization.
• the mixture composition may vary from a ratio of 20 molar percent of dichlorodiphenylsilane and 80 molar percent of dimethyldichlorosilane to a ratio of 80 molar percent dichlorodiphenylsilane and 20 molar percent dichlorodimethylsilaue although the preferred mixture is 1:1 on a molar basis.
• the hydrocarbon polymer derived from the deep cracking of petroleum is a pure hydrocarbon thermoplastic terpene polymer composed essentially of fi-pinene.
• resinous binders useful as carriers for the zinc oxide are polystyrene, chlorinated rubber, rubber chloro- Ihydrate, shellac, cellulose ethers, cellulose esters, poly- (vinyl butyral), poly(vinyl chloride), poiy(vinyl acetate) and copolymers of vinyl chloride and vinyl acetate.
• Inert solvents may be used to form a coating mixture and may be selected from mixtures of various solvents such as toluene, Z-butanone, 2-methyl-4-pentanone, metha- Nora-Alkyd represents a mixture of hexadeoyl, octadecenyl, 0cm dcoadienyl, and octadeeatrienyl in approximately 11112.5:5 by weight.
• various solvents such as toluene, Z-butanone, 2-methyl-4-pentanone, metha- Nora-Alkyd represents a mixture of hexadeoyl, octadecenyl, 0cm dcoadienyl, and octadeeatrienyl in approximately 11112.5:5 by weight.
• Toluene, methanol, sodium dioctyl sulfosuccinate, N- alkyltrirnethylenediamine, and zinc oxide are placed in a Waring Blendor and mixed for 20 minutes.
• the butadiene-styrene copolymer, polysiloxane silicone resin, and hydrocarbon thermoplastic terpene polymer are added andmixed an additional 5 minutes. This composition is then coated on an aluminum laminated support.
• a sheet of this coating containing the photoconductive layer prepared from the composition described above is exposed for 15 seconds to 600 f.c. tungsten radiation incident upon a 0-3, 0.3 log E increment silver step tablet in contact with the photoconductive surface.
• the layer is developed in a manganese nitrate-silver nitrate developer-toner system by using a viscous sponge brush electrode, held at 80 volts positive with respect to the zinc oxide layer, with a 1% manganous nitrate solution and 10 strokes development.
• a faint yellowish-brown image ofmanganous hydroxide is produced on the surface of the photoconductor.
• This image is converted to the black adsorption complex of manganese dioxide and reduced silver chemically by treating itwith 5% silver nitrate solution.
• the H and D curve prepared nol, ethanol, xylene, benzene, dioxane, acetone, Solvesso 100, :50 xylene-hexane, and the like, which are common solvents for at least one of the components of the resinous mixture.
• the photocouducting layer After being coated on the substrate and dried, the photocouducting layer should have a weight in the range of 2 to 8 g./ft. with the preferred weight being about 4 g./ft.
• the zinc oxide which can be used in our invention is known as photoconductive zinc oxide. It may be prepared by the French process, the American process, or any other process which produces photoconductive zinc oxide. It may be modified and/or sensitized in accordance with known methods or in accordance with the teach- Containing Zinc Oxide, now U.S. Patent No. 3,132,941.
• butadiene-styrene copolymer, polysiloxane silicone resin, and hydrocarbon thermoplastic terpene polymer are added and themixture is mixed 5 minutes. This composition is then coated on an aluminum laminated support.
• Example 1 A sheet of this coating containing the photoconductive layer prepared from the composition above was exposed for 5 seconds to 400 f.c. tungsten radiation as described in Example 1. Upon termination of exposure, the coating was developed as in Example 1. The H and D curve prepared from this sample indicated that 28 f.c.s. exposure was necessary to produce a density of 0.6 above base.
• N-alkyltrimethylenediamine reduces the exposure required to produce the same density to approximately one-ninth that required by a coating containing no N-alkyltrimethylenediamine. Therefore, the incorporation of N-alkyltrimethylenediamine to optically sensitized zinc oxide dispersions increases photographic speed by nine times.
• polysiloxane silicone resin N-alkyltrimethylenediamine, sodium dioctyl sulfosuccinate, and zinc oxide are placed in a Waring Blendor and mixed minutes.
• HCl gas is added slowly during rapid agitation and the mixture is mixed an additional 30 minutes.
• Sensitizing dye (Crystal Violet) dissolved in methanol is added and the mixture is mixed an additional 5 minutes.
• Butadienestyrene copolymer, polysiloxane silicone resin, and hydrocarbon thermoplastic terpene polymer are added and the mixture is mixed an additional 5 minutes. This composition is then coated on an aluminum laminated support.
• Example 1 A sheet of this coating containing the photoconductive layer prepared from the composition above was exposed for 5 seconds to 400- f.c. tungsten radiation as described in Example 1. Upon termination of exposure, the coat ing was developed as in Example 1. The H and D curve prepared from this sample indicated that 53 f.c.s. exposure was necessary to produce a density of 0.6 above base.
• N-alkyltrimethylenediamine reduces the exposure required to produce the same density to approximately one-fourth that required by a coating containing no N-alkyltrimethylenediamine. Therefore, the incorporation of N-alkyltrimethylenediamine to chemically sensitized oxide dispersions increases speed by four times.
• Photographic speed 1 Alkyl here represents a mixture of octadeeenyl, octadecyl, eicosyl and docosyl in approximately 1': 3 3 3 by weight
• EXAMPLE 5 Optically sensitized zinc oxide dispersion:
• N-alkyltrimethylenediamine, sodium bistridecyl sulfosuccinate, and zinc oxide are placed in a Waring Blendor and mixed 20 minutes.
• Sensitizing dye Rositizing dye (Rose Bengal) dissolved in methanol is added and the mixture is mixed an additional 5 minutes.
• Butadiene-styrene copolymer, polysiloxane silicone resin, and hydrocarbon thermoplastic terpene polymer are added and the mixture an aluminum laminated support.
• a sheet of this coating containing the photoconductive layer prepared from the composition above was exposed for 5 seconds to 400 f.c. tungsten radiation as described in Example 1.
• the coating was developed using an electrolytic developing system involving a developing solution of the following composition:
• An optically sensitized zinc oxide coating was prepared identically using the same composition of materials except that the N-alkyltrime-thylenediamine was omitted. This coating was exposed and developed in the same man- This composition is then coated on H OSK 3 a 6 2] n where n is 3-20.
• the zinc oxide may be used in a ratio of from less than 0521 up to about 10: 1 zinc oxide to binder, although our preferred range is from 1:1 up to 6:1 zinc oxide to binder.
• surfactants improves wettability of the coating and in some instances improves the photographic characteristics.
• sensitizing dyes may be added to the coating composition such as Rose Bengal, fiuorescein, and the like.
• our preferred embodiment employs a developer of manganese nitrate and silver nitrate, other developers may be used including a simple solution of thiourea and silver nitrate in water. Inasmuch as the proportions are disclosed in the copending applications referred to above, this information is not believed critical but may be determined by one skilled in the art regarding the proportions and the particular developers which may be desired.
• an organic amine selected from the class consisting of NR and R NX in which the Rs may be the same or ditferent radicals selected from the class consisting of hydrogen, (CH NH in which n may be 2 to 22, (CH CH NH),,H in which u may be 1 to 11, and alkyl groups derived from fatty acids having 1 to 22 carbon atoms, and X is a halide.
• a photoconductographic element comprising a conductive support having coated thereon a composition con taining 40 to 11% by weight of a copolymer of butadiene and styrene, 5 to 1.4% by weight of a silicone resin, 5 to 1.4% by weight of a hydrocarbon thermoplastic ter-- pene resin, 50 to 86% by weight zinc oxide, and .01 to 4.0% by weight based on the Zinc oxide content of the coating of an organic amine selected from the class consisting of NR; and R NX in which the Rs may be the same or different radicals selected from the class consisting of hydrogen, (CH ),,NH in which n may be 2 to 22, (CH CH NPD H in which 12 may be 1 to 11, and alkyl groups derived from fatty acids having 1 to 22 carbon atoms, and X is a halide.
• a photoconductographic element described in claim 2 having a glass conductive support.
• a photoconductographic element comprising a conductive support having coated thereon a composition containing 14 to 50% by weight of an organic polymeric binder, 50 to 86% by weight zinc oxide, and .01 to 4.0% by weight based on the zinc oxide content of the coating of an organic amine selected from the class consisting of NR and R NX in which the Rs may be the same or 8 difierent radicals selected from'the class consisting of hydrogen, (CH NH in which It may be 2 to 22, (CH CH NH) H in which rt may be 1 to 11, and alkyl groups derived from fatty acids having 1 to 22 carbon atoms, and X is a halide.
• a photoconductographic element comprising a conductive support having coated thereon a composition containing 40 to 11% by weight of a copolymer of butadiene and styrene, 50 to 86% by weight zinc oxide, and .01 to 4.0% by weight based on the Zinc oxide content of the coating of an organic amine selected from the class consisting of NR and R NX in which the Rs may be the same or difierent radicals selected from the class consisting of hydrogen, (CH ,NH in which It may be 2 to 22, (CH CH NI-D H in which n may be 1 to 11, and alkyl groups derivedfrom fatty acids having 1 to 22 carbon atoms, and X is a halide.
• a photoconductographic element comprising a conductive support having coated thereon a composition containing 40 to 11% by weight of a copolymer of vinyl chloride and vinyl acetate, 50 to 86% by weight zinc oxide, and .01 to 4.0% by weight based on the zinc oxide content of the coating of an organic amine selected from the class consisting of NR and R NX in which the Rs may be the same or different radicals selected from the class consisting of hydrogen, (CH NH in which It may be 2 to 22, (CH CH NHLJ-I in which n may be 1 to 11,
• a coating composition comprising dry basis 40 to 11% by weight of a copolymer of butadiene and styrene, 5 to 1.4% by Weight of a silicone resin, 5 to 1.4% by weight of a hydrocarbon thermoplastic terpene resin, 50 to 86% by weight zinc oxide, and .01 to 4.0% by weight based on the zinc oxide content of the coating of an organic amine selected from the class consisting of NR and R NX in which the Rs maybe the same or different radicals selected from the class consisting of hydrogen, (CH J NH in which it may be 2 to 22 (CH CH NH),,H in which 12 may be 1 to 11, and alkyl groups derived from fatty acids having 1 to 22 carbon atoms, and X is a halide.
• an organic amine selected from the class consisting of NR and R NX in which the Rs maybe the same or different radicals selected from the class consisting of hydrogen, (CH J NH in which it may be 2 to 22 (CH CH NH),,H in which 12 may be

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Citations (13)

• 0
  • BE BE617025D patent/BE617025A/xx unknown
• 1961
  • 1961-05-01 US US106531A patent/US3250613A/en not_active Expired - Lifetime
• 1962
  • 1962-03-10 DE DEE22525A patent/DE1170780B/de active Pending
  • 1962-05-01 GB GB16623/62A patent/GB1006609A/en not_active Expired

Patent Citations (13)

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