US3743503A - Electro-photographic process using a liquid developer containing a polymeric dye - Google Patents

Electro-photographic process using a liquid developer containing a polymeric dye Download PDF

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US3743503A
US3743503A US00013826A US3743503DA US3743503A US 3743503 A US3743503 A US 3743503A US 00013826 A US00013826 A US 00013826A US 3743503D A US3743503D A US 3743503DA US 3743503 A US3743503 A US 3743503A
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polymeric
dye
radical
diazo
styrene
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M Goldman
S Merrill
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Eastman Kodak Co
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Eastman Kodak Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/12—Developers with toner particles in liquid developer mixtures
    • G03G9/13—Developers with toner particles in liquid developer mixtures characterised by polymer components
    • G03G9/131—Developers with toner particles in liquid developer mixtures characterised by polymer components obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/12—Developers with toner particles in liquid developer mixtures
    • G03G9/122—Developers with toner particles in liquid developer mixtures characterised by the colouring agents

Definitions

  • Liquid developer compositions for use in developing electrostatic charge patterns are formed of an electrically insulating organic carrier liquid having dispersed therein marking particles comprised of a polymeric dye having a linear backbone chain to which are attached pendant side chains containing a chromophoric moiety.
  • This invention relates to electrophotography and more particularly, to the development of electrostatic images using liquid development techniques and compositions.
  • an element comprised of a support having on it a layer of a photoconductive composition comprising a resinous binder and a photoconductor, either organic or inorganic, which in the dark will accept and retain an electrostatic charge
  • a photoconductive composition comprising a resinous binder and a photoconductor, either organic or inorganic, which in the dark will accept and retain an electrostatic charge
  • the element is then exposed in any suitable manner so as to vary the charge thereon in accordance with the relative energy received by the element during the exposure.
  • the element is usually developed by applying thereto a charge powder which is drawn to the element in conformity with the charge pattern produced by exposure. The powder is then fixed or fused in some manner thus producing a powder image.
  • Liquid developers such as those disclosed previously in US. Pat. No. 2,907,674, are usually composed of an insulating carrier liquid, a pigment such as carbon black and a resin to bind the pigment.
  • a pigment such as carbon black
  • a resin to bind the pigment.
  • the pigment when the pigment is deposited in an imagewise fashion, it scatters unabsorbed light rather than transmitting it. Such scattering of light makes pigment-containing developers of this type unsuitable for possible application in a multicolor subtractive process.
  • a further difiiculty with pigment-containing liquid developers of this type is that the pigment and the resin binder do not necessarily have the same electrostatic charge polarity. Such bicharging can result in unwanted background density in images prepared from these developers. Still another problem encountered is that the pigment and the binder are not always depleted at the same rate. This latter problem results in a continually changing developer concentration with use. Such a condition is highly undesirable in that each of a series of images developed in one developer solution will not be uniform in quality. Still another problem that is sometimes encountered is that of the color leaching out of developed images.
  • Still another object of this invention is to provide methods for preparing novel liquid developers containing substantially transparent, non-leachable colored dyes.
  • a liquid developer composition comprised of a carrier liquid containing a polymeric dye.
  • the polymeric dyes used in this invention are comprised of a linear backbone chain having attached thereto pendant side chains containing a chromophoric moiety.
  • the polymeric dyes of this invention are typically prepared by forming a polymeric coupler which is then reacted with a suitable material to form the polymeric dye.
  • polymeric couplers polymers having nuclei which are capable of coupling with, for example, the oxidation products of color coupling aromatic primary amino developing agents such as formed on development of silver salt images to form an azomethine dye.
  • Such polymeric couplers also include polymers having nuclei which are capable of coupling with diazotized aromatic amines to form azo dyes. Nuclei of the above type are well known in the dye art and color photography art. They are sometimes called color-forming couplers, colorformers, coupling components, etc.
  • dye intermediate nuclei or coupling nuclei generally have as the active coupling group one of the following: (a) an active openchain methylene group; (b) an active cyclic methylene group; and (c) a phenolic nucleus bearing an active methine group.
  • the hydrogen atom at the coupling position of the coupler can be replaced by a moiety which is readily eliminated in the coupling reaction, e.g., halogen, sulfonic acid, carboxylic acid, etc.
  • Yellow couplers usually contain group (a) above, magenta couplers generally contain group (a) or (b) while cyan couplers typically contain group (c).
  • a suitable first vinyl monomer and a vinyl-containing dye intermediate or color-former are polymerized together to form a hydrophobic polymeric coupler having a linear backbone chain with pendant side chains attached thereto containing a color-forming nucleus.
  • the first vinyl monomer, which contains no color-former can be selected from a wide variety of materials depending upon the physical properties desired in the final polymer.
  • Useful monomers would include styrene, including substituted styrene having such substituents as an amino radical and alkyl radicals preferably having about 4 to 18 carbon atoms; alkyl acrylates having from about 4 to 18 carbon atoms in the alkyl moiety such as isobutyl, pentyl, hexyl, decyl, dodecyl, pentadecyl, octadecyl acrylates, e'tc.; vinyl acetate; vinyl chloride; vinyl alkyl ethers having from about 4 to 18 carbon atoms in the alkyl moiety such as isobutyl, pentyl, hexyl, decyl, dodecyl, pentadecyl, octadecyl, etc.; alkyl methacrylates having from about 4 to 18 carbon atoms in the alkyl moiety such as isobutyl, pentyl, hex
  • Monomers containing these longer alkyl radicals produce polymeric dyes having an enhanced compatibility with the hydrocarbon carrier liquids used in forming the liquid developers of the present invention.
  • mixtures of a predominant amount of the preferred monomers with monomers which do not contain the longer alkyl radicals are also useful.
  • the second vinyl monomer used in forming the polymeric couplers is, in general, similar to the first vinyl monomer, only attached thereto is a substituent which contains a color-forming nucleus.
  • This color-forming nucleus can be (a) an active open chain methylene group, (b) an active cyclic methylene group or (c) a phenolic nucleus having an active methine group attached.
  • the first and second monomers are then copolymerized by typical vinyl polymerization techniques to form a suitable polymeric coupler.
  • useful polymeric couplers can be prepared by forming a linear polymer having reaction sites where color-forming substituents can subsequently be attached.
  • the resultant polymeric couplers are comprised of a linear backbone chain having pendant side chains containing as the coupling unit one of the following: (a) an open chain methylene coupling moiety, (b) a cyclic methylene coupling moiety and (c) an active methinesubstituted phenolic coupling moiety.
  • polymeric couplers described above can be readily converted to polymeric dyes useful in developers of the present invention.
  • the polymeric couplers are reacted with oxidation products of color coupling aromatic primary amine developing agents such as p-phenylenediamines and p-aminophenol.
  • aromatic primary amine developing agents include:
  • the resultant polymeric dyes are azomethine dyes.
  • diazotized aromatic amines diazotized aromatic amines
  • azo dyes diazotized aromatic amines
  • Advantageous diazonium salts include benzene diazonium salts such as those having the formula:
  • an amino radical including substituted amino radicals which can be cyclic radicals including the amino nitrogen atom and other hetero atoms such as oxygen, sulfur, nitrogen, etc.
  • Z is an acid anion.
  • These compounds can also be substituted on one or more of the nuclear benzene carbons with, for example, at least one of either a halogen atom,
  • Aliphatic alkyl radicals are defined herein to inelude straight and branched chain alkyl radicals having from 1 to 8 carbon atoms such as methyl, ethyl, isopropyl, tert-vutyl, n-amyl, octyl and the like.
  • useful diazonium salts include p-aminobenzenediazonium salts having the formula as described above wherein M is either an amino radical including substituted amino radicals or a thioether radical such as described above, and wherein the benzene nucleus is unsubstituted or substituted in at least one of the 2-position and the 5-position with either an aliphatic alkyl radical or an alkoxy radical.
  • M is either an amino radical including substituted amino radicals or a thioether radical such as described above
  • benzene nucleus is unsubstituted or substituted in at least one of the 2-position and the 5-position with either an aliphatic alkyl radical or an alkoxy radical.
  • This class of useful diazonium salts can be represented by the formula:
  • D is either a sulfur atom or a radical having the formula NR
  • R when taken alone, is either a hydrogen atom when D is NR or a lower aliphatic alkyl radical, a lower alkoxy radical, an acyl radical having the formula:
  • T is either an aryl radical or an alkyl radical as described elsewhere herein, or a phenyl radical when D is either a sulfur atom or NR 3)
  • R when taken alone, is either a hydrogen atom, a lower alkyl radical or a lower alkoxy radical
  • R and R when taken alone, is a lower alkyl radical
  • R and R when taken together, are the number of carbon and hetero oxygen atoms necessary to complete a morpholino radical
  • R and R is a hydrogen atom, a lower alkyl radical or a lower alkoxy radical
  • Z is either a chlorozincate anion, a fluoroborate anion, a sulfate anion, a phosphate anion, or a chlorostannate anion.
  • R and R are alkoxy radicals when R and R complete a morpholino radical
  • R and R are each a hydrogen atom when R and R are each a lower alkyl radical.
  • Suitable diazonium salts are compounds as the salts of l-diazo-2,5-dimethoxybenzene; 1-diazo-2,5-diethoxyb enzene; 1-diazo-4-chloro-2,S-diethoxybenzene; 4-diazo-2,5-dimethoxybiphenyl; 4- diam-2,5 ,4-triethoxybiphenyl; 1-diazo-4-dimethylaminobenzene; l-diazo-4- (diethoxyamino) benzene; 1-diazo-4- [bis (hydroxypropyl) amino] benzene; l-diazo-4- (N-methyl-N-allylamino benzene; 1-diazo-4- (diamylamino benzene; 1-diazo-4- (oxazolidino) benzene; 1-diazo-4- (cyclohexylamino benzene; 1-d
  • substituted diazonium salts are also useful. Any or all of the remaining carbon atoms can be substituted with a variety of substituents such as a lower alkyl radical of 1 to 5 carbon atoms, a lower alkoxy radical having 1 to 5 carbon atoms, an aryl radical such as phenyl, tolyl, etc., a halogen atom such as chlorine, etc., a heterocyclic radical such as morpholino, etc., a nitro radical, an amino radical, including substituted amino radicals, and the like.
  • substituents such as a lower alkyl radical of 1 to 5 carbon atoms, a lower alkoxy radical having 1 to 5 carbon atoms, an aryl radical such as phenyl, tolyl, etc., a halogen atom such as chlorine, etc., a heterocyclic radical such as morpholino, etc., a nitro radical, an amino radical, including substituted amino radicals, and the like.
  • Azo and azomethine type polymeric dyes are representative of a wide variety of polymeric dyes which are suitable for use in the formation of liquid developer compositions in accordance with this invention.
  • Thiazone type polymeric dyes can be formed using N-acrylamidomethylthionine prepared as described in J. Polymer Sci., A-6, 2967 (1968) and copolymerizing with styrene or other suitable monomer to produce a blue polymeric dye.
  • Triphenylmethane type dyes can 'be prepared using the polymerizable triphenylmethane, base, bis(p-aminopheny1)-p-vinyl-phenyl carbinol, Ber.
  • Anthraquinone type polymeric dyes can be prepared by copolymerizing glycidyl methacrylate with styrene or acrylic esters and treating the resultant polymer With 1,4-diaminoanthraquinone to give a blue dye (GA. 65 13853).
  • Polymeric styryl dyes are prepared, for example, by copolymerizing vinyl phthalic anhydride with styrene or other suitable monomers and treating the product with 2-(4-hydroxyethoxystyryl)pyridinium chloride to form a yellow dye.
  • suitable polymeric dyes can be formed by copolymerizing a dye containing a polymerizable group with a suitable monomer.
  • suitable materials can be prepared by copolymerizing azo and anthraquinone 6 dyes containing a polymerizable group, said polymerizable group having the general formula:
  • R represents a hydrogen atom or a lower alkyl radical having from 1 to 3 carbon atoms such as methyl, ethyl, isopropyl, etc.
  • Suitable materials for copolymerizing with the above dyes would include the following: vinyl chloride, vinyl sulfonic acid, styrene and derivatives substituted on the benzene nucleus, acrylic acid, u-chloroacrylic acid, acrylic acid esters, methacrylic acid esters of methacrylic acid, a-chloroacrylic acid esters, esters of maleic acid, fumaric acid, crotonic acid, maleic anhydride, acrylamide or acrylonitrile, esters of vinyl alcohol and of allyl alcohol With organic acids, vinyl ethers, N-vinylcarbazole, N-vinylpyrrolidone, vinylidene chloride or vinylidene cyanide. Mixtures of the above dyes can be used as can mixtures of the above polymerizable groups.
  • polymeric dyes can be prepared in several different ways; however, the resultant materials have features in common.
  • the final polymeric dyes typically have a linear backbone to which are attached pendant side chains containing a chromophore.
  • the number of side chains attached to the linear backbone can be very large, but the number of side chains containing a chromophoric moiety canbe quite small in comparison.
  • the chromophoric moieties which are functional in the useful polymeric dyes can include azo, azomethine (including indoaniline), thiazine, triphenylmethane, styryl, anthraquinone, oxazine and the like dye moieties, with azo and azomethine dye moieties being among the preferred.
  • the chromophoric moiety typically comprises only a minor portion of the polymeric dye. In general, the polymeric dyes used in this invention contain from about 5 to about 50% by weight of the chromophoric moiety.
  • the electrostatic charge polarity of the marking particles of the present invention can be enhanced or altered by the addition of suitable charge control agents.
  • suitable charge control agents A variety of materials can be used as charge control agents. Illustrative of suitable materials would be polyoxyethylated alkyl surfactants such as polyoxyethylated alkylamine, polyoxyethylene palmitate, polyoxyethylene stearate, etc. Other useful materials are magnesium and heavier soaps of fatty and aromatic acids as described in Beyer US. Pat. No. 3,417,019.
  • Useful metal soaps include cobalt naphthenate, magnesium naphthenate, manganese naphthenate, zinc resinate, calcium naphthenate, zinc linoleate, aluminum resinate, isopropyl titanium stearate, aluminum stearate, and others many of which are also described in US. Pat. No. 3,259,581.
  • the polymeric dyes of the present invention can be used alone or in conjunction with a colorless resin.
  • Suitable colorless resins can be used if desired to facilitate binding of the colorant to the surface to be developed.
  • Suitable resinous materials for this purpose can be selected from a wide variety of substances.
  • rosins including hydrogenated rosins and esters of hydrogenated rosins
  • alkyl methacrylate copolymers having from 1 to 18 carbon atoms in each alkyl moiety, such as isobutyl methacrylate, n-butyl methacrylate copolymers, etc.
  • phenolic resins including modified phenolic resins such as phenol formaldehyde resins; pentaearythritol phthalate, coumarone-indene resins; ester gum resins; vegetable oil polyamides
  • alkyd resins including modified alkyd resins such as soya-oil-modified and linseed-oil-modified alkyds, phthalic, maleic and styrenated alkyds, etc., and the like.
  • Suitable colorless resins are typically used in amounts between about 25 to 75% by weight based on the total toner composition.
  • Developers according to the present invention are typically prepared by forming suitable size particles of the polymeric dye and any other desired addenda and dispersing these particles in an insulating liquid.
  • the marking particles can be prepared by various methods. Two convenient techniques for producing these particles are spray-drying or melt-blending followed by grinding.
  • the spray-drying technique involves dissolving the polymeric dye typically in a volatile organic solvent such as dichloromethane. This solution is then sprayed through an atomizing nozzle using a substantially nonreactive gas such as nitrogen as the atomizing agent. During atomization, the volatile solvent evaporates from the airborne droplets, producing particles of polymeric dye.
  • the ultimate particle size is determined by varying the size of the atomizing nozzle and the pressure of the gasous atomizing agent. conventionally, particles of a diameter between about A and about 25 microns are used, with particles between about 1 and 15 microns being preferred, although both larger and smaller particles can be used where desired for particular developer conditions or developer compositions.
  • suitable toner particles can also be prepared by melt-blending. This technique involves melting a polymeric dye and any of the other desired additives. The materials can be readily melted on heated compounding rolls which are also useful to stir or other- Wise blend the various ingredients. After thorough blending, the mixture is cooled and solidified. The resultant mass is then broken into small pieces and finely ground to form a free-flowing powder of toner particles.
  • the resultant particles usually range in size from about A to about 25 microns as above.
  • Carrier liquids which may be used to form the present developers can be selected from a wide variety of materials. Preferably, this liquid has a low dielectric constant and a very high electrical resistance such that it will not disturb or destroy the electrostatic latent image being developed. In general, useful carrier liquids should have a dielectric constant of less than about 3, should have a volume resistivity of greater than about 10 ohm-cm. and should be stable under a variety of conditions.
  • Suitable carrier liquids include halogenated hydrocarbon solvents, for example, fluorinated lower alkanes, such as trichloromonofiuoromethane, trichlorotrifluoroethane, etc., having a typical boiling range of from about 2 to about 55 C.
  • Other hydrocarbon solvents are also useful such as isoparaffin hydrocarbons having a boiling range of from about 150 to about 185 C. such as Isopar G (Humble Oil and Refining Co.).
  • Additional useful carrier liquids include polysiloxanes, odorless mineral spirits, octane, cyclohexane, etc. Another property of the carrier liquid is that it cannot be a complete solvent for the polymeric dye. When colorless resins are also used, a small degree of solubility of the resin in the carrier can be tolerated.
  • Developer compositions can also be prepared by dissolving the present polymeric dyes in a small amount of solvent followed by dispersing this solution in a nonsolvent for the polymeric dye.
  • Useful developer compositions prepared by suitable means typically have from about 0.1 to about 10 g. of toner material per liter of carrier liquid, with a preferred concentration of about /2 to g./l.
  • EXAMPLE 1Yellow polymeric dye A mixture of 56 g. of styrene, 14 g. of p-aminostyrene and 2 g. of azobisisobutyronitrile is flushed with nitrogen and heated to 100 C. for 16 hours. This gives solid poly (styrene-co-p-arninostyrene) with an amine equivalent weight of 595. Next, 9 g. (.015 mole of amine) of the above copolymer are dissolved in 40 ml. of pyridine to which is added 6.5 g. (.020 mole) of a-pivalyl-4-chlorosulfonylacetanilide. The mixture is stirred for 2 hours at 65 C.
  • the yield of poly ⁇ u(4-diethylamino- Z-methylphenylimino) a pivalyl 4 [N-(4-vinylphenyl)sulfamyl]acetanilide-co-styrene ⁇ is 2.8 g.
  • the absorption maximum of a chloroform solution of this yellow dye is 450 nm.
  • EXAMPLE 2-Magenta polymeric dye A mixture of 126 g. of styrene and 14 g. of p-arninostyrene are copolymerized as in Example 1. To 20 g. (0.017 mole) of the poly(styrene-co-p-aminostyrene) in ml. of tetrahydrofuran and 3 ml. of pyridine is added 6.2 g. (0.018 mole) of 1-phenyl-3-(2-chlorocarbonylbenzamido)-5-pyrazolone in 60 ml. of tetrahydrofuran at 10 C. The mixture is stirred at 40 to 50 C. for 2 hours and poured into water to precipitate the product.
  • EXAMPLE 3-Cyan polymeric dye A solution of 45 g. of styrene, 5 g. of N-(3,5-dichloro- 2-hydroxy-4-methylphenyl)acrylamide and 2.5 g. of a20- bisisobutyronitrile in 20 ml. dimethylformamide is flushed with nitrogen and heated at 60 C. for 20 hours. The resultant copolymer, poly[N-(3,5-dichloro-2-hydroxy 4- methylphenyl)acrylamide-co-styrene], is recovered by precipitation in methanol.
  • the polymeric coupler is converted to a cyan dye, poly ⁇ 6-acrylamido-2-chloroN-[(4-diethylamino-2-methyl)phenyl] 3 methyl p benzoquinone imine-co-styrene ⁇ , in accordance with the coupling procedure of Example 1.
  • the polymeric dye in a chloroform solution has an absorption maximum at 665 nm.
  • EXAMPLES 4-6 Each of the dyes produced according to Examples 1 through 3 is dissolved in a separate portion of dichloromethane using 1 g. of dye in about 84 g. of solvent. The solution is then spray-dried through a pneumatic atomizing nozzle using nitrogen gas at 10 p.s.i.g. as the atomizing gas. The solvent is dried off at room temperature to produce toner particles having an average particle size of about 2 microns. Developer compositions A, B and C are prepared using the toner particles containing the polymeric dyes of Examples 1, 2 and 3, respectively. A 0.5 g. portion of the spray-dried toner particles is dispersed in 250 ml. of an Isopar G (supra).
  • Each of the three developers is then used to develop an electrostatic charge pattern on an electrophotographic element.
  • This element is comprised of a conductive support having thereon a photoconductive layer containing an organic photoconductor dispersed in a polycarbonate binder. This element is uniformly charged by subjecting it to a negative polarity corona discharge in the dark. The element is given an imagewise exposure which causes dissipation of the charge in the exposed areas thus forming an electrostatic charge pattern. The element is then placed into contact with one of the above developers. This procedure is repeated for all three developers using a different element each time. The resultant positive images are not fixed; however, exposure to dichloromethane vapor for a brief period causes the images to be fixed. All three images are of good quality.
  • EXAMPLE 7-Azo polymeric dyes The polymeric coupler, poly ⁇ u pivalyl-4-[N-(4-vinylphenyl)-sulfamyl] acetanilide-co-styrene ⁇ , of Example 1 is added to a molar excess of an alkaline aqueous solution of 4-diethylaminobenzene-diazonium zinc chloride double salt. The mixture is stirred for about 30 minutes at room temperature and a yellow polymeric dye (No.
  • poly ⁇ a- (4-diethylaminophenylazo) a pivalyl-4-[N-(4-vinylphenyl) sulfamyl] acetanilide-co-styrene ⁇ is precipitated.
  • This same procedure is repeated using the polymeric coupler of Example 2 to produce a magenta dye (No. poly ⁇ N-4 vinylphenyl) N [4-(4-diethylaminophenylazo) 1 phenyl 5 pyrazolon 3 -yl]phthalamic acidco-styrene ⁇ .
  • the polymeric coupler, poly[N-(3, 5-dichloro-2-hydroxy-4-methylphenyl) acrylamide costyrene] of Example 3 is treated with a molar excess of the above diazonium salt under alkaline conditions to form a cyan dye (No. 6), poly[6-acrylamido 2 chloro- 4 (4 diethylaminophenylazo) 3 methylphenol costyrene].
  • Polymeric dyes Nos. 4, 5 and 6 are each dissolved in dichloromethane and spray-dried as in Examples 4-6 to produce dye particles. About /2 g. of dye is dispersed in 250 ml. of Isopar G to form three developer compositions D, E and F, respectively. Each of these developers is then used to develop an electrostatic charge pattern as described in Examples 4-6. The resultant images are all of good quality.
  • liquid developer comprised of an electrically insulating hydrocarbon carrier liquid having a dielectric constant of less than about 3 and a volume resistivity of greater than 10 0hm-cm., said liquid having dispersed therein marking particles comprising at least one polymeric dye, said polymeric dye consisting essentially of the reaction product of (1) a polymeric coupler having a linear backbone chain to which are attached pendant side chains containing a coupling unit selected from the group consisting of an open chain active methylene coupling moiety, a.
  • marking particles having a particle size Within the range of from about 0.25 to about 25 microns and wherein said marking particles are present in said liquid developer in a concentration of about 0.1 to 10 grams per liter of developer.
  • oxidation product developing agents are selected from the group consisting of oxidized p-phenylene diamines and oxidized p-aminophenols.
  • diazonium salt is a p-amino-benzene diazonium salt.
  • polymeric dye is comprised of a linear backbone chain formed of a vinyl polymer.
  • linear backbone chain contains polymerized monomers selected from the group consisting of styrene, alkyl acrylates having from about 4 to 18 carbon atoms in the alkyl moiety, vinyl acetate, vinyl chloride, vinyl alkyl ether having from about 4 to 18 carbon atoms in the alkyl moiety, alkyl methacrylate having from about 4 to 18 carbon atoms in the alkyl moiety and mixtures thereof.
  • marking particles contain from about 25 to by weight of a colorless resin.
  • polymeric dye is selected from the group consisting of poly ⁇ 6acrylamido-2-chloro-N- (4-diethylamino-2-metlily phenyl] -3 -methyl-p-benzoquinone imine-co-styrene ⁇ ,

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Cited By (8)

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US4308327A (en) * 1979-10-26 1981-12-29 George Bird Motion picture film having digitally coded soundtrack and method for production thereof
US4366217A (en) * 1979-10-26 1982-12-28 George Bird Motion picture film having digitally coded soundtrack and method for production thereof
US5023160A (en) * 1989-11-08 1991-06-11 Xerox Corporation Liquid developer compositions
US5521271A (en) * 1994-09-29 1996-05-28 Minnesota Mining And Manufacturing Company Liquid toners with hydrocarbon solvents
US5530067A (en) * 1994-05-17 1996-06-25 Minnesota Mining And Manufacturing Company Liquid toners utilizing highly fluorinated solvents
US5604070A (en) * 1995-02-17 1997-02-18 Minnesota Mining And Manufacturing Company Liquid toners with hydrocarbon solvents
US20060032748A1 (en) * 2004-08-13 2006-02-16 Mcpheron Douglas A Method for coating objects
US20060160009A1 (en) * 2005-01-18 2006-07-20 Itipon Padunchwit Color toner and developer compositions and processes for making and using such compositions

Cited By (16)

* Cited by examiner, † Cited by third party
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US4366217A (en) * 1979-10-26 1982-12-28 George Bird Motion picture film having digitally coded soundtrack and method for production thereof
US4308327A (en) * 1979-10-26 1981-12-29 George Bird Motion picture film having digitally coded soundtrack and method for production thereof
US5023160A (en) * 1989-11-08 1991-06-11 Xerox Corporation Liquid developer compositions
US5530053A (en) * 1994-05-17 1996-06-25 Minnesota Mining And Manufacturing Company Liquid toners utilizing highly fluorinated solvents
US5530067A (en) * 1994-05-17 1996-06-25 Minnesota Mining And Manufacturing Company Liquid toners utilizing highly fluorinated solvents
US5663024A (en) * 1994-09-29 1997-09-02 Minnesota Mining And Manufacturing Company Liquid toners with hydrocarbon solvents
US5599886A (en) * 1994-09-29 1997-02-04 Minnesota Mining And Manufacturing Company Liquid toners with hydrocarbon solvents
US5521271A (en) * 1994-09-29 1996-05-28 Minnesota Mining And Manufacturing Company Liquid toners with hydrocarbon solvents
US5604070A (en) * 1995-02-17 1997-02-18 Minnesota Mining And Manufacturing Company Liquid toners with hydrocarbon solvents
US5753763A (en) * 1995-02-17 1998-05-19 Minnesota Mining And Manufacturing Company Process for preparing liquid toners with hydrocarbon solvents
US5919866A (en) * 1995-02-17 1999-07-06 Minnesota Mining And Manufacturing Company Liquid toners with hydrocarbon solvents
US20060032748A1 (en) * 2004-08-13 2006-02-16 Mcpheron Douglas A Method for coating objects
US20060160009A1 (en) * 2005-01-18 2006-07-20 Itipon Padunchwit Color toner and developer compositions and processes for making and using such compositions
WO2006078616A1 (en) * 2005-01-18 2006-07-27 Milliken & Company Color toner and developer compositions and processes for making and using such compositions
US7399566B2 (en) 2005-01-18 2008-07-15 Milliken & Company Color toner and developer compositions and processes for making and using such compositions
CN100561362C (zh) * 2005-01-18 2009-11-18 美利肯公司 彩色色调剂和显影剂组合物及该组合物的制造和使用方法

Also Published As

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GB1342318A (en) 1974-01-03
CA941213A (en) 1974-02-05
DE2104310B2 (de) 1976-01-29
FR2078701A5 (cg-RX-API-DMAC10.html) 1971-11-05
DE2104310A1 (de) 1971-09-02
BE763107A (fr) 1971-07-16

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