EP0609443B1 - Farbtoner für die entwicklung elektrostatischer bilder - Google Patents

Farbtoner für die entwicklung elektrostatischer bilder Download PDF

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Publication number
EP0609443B1
EP0609443B1 EP92921832A EP92921832A EP0609443B1 EP 0609443 B1 EP0609443 B1 EP 0609443B1 EP 92921832 A EP92921832 A EP 92921832A EP 92921832 A EP92921832 A EP 92921832A EP 0609443 B1 EP0609443 B1 EP 0609443B1
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EP
European Patent Office
Prior art keywords
toner
particles
value
developing electrostatic
electrostatic images
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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EP92921832A
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English (en)
French (fr)
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EP0609443A1 (de
EP0609443A4 (de
Inventor
Hiroshi Kamada
Hitoshi Masuda
Yukinobu Hasegawa
Hiroyoshi Shimomura
Hiroshi Serizawa
Kensuke Okuda
Masatoshi Maruyama
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Nippon Carbide Industries Co Inc
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Nippon Carbide Industries Co Inc
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Priority claimed from JP3301214A external-priority patent/JP3037799B2/ja
Priority claimed from JP03308237A external-priority patent/JP3114295B2/ja
Application filed by Nippon Carbide Industries Co Inc filed Critical Nippon Carbide Industries Co Inc
Publication of EP0609443A1 publication Critical patent/EP0609443A1/de
Publication of EP0609443A4 publication Critical patent/EP0609443A4/de
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Publication of EP0609443B1 publication Critical patent/EP0609443B1/de
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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
    • G03G9/09—Colouring agents for toner particles
    • G03G9/0906—Organic dyes
    • 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
    • G03G9/0802—Preparation methods
    • G03G9/0804—Preparation methods whereby the components are brought together in a liquid dispersing medium
    • 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
    • G03G9/0821—Developers with toner particles characterised by physical parameters
    • 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
    • G03G9/0825—Developers with toner particles characterised by their structure; characterised by non-homogenuous distribution of components
    • 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
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08791—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by the presence of specified groups or side chains

Definitions

  • This invention relates to a colored toner for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc.
  • toners used generally widely have been prepared by suitably dry blending a colorant such as carbon black, a charge control agent and/or a magnetic substance, with styrene/acrylate copolymer powder obtained by the suspension polymerization method; melting and kneading the blend by an extruder or the like; and then pulverizing and classifying the kneaded matter.
  • a colorant such as carbon black, a charge control agent and/or a magnetic substance
  • toners obtained by such melting, kneading and pulverizing method there have been problems that there is a limit in controlling the particle size of the toners, it is difficult to prepare the toners of a small particle size in good yields, and further the dispersion becomes ununiform and the charge quantity distribution becomes broad, and thus when the toners are used as a developer, the resolution is low and moreover it is impossible to avoid the drawbacks that fog and splash, etc. occur.
  • This invention aims to provide a toner which has a high image density and a high resolution, and wherein fog, splash, etc. do not occur, and coloring properties, color reproduction, color transmittance when copying to OHP sheets was made, etc. are excellent.
  • This invention provides an electrophotographic colored toner for developing electrostatic images which has a degree of gelation of 2.0% or less and comprises an association of secondary particles containing polymer particles having acidic polar groups or basic polar groups, and an organic pigment and/or an organic dye which have (has) previously been treated with a treatment agent including a surface treatment agent, which has the same ionic character as the polymer particles so that the absolute value of ⁇ -potential becomes 10 to 100 mV at pH 5.
  • the shape factor S value of the toner particles is preferably 100.5 to 160.0.
  • the mean diameter of the toner particles obtained from the distance between circumscribed parallel lines is expressed as rm
  • the mean minimal value of the radius of curvature, on the surface of the toner particles, of each associated particle constituting the toner is expressed as rn
  • V is assumed to be rm/rn
  • V, rm and rn can take the following values: 1.01 ⁇ v ⁇ 320 2.5 ⁇ m ⁇ rm ⁇ 16 ⁇ m 0.05 ⁇ m ⁇ rn ⁇ rm
  • this invention provides a developer for electrostatic images which comprises the above electrophotographic colored toner for developing electrostatic images and a carrier.
  • the toner of this invention comprises associated particles which occurred by association of secondary particles composed of polymer particles having acidic or basic polar groups (hereafter these are sometimes referred to as primary particles) and an organic pigment and/or an organic dye treated specifically as later-described.
  • association means that plural secondary particles aggregate to form particles having a larger particle size.
  • a preferred example of the polymer having acidic polar groups or basic polar groups is a copolymer of a styrene, an alkyl (meth)acrylate and a comonomer having acidic polar groups or basic polar groups (hereafter referred to as "comonomer having polar groups").
  • a preferred specific examples of such copolymers is a copolymer comprising
  • the above copolymer can freely contain a copolymerizable comonomer in an extent of not spoiling the performance of the toner of this invention, besides the monomers of (a), (b) and (c).
  • styrene there can, for example, be mentioned styrene, n-methylstyrene, m-methylstyrene, p-methylstyrene, ⁇ -methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-chloromethylstyrene,
  • alkyl (meth)acrylates there can, for example, be mentioned methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl, acrylate, dodecyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, methyl ⁇ -chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, etc.
  • comonomers having acidic polar groups there can, for example, be mentioned ⁇ , ⁇ -ethylenic unsaturated compounds having a carboxyl group and ⁇ , ⁇ -ethylenic unsaturated compounds having a sulfone group.
  • ⁇ , ⁇ -ethylenic unsaturated compounds having a carboxyl group there can, for example, be mentioned acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid, maleic acid monobutyl ester, maleic acid monooctyl ester, and their metal salts such as sodium salts and zinc salts, etc.
  • ⁇ , ⁇ -ethylenic unsaturated compounds having a sulfone group there can, for example, be mentioned sulfonated ethylene, its Na salt, arylsulfosuccinic acid, octyl arylsuccinic acid and their Na salts.
  • (meth)acrylic esters which have an amine group or a quaternary ammonium group and wherein the carbon atom number of the ester portion is 1 to 12, preferably 2 to 8; (meth)acrylamide or (meth)acrylamides mono- or di-substituted by an alkyl group having 1 to 18 carbon atoms on optional N(s); vinyl compounds substituted by a heterocyclic group having N as a ring member; and N,N-diallyl-alkylamines or their quaternary ammonium salts.
  • (meth)acrylic esters of aliphatic alcohols having an amine group or a quaternary ammonium group are preferably used as the comonomers having a basic polar group.
  • (meth)acrylic esters of aliphatic alcohols having an amine group or a quaternary ammonium group there can, for example, be mentioned dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, their quaternary ammonium salts, 3-dimethylaminophenyl acrylate, 2-hydroxy-3-methacryloxypropyltrimethylammonium salts, etc.
  • (meth)acrylamide or (teeth)acrylamides mono- or di-substituted by an alkyl group having 1 to 18 carbon atoms or optional N(s) there can, for example, be mentioned acrylamide, N-butylacrylamide, N,N-dibutylacrylamide, piperidylacrylamide, methacrylamide, N-butylmethacrylamide, N,N-dimethylacrylamide, N-octadecylacrylamide, etc.
  • vinylpyridine vinylpyrrolidone
  • vinyl N-methylpyridinium chloride vinyl N-ethylpyridinium chloride, etc.
  • N,N-diallyl-alkylamines there can, for example, be mentioned N,N-diallylmethylammonium chloride, N,N-diallylethylammonium chloride, etc.
  • the polymer particles of this invention can be obtained by polymerizing the above monomer composition by the emulsion polymerization method, the suspension polymerization method, the precipitation polymerization method or the interfacial polymerization method (including the coacervate method). It is also possible to mechanically pulverize synthetic resin pieces to give particles. Further, if necessary, it is also possible to use a method which comprises associating primary particles of the polymer utilizing the ⁇ -potential. Preferred methods for preparing polymer particles are the emulsion polymerization method, the suspension polymerization method and the method utilizing the ⁇ -potential.
  • the above polymer is used in a quantity of 40 to 99.9 wt% in the toner.
  • the above polymer has a glass transition point of preferably -90 to 100°C, more preferably -30 to 80°C, still further preferably -10 to 70°C.
  • the glass transition point is above the above upper limit, there is a tendency that low temperature fixing properties become bad, and when it is under the above lower limit, there is a tendency that powder fluidity lowers.
  • the mean particle size of the primary particles of the above polymer is preferably 0.01 to 10 ⁇ m, more preferably 0.01 to 8 ⁇ m, still further preferably 0.01 to 5 ⁇ m, particularly preferably 0.01 to 3 ⁇ m.
  • the ⁇ -potential of the particles of the above polymer desirably takes an appropriate value. It is preferable that the ⁇ -potential ( ⁇ P 5 ) in pH 5 of the acidic polar groups-containing polymer particles is -2 to -60 mV and the ⁇ -potential ( ⁇ P 9 ) in pH 9 thereof is -20 to -100 mV, and ⁇ P 5 is larger than ⁇ P 9 .
  • ⁇ P 5 of the polymer particles is +20 to +100 mV
  • ⁇ P 9 thereof is +2 to +60 mV
  • ⁇ P 5 is larger than ⁇ P 9 .
  • the organic pigment and the organic dye used in this invention are those which were treated with a surface treatment agent having the same ionic character as the polymer particles used, and, as a result, wherein the absolute value of ⁇ -potential at pH 5 became 10 to 100 mV. It was found that by use of the thus treated organic pigment and/or organic dye, reaction between the polar groups in the polymer and the pigment or dye is inhibited, and as a result a colored toner having a degree of gelation of 2.0% or less.
  • the absolute value of the ⁇ -potential at pH 5 is made to be 10 to 100 mV by the above treatment agent, a disperse dye which is used in such a state that the dye was dispersed in a medium is used as the organic dye used in this invention.
  • organic pigment and organic dye used so long as they show coloring other than black, and it is also possible to combine one or two or more organic pigments and/or organic dyes, if necessary. Further, there is no hindrance if a metal is contained in these organic pigments and organic dyes.
  • organic fluorescent dyes In addition, organic fluorescent dyes, Aniline Black, etc.
  • organic dyes there can be used Nigrosine dyes, Aniline dyes, etc.
  • Polyoxyethylene lauryl ethers polyoxyethylene cetyl ethers, polyoxyethylene stearyl ethers, polyoxyethylene oleyl ethers, polyoxyethylene higher alcohol ethers, polyoxyethylene octylphenyl ethers, polyoxyethylene nonylphenyl ethers, oxyethylene-oxypropylene block copolymers, sorbitan monolaurylate or monopalmitate or monostearate or tristearate or monooleate or trioleate or sesquioleate or distearate, polyoxyethylenesorbitan monolaurylate monopalmitate or monostearate or tristearte or monooleate or trioleate or sesquioleate or distearate, silicone surface active agents, fluorine surface active agents, etc.
  • Tetraoleic acid polyoxyethylenesorbitol esters coconut amine acetates, stearylamine acetate, coconut amine hydrochlorides, stearylamine hydrochloride, starylamine oleate, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylamonium chloride, alkylbenzyldiroethylaroroonium chloride, laurylbetaine, stearylbetain, lauryldimethylamine oxide, laurylcarboxymethylhydroxyethylimidazoliniumbetaine, silicone surface active agents, fluorine surface active agents, etc.
  • surface active agents which have both of a nonionic portion and a anionic portion in one molecule
  • surface active agents which have both of a nonionic portion and a cationic portion in one molecule.
  • the organic pigment and/or the organic dye can be used in the range of 60 to 0.1 wt% in the toner.
  • the preparation of the toner of this invention can be made by aggregating a mixture of the above polymer particles (primary particles) with the surface-treated organic pigment and/or organic dye and optionally a charge control agent, a mold releasing agent or the like to prepare secondary particles, and further aggregating these secondary particles to form associated particles.
  • the secondary particles constituting the above associated particles which are the toner of this invention, their form is not limited so long as it spoils this invention, but preferably, the secondary particles are those wherein the primary particles of the polymer and the colorant particles are aggregated by bonding strengths such as ionic bond, hydrogen bond, metal bond and weak acid-weak base bond.
  • association methods wherein the ⁇ -potential is utilized, coacervate, an association method such as interfacial polymerization, a method which comprises heat fusing the interfaces of the secondary particles and then pulverizing the heat fused particles, etc., and among them, the association methods are preferably used.
  • the mean particle size of the above secondary particles is preferably 0.05 to 12 ⁇ m, more preferably 0.2 to 8 ⁇ m, particularly preferably 0.5 to 5 ⁇ m. Further, the particle size of the associated particles of this invention is preferably 2.5 to 12 ⁇ m, more preferably 2.5 to 11 ⁇ m.
  • a pigment and/or a dye or other compouding substances are added to a polymer dispersion obtained by emulsion polymerization and uniformly dispersed therein, and then stirring is continued for 0.5 to 10 hours, preferably 1 to 5 hours and thereby the primary particles of the polymer having Dolar groups and the surface-treated organic pigment or the like are aggregated to form secondary particles of 1-5 ⁇ m in size.
  • the dispersion is further stirred for 0.5-10 hours, preferably 1-5 hours under heating, aggregation of the secondary particles advances and they grow into associated particles of 1 to 20 ⁇ m.
  • the resultant dispersion of the associated particles is stabilized and then heated, and stirring is continued at a temperature higher than the glass transition point of the polymer, preferably a temperature 20°C or more higher than that for 1 to 12 hours, preferably 1 to 10 hours.
  • a temperature higher than the glass transition point of the polymer preferably a temperature 20°C or more higher than that for 1 to 12 hours, preferably 1 to 10 hours.
  • the resultant dispersion of the associated particles is dehydrated, washed and dried to give a toner as associated particles.
  • the secondary particles mutually make a membrane and fuse, and thus they become a toner wherein the secondary particles seldom collapse at the times of storage, transportation, preparation of magnetic developers, etc.
  • the above preparation method is an example of the association method utilizing the ⁇ -potential.
  • the ⁇ -potentials of the polymer particles and the surface-treated pigment particles are lowered in proportion to temperature rise, and as a result aggregation and association of the secondary particles are promoted.
  • methods for lowering the ⁇ -potential there can be mentioned a method of utilizing control of pH, a method utilizing addition of a metal salt, etc.
  • the toner of this invention can contain performance-imparting agents such as a fluidizing agent, a life stabilizer and a printing durability improper in such a range that its performance is not impaired, or such performance-imparting agents can be added to the magnetic toner.
  • performance-imparting agents such as a fluidizing agent, a life stabilizer and a printing durability improper in such a range that its performance is not impaired, or such performance-imparting agents can be added to the magnetic toner.
  • metal oxides such as silica, titanium oxide, aluminum oxide, zinc oxide, cerium oxide and magnetite and substances obtained by making these metal oxides hydrophobic
  • metal salts of higher fatty acids metal soaps
  • metal soaps such as Cd, Mn, Pb, Ba, Ni, Co, Sr, Cu, Mg, Ca, Fe, Al and Zn salts of stearic acid, Cd, Mn, Pb, Ba, Ni, Co, Sr, Cu, Mg, Ca, Fe, Al and Zn salts of oleic acid, Cd, Mn, Pb, Ba, Ni, Co, Sr, Cu, Mg, Ca, Fe, Al and Zn salts of palmitic acid, Cd, Mn, Pb, Ba, Ni, Co, Sr, Cu, Mg, Ca, Fe, Al and Zn salts of linolic acid, Zn and Cd salts of ricinolic acid, Pb salt of caprylic acid, and
  • the toner of this invention has a low degree of gelation of 2% or less. When the degree of gelation goes beyond 2%, the light transmittance of the toner becomes low and good coloring properties cannot be obtained.
  • the degree of gelation is preferably 1.80% or less, more preferably 1.00% or less, particularly preferably 0.50% or less.
  • the shape factor S value expressing the shape of the toner of this invention is preferably 100.5 to 160, further preferably 102.0 to 155, more preferably 105.0 to 155, still more preferably 107.0 to 140, particularly preferably 110.0 to 135.
  • the S value expresses the feeling of plane unevenness, and in proportion as the shape of the toner particles becomes close to circle (sphere), the value becomes close to 100, and in proportion as the peripheral shape becomes complicated, the value becomes a larger value.
  • the toner particles become close to spheres, and when they are used as a developer, the charge quantity becomes low, the shortage of image density or fog is liable to take place, and in life characteristics, there is a tendency that defective cleaning, etc. occur and the lifetime is shortened.
  • the V value is preferably 1.01 to 320, more preferably 1.05 to 300, particularly preferablv 2.00 to 250.
  • the diameter of the particles of the toner is obtained from the distance between two circumscribed parallel lines.
  • the above toner has a volume mean particle size of 2.5 to 12 ⁇ m.
  • the above S value expresses the feeling of plane unevenness, whereas the V value hereinabove referred to further expresses unevenness sterically.
  • Such feeling of unevenness is due to primary particles of the polymer, particles of the coloring agent, the charge-controlling agent or their secondary particles.
  • the feeling of the unevenness of the surfaces of the particles can be expressed as a numerical value using the radius of curvature, and it is possible to express the feeling of unevenness of all the toner particles (particularly as associated particles) by deducing the relation of the radius of curvature with the mean particle size of each toner.
  • the toner particles are in such a state that their surface state is substantially free of unevenness and smooth and become close to spheres.
  • the charge quantity becomes low, and the shortage of image density or occurrence of fog are liable to occur.
  • life characteristics in the system of electrophotography wherein cleaning is made by a cleaning blade, there is a tendency that the hang-up frictional force of the toner against the blade extremely decreases, and defective cleaning, etc. occur and the lifetime is shortened.
  • the colored toner obtained by this invention is a colored toner which is excellent in coloring properties due to very good transmittance, is excellent in color reproduction and resolution, exhibits only a small extent of fog and splash, and is excellent in various physical properties.
  • a developer can be prepared by mixing the toner of this invention with a magnetic carrier.
  • the developer can be prepared by stirring and mixing 20 to 95 weight parts of the magnetic carrier and 5 to 80 weight parts of the toner in a V-type mixer or a ball mill, to charge the toner.
  • the magnetic substance there can be used iron hitherto well known, or ferrite or the like. Further, there can also be used a product obtained by binding fine particles of a ferromagnetic substance using a resin.
  • the mean particle size of the magnetic substance carrier is preferably 10 to 200 ⁇ m, further preferably 20 to 180 ⁇ m, particularly preferably 30 to 170 ⁇ m.
  • the particles block the space between the doctor blade and the sleeve in control of the magnetic brush of the developer, and therefore it is recommended to use a particle size of 1/2 or less, preferably 1/5 or less of the doctor gap.
  • the above monomer mixture was added to the following aqueous solution mixture of Water 100 parts Nonionic emulsifier (Emulgen 950 produced by Kao Corporation) 1 part Anionic emulsifier (Neogen R produced by Dai-ichi Kogyo Seiyaku Co. Ltd.) 1.5 parts , and the mixture was subjected to polymerization at 80°C for 8 hours under stirring using potassium persulfate as a catalyst to give an acidic polar groups-containing resin emulsion having a solid content of 50%. (preparation of a surface-treated organic pigment) Water 92 parts C.I.
  • Anionic surface treatment agent 1 (Neogen R produced by Dai-ichi Kogyo Seiyaku Co., Ltd.) 1 part Anionic surface treatment agent 2 (Sodium salt of ⁇ -naphthalene sulfonic acid-formaline condensate; Demol N produced by Kao Corporation) 2 parts
  • the above mixture was held at about 25°C for 2 hours while dispersed and stirred with a disper to give a mixed liquid of the surface-treated organic pigment.
  • the above acidic polar groups-containing resin emulsion 200 parts
  • the above organic pigment mixed liquid 100 parts Water 250 parts
  • the above mixture was held at about 30°C for 2 hours while dispersed and stirred with a slasher. Then the mixture was heated to 80°C under stirring and held for 3 hours. Meanwhile observation was made by an optional microscope, and thereby it was confirmed that the particle size of the secondary particles composed of the polymer particles and the organic pigment grew to 1.2 ⁇ , and further, the particle size of the associated particles (toner particles) wherein the secondary particles were associated grew to about 6.5 ⁇ m. After cooling, the resultant toner was separated by a dispersion centrifuge, washed with water and vacuum dried at 50°C for 10 hours. The gel content of the resultant toner was measured to be 0.3%. Further, as a result of the image processing of this toner, the S value was 119.5 and the V value was 2.35.
  • hydrophobic silica 0.8 part was added as a fluidizing agent to 100 parts of the resultant toner, and the mixture was mixed by a Henschel mixer to give a toner for tests.
  • This toner was mixed with a commercially available ferrite carrier to give a developer for tests having a toner concentration of 3%. This was subjected to a copy test using a commercially available full color copying machine ARTAGE 8000 REALA produced by RICOH COMPANY, LTD., and as a result an image having a high density and a high resolution was obtained. Further, the coloring properties of color was good, and when the image was copied on an OHP sheet, the sheet had very good transparency. The results are shown in Tables 1 and 2.
  • the mean particle size of the primary particles (particles of the resin emulsion) of the above acidic polar groups-containing polymer was 0.08 ⁇ m, the ⁇ -potential ⁇ P 5 at pH5 was -21 mV, and the ⁇ -potential ⁇ P 9 at pH 9 was -80 mV, and the mean particle size of the above surface-treated organic pigment was 0.2 ⁇ m, and the ⁇ -potential ⁇ P 5 at pH 5 was -23 mV.
  • Toners were obtained in the same manner as in Example 1 except that C.I. Pigment Yellow Y-17 was used in Example 2 in place of the organic pigment of Example 1, and C.I. Pigment Blue B-15:3 was used in Example 3 in place thereof.
  • the toners of Examples 2 and 3 were put in the aforesaid copying machine and subjected to the test to give images excellent in color reproduction. The results are shown in Tables 1 and 2.
  • the above mixture was held at about 25°C for 2 hours while dispersed and stirred with a disper, and then the mixture was subjected to dispersion treatment agent by a Gaurin homogenizer to give a mixed liquid of the surface-treated organic pigments.
  • the above basic polar groups-containing resin emulsion 200 parts
  • the above surface-treated organic pigments mixed liquid 100 parts Water 250 parts
  • the above mixture was held at about 30°C for 5 hours under stirring with a slasher. Then the mixture was heated to 80°C under stirring and held for 3 hours. Meanwhile the mixture was observed by an optical microscope, whereby it was confirmed that the associated particles of the secondary particles composed of the polymer particles and the organic pigment grew to about 5.2 ⁇ m. After cooling, the resultant toner dispersion was subjected to separation by a centrifuge, and the obtained toner was washed with water and vacuum dried at 50°C for 10 hours.
  • the gel content of the resultant toner was measured to be 0.2%.
  • 1.2 parts of hydrophobic silica was added as a fluidizing agent to 100 parts of the toner, and the mixture was mixed using a Henschel mixer to give a toner for tests.
  • This toner was mixed with a commercially available ferrite carrier to give a developer for tests having a toner concentration of 5%.
  • Toners were obtained in the same manner as in Example 4 except that C.I. Pigment Yellow Y-17 was used in Example 5 in place of the organic pigment of Example 4, and C.I. Pigment Blue B-15:3 was used in Example 6 in place thereof.
  • the toners of Examples 5 and 6 were put in the aforesaid copying machine and subjected to the test to give images excellent in color reproduction. The results are shown in Tables 1 and 2.
  • Toners were obtained in the same manners as in Examples 1, 2 and 3, respectively, using Styrene 90 parts 2-Ethylhexyl acrylate 10 parts Methacrylic acid 8 parts in place of the polymerization monomer of Example 1. These toners were put in the copying machine of Example 1 and subjected to the test, respectively, whereby image densities excellent in color reproduction and having good transmittance were obtained. The results are shown in Tables 1 and 2.
  • a toner was obtained in the same manner as in Example 1 except that the organic pigment in preparation of the surface-treated organic pigment and dye of Example 1 was replaced by Organic dye C.I. Disperse Red 130 (SRF-46 produced by NIPPON KAYAKU CO., LTD.) 6 parts Organic pigment C.I. Pigment Red 122 2 parts This toner was put in the copying machine of Example 1 and tested to give an image having good transmittance. The results are shown in Tables 1 and 2.
  • a toner was obtained in the same manner as in Example 1 except that the organic pigment in preparation of the surface-treated organic pigment and dye of Example 1 was replaced by Organic dye C.I. Disperse Red 130 (SRF-46 produced by NIPPON KAYAKU CO., LTD.) 8 parts , and the stirring condition in the preparation of the toner of Example 1 was changed so that the mixture is held at about 30°C for 5 hours, and then heated to 93°C and held at that temperature for 5 hours.
  • This toner was put in the copying machine of Example 1 and tested, whereby an image having good transmittance was obtained. The results are shown in Tables 1 and 2.
  • Example 1 Suspension polymerization was carried out on the same monomer composition as in Example 1 using benzoyl peroxide as a catalyst to give a resin for toners.
  • the organic pigment used in Example 1 was added, without being surface-treated, in the same compounding ratio, to this resin, and the mixture was melted and kneaded, and pulverized by a jet mill to give a toner having a mean particle size of 9.3 ⁇ m.
  • the gel content of this toner was 6.5%.
  • a developer was prepared in the same manner as in Example 1 using this toner, and subjected to the same copying test as therein to give an image having bad transmittance and a low resolution. The results are shown in Tables 1 and 2.
  • Example 1 An acidic polar groups-containing emulsion was obtained in the same manner as in Example 1.
  • a toner was prepared in the same manner as in Example 1 using the organic pigment without surface treatment agent, and subjected to the same copying test as therein.
  • the gel content of this toner was 4.2%. The results are shown in Tables 1 and 2.
  • the toner obtained in Comparative example 1 was subjected to processing for making the particles sherical using a hybridizer (produced by Nara Kikai Co., Ltd.), and a copying test was carried out in the entirely same manner as in Example 1 using this toner.
  • the results are shown in Tables 1 and 2.

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  • Spectroscopy & Molecular Physics (AREA)
  • Developing Agents For Electrophotography (AREA)

Claims (4)

  1. Elektrophotographischer Farbtoner für die Entwicklung elektrostatischer Bilder mit einem Gelatierungsgrad von 2,0% oder weniger und enthaltend in Assoziierung sekundäre Teilchen, enthaltend Polymerteilchen mit sauren polaren Gruppen oder basischen polaren Gruppen, und ein organisches Pigment und/oder einen organischen Farbstoff, das bzw. der bzw. die zuvor mit einem Behandlungsmittel einschließlich eines Oberflächenbehandlungsmittels behandelt wurde(n), wobei das Oberflächenbehandlungsmittel den gleichen ionischen Charakter wie die Polymerteilchen aufweist, so daß der absolute Wert des ζ-Potentials 10 bis 100 mV bei pH 5 beträgt.
  2. Farbtoner für die Entwicklung elektrostatischer Bilder nach Anspruch 1, dadurch gekennzeichnet, daß der Formfaktor-S-Wert der Tonerteilchen 100,5 bis 160,0 beträgt.
  3. Farbtoner für die Entwicklung elektrostatischer Bilder nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der mittlere Durchmesser der Tonerteilchen, erhalten aus der Entfernung zwischen begrenzenden parallelen Linien, als rm ausgedrückt, der mittlere minimale Wert des Krümmungsradius auf der Oberfläche der Tonerteilchen von jedem assoziierten Teilchen, das den Toner ergibt, als rn ausgedrückt wird, und V als rm/rn angenommen wird, wobei V, rm und rn aus den folgenden Werten erhalten werden: 1,01 ≤ v ≤ 320 2,5 µm ≤ rm ≤ 16 µm 0,05 µm ≤ rn < rm.
  4. Entwickler für elektrostatische Bilder, enthaltend einen Farbtoner für die Entwicklung elektrostatischer Bilder nach einem der Ansprüche 1 bis 3 und einen Träger.
EP92921832A 1991-10-22 1992-10-21 Farbtoner für die entwicklung elektrostatischer bilder Expired - Lifetime EP0609443B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP3301214A JP3037799B2 (ja) 1991-10-22 1991-10-22 静電荷像現像用カラ−トナ−
JP301214/91 1991-10-22
JP308237/91 1991-10-29
JP03308237A JP3114295B2 (ja) 1991-10-29 1991-10-29 静電荷像現像用トナ−
PCT/JP1992/001371 WO1993008510A1 (en) 1991-10-22 1992-10-21 Colored toner for developing electrostatic image

Publications (3)

Publication Number Publication Date
EP0609443A1 EP0609443A1 (de) 1994-08-10
EP0609443A4 EP0609443A4 (de) 1995-04-19
EP0609443B1 true EP0609443B1 (de) 1999-01-27

Family

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Application Number Title Priority Date Filing Date
EP92921832A Expired - Lifetime EP0609443B1 (de) 1991-10-22 1992-10-21 Farbtoner für die entwicklung elektrostatischer bilder

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CA (1) CA2121893C (de)
DE (1) DE69228314T2 (de)
WO (1) WO1993008510A1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9708815D0 (en) 1997-05-01 1997-06-25 Zeneca Ltd Process for making particulate compositions
GB9806934D0 (en) 1998-04-01 1998-05-27 Zeneca Ltd Process for making particulate compositions
JP6310827B2 (ja) * 2014-09-16 2018-04-11 株式会社東芝 電子写真用トナーの製造方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3615749A (en) * 1970-06-19 1971-10-26 American Cyanamid Co Printing ink of improved blackness
US4218530A (en) * 1977-05-02 1980-08-19 Xerox Corporation Single component magnetic toner
US4621039A (en) * 1984-12-18 1986-11-04 Xerox Corporation Developer compositions with fast admixing characteristics
JPH0687174B2 (ja) * 1986-11-11 1994-11-02 東洋インキ製造株式会社 静電荷現像用トナ−
JP2547014B2 (ja) * 1987-05-15 1996-10-23 日本カーバイド工業株式会社 静電荷像現像用トナ−
JP2537503B2 (ja) * 1987-01-29 1996-09-25 日本カーバイド工業株式会社 静電荷像現像用トナ−
WO1988005930A1 (en) * 1987-01-29 1988-08-11 Nippon Carbide Kogyo Kabushiki Kaisha Toner for developing electrostatically charged image
JPH01186964A (ja) * 1988-01-20 1989-07-26 Minolta Camera Co Ltd 光導電性トナーおよびその製造方法
JPH03267947A (ja) * 1989-07-31 1991-11-28 Ricoh Co Ltd 静電荷像現像用カラートナー
US5118588A (en) * 1990-03-30 1992-06-02 Eastman Kodak Company Toner particles having improved transfer efficiency and which comprise a pigment surface modifier

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DE69228314T2 (de) 1999-06-10
CA2121893C (en) 2003-01-21
CA2121893A1 (en) 1993-04-29
DE69228314D1 (de) 1999-03-11
EP0609443A1 (de) 1994-08-10
EP0609443A4 (de) 1995-04-19
WO1993008510A1 (en) 1993-04-29

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