EP0488744A1 - Toneur électrophotographique pour charger négativement - Google Patents

Toneur électrophotographique pour charger négativement Download PDF

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Publication number
EP0488744A1
EP0488744A1 EP91311035A EP91311035A EP0488744A1 EP 0488744 A1 EP0488744 A1 EP 0488744A1 EP 91311035 A EP91311035 A EP 91311035A EP 91311035 A EP91311035 A EP 91311035A EP 0488744 A1 EP0488744 A1 EP 0488744A1
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EP
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Prior art keywords
charge
toner
controlling
toner according
distribution
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EP91311035A
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German (de)
English (en)
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EP0488744B1 (fr
Inventor
Noriaki Tsubota
Masahiko Kubo
Kazuo Fuji
Akihiro Watanabe
Yoshihisa Kuramae
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Kyocera Mita Industrial Co Ltd
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Mita Industrial Co Ltd
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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
    • G03G9/097—Plasticisers; Charge controlling agents
    • G03G9/09733—Organic compounds
    • G03G9/09741—Organic compounds cationic
    • 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
    • G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08726—Polymers of unsaturated acids or derivatives thereof
    • 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
    • G03G9/097—Plasticisers; Charge controlling agents
    • G03G9/09733—Organic compounds
    • G03G9/0975—Organic compounds anionic

Definitions

  • the present invention relates to an electrophotographic toner for negative charging. More particularly, the present invention relates to an electrophotographic toner for negative charging, which is capable of forming a high-density image without scattering of the toner.
  • the developing toner is generally formed by pulverizing a resin composition comprising a fixing resin, a colorant and a charge-controlling agent as indispensable components into an average particle size of 5 to 15 ⁇ m.
  • a charge-controlling agent exerting a negative charge-controlling action at the frictional charging is used in case of a toner for negative charging.
  • the average value of the charge quantity as the entire toner is controlled according to the kind of the charge-controlling agent or the amount added of the charge-controlling agent.
  • the average value of the charge quantity as the entire toner can be controlled, it is very difficult to strictly control the distribution of the charge quantity in toner particles.
  • Japanese Unexamined Patent Publication No. 54-34243 discloses a developer for developing an electrostatically charged image, comprising a toner and a carrier, in which the toner is a toner for negative charging, which comprises a dye positively charged by friction with the carrier.
  • Japanese Unexamined Patent Publication No. 57-196264 discloses an electrically insulating magnetic one-component developer comprising an electrically insulating fixing medium and, dispersed in the fixing medium, a magnetic material powder and a charge-controlling agent, in which the charge-controlling agent comprises a negative or positive charge-controlling agent and a charge-controlling agent having a reverse polarity at a weight ratio of from 1/0.05 to 1/1.5.
  • Particles of the former highly charged toner are electrically strongly attracted to surfaces of the carrier particles and are present in a hardly separable state, and they extraordinarily inhibit frictional chargeability performances of the carrier particles. Accordingly, even in case of a toner causing no particular problem at the initial stage of the development, with the lapse of the developing time, the proportion of the uncharged or lowly charged toner increases, and such troubles as scattering of the toner, fogging and reduction of the image density are caused.
  • Another object of the present invention is to provide a toner for negative charging, in which the distribution of the charge quantity of the toner is sharp, rise of the charge is quick at the time of charging, and at the long-time operation the charging characteristics are hardly degraded.
  • an electrophotographic toner for negative charging comprising a fixing resin, a colorant, a charge-controlling agent for negative charging, and a charge-controlling assistant
  • the charge-controlling assistant is a positive charge-controlling substance which is incompatible with the fixing resin and has a dispersibility in the fixing resin.
  • the positive charge-controlling substance used as the charge-controlling assistant in the present invention there are preferably used quaternary ammonium salts, especially quaternary ammonium salts containing an oxyacid anion as the anion.
  • the charge-controlling agent (A) and the charge-controlling assistant (B) be present at an (A)/(B) weight ratio of from 1/0.05 to 1/1, especially from 1/0.1 to 1/0.7, and it also is preferred that the charge-controlling agent and charge-controlling assistant be used in a total amount of 0.5 to 5 parts by weight, especially 2 to 4 parts by weight, per 100 parts by weight of the fixing resin.
  • Fig. 1 is a diagram illustrating the distribution of the charge quantity of the toner of the present invention (Example 1).
  • Fig. 2 is a diagram illustrating the distribution of the charge quantity of the toner for negative charging (Comparative Example 1), in which the positive charge-controlling substance is not incorporated.
  • Fig. 3 is a diagram illustrating the distribution of the charge quantity of a toner in which a charge-controlling agent for negative charging and a positively chargeable dye compatible with a fixing resin are incorporated in combination.
  • Fig. 4 is a diagram illustrating an apparatus for measuring the charge quantity of the toner.
  • Fig. 5 is a diagram illustrating the distribution of the charge quantity after formation of 50,000 copies, observed with respect to the toner of Example 1.
  • Fig. 6 is a diagram illustrating the distribution (curve A) of the initial charge quantity and the distribution (curve B) of the charge quantity after formation of 5,000 copies, observed with respect to the toner of Comparative Example 3.
  • Fig. 7 is a diagram illustrating the distribution (curve A) of the initial charge quantity and the distribution (curve B) of the charge quantity after formation of 50,000 copies, observed with respect to the toner of Example 3.
  • Fig. 8 is a diagram illustrating the distribution (curve A) of the initial charge quantity and the distribution (curve B) of the charge quantity after formation of 50,000 copies, observed with respect to the toner of Example 5.
  • Fig. 9 is a diagram illustrating the distribution (curve A) of the initial charge quantity and the distribution (curve B) of the charge quantity after formation of 50,000 copies, observed with respect to the toner of Example 7.
  • the present invention is based on the finding that if a positive charge-controlling substance incompatible with a fixing resin but dispersible therein is combined as the charge-controlling assistant with a charge-controlling agent for negative charging, instead of a positively chargeable dye compatible with the fixing resin, conventionally used, the distribution of the charge quantity can be made conspicuously sharper than in the conventional toner, with the result that generation of a highly charged toner not used for the development or a lowly charged toner causing scattering of the toner can be effectively controlled.
  • the distributions of charge quantities shown in Figs. 1 through 3 are determined by using a charge quantity-measuring apparatus shown in Fig. 4 according to the following method.
  • the charge quantity-measuring apparatus shown in Fig. 4 comprises a separating portion 2 arranged in a cylindrical housing 1 to separate a toner from a developer, a measuring portion 3 for measuring the distribution of the charge quantity of the separated toner, and a sucking device 11 such as an air pump.
  • the separating portion 2 is separated from the measuring portion 3 by a partition plate 7.
  • a circulating hole 1a for introducing air into the housing 1 is formed on the side wall of the housing 1 slightly below the partition plate 7.
  • An air-rectifying filter 8 is arranged slightly below the circulating hole 1a.
  • compressed air is blown by an air needle 5 to a developer maintained on a magnet 4, whereby only the light toner is blown up and scattered while leaving a carrier attracted magnetically to the magnet 4.
  • a funnel 6 supported by the partition plate 7 is arranged between the separating portion 2 and the measuring portion 3.
  • a receiving opening 6d on the top end of the funnel 6 projects above the partition plate 7, and a dent 6a on the lower end pierces through the filter 8 and is exposed to the side of the measuring portion 3.
  • the sucking device 11 forms a main air current flowing from the outside of the housing 1 to the measuring portion 3 through the circulating hole 1a and the rectifying filter 8 and also forms an air current for sucking the toner into the funnel 6 above the funnel 6.
  • the toner particles separated by the separating portion 2, collected by the funnel 6 and introduced into the measuring portion are vertically dropped while being carried by the air current formed by the sucking device 11 and are allowed to fall on the filter 10 through between the electrode rods 9a and 9b. Since the toner particles fall down in the horizontal parallel electric field between the electrode rods 9a and 9b under Coulomb force H corresponding to the charge quantity in the horizontal direction and gravity V in the vertical direction. Accordingly, the toner particles are dispersed on the filter 10 at a position corresponding to the mass or charge quantity thereof. Then, from the distribution of falling positions of the toner particles, the distribution of the charge quantity of the toner is calculated by an image treatment.
  • toner A where a controlling agent for negative charging alone is used (toner of Comparative Example 1), as shown in Fig. 2, a highly charged toner in area a is present in a large quantity, and a reversely charged toner or an uncharged toner in zone d is contained in a considerable proportion.
  • toner B of the prior art where a positively chargeable dye is combined with a controlling agent for negative charging (toner of Comparative Example 2), as shown in Fig.
  • the average value of the charge quantity can be shifted to a low charge quantity side but the distribution width is not substantially changed from that of toner A, the amount of the highly charged toner is reduced but the highly charged toner is still present, and the proportion of the reversely charged toner or uncharged toner in area d increases.
  • toner C of the present invention where a controlling agent for negative charging is combined with a positive charge-controlling assistant in compatible with a fixing resin (toner of Example 1), the quantity of the toner present in appropriate charging areas b and c increases and the width of the distribution of the charge quantity is drastically narrowed, and the quantity of the highly charged toner in area a or the reversely charged or uncharged toner in area d is reduced (is not present in this case).
  • the toner of the present invention has such preferred charging characteristics that variation of the image density, formation of fogging of the image and scattering of the toner can be controlled.
  • the toner of the present invention not only at the initial stage of the development, but also when the development is continued for a long time, variation of the image density, occurrence of fogging and scattering of the toner are not caused and a high effect of preventing the deterioration can be attained.
  • one of serious defects of the combination of the positive charge-controlling substance as the assistant with the negative charge-controlling agent is that when a developer comprising this toner and a carrier is stirred in the developing device, rising of the charge is delayed, even though the charge of the toner particles is finally controlled to a negative value.
  • the toner having the composition and dispersion structure specified in the present invention when the developer is stirred to initiate stirring, rising of the charge is as quick as in case of the negatively chargeable toner comprising a negative charge-controlling agent alone. This is another advantage attained by the present invention.
  • copolymer composed of an acrylamide-type monomer of general formula (1) and a vinyl-type monomer.
  • This copolymer dissolves in the form of a transpatent or pale-colored transparent state in the fixing resin and gives a very stable negative charging properties.
  • the toner of this invention as shown in Examples, shows almost the same charging property as in the initial state even when a copying step was repeated many times. The use of such a copolymer as a negative charge controlling agent is one example for this reason.
  • the negatively chargeable toner of the present invention can be effectively used not only as a toner for forming an ordinary single-color image but also as a toner for forming a so-called full-color image.
  • a full-color image can be formed by lapping a cyan toner, a yellow toner and a magenta toner, but it sometimes happens that the charging characteristics of the respective color toners are changed by a mechanical impact force or heat generated by the stirring operation in the developing device. More specifically, even if the distribution of the charge quantity of each color toner is sharp, it is difficult to maintain this state while continuing the copying operation.
  • the positive charge-controlling substance used as the charge-controlling assistant in the present invention is incompatible with the fixing resin but dispersible therein and has a charge-controlling action of a polarity reverse to that of the charge-controlling agent for negative charging. More specifically, a quaternary ammonium salt is used.
  • quaternary ammonium salt there is preferably used a compound represented by the following formula: (2): wherein at least one of groups R represents a long-chain alkyl or long-chain alkenyl group having at least 8 carbon toms, especially 8 to 22 carbon atoms, other groups R represent a lower alkyl group, a benzyl group, a long chain alkyl group of a long-chain alkyl group, with the proviso that at least 2 of these groups R represent a lower alkyl group having up to 4 carbon atoms or a benzyl group, and A represents an anion, preferably an oxyacid anion.
  • groups R represents a long-chain alkyl or long-chain alkenyl group having at least 8 carbon toms, especially 8 to 22 carbon atoms
  • other groups R represent a lower alkyl group, a benzyl group, a long chain alkyl group of a long-chain alkyl group, with the proviso that at least 2 of these groups
  • oxyacid anion there can be mentioned anions of oxyacids such as orthophosphoric acid and pyrophosphoric acid, molybdic acid, tungstic acid, antimonic acid and bismuthic acid. These quaternary ammonium salts are especially suitable for sharpening the distribution of the charge quantity without delaying rising of charging of the toner.
  • X1 is a hydrogen atom or a methyl group, preferably a hydrogen atom
  • X2 is a divalent hydrocarbon group having 1 to 6 carbon atoms, such as an alkylene group.
  • Specific examples of the acrylamide-type monomer include 3-acrylamide-3-methylbutylsulfonic acid, 2-acrylamide-2-methylbutylsulfonic acid, and 2-acrylamide-2-butylpropanesulfonic acid. Most preferred is 2-acrylamide-2-methylsulfonic acid.
  • vinyl-type monomer various known monomers may be used.
  • styrene and ⁇ -methyl-styrene Preferably, styrene may be used.
  • the content of the acrylamide-type copolymer is preferably 2 to 20 % by weight, the negative charging property tends to be lost. Furthermore, the weight average molecular weight (Mw) of the copolymer is preferably 2,000 and 15,000.
  • the charge-controlling agent and the charge-controlling assistant are preferably used at a weight ratio of from 1/0.005 to 1/1, especially from 1/0.1 to 1/0.7. It is preferred that the combination of the charge-controlling agent and charge-controlling assistant be present in an amount of 1 to 5 parts by weight, especially 2 to 4 parts by weight, per 100 parts by weight of the fixing resin.
  • a known resin which is not compatible with the charge-controlling assistant but is capable of dispersing the charge-controlling assistant therein is used as the fixing resin. Since the fixing resin negatively charges the toner, it is preferred that the fixing resin should have a tendency to be negatively charged.
  • a styrene resin, an acrylic resin, a styrene-acrylic resin and a polyester resin are generally used.
  • styrene monomer constituting the fixing resin there can be mentioned monomers represented by the following formula: wherein R1 represents a hydrogen atoms, a lower alkyl group (having up to 4 carbon atoms) or a halogen atom, R2 represents a hydrogen atom or a substituent such as a lower alkyl group or a halogen atom, such as styrene, vinyltoluene, ⁇ -methylstyrene, ⁇ -chlorostyrene and vinylxylene, and vinylnaphthalene.
  • R1 represents a hydrogen atoms, a lower alkyl group (having up to 4 carbon atoms) or a halogen atom
  • R2 represents a hydrogen atom or a substituent such as a lower alkyl group or a halogen atom, such as styrene, vinyltoluene, ⁇ -methylstyrene, ⁇ -chlorostyrene and vinylxy
  • acrylic monomer there can be mentioned monomers represented by the following formula: wherein R3 represents a hydrogen atom or a lower alkyl group, and R4 represents a hydrogen atom or a substituted or unsubstituted alkyl group having up to 18 carbon atoms, such as ethyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, acrylic acid and methacrylic acid.
  • acrylic monomer there can be used other ethylenically unsaturated carboxylic acids and anhydrides thereof, such as maleic anhydride, crotonic acid and itaconic acid.
  • a styrene acrylic copolymer resin is one of preferred fixing resins, and the weight ratio A/B of the styrene monomer (A) to the acrylic monomer (B) is preferably from 50/50 to 90/10, especially preferably from 60/40 to 85/15.
  • the acid value of the resin used is 0 to 25. From the viewpoint of the fixing property, it is preferred that the resin should have a class transition temperature (Tg) of 50 to 75°C.
  • polyester resin obtained by polycondensing a diol component represented by the formula: wherein R is an ethylene group or propylene group, and m or n is a positive integer, with a polycarboxylic acid or acid anhydride as an acid component or its derivative.
  • diol component examples include polyoxypropylene-2,2-bis(4-hydroxyphentl) propane, polyoxyethylene-2,2-bis(4-hydroxyphentl)propane, and polyoxypropylene-polyoxyethylene-2,2-bis(4-hydroxyphenyl) propane.
  • carboxylic acid examples include maleic acid, fumaric acid, mesaconic acid, citraconic acid, taconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacid acid, malonic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,3-dicarboxy-2-methylcarboxypropen, 1,3-dicarboxylic-2-methyl-2-methylcarboxy propane tetra(methylene carboxy)methane, 1,2,7,8-oct
  • This polyester resin may be produced by polycondensing the diol component with the polycarboxylic acid component. It the reaction, other diol components such as ethylene glycol and bisphenol A in addition to 10 mole% of may be concurrently used etherified bisphenols A of the above formula.
  • the colorant to be incorporated into the binder resin there can be used at least one member selected from the group consisting of inorganic and organic pigments and dyes, for example, carbon blacks such as furnace black and channel black, iron blacks such as triiron tetroxide, rutile titanium dioxide, anatase titanium dioxide, Phthalocyanine Blue, Phthalocyanine Green, cadmium yellow, molybdenum orange, Pyrazolone Red and Fast Violet B.
  • carbon blacks such as furnace black and channel black
  • iron blacks such as triiron tetroxide
  • rutile titanium dioxide such as furnace black and channel black
  • rutile titanium dioxide anatase titanium dioxide
  • Phthalocyanine Blue Phthalocyanine Green
  • cadmium yellow molybdenum orange
  • Pyrazolone Red and Fast Violet B for example, carbon blacks such as furnace black and channel black, iron blacks such as triiron tetroxide, rutile titanium dioxide, anatase titanium dioxide, Phthalo
  • the toner of the present invention is used as the yellow toner for full-color development
  • benzidine pigments such as C.I. Pigment Yellow 13 (Benzidine Yellow GR), C.I. Pigment Yellow 14 (Vulcan Fast Yellow G), C.I. Pigment Yellow 17, C.I. Pigment Yellow 55, C.I. Pigment Yellow 12 and C.I. Pigment Yellow 83.
  • a yellow colorant such as chrome yellow, titanium yellow or quinoline yellow lake can be used in addition to the benzidine pigment according to need.
  • quinacridone pigments such as C.I. Pigment Red 122 (Quinacridone Magneta), C.I. Pigment Red 192, C.I. Pigment Red 209 and C.I. Pigment Violet 19 (Quinacridone Violet) are preferably used.
  • copper phthalocyanine pigments such as C.I. Pigment Blue 15 (Phthalocyanine Blue), C.I. Pigment 16 (Heliogen Blue G) and C.I. Pigment Blue 17 (Fast Sky Blue) are preferably used.
  • the colorant is generally used in an amount of 2 to 15 parts by weight, preferably 3 to 10 parts by weight, per 100 parts by weight of the resin.
  • the particle size of toner particles is such that the volume-based median diameter measured by a Coulter Counter is 5 to 15 um, especially 7 to 12 um.
  • the particles can have an indeterminate shape formed by melt-mixing and pulverization or a spherical shape formed by dispersion or suspension polymerization.
  • the toner of the present invention is combined with a known magnetic carrier and used as a two-component magnetic developer to exert excellent charging characteristics.
  • the magnetic carrier there can be used a ferrite carrier and an iron powder carrier.
  • the carrier can be used in an uncoated stated or resin-coated stated.
  • a ferrite carrier is preferably used.
  • sintered ferrite particles composed of at least one member selected from the group consisting of zinc iron oxide (ZnFe2O4), Yttrium iron oxide (Y3Fe5O12), cadmium iron oxide (CdFe2O4), gadolinium iron oxide (Gd3Fe5O12), copper iron oxide (CuFe2O4), lead iron oxide (PbFe12O19), nickel iron oxide (NiFe2O4), neodium iron oxide (NdFeO3), barium iron oxide (BaFe12O19), magnesium iron oxide (MgFe2O4), manganes iron oxide (MnFe2O4) and lanthanum iron oxide (LaFeO3).
  • soft ferrites containing at least one member, preferably at least two members, selected from the group consisting of Cu, Zn, Mg, Mn and Ni, for example, a copper/zinc/magnesium ferrite, can be used.
  • the coating resin for magnetic carriers there are known an acrylic resin, a styrene resin, a silicone resin, a fluorine resin and an amino-modified resin.
  • a resin that controls indirectly the toner charge to a negative level by controlling the charge of the resin-coated magnetic carrier to a positive level is preferably used.
  • this carrier-coating resin even if this carrier-coating resin is not present, control of the charge can be accomplished effectively and assuredly.
  • the saturation magnetization of the carrier be 40 to 75 emu/g, especially 45 to 70 emug.
  • the mixing ratio of the toner and the magnetic carrier depends on the physical properties of the toner and the magnetic carrier, but it is preferred that the mixing weight ratio be in the range of from 1/99 to 10/90, especially from 2/98 to 5/95.
  • the resistivity of the developer as a whole be 5 x 109 to 5 x 1012 ⁇ -cm, especially 5 x 109 to 5 x 1011 ⁇ -cm.
  • the above-mentioned toner and magnetic carrier are mixed, a magnetic brush having a predetermined length is formed on a developing sleeve having a magnet roll arranged therein, and the magnetic brush is brought into sliding contact with a photosensitive material having the electrostatic image, or the magnetic brush is brought into close proximity to the electrostatic image-holding photosensitive material in a field to which a vibrating electric field is applied.
  • a twin-screw kneader 100 parts by weight of a styrene/acrylic copolymer as the fixing resin, 5 parts by weight of carbon black as the colorant, 1.5 parts by weight of low-molecular-weight polypropylene as the offset-preventing agent, 2 parts by weight of a copolymer of styrene and 2-acrylamide-2-methylpropane sulfonic acid (styrene content; 91%, Mw: 8000) as the charge-controlling agent for negative charging and 0.5 part by weight of a quaternary ammonium salt represented by the following formula: as the charge-controlling assistant incompatible with the styrene/acrylic copolymer were melt-kneaded, and the melt-kneaded mixture was cooled, pulverized and sieved to obtain a toner having an average particle size of 11 um.
  • the toner was mixed and stirred with a resin-coated ferrite carrier having an average particle size of 85 ⁇ m at a toner concentration of 4.5% to form a developer.
  • the distribution of the charge quantity was measured by the toner charge quantity-measuring apparatus shown in Fig. 4. The obtained results are shown in Fig. 1.
  • a toner having an average particle size of 11 ⁇ m was prepared in the same manner as described in Example 1 except that 2 parts by weight of a copolymer (Mw: 10,000) as the charge-controlling agent and 0.5 part by weight of a quaternary ammonium salt represented by the following formula: was used as the charge-controlling assistant.
  • Example 1 a developer was formed and 50,000 prints were continuously formed. As in Example 1, a good image was obtained, and scattering of the toner in the machine was not caused. Furthermore, the distribution of the charge quantity of the toner was as sharp as in Example 1.
  • a toner was prepared in the same manner as described in Example 1 except that the charge-controlling assistant was not used.
  • the distribution of the charge quantity of the toner was measured in the same manner as described in Example 1. The obtained results are shown in Fig. 2.
  • 50,000 prints were continuously formed in the same manner as described in Example 1.
  • the image density was unstable and dropping of the image density often occurred. Fogging of the image or scattering of the toner was sometimes caused.
  • a toner was prepared in the same manner as described in Example 1 except that 2 parts by weight of Solvent Yellow 56, compatible with the fixing resin, was used instead of the charge-controlling assistant used in Example 1.
  • the distribution of the charge quantity of the toner was measured in the same manner as described in Example 1. The obtained results are shown in Fig. 3.
  • 50,000 prints were continuously formed in the same manner as described in Example 1. Fogging of the image and scattering of the toner were conspicuous. The image density was satisfactory to some extent, but the density often became uneven.
  • a toner was prepared in the same manner as described in Example 1 except that 2 parts by weight of a chromium-containing monoazo dye was used instead of the negative charge-controlling agent used in Example 1.
  • the distribution of the charg quantity of the resulting toner is shown in curve A in Fig. 6.
  • a good image was obtained in the early times and scattering of the toner was none in the apparatus. But at the end (from 4,500 print soon) small fog density and variation in the density of the image were noted.
  • a toner (yellow toner) having an average particle size of 11 ⁇ m was prepared in the same manner as described in Example 1 by using 100 parts by a styrene/acrylic copolymer as the fixing resin, 5 parts by weight of C.I. Pigment Yellow 17 as the colorant, 1.5 parts by weight of low-molecular-weight polypropylene as the offset-preventing agent, 2 parts by weight of the copolymer used in Example 1 as the charge-controlling agent for negative charging and 0.5 part by weight of the quaternary ammonium salt used in Example 1.
  • Example 2 Furthermore, in the same manner as described in Example 1, 50,000 prints were continuously formed and the image characteristics were observed, and the distribution of the charge quantity was measured. A good image having no scattering of the toner was obtained.
  • a toner (yellow toner) was prepared in the same manner as described in Example 3 except that 5 parts by weight of C.I. Pigment Yellow 13 was used as the colorant and 0.5 part by weight of the quaternary ammonium salt used in Example 2 was used as the charge-controlling assistant.
  • the distribution of the charge quantity was measured in the same manner as described in Example 1.
  • the obtained distribution curve was sharp and similar to the curve A in Fig. 7.
  • Example 3 Furthermore, in the same manner as described in Example 3, the image characteristics were observed after 50,000 prints were continuously formed, and the distribution of the charge quantity was measured. Scattering of the toner was not caused and a good image was obtained, and the distribution of the charge quantity was substantially as sharp as in the initial stage.
  • a toner was prepared in the same manner as described in Example 3 except that 0.5 part by weight of C.I. Solvent Yellow 56 compatible with the fixing resin was used instead of the charge-controlling assistant used in Example 3.
  • the distribution of the charge quantity of the toner was measured in the same manner as described in Example 1. A board distribution similar to that shown in Fig. 3 was observed.
  • a toner (magenta toner) was prepared in the same manner as described in Example 3 except that 5 parts by weight of C.I. Pigment Red 122 was used as the colorant. A sharp distribution shown in the curve A in Fig. 8 was obtained.
  • a toner (magenta toner) was prepared in the same manner as described in Example 4 except that 5 parts by weight of C.I. Pigment Red 122 was used as the colorant. A sharp distribution similar to that shown in the curve A in Fig. 8 was obtained.
  • a toner (cyan toner) was prepared in the same manner as described in Example 3 except that 5 parts by weight of C.I. Pigment Blue 15 was used as the colorant. A sharp distribution similar to that shown in the curve A in Fig. 9 was obtained.
  • a toner (cyan toner) was prepared in the same manner as described in Example 4 except that 5 parts by weight of C.I. Pigment Blue 15 was used as the colorant. A sharp distribution similar to that shown in the curve A in Fig. 9 was obtained.

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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)
EP19910311035 1990-11-28 1991-11-28 Toneur électrophotographique pour charger négativement Expired - Lifetime EP0488744B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP328363/90 1990-11-28
JP2328363A JP2609358B2 (ja) 1990-11-28 1990-11-28 負帯電用電子写真トナー

Publications (2)

Publication Number Publication Date
EP0488744A1 true EP0488744A1 (fr) 1992-06-03
EP0488744B1 EP0488744B1 (fr) 1996-07-17

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP19910311035 Expired - Lifetime EP0488744B1 (fr) 1990-11-28 1991-11-28 Toneur électrophotographique pour charger négativement

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EP (1) EP0488744B1 (fr)
JP (1) JP2609358B2 (fr)
DE (1) DE69120908T2 (fr)
ES (1) ES2091884T3 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999052019A1 (fr) * 1998-03-31 1999-10-14 Nippon Zeon Co., Ltd. Toner destine au developpement d'une image electrostatique, et procede de production associe
JP2000347445A (ja) 1999-03-26 2000-12-15 Nippon Zeon Co Ltd 静電荷像現像用トナー

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0203818A2 (fr) * 1985-05-30 1986-12-03 Mita Industrial Co. Ltd. Toner électrophotographique
EP0276963A2 (fr) * 1987-01-28 1988-08-03 Fujikura Kasei Co., Ltd. Toner de charge négative pour l'électrophotographie sèche
EP0284000A2 (fr) * 1987-03-25 1988-09-28 Hodogaya Chemical Co., Ltd. Sel d'ammonium quaternaire et toner électrophotographique
EP0330287A2 (fr) * 1988-02-26 1989-08-30 Mita Industrial Co., Ltd. Révélateur pour le développement d'images de charge électrostatique, procédé pour sa préparation
EP0430700A2 (fr) * 1989-11-30 1991-06-05 Mita Industrial Co., Ltd. Toneur pour le développement d'images électrostatiques

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2623684B2 (ja) * 1988-05-12 1997-06-25 ミノルタ株式会社 トナー
JP2710342B2 (ja) * 1988-07-11 1998-02-10 株式会社リコー 静電荷像現像用トナー

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0203818A2 (fr) * 1985-05-30 1986-12-03 Mita Industrial Co. Ltd. Toner électrophotographique
EP0276963A2 (fr) * 1987-01-28 1988-08-03 Fujikura Kasei Co., Ltd. Toner de charge négative pour l'électrophotographie sèche
EP0284000A2 (fr) * 1987-03-25 1988-09-28 Hodogaya Chemical Co., Ltd. Sel d'ammonium quaternaire et toner électrophotographique
EP0330287A2 (fr) * 1988-02-26 1989-08-30 Mita Industrial Co., Ltd. Révélateur pour le développement d'images de charge électrostatique, procédé pour sa préparation
EP0430700A2 (fr) * 1989-11-30 1991-06-05 Mita Industrial Co., Ltd. Toneur pour le développement d'images électrostatiques

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 10, no. 305 (P-507)(2361) 17 October 1986 & JP-A-61 118 761 ( FUJITSU LTD ) 6 June 1986 *
PATENT ABSTRACTS OF JAPAN vol. 14, no. 167 (P-1031)(4110) 30 March 1990 & JP-A-2 022 670 ( RICOH ) 25 January 1990 *

Also Published As

Publication number Publication date
ES2091884T3 (es) 1996-11-16
DE69120908T2 (de) 1996-11-28
JPH04195166A (ja) 1992-07-15
JP2609358B2 (ja) 1997-05-14
DE69120908D1 (de) 1996-08-22
EP0488744B1 (fr) 1996-07-17

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