EP0136744A2 - Verfahren zum Entwickeln von latenten magnetischen Bildern - Google Patents

Verfahren zum Entwickeln von latenten magnetischen Bildern Download PDF

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Publication number
EP0136744A2
EP0136744A2 EP84201209A EP84201209A EP0136744A2 EP 0136744 A2 EP0136744 A2 EP 0136744A2 EP 84201209 A EP84201209 A EP 84201209A EP 84201209 A EP84201209 A EP 84201209A EP 0136744 A2 EP0136744 A2 EP 0136744A2
Authority
EP
European Patent Office
Prior art keywords
magnetic
toner
carbon atoms
image
acid
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.)
Withdrawn
Application number
EP84201209A
Other languages
English (en)
French (fr)
Other versions
EP0136744A3 (de
Inventor
Stephen L. Gaudioso
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xerox Corp
Original Assignee
Xerox Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US06/115,973 external-priority patent/US4271248A/en
Priority claimed from US06/115,974 external-priority patent/US4288516A/en
Application filed by Xerox Corp filed Critical Xerox Corp
Publication of EP0136744A2 publication Critical patent/EP0136744A2/de
Publication of EP0136744A3 publication Critical patent/EP0136744A3/de
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • G03G9/083—Magnetic toner particles
    • G03G9/0831—Chemical composition of the magnetic components
    • G03G9/0833—Oxides
    • 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
    • G03G9/083—Magnetic toner particles
    • G03G9/0831—Chemical composition of the magnetic components
    • G03G9/0832—Metals
    • 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
    • G03G9/087—Binders for toner particles
    • G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08755—Polyesters

Definitions

  • This invention relates to methods for developing magnetic latent images.
  • the latent magnetic image may be provided by any suitable magnetization procedure. Typically, a magnetizable layer of marking material is arranged in imagewise configuration on a magnetic substrate. Well-known electrostatographic methods are sometimes used to accomplish this. The latent image may then be developed and fused. There a number of known methods for creating the latent image which are described, for example, in US-A-4 032 923; 4 060 811; 4 074 276; 4 030 105; 4 035 810; 4 101 904 and 4 121 261.
  • the magnetizable toner is developed in imagewise configuration onto an electrophotographic recording surface.
  • the toner is then magnetized, for example, by an electronic recording head.
  • the layer supporting the magnetized toner is then brought into contact with a magnatizable layer and the magnetized toner magnetizes the magnetizable layer in image configuration.
  • a latent magnetic image is thus formed in the magnetizable layer corresponding to the imagewise arrangement of magnetized toner particles.
  • Typical fusing methods used in magnetic imaging include, for example, heating the toner image to cause the resin thereof to melt at least partially and become adhered to the transfer medium, followed by application of pressure to the toner, such as by use of a heated roller. Solvent or solvent vapor fusing has also been used, wherein the resin component of the toner is partially dissolved.
  • a non-contact flash fusing system such as that well known in electrophotographic machines, should be used. Aside from higher process speed, improved reliability, especially for paper handling, and higher copy quality are attained.
  • toner materials which function satisfactorily with a hot-pressure roll fuser do not perform satisfactorily with a flash fuser. This is because of the significantly-different process-related rheological criteria for these two systems.
  • toner For contact pressure roll fusing, one needs a toner with shear-dependent viscosity (i.e., low viscosity at high shear and relatively high viscosity at low shear) and sufficient viscoelasticity to avoid hot set-off to the fuser roll over the fusing temperature interval of interest.
  • shear- dependent viscosity i.e., low viscosity at high shear and relatively high viscosity at low shear
  • sufficient viscoelasticity to avoid hot set-off to the fuser roll over the fusing temperature interval of interest.
  • non-contact flash fusing one desires a toner with a strongly temperature-dependent viscosity and minimal elasticity such that the molten toner will rapidly flow and penetrate the paper fibers at the fusing temperature without benefit of contact-induced shear.
  • the toner materials designed for, and found most acceptable in, roll fusing do not have the desired rheological properties for flash fusing.
  • Diphenols wherein R represents an alkylidene radical having from 2 to 4 carbon atoms, and R' and R" represent an alkylene radical having from 3 to 4 carbon atoms are preferred because greater blocking resistance, increased definition of characters and more complete transfer of toner images are achieved.
  • Optimum results are obtained with diols in which R is a isopropylidene radical, and R' and R" are propylene or butylene radicals because the resins formed from these diols possess higher agglomeration resistance and penetrate extremely rapidly into paper sheets under fusing conditions.
  • Dicarboxylic acids having from 3 to 5 carbon atoms are preferred because the resulting toner resin possess greater resistance to film formation on reusable imaging surfaces and resist the formation of fines under machine operation conditions.
  • alpha unsaturated dicarboxylic acids including fumaric acid, maleic acid or maleic acid anhydride because maximum resistance to physical degradation of the toner as well as rapid melting properties are achieved. It is believed that the presence of the unsaturated bonds in the alpha unsaturated dicarboxylic acid reactants provides the resin molecules with a greater degree of toughness without adversely affecting the fusing and comminution characteristics.
  • Diphenolic reactants are well known and may be prepared, for example, by reacting the alkali salts of an alkylidene or cycloalklidene diphenol and the appropriate olefin chlorhydrin as disclosed, for example, in US-A-2 331 265.
  • Another well-known method for preparing the diphenolic alcohols represented by the formula above consists of the direct addition of an alkylene oxide or arylene oxide to alkylidene or cycloalkylidene diphenols.
  • the alkylene oxides react preferentially with the phenolic hydroxyl groups.
  • both phenolic hydroxyl groups are substantially etherified, and the requirement in the formula set forth above that both n 1 and n 2 shall equal at least one is satisfied.
  • slightly more than the stoichiometric amount of alkylene or arylene oxide is often added to produce a more flexible molecule.
  • an excess of alkylene or arylene oxide is used, a random distribution of the oxyalkylene or oxyarylene groups between the two hydroxy either groups occurs. Therefore, the oxyalkylene or oxyarylene groups per mole are designated generically by an average of n l +n 2 oxyalkylene groups per mole.
  • n l +n2 is preferably less than about 21 because the toner resin then possesses greater resistance to filming on imaging surfaces.
  • Any suitable diphenol represented by the formula above may be employed. Typical diphenols having the foregoing general structure include: 2,2-bis(4-beta hydroxy ethoxy phenyl)-propane, 2,2-bis(4-hydroxy isopropoxy phenyl) propane, 2,2-bis(4-beta hydroxy ethoxy phenyl) pentane, 2,2-bis(4-beta hydroxy ethoxy phenyl) butane, 2,2- bis(4-hydroxy-propoxy-phenyl) propane, 2,2-bis(4-hydroxy-propoxy-phenyl) propane, 1,1-bis(4-hydroxy-ethoxy-phenyl) butane, 1,1-bis(4-hydroxy- isopropoxy-phenyl) heptane, 2,2-bis(3-metyl-4-beta-hydroxy ethoxy-pheny
  • Diphenols wherein R represents an alkylidene radical having from 2 to 4 carbon atoms and R' and R" represent an alkylene radical having from 3 to 4 carbon atoms are preferred because greater blocking resistance, increased definition of imaged characters and more complete transfer of toner images are achieved.
  • Optimum results are obtained with diols in which R is isopropylidene and R' and R" are propylene or butylene because the resins formed from these diols possess higher agglomeration resistance and penetrate extremely rapidly into paper receiving sheets under fusing conditions.
  • Any suitable dicarboxylic acid may be reacted with the diols described above to form the toner resins.
  • These acids may be substituted, unsubstituted, saturated or unsaturated.
  • These acids have the general formula: HOOCR'"n 3 COOH wherein R'" represents a substituted or unsubstituted alkylene radical having from 1 to 12 carbon atoms, arylene radicals or alkylene arylene radicals having from 10 to 12 carbon atoms and n 3 is less than two.
  • R'dicarboxylic acid' includes anhydrides of such acids where such anhydrides exist.
  • Typical dicarboxylic acids include: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azalaic acid, sebacic acid, phthalic acid, mesaconic acid, homophthalic acid, isophthalic acid, terephthalic acid, o-phenyleneacetic-beta-propionic acid, itaconic acid, maleic acid, maleic acid anyhdrides, fumaric acid, phthalic acid anhydride, traumatic acid, citraconic acid, and the like.
  • Dicarboxylic acids having from 3 to 5 carbon atoms are preferred because the reslting toner resins possess greater resistance to film formation on reusable imaging surfaces and resist the formation of 'fines' under machine operation conditions.
  • Optimum results are obtained with alpha unsaturated dicarboxylic acids including fumaric acid, maleic acid, or maleic acid anhydride because maximum resistance to physical degradation of the toner as well as rapid melting properties are achieved.
  • the presence of the unsaturated bonds in the alpha unsaturated dicarboxylic acid reactants provides the resin molecules with a greater degree of toughness without adversely affecting the fusing and comminution characteristics.
  • Suitable esterification processes may be used to form the linear resins. These are discussed in US-A- 3 590 000.
  • Any suitable magnetic material may be employed. While about 40% to about 80% by weight of Mapico Black is preferred, with about 65% Mapico Black being optimum, other suitable materials such as metals including iron, cobalt, nickel, various magnetic oxides including Fe203, Fe 3 0 4 and other magnetic oxides; certain ferrites such as zinc, cadmium, barium, maganese; chromium dioxide; various of the permalloys and other alloys such as cobalt-phosphorus, cobalt-nickel and the like; or mixtures of any of these may be used. Other magnetic materials are embraced within the present invention and it is not intended to be limited to those mentioned as illustrative examples. Also, any suitable pigment or colorant may be included in the toner. These may include, for example, carbon black, nigrosine dye, aniline blue, chalco blue, chrome yellow, ultramarine blue, methylene blue chloride, phthalocyanine blue and mixtures thereof.
  • the amount of magnetic pigment material ranges from about 40% to about 90% by weight and preferably from about 50% to about 75% in order to achieve adequate development and fusing at high speed, as for example, with flash fusing.
  • the amount of resin used ranges from about 10% to about 60% by weight and preferably from about 25% to about 50% by weight.
  • Additional additives of various types may be added to or used in conjunction with the toners described herein in order to enhance process performance in one or more aspects.
  • Silanox 101 fumed silica
  • zinc stearate or other suitable powder flow agents may be used with the toners to aid development.
  • Certain plasticizers, such as diphenylphthalate are known to alter dramatically the melt viscosity of the toners, and may be used to reduce substantially the energy required to fuse the toners to a substrate, such as paper.
  • surface treatment or blending of the toners with magnetic and/or conductive additives for example, certain melt powders, magnetites or carbon blacks, can be used to impart desirable process characteristics, particularly for development, to the toners.
  • the toners may be prepared by various known methods such as spray drying.
  • spray-drying method the appropriate polymer is dissolved in an organic solvent, like toluene or chloroform or suitable solvent mixture.
  • the toner colorant and/or pigments are also added to the solvent. Vigorous agitation, such as that obtained by the ball milling processes, assist in ensuring good dispersion of the colorant or pigment.
  • the solution is then pumped through the atomizing nozzle while using an inert gas, such as nitrogen, as the atomizing agent.
  • the solvent evaporates during atomization resulting in toner varies depending on the size of the nozzle. However, particles of a diameter between 0.1 ⁇ m and 100 11 m generally are obtained.
  • Melt blending or dispersion processes can also be used for preparing the toner compositions. This involves melting a powdered form of an appropriate polymeric resin and mixing it with suitable colorants and/or pigments. The resin can be melted by heated rolls, which rolls can be used to stir and blend the resin. After thorough blending, the mixture is cooled and solidified. The solid mass that results is broken into small pieces and subsequently finely ground so as to form free-flowing toner particles which range in size of from about 0.1 to about 100 microns. Other methods for preparing the toners include dispersion polymerization, emulsion polymerization and melt blending/cryogenic grinding.
  • the toners may be of any suitable size, although particles ranging in size from about 3 microns to about 20 microns, and preferably from about 5 microns to about 12 microns, fuse particularly well in magnetic imaging systems employing flash fusing. When the particles are too fine, poor development with high background may occur. Optimum results are attained with toner particles ranging in size from about 6 to about 9 microns.
  • Toner pile height that is, the average nominal height of the unfused toner layer in the developed image areas of a magnetic image on an appropriate substrate, such as paper, can be an important parameter in influencing the degree or level or image fix (i.e., image permanence) attained for given flash fusing energies.
  • Toner pile heights of from approximately 3 ⁇ m to about 30 ⁇ m can be employed, with pile heights from about 5 ⁇ m to about 20 ⁇ m preferred, and pile heights from about 7 ⁇ m to about 15 ⁇ m optimum.
  • magnetic dipole development is particularly suited to the creation of flash-fusible images, since the development forces can be controlled to produce extremely uniform toner layers of a given thickness across both line and solid area imges.
  • a toner consisting of 35 parts by weight of a propoxylated bisphenol umerate resin, a polymeric condensation product of 2,2 bis (4-hydroxy-isopropoxy-phenyl)-propane and fumaric acid, having a melt index of approximately 10, and 65 parts by weight of the magnetite, Mapico Black, commercially available from the Columbian Chemicals Div. of Cities Service Company, is prepared by conventional milling and jetting techniques.
  • the resulting black toner material has a volume average particle size of about 13.3 pm.
  • the material is subsequently dry blended with about 0.4 percent by weight of a flow agent additive, Silanox 101, commercially available from Cabot Company, to produce a free-flowing, magnetic developer.
  • This toner when used in a magnetic imaging system for developing magnetic images, produced images of uniform, high optical density and excellent resolution. Excellent fixing of these images is obtained for flash fusing input energies from about 0.74 J/cm 2 to about 1.00 J/cm for unfused toner pile heights from about 6 ⁇ m to about 12 ⁇ m, respectively.
  • a toner is prepared in accordance with Example I, with the exception that the resulting black toner material has a volume average particle size of about 7.1 ⁇ m, and substantially similar results to those of Example I are obtained with this toner.
  • Example I The procedure of Example I is repeated with the exception that a propoxylated disphenol fumerate resin having a melt index of approximately 14 is used (volume average particle size ws about 6.35 ⁇ m), and substantially similar results are obtained when such a toner is used for developing a magnetic image.
  • Example I The procedure of Example I is repeated with the exception that a propoxylated bisphenol fumerate resin having a melt index of approximately 18 is used (volume average particle size was about 8.5 ⁇ m), and substantially similar results were obtained when such a toner was used for developing a magnetic image.
  • Example IV The procedure of Example IV is repeated with the exception that a toner consisting of 59 parts by weight of the propoxylated bisphenol fumerate resin, having a melt index of 18, and 41 parts by weight of the Mapico Black magnetite is prepared by conventional milling and jetting.
  • the resulting toner has a volume average particle size of about B.0 ⁇ m.
  • This toner when used in a magnetic imaging system for developing magnetic images, produces images of uniform, high optical density and excellent resolution. Excellent fixing of these images is obtained for flash fusing input energies from about 0.62 J/cm 2 to about 1.00 J/cm'.
  • the resulting black toner material has a volume average particle size of about 12.5 ⁇ m.
  • This material is subsequently dry blended with about 0.4 percent by weight of a flow additive, Silanox 101, commercially available from Cabot Company, to produce a free-flowing, magnetic developer.
  • Example V The procedure of Example V is repeated with the exception that the magnetic pigment used was the acicular magnetite, MO-4431, commercially available from the Pigments Division of Pfizer Corporation.
  • the magnetic pigment used was the acicular magnetite, MO-4431, commercially available from the Pigments Division of Pfizer Corporation.
  • This toner (volume average particle size was about 13.7 pm), when used in a magnetic imaging system for developing magnetic images, produced images of uniform, high optical density and excellent resolution. Adequate fixing of these images is obtained for flash fusing input energies from about 0.93 J/cm' to about 1.32 J/cm'.
  • Example I The procedure of Example I is repeated with the exception that a branched, propoxylated bisphenol fumerate resin, having a melt index substantially less than 10 was used.
  • This toner (volume average particle size was about 12.0 ⁇ m), when used in a magnetic imaging system for developing magnetic images, produces images of uniform, high optical density and excellent resolution. Adequate fixing of these images is obtained for flash fusing input energies from about 0.90 J/cm' to about 1.32 J/cm 2 .
  • Example I The procedure of Example I is repeated four separate times using the following materials:
  • Each of the above toners when used in a magnetic imaging system, produces images of uniform, high optical density and excellent resolution.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Polyesters Or Polycarbonates (AREA)
EP84201209A 1980-01-28 1981-01-28 Verfahren zum Entwickeln von latenten magnetischen Bildern Withdrawn EP0136744A3 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US115973 1980-01-28
US06/115,973 US4271248A (en) 1980-01-28 1980-01-28 Magnetic latent image toner material and process for its use in flash fusing developing
US06/115,974 US4288516A (en) 1980-01-28 1980-01-28 Polyester resin containing magnetic toner material and process for its use in flash fuser
US115974 1980-01-28

Related Parent Applications (2)

Application Number Title Priority Date Filing Date
EP81300371A Division EP0033248B1 (de) 1980-01-28 1981-01-28 Magnetischer Toner und ihn verwendendes Entwicklungsverfahren
EP81300371.2 Division 1981-01-28

Publications (2)

Publication Number Publication Date
EP0136744A2 true EP0136744A2 (de) 1985-04-10
EP0136744A3 EP0136744A3 (de) 1987-09-02

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Family Applications (2)

Application Number Title Priority Date Filing Date
EP84201209A Withdrawn EP0136744A3 (de) 1980-01-28 1981-01-28 Verfahren zum Entwickeln von latenten magnetischen Bildern
EP81300371A Expired EP0033248B1 (de) 1980-01-28 1981-01-28 Magnetischer Toner und ihn verwendendes Entwicklungsverfahren

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP81300371A Expired EP0033248B1 (de) 1980-01-28 1981-01-28 Magnetischer Toner und ihn verwendendes Entwicklungsverfahren

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EP (2) EP0136744A3 (de)
DE (1) DE3174121D1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4634649A (en) * 1980-12-24 1987-01-06 Xerox Corporation Developer compositions
JPS5938754A (ja) * 1982-08-30 1984-03-02 Konishiroku Photo Ind Co Ltd 熱ローラ定着方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3590000A (en) * 1967-06-05 1971-06-29 Xerox Corp Solid developer for latent electrostatic images
US3627682A (en) * 1968-10-16 1971-12-14 Du Pont Encapsulated particulate binary magnetic toners for developing images
BR7017882D0 (pt) * 1969-05-28 1973-01-25 Xerox Corp Material revelador eletrogragico e processo de formacao de imagens que usam o mesmo
US4031021A (en) * 1974-03-25 1977-06-21 Deming Philip H Magnetic toner compositions

Also Published As

Publication number Publication date
EP0033248A1 (de) 1981-08-05
EP0136744A3 (de) 1987-09-02
DE3174121D1 (en) 1986-04-24
EP0033248B1 (de) 1986-03-19

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