EP0575805A1 - Ladungskontrollmittelzusammensetzung und elektrophotographischer Toner - Google Patents

Ladungskontrollmittelzusammensetzung und elektrophotographischer Toner Download PDF

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Publication number
EP0575805A1
EP0575805A1 EP93109119A EP93109119A EP0575805A1 EP 0575805 A1 EP0575805 A1 EP 0575805A1 EP 93109119 A EP93109119 A EP 93109119A EP 93109119 A EP93109119 A EP 93109119A EP 0575805 A1 EP0575805 A1 EP 0575805A1
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EP
European Patent Office
Prior art keywords
group
carbon atoms
group containing
quaternary ammonium
ammonium salt
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.)
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EP93109119A
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English (en)
French (fr)
Inventor
Shinichi c/o Hodogaya Chemical Co. Ltd. Sato
Hiroyoshi C/O Hodogaya Chemical Co. Ltd. Yamaga
Junichi c/o Hodogaya Chemical Co. Ltd. Hagiwara
Noboru C/O Hodogaya Chemical Co. Ltd. Akuzawa
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Hodogaya Chemical Co Ltd
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Hodogaya Chemical Co Ltd
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Publication date
Priority claimed from JP5094842A external-priority patent/JPH0659518A/ja
Priority claimed from JP11238593A external-priority patent/JP3262892B2/ja
Application filed by Hodogaya Chemical Co Ltd filed Critical Hodogaya Chemical Co Ltd
Publication of EP0575805A1 publication Critical patent/EP0575805A1/de
Withdrawn legal-status Critical Current

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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
    • G03G9/09708—Inorganic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/097—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
    • G03G9/097—Plasticisers; Charge controlling agents
    • G03G9/09733—Organic compounds
    • G03G9/09758—Organic compounds comprising a heterocyclic ring

Definitions

  • This invention relates to a charge controlling agent composition useful for toners which are electrophotographic developers. It also relates to an electrophotographic toner containing the composition.
  • an electrostatic latent image is formed on an inorganic photoconductive material composed of selenium, a selenium alloy, cadmium sulfide, amorphous silicone or the like or an organic photoconductive material using a charge generating agent and a charge transfer agent, developed with a toner, and then the developed image is transferred to paper or a plastic film, followed by fixing to give a visible image.
  • an inorganic photoconductive material composed of selenium, a selenium alloy, cadmium sulfide, amorphous silicone or the like or an organic photoconductive material using a charge generating agent and a charge transfer agent, developed with a toner, and then the developed image is transferred to paper or a plastic film, followed by fixing to give a visible image.
  • the photoconductive material has positive electrification property or a negative electrification property according to its construction.
  • Toners are composed of a binder resin, a colorant, and other additives.
  • a charge controlling agent is further added to the toners in order to impart a desirable friction electrification property (charge velocity, charge level, charge stability), a stability with the passage of time, or an environmental stability.
  • a desirable friction electrification property charge velocity, charge level, charge stability
  • a stability with the passage of time or an environmental stability.
  • a two-component type toner is charged by the friction with a carrier, while a one-component type toner is charged by the friction with a sleeve.
  • a latent image on the photoconductive material is developed with the toner thus charged.
  • the amount of charge of the toner is often set to a value in the range of about 10 to 30 ⁇ C/g.
  • the control of the chargeability of the toner is the most important matter for the toner.
  • the charging characteristics of the toner depend on the resin which is the principal component thereof.
  • desired friction charging characteristics are obtained by using a charge controlling agent.
  • a charge controlling agent There have been recently demanded more higher image quality, higher reliability and more speed-up. Closer charge control has been required in comparison with conventional charge control. Particularly, it has been highly demanded to develop a charge controlling agent which has a rapid rise of charging and is stable against environmental change and passage of time.
  • One of characteristics required for toners to carry out good development is how the toner freshly fed is made to rapidly rise to a predetermined amount of charge.
  • the toner is made to poorly rise, lowly charged toner is formed and not sufficiently transferred onto a photoreceptor and a lowering in density is caused.
  • the initial rise of charge quantity can be covered to a certain extent by stirring in the development zone.
  • a rapid rise of charging is required because the toner freshly fad is more rapidly transferred from the development zone onto the photoreceptor in proportion as the speed is increased.
  • the toner In the case of the one-component toner, the toner must be charged not by the friction between the toner and the carrier, but only by the friction between the toner and the sleeve. Accordingly, the rise in the one-component toner is more important than that in the two-component toner.
  • JP-A-62-53944 the term "JP-A” as used herein means an "unexamined published Japanese patent application”
  • JP-A-62-71968 the term "JP-A-62-3259.
  • the proposed charge controlling agents do not have satisfactory compatibility with resins and are difficultly mixed with the resins in the preparation of the toners. Hence, there are many problems with regard to the characteristics of the toners.
  • Toners obtained by using the proposed quaternary ammonium salts, etc. have problems in that charging is unstable under high temperature and humidity conditions, etc., and the proposed quaternary ammonium salts are not considered to be fully satisfying as charge controlling agents for toners.
  • JP-A-58-91462 discloses a toner wherein barium sulfate is internally added.
  • JP-A-1-200367 discloses a toner wherein tin oxide is internally added.
  • Quaternary ammonium salt-modified polymers to be used as a charge controlling agent for a toner have been proposed.
  • JP-A-62-210472 discloses a copolymer of styrene with a methyl chloride-quaternized product of dimethylaminoethylmethacrylate
  • JP-A-58-162959 discloses a quaternary salt of a polymer of dialkylaminomethacrylamide
  • JP-A-59-189354 discloses a quaternary ammonium salt of a vinylpyridine copolymer
  • JP-A-59-189351 discloses a quaternary ammonium salt of a dimethylaminomethacrylate copolymer.
  • toner comprising a composition obtained by adsorbing an unique fluorine surfactant onto silica gel is disclosed in JP-A-3-1162.
  • the present inventor have eagerly made studies to solve the above-described problems. As a result, the present inventors have found that a charge controlling agent composition, which is prepared from a specific quaternary ammonium salt as a charge controlling agent and a specific inorganic pigment and modified, has such a characteristics that the dispersibility of the composition in resins is very good. Further, the present inventors have ascertained that a toner obtained by using the thus-prepared charge controlling agent composition comprising a quaternary ammonium salt modified with an inorganic salt is freed from the above-described problems, namely, the toner can expedite the rise of charging, can improve the stability of the charging performance of thereof, can be prevented from being scattered and can prevent a defect in image from being caused. The present invention has been accomplished on the basis of this finding.
  • an object of the present invention is to provide a charge controlling agent composition of good performance which has a good rise of charging and is not affected by the change of temperatures and humidity even when development is repeatedly carried out continuously and moreover which can reproduce an image stable over a long period of time.
  • Another object of the present invention is to provide a toner in which charge controlling agent composition internally added.
  • the present invention relates to a charge controlling agent composition
  • a charge controlling agent composition comprising a quaternary ammonium salt and a specific inorganic pigment.
  • the present invention relates to an electrophotographic toner comprising the charge controlling agent composition.
  • Fig. 1 is a graph illustrating a rise of tribo charge quantity of each of the toners obtained in Examples 1 to 3 and Comparative Example 2, wherein the abscissa axis represents a stirring (mixing) time with iron powder carrier, and the ordinate axis represents tribo charge quantity ( ⁇ C/g).
  • X ⁇ represents an anion such as an ion of a halogen atom (e.g., Cl ⁇ , Br ⁇ , I ⁇ ), ClO4 ⁇ , BF4 ⁇ , PF4 ⁇ , sulfate ion, nitrate ion, borate ion, phosphate ion, an organic sulfate ion (e.g., methylsulfate ion), an organic phosphate ion (e.g., phenylphosphate ion), a carbonic acid ion (e.g., anions of acetic acid, benzoic acid, stearic acid and oleic acid), a tetraphenyl borate ion (e.g., anions of tetraphenyl borate, p-chlorotetraphenyl borate, p-methyltetraphenyl borate and tetranaphthyl bo
  • a halogen atom e.
  • oligomers having a quaternary ammonium salt group and polymers having a quaternary ammonium salt group can also be used as the quaternary ammonium salt.
  • Examples thereof include oligomers and polymers represented by the following formula (X): wherein R24 and R25 may be the same or different and each represents an alkyl or alkoxy group containing 1 to 30 carbon atoms, an aralkyl group containing 7 to 30 carbon atoms, an aryl group containing 6 to 30 carbon atoms, or an aryloxy group containing 6 to 30 carbon atoms each of which may have an ether bond, a thioether bond, a carboxylic acid amide group, a sulfonic acid amide group, an urethane bond, a chloromethyl group, a nitro group, or a pyridinum group; R26 represents a hydrogen atom or an alkyl group containing 1 to 10 carbon atoms; and s represents an integer of 2 to 100; provided that one of R24 and R25 has a quaternary ammonium salt group.
  • R24 and R25 may be the same or different and each represents an alkyl or alkoxy group
  • quaternary ammonium salts of oligomers and polymers obtained from monomers selected from those represented by the following formulas (XI) to (XVI) are preferably used: wherein R27 represents an alkylene group containing 1 to 12 carbon atoms; and R28 and R29 independently represent a hydrogen atom or an alkyl group containing 1 to 30 carbon atoms; wherein R30 represents a hydrogen atom or a lower alkyl group; wherein R31, R32, R33 and R34 independently represent a hydrogen atom or an alkyl group containing 1 to 20 carbon atoms; wherein R35 and R36 independently represent a hydrogen atom or an alkyl group containing 1 to 10 carbon atoms; R37 and R38 independently represent a hydrogen atom, an alkyl group containing 1 to 20 carbon atoms or an aryl group; and R39 represents an alkylene group containing 1 to 20 carbon atoms.
  • Examples of the inorganic pigment which can be used in the present invention include barium sulfate, magnesium hydroxide, aluminum hydroxide, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, zinc silicate, calcium silicate, aluminum silicate, magnesium silicate and magnesium hydrogenphosphate. These inorganic pigments may be coated with organic compounds, organic polymers, hydrophobic treating agents or titanate coupling agents.
  • the particle size of the inorganic pigment is preferably 25 ⁇ m or below.
  • the particle size of the aggregation may be 25 ⁇ m or more.
  • the inorganic pigments may be any of synthetic products and natural pigments. Further, inorganic pigment-containing reaction mixtures (solutions) formed by reaction of inorganic compounds can be used.
  • a mixture of barium sulfate and aluminum hydroxide obtained by reaction barium chloride with aluminum sulfate and an alkali a mixture of zinc carbonate and sodium sulfate obtained by reacting sodium carbonate with zinc sulfate, calcium carbonate obtained by reacting sodium carbonate with calcium chloride, or calcium sulfate obtained by reacting sodium sulfate with calcium chloride can be used.
  • the charge controlling agent composition of the present invention is prepared from the aforesaid quaternary ammonium salt and the aforesaid inorganic pigment. Any methods can be employed to prepare the charge controlling agent composition from the quaternary ammonium salt and the inorganic pigment can be used so long as a homogeneous composition of them can be obtained.
  • the homogeneous composition may be either a composition comprising particles in which the quaternary ammonium salt and the inorganic pigment are contained, or a composition comprising particles of the quaternary ammonium salt on which the inorganic pigment uniformly adheres.
  • the particles in which the quaternary ammonium salt and the inorganic pigment are contained is preferably prepared by adding the inorganic pigment or inorganic compounds which form the inorganic pigment at any one stage during the preparation of the quaternary ammonium salt, separating the resulting quaternary ammonium salt containing the inorganic pigment, then drying the quaternary ammonium salt.
  • the inorganic pigment is, or the inorganic compounds which form the inorganic pigment are, allowed to exist together with starting compounds in a reaction system for preparing the quaternary ammonium salt.
  • inorganic compounds which form the inorganic pigment those mentioned above can be used.
  • the inorganic pigment may be added to a reaction mixture which is transferred from reaction step for the formation of the quaternary ammonium salt to purification step therefor, or it may be added to a wet filter cake obtained in the purification step.
  • the particles in which the quaternary ammonium salt and the inorganic pigment are contained can be prepared by mixing the dried quaternary ammonium salt and the inorganic pigment in the presence of an appropriate solvent, and then drying the resulting mixture.
  • the mixing of the quaternary ammonium salt and the inorganic pigment can be effected by kneading them in the presence of a slight amount of the solvent, or by preparing a slurry comprising the quaternary ammonium salt, the inorganic pigment and the solvent and stirring the slurry.
  • the solvent may be water, an organic solvent, or a mixture of water and an organic solvent.
  • organic solvent examples include alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone and MIBK (methyl isobutyl ketone); dimethylformaldehyde and dimethylsulfonamide.
  • the particles of the quaternary ammonium salt on which the inorganic pigment uniformly adheres can be prepared by mechanically mixing and stirring the dried quaternary ammonium salt and the inorganic pigment so as to adhere the inorganic pigment uniformly onto the surface of the particles of the quaternary ammonium salt.
  • a ball mill, a Henschel mixer, a speed kneader, and the like can be used as means for mixing.
  • the particles obtained in the afore-mentioned manners can be used as the charge controlling agent composition for the preparation of the toner as such. If desired, the particles may be further pulverized, classified, and then used.
  • the content of the inorganic pigment in the thus-obtained charge controlling agent composition is such an amount that the characteristics of the charge controlling agent composition as a charge controlling agent is not adversely affected.
  • the weight ratio of the quaternary ammonium salt to the inorganic pigment in the charge controlling agent composition is preferably from 0.5 to 99.5, more preferably from 5 to 95.
  • the charge controlling agent composition of the present invention has good dispersibility in binder resins, and a toner obtained by using the charge controlling agent composition has a good rise of charging and is freed from the problems associated with conventional toner with regard to the unstable chargeability of the toner and the scattering of the toner even when the toner is used over a long period of time under a low temperature and humidity condition or a high temperature and humidity condition. Accordingly, a clear developed image can be obtained.
  • the toner of the present invention is prepared by mixing the aforesaid charge controlling agent composition according to the present invention with the other components.
  • a binder resin is placed into a Henschel mixer and then a colorant and a charge controlling agent are added thereto, followed by preliminary mixing. Subsequently, the resulting mixture is kneaded by means of an EXTRUDER generally at 150°C or below, and then the resulting product is pulverized and classified to give a toner having a particle size distribution ranging from 5 to 25 ⁇ m.
  • an EXTRUDER generally at 150°C or below
  • the resulting product is pulverized and classified to give a toner having a particle size distribution ranging from 5 to 25 ⁇ m.
  • a one-component type toner can be obtained in the aforementioned method except for that the colorant is replaced by a magnetic powder.
  • the toner of the present invention can be obtained in the aforementioned methods provided that the charge controlling agent composition of the present invention is used in place of the conventional charge controlling agent.
  • An amount of the charge controlling agent composition of the present invention in the toner is preferably from 0.1 to 15 % by weight, more preferably from 0.5 to 10 % by weight, based on the weight of the toner.
  • the charge controlling agent composition of the present invention is in the form particles having a particle size distribution ranging from 0.5 to 25 ⁇ m. It is also preferred that the quaternary ammonium salt is in the form of particles having a particle size distribution ranging from 0.5 to 25 ⁇ m.
  • the toner of the present invention comprises a binder resin and a colorant in addition to the charge controlling agent composition.
  • other materials which are conventionally used as binder resins for toners can also be used in the present invention.
  • Examples of the colorant which can be used in the present invention include C.I. Pigment Yellow-12, C.I. Solvent Yellow-18, C.I. Disperse Yellow-33, C.I. Pigment Red-122, C.I. Solvent Red-19, C.I. Pigment Blue-15, C.I. Pigment Black-1, C.I. Solvent Black-3, C.I. Solvent Black-22 and carbon black.
  • the colorant is contained in the toner according to the present invention in an amount of preferably from 3 to 10 % by weight.
  • the mixing of the charge control agent composition and the other ingredient to give the toner of the present invention can be effected by melt-mixing the binder resin with 0.1 to 50 % by weight based on the binder resin of the charge controlling agent composition, solidifying the resulting mixture, coarsely crushing the solidified mixture by means of a crushing device such as a hammer mill, finely crushing the crushed particles by means of a jet mill crusher, and then classifying the finely crushed particles by means of an air stream classifier.
  • it may be effected by adding a polymerization initiator to a monomer or a monomer mixture for the binder resin, adding the charge controlling agent composition to the mixture in an amount of 0.1 to 50 % by weight based on the weight of the monomer component, polymerizing the monomer component while suspending in water, and then recovering and drying the resulting toner.
  • a dye or carbon black as the colorant may added during these steps.
  • the thus-prepared toner can be charged by an amount of charge suitable for carrying out the development of an electrostatic latent image by the friction between the toner and the carrier. Even when development is repeatedly carried out, the toner is not affected by the change of temperature and humidity, the charge quantity can be retained constantly, and the charge distribution is uniform and can be kept constant.
  • Examples of the carrier which can be used in the present invention include iron powder and carriers obtained by coating a magnetic core with a styrene-methyl methacrylate copolymer, a silicone resin, a mixed resin of a styrene-methyl methacrylate copolymer and a silicone resin or a tetrafluorostyrene resin.
  • the charge controlling agent composition of the present invention can provide excellent charging characteristics even when used in one-component developer containing a magnetic substance. Further, the charge controlling agent composition of the present invention can be used for capsule toners and polymerization toners.
  • magnétique materials which can be used as the magnetic substance include fine powders of metals such as iron, nickel and cobalt; alloys of metals such as iron, cobalt, copper, aluminum, nickel and zinc; metal oxides such as aluminum oxide, iron oxide and titanium oxide; ferrites of iron, manganese, nickel, cobalt and zinc; nitrides such as vanadium nitride and chromium nitride; carbides such as tungsten carbide and silicon carbide; and mixtures thereof.
  • metals such as iron, nickel and cobalt
  • alloys of metals such as iron, cobalt, copper, aluminum, nickel and zinc
  • metal oxides such as aluminum oxide, iron oxide and titanium oxide
  • nitrides such as vanadium nitride and chromium nitride
  • carbides such as tungsten carbide and silicon carbide; and mixtures thereof.
  • Preferred examples of the magnetic substance include iron oxides such as magnetite, hematite and ferrite.
  • the toner was put into a development device, and continuous copying was carried out to make an image test. A good image was obtained at the initial stage of running. After obtaining 50,000 copies, the image quality was not change, and neither toner scattering nor off-set occurred. Further, the continuous copying test was carried out under high temperature and humidity conditions at 35°C and 85% RH and under low temperature and humidity conditions at 10°C and 30% RH. An image quality substantially equal to that obtained in the copying test under normal temperature and humidity conditions was obtained. Neither toner scattering nor off-set occurred.
  • Composition 2 composed of the quaternary ammonium salt (Compound 1) and aluminum hydroxide (50:50).
  • a toner was prepared in the same manner as in Example 1 except that Composition 2 was used in place of Composition 1.
  • the tribo charge quantity of the toner was measured. As a result, it was found that, after stirring of the toner with an iron powder carrier for 30 seconds, one minute, 3 minutes, 5 minutes, 10 minutes, 30 minutes and 2 hours, tribo charge quantities ( ⁇ C/g) were 3.6, 4.9, 9.0, 9.6, 9.8, 9.9 and 10.2, respectively. Tribo charge quantity after stirring for 5 minutes was 94% of that after 2 hour-stirring. Thus, there was obtained a toner having good rise of charging in a short period of time.
  • the toner was put into a development device, and continuous copying was carried out to make an image test. A good image was obtained at the initial stage of running. After obtaining 50,000 copies, the quality of the image was not changed, and neither toner scattering nor offset occurred. The toner was not affected under high temperature and humidity environmental conditions as well as under low temperature and humidity environmental conditions, and a good image quality was obtained.
  • the quaternary ammonium salt (Compound 1) was synthesized in the same manner as in Example 2, recovered by filtration and dried. Immediately after drying, the same aluminum hydroxide (2 ⁇ m) as that used in Example 1 was added thereto, and the mixture was pulverized to obtain Composition 3 composed of the quaternary ammonium salt and aluminum hydroxide (50:50).
  • a toner was prepared in the same manner as in Example 1 except that Composition 3 was used in place of Composition 1. Tribo charge quantity was measured. After stirring of the toner with an iron powder carrier for 30 seconds, one minute, 3 minutes, 5 minutes, 10 minutes, 30 minutes and 2 hours, tribo charge quantities ( ⁇ C/g) were 3.4, 4.8, 8.8, 9.3, 9.5, 9.6 and 10.3, respectively. The value measured after stirring for 5 minutes was 90.3% of that after 2 hours. There was obtained a toner having good rise of charging in a short period of time.
  • the toner was put into a development device, and continuous copying was carried out to make an image test. A good image was obtained at the initial stage of running. After obtaining 50,000 copies, the image quality was not changed, and neither toner scattering nor offset occurred.
  • the continuous copying test was carried out under high temperature and humidity conditions at 35°C and 85% RH and under low temperature and humidity conditions at 10°C and 30% RH. An image quality substantially equal to that obtained under normal temperature and humidity conditions was obtained. Neither toner scattering nor offset occurred.
  • Tribo charge quantity was measured. After stirring of the developer for 30 seconds, one minute, 3 minutes, 5 minutes, 10 minutes, 30 minutes and 2 hours, tribo charge quantities ( ⁇ C/g) were 2.0, 2.8, 4.9, 6.5, 8.7, 9.2 and 10.0, respectively. Tribo charge quantity after stirring for 5 minutes was 65% of that after 2 hours. Hence, a rise of charging was very poor.
  • Example 2 In the same manner as in Example 1, an image test was made. A clear image which was not fogged was obtained at the initial stage of running. However, after obtaining about 1,000 copies, an image which was fogged and not clear was obtained.
  • the quaternary ammonium salt (Compound 1) synthesized and dried in the same manner as in Example 2 was used, and a toner was prepared in the same manner as in Example 1 by using the following composition.
  • Styrene-n-butyl methacrylate copolymer resin Himer SBM-73F manufactured by Sanyo Kasei KK
  • Low-molecular polypropylene VISCOL 550-P manufactured by Sanyo Kasei KK
  • Carbon black #44 manufactured by Mitsubishi Kasei Corporation
  • Quaternary ammonium salt (Compound 1) 1 part Aluminum hydroxide (2 ⁇ m) 1 part
  • Example 2 In the same manner as in Example 1, a developer was prepared by using the resulting toner. After stirring with an iron powder carrier for 30 seconds, one minute, 3 minutes, 5 minutes, 10 minutes, 30 minutes and 2 hours, tribo charge quantities ( ⁇ C/g) were 2.0, 3.0, 5.3, 7.0, 9.0, 9.5 and 10.4, respectively. Tribo charge quantity after stirring for 5 minutes was 67% of that after 2 hours. Hence, a rise of charging was poor.
  • Fig. 1 is a graph illustrating a rise of tribo charge quality of each of the toners obtained in Examples 1 to 3 and Comparative Example 2, wherein the abscissa axis represents a stirring time (mixing time) of the toner with iron powder carrier, and the ordinate axis represents tribo charge quantity ( ⁇ C/g). It can be seen from these results that the toners containing the charge controlling agent composition of the present invention are very excellent in a rise of charging.
  • the toner and the carrier are uniformly dispersed in each other in a short period of time to obtain a rapid rise characteristics of charging.
  • a developer was prepared by blending 3 parts of the toner with 97 parts of the carrier (iron powder carrier TEFV 200/300 manufactured by Nippon Teppun KK), and an image was copied by using a copying machine.
  • the toners containing the charge controlling agent composition of the present invention prepared in Examples 1 to 3 showed that the dispersed state of the toner and the carrier was nearly uniform, while the dispersed state of the toners of Comparative Examples 1 and 2 were speckled and non-uniform.
  • the toners of Examples 1 to 3 were dispersed, the dispersion of the toner and the carrier in each other could be attained in a short period of time, resulting in an excellent rise of charging as shown in Fig. 1.
  • the toners of Examples 1 to 3 gave a good image which had a good image quality and scarcely suffered from ground fog. The results are thought to be due to the charging characteristics obtained by a difference in the dispersed state of the quaternary ammonium salt and the inorganic pigment.
  • Composition 4 was prepared in the same manner as in Example 1 except that aluminum hydroxide (30 ⁇ m) was used in place of aluminum hydroxide (2 ⁇ m).
  • a toner was prepared in the same manner as in Example 1 except that Composition 4 was used in place of Composition 1.
  • the tribo charge quantity of the toner was measured. After the mixing of the toner with the carrier for 30 seconds, one minute, 3 minutes, 5 minutes, 10 minutes, 30 minutes and 2 hours, tribo charge quantities ( ⁇ C/g) were 3.8, 5.6, 9.2, 9.9, 10.1, 10.2 and 10.2, respectively.
  • the value after stirring for 5 minutes was 97.0% of that after 2 hours, and hence a rise of charging was good.
  • the toner was put into a development device, and continuous copying was carried out to make an image test. A good image was obtained at the initial stage of running. After obtaining 50,000 copies, the image quality was not changed, and neither toner scattering nor offset occurred.
  • compositions 5 to 30 containing quaternary ammonium salts indicated in Table 1 were prepared in the same manner as in Example 1 and used in Examples 5 to 19 shown in Table 2.
  • Binder resins, charge quantity-measuring method and the criterion of each evaluation item in Tables 2 and 3 are as follows. Binder resins used in the preparation of toners:
  • a toner was prepared in the same manner as in Example 1 except that Composition 31 was used in place of Composition 1. The tribo charge quantity of the toner was measured.
  • the tribo charge quantities were 3.0, 4.2, 7.0, 9.0, 9.1, 9.2 and 9.3, respectively.
  • the value after 5 minutes was 96.8% of that after 2 hours. Accordingly, a rise of charging was good.
  • the toner was put into the development device, and continuous copying was carried out to make an image test. A good image was obtained at the initial stage of running. After obtaining 50,000 copies, the image quality was not changed, and neither toner scattering nor offset occurred.
  • a toner was prepared in the same manner as in Example 1 except that Composition 32 was used in place of Composition 1. The tribo charge quantity of the toner was measured.
  • the toner was put into a development device, and continuous copying was carried out to make image test. A good image was obtained at the initial stage of running. After obtaining 50,000 copies, the image quality was not charged, and neither toner scattering nor offset occurred.
  • the quaternary ammonium salt (Compound 27) synthesized in the same manner as in Example 22 was recovered by filtration, thoroughly washed with water and dried. Immediately after drying, the same calcium carbonate (1.5 ⁇ m) as that used in Example 20 was mixed with the salt. The mixture was pulverized in a pulverizer to obtain Composition 33 composed of the quaternary ammonium salt and calcium carbonate (75:25).
  • a toner was prepared in the same manner as in Example 1 except that Composition 33 was used in place of Composition 1. The tribo charge quantity of the toner was measured.
  • the tribo charge quantity ( ⁇ C/g) were 2.6, 3.8, 6.0, 8.5, 8.8, 8.9 and 9.3, respectively.
  • the toner was put into a development device, and continuous copying was carried out to make an image test. A good image was obtained at the initial stage of running. After obtaining 50,000 copies, the image quality was not changed, and neither toner scattering nor offset occurred.
  • Example 27 One part of the quaternary ammonium salt (Compound 27) synthesized and dried in the same manner as in Example 21 was used, and a toner was prepared in the same manner as in Example 1 except that aluminum hydroxide was omitted. The tribo charge quantity of the toner was measured.
  • Example 2 An image test was made in the same manner as in Example 1. A clear image which was not fogged was obtained at the initial stage of running. However, after obtaining about 1,000 copies, an image which was fogged and not clear was obtained.
  • a toner was prepared in the same manner as in Example 1 by using the quaternary ammonium salt (Compound 27) synthesized and dried in the same manner as in Example 21 and the following composition.
  • Styrene-n-butyl methacrylate copolymer resin Himer SBM-73F manufactured by Sanyo Kasei KK
  • Low-molecular polypropylene VISCOL 550-P manufactured by Sanyo Kasei KK
  • Carbon black #44 manufactured by Mitsubishi Kasei Corporation
  • Quaternary ammonium salt Compound 27
  • Calcium carbonate 1.5 ⁇ m
  • the tribo charge quantity of the resulting toner was measured. After stirring of the toner with an iron powder carrier for 30 seconds, one minute, 3 minutes, 5 minutes, 10 minutes and 2 hours, the tribo charge quantities ( ⁇ C/g) were 2.1, 3.3, 5.3, 6.0, 7.7, 8.0 and 9.2, respectively. The value after 5 minutes was 65.2% of that after 2 hours. Hence, the toner had a poor rise of charging.
  • Example 2 In the same manner as in Example 1, an image test was carried out. A clear image which was not fogged was obtained at the initial stage of running. However, after obtaining about 1,000 copies, an image which was fogged and not clear was obtained.
  • compositions 34 to 68 indicated in Table 4 were prepared by adding inorganic pigments during the course of the preparation of the quaternary ammonium salt in the same manner as in Example 20, and used in Examples 23 to 46 shown in Table 5.
  • Compositions were prepared in the same manner as in Comparative Example 19 by using the quaternary ammonium salt synthesized and dried in the same manner as in Example 21, and used in Comparative Examples 20 to 43 shown in Table 6. The results are shown in Tables 5 to 6.
  • Binder resins, charge quantity-measuring method and the criterion used in the Tables are as follows. Binder resins used in the preparation of toners:
  • a toner was prepared in the same manner as in Example 1 except that Composition 69 was used in place of Composition 1.
  • the tribo charge quantity of the toner was measured. After stirring time for 30 seconds, one minute, 3 minutes, 5 minutes, 10 minutes, 30 minutes and 2 hours, the tribo charge quantities ( ⁇ C/g) were 2.5, 4.0, 6.1, 8.8, 9.0, 9.2 and 9.3, respectively. The value after 5 minutes was 94.6% of that after 2 hours. Hence, a rise of charging was good.
  • the toner was put into a development device, and continuous copying was carried out to make an image test. A good image was obtained at the initial stage of running. After obtaining 50,000 copies, the image quality was not changed, and neither toner scattering nor offset occurred.
  • Composition 70 composed of the quaternary ammonium salt (Compound 63) and aluminum hydroxide (80:20).
  • a toner was prepared in the same manner as in Example 1 except that Composition 70 was used in place of Composition 1.
  • the tribo charge quantity of the toner was measured. After stirring of the toner with an iron powder carrier for 30 seconds, one minute, 3 minutes, 5 minutes, 10 minutes, 30 minutes and 2 hours, the tribo charge quantities ( ⁇ C/g) were 2.3, 4.0, 5.4, 8.6, 8.9, 9.0 and 9.3, respectively.
  • the tribo charge quantity after stirring for 5 minutes was 92.5% of that after 2 hours. Hence, there was obtained a toner having a good rise of charging in a short period of time.
  • the toner was put into a development device, and continuous copying was carried out to make an image test. A good image was obtained at the initial stage of running. After obtaining 50,000 copies, the image quality was not changed, and neither toner scattering nor offset occurred. Further, the continuous copying test was carried out under high temperature and humidity conditions and under low temperature and humidity conditions. An image of good quality was obtained without being affected by environmental conditions.
  • the quaternary ammonium salt (Compound 63) synthesized in the same manner as in Example 48 was recovered by filtration and dried. Immediately after drying, the same aluminum hydroxide (2 ⁇ m) as that used in Example 47 was mixed with the salt. The mixture was pulverized in a pulverizer to obtain Composition 71 composed of the quaternary ammonium salt and aluminum hydroxide (80:20).
  • a toner was prepared in the same manner as in Example 1 except that Composition 71 was used in place of Composition 1.
  • the tribo charge quantity of the toner was measured. After stirring of the toner with an iron powder carrier for 30 seconds, one minute, 3 minutes, 5 minutes, 10 minutes, 30 minutes and 2 hours, the tribo charge quantities ( ⁇ C/g) were 2.4, 4.1, 5.6, 8.4, 8.8, 9.0 and 9.2, respectively. The value measured after stirring for 5 minutes was 91.3% of that after 2 hours. Hence, there was obtained a toner having a good rise of charging in a short period of time.
  • the toner was put into a development device, and continuous copying was carried out to make an image test. A good image was obtained at the initial stage of running. After obtaining 50,000 copies, the image quality was not changed, and neither toner scattering nor offset occurred.
  • Example 63 One part of the quaternary ammonium salt (Compound 63) synthesized and dried in the same manner as in Example 48 was used, and a toner was prepared in the same manner as in Example 1 except that aluminum hydroxide was omitted.
  • the tribo charge quantity of the toner was measured. After stirring of the resulting developer for 30 seconds, one minute, 3 minutes, 5 minutes, 10 minutes, 30 minutes and 2 hours, the tribo charge quantities ( ⁇ C/g) were 1.8, 3.0, 4.4, 6.0, 7.6, 8.6 and 9.4, respectively.
  • the tribo charge quantity after stirring for 5 minutes was 63.8% of that after 2 hours. Hence, a rise of charging was very poor.
  • Example 2 An image test was carried out in the same manner as in Example 1. A clear image which was not fogged was obtained at the initial stage of running. However, after obtaining about 1,000 copies, an image which was fogged and not clear was obtained.
  • a toner was prepared by using the quaternary ammonium salt (Compound 63) synthesized and dried in the same manner as in Example 48 and the following composition in the same manner as in Example 1.
  • Styrene-n-butyl methacrylate copolymer resin Himer SBM-73F manufactured by Sanyo Kasei KK
  • Low-molecular polypropylene VISCOL 550-P manufactured by Sanyo Kasei KK
  • Carbon black #44 manufactured by Mitsubishi Kasei Corporation
  • Quaternary ammonium salt Compound 63
  • a developer was prepared by using the resulting toner in the same manner as in Example 1. After stirring of the toner with an iron powder carrier for 30 seconds, one minute, 3 minutes, 10 minutes, 30 minutes and 2 hours, the tribo charge quantities ( ⁇ C/g) were 1.9, 3.1, 4.8, 6.5, 7.8, 8.7 and 9.5, respectively. The tribo charge quantity after stirring for 5 minutes was 68.4% of that after 2 hours. Hence, a rise of charging was poor.
  • Example 2 An image test was carried out in the same manner as in Example 1. A good image which was not fogged was obtained at the initial stage of running. However, after obtaining about 1,000 copies, an image which was fogged and not clear was obtained.
  • Composition 72 was prepared in the same manner as in Example 47 except that aluminum hydroxide (30 ⁇ m) was used in place of aluminum hydroxide (2 ⁇ m).
  • a toner was prepared in the same manner as in Example 1 except that Composition 72 was used in place of Composition 1.
  • the tribo charge quantity of the toner was measured. After the mixing of the toner with an iron powder carrier for 30 seconds, one minute, 3 minutes, 5 minutes, 10 minutes, 30 minutes and 2 hours, the tribo charge quantities ( ⁇ C/g) were 2.6, 4.3, 6.3, 8.9, 9.0, 9.3 and 9.3, respectively. The value after stirring for 5 minutes was 95.7% of that after 2 hours. Hence, a rise of charging was good.
  • the toner was put into a development device, and continuous copying was carried out to make an image test. A good image was obtained at the initial stage of running. After obtaining 50,000 copies, the image quality was not changed, and neither toner scattering nor offset occurred.
  • a toner was prepared in the same manner as in Example 1 except that Composition 73 was used in place of Composition 1.
  • the tribo charge quantity of the toner was measured. After stirring for 30 seconds, one minute, 3 minutes, 5 minutes, 10 minutes, 30 minutes and 2 hours, the tribo charge quantities ( ⁇ C/g) were 3.3, 5.3, 7.2, 9.9, 10.1, 10.3 and 10.4, respectively.
  • the value after stirring for 5 minutes was 95.2% of that after 2 hours. Hence, a rise of charging was good.
  • the toner was put into a development device, and continuous copying was carried out to make an image test. A good image was obtained at the initial stage of running. After obtaining 50,000 copies, the image quality was not changed, and neither toner scattering nor offset occurred.
  • Composition 74 composed of the quaternary ammonium salt (Compound 64) and calcium carbonate (50:50).
  • a toner was prepared in the same manner as in Example 1 except that Composition 74 was used in place of Composition 1.
  • the tribo charge quantity of the toner was measured. After stirring the toner with an iron powder carrier for 30 seconds, one minute, 3 minutes, 5 minutes, 10 minutes, 30 minutes and 2 hours, the tribo charge quantities ( ⁇ C/g) were 3.0, 5.0, 7.1, 9.5, 9.9, 10.2 and 10.3, respectively.
  • the tribo charge quantity after stirring for 5 minutes was 92.2% of that after 2 hours. Hence, there was obtained a toner having a good rise of charging in a short period of time.
  • the toner was put into a development device, and continuous copying was carried out to make an image test. A good image was obtained at the initial stage of running. After obtaining 50,000 copies, the image quality was not changed, and neither toner scattering nor offset occurred. Further, the continuous copying test was carried out under high temperature and humidity conditions and under low temperature and humidity conditions. An image of good quality was obtained without being affected by environmental conditions.
  • a toner was prepared in the same manner as in Example 1 except that 1.0 part of the quaternary ammonium salt (Compound 64) synthesized and dried in the same manner as in Example 52 was used, water was not used and aluminum hydroxide was omitted.
  • the tribo charge quantity of the toner was measured. After stirring the resulting developer for 30 seconds, one minute, 3 minutes, 5 minutes, 10 minutes, 30 minutes and 2 hours, the tribo charge quantities ( ⁇ C/g) were 1.8, 3.0, 4.2, 5.3, 6.0, 6.8 and 7.3, respectively.
  • the tribo charge quantity after stirring for 5 minutes was 72.6% of that after 2 hours. Hence, the toner had a very poor rise of charging.
  • Example 2 An image test was carried out in the same manner as in Example 1. A clear image which was not fogged was obtained at the initial stage of running. However, after obtaining about 1,000 copies, an image which was fogged and not clear was obtained.
  • compositions 75 to 87 containing the quaternary ammonium salts indicated in Table 7 were prepared in the same manner as in Example 47 and used in Examples 53 to 62 shown in Table 8. Further, the quaternary ammonium salts were used in Comparative Examples 47 to 56 in the same manner as in Comparative Example 45. The results are shown in Tables 8 and 9.
  • Binder resins, charge quantity-measuring method and the criterion of the evaluation of each item used in Tables 8 and 9 are as follows. Binder resins used in the preparation of toners:

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Developing Agents For Electrophotography (AREA)
EP93109119A 1992-06-09 1993-06-07 Ladungskontrollmittelzusammensetzung und elektrophotographischer Toner Withdrawn EP0575805A1 (de)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP173681/92 1992-06-09
JP17368292 1992-06-09
JP17368192 1992-06-09
JP173682/92 1992-06-09
JP5094842A JPH0659518A (ja) 1992-06-09 1993-03-16 電荷制御剤組成物および電子写真用トナー
JP94842/93 1993-03-16
JP11238593A JP3262892B2 (ja) 1993-04-16 1993-04-16 電荷制御剤組成物および電子写真用トナー
JP112385/93 1993-04-16

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0654474A1 (de) * 1993-11-24 1995-05-24 Basf Aktiengesellschaft Verdoppelte Benzimidazole und ihre Anwendung als Ladungsstabilisatoren
US5573999A (en) * 1991-07-27 1996-11-12 Basf Aktiengesellschaft β-substituted cinnamic acid derivative
EP0803780A1 (de) * 1996-04-23 1997-10-29 Orient Chemical Industries, Ltd. Ladungssteuermittel und Toner zur Entwicklung elektrostatischer Bilder
US5928826A (en) * 1995-09-06 1999-07-27 Hodogaya Chemical Co., Ltd. Electrostatic image developing toner
US7309558B1 (en) 1999-11-27 2007-12-18 Clariant Produkte (Deutschland) Gmbh Use of salt-like structured silicas as charge control agents
US7749671B2 (en) * 2005-09-15 2010-07-06 Ricoh Company, Ltd. Toner for developing a latent electrostatic image, image-forming method, image-forming apparatus and process cartridge using the same
US7838193B2 (en) * 2006-02-14 2010-11-23 Ricoh Company Limited Toner and image forming method using the toner
WO2013023673A1 (en) * 2011-08-12 2013-02-21 Tetra Laval Holdings & Finance S.A. Novel marking compound

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0022347A1 (de) * 1979-07-02 1981-01-14 Xerox Corporation Elektrostatographische Entwicklermischung
US4828954A (en) * 1986-08-14 1989-05-09 Fuji Xerox Co., Ltd. Toner composition with treated inorganic powder
EP0347918A1 (de) * 1988-06-24 1989-12-27 Konica Corporation Verfahren zur Herstellung elektrophotographischer Bilder

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0022347A1 (de) * 1979-07-02 1981-01-14 Xerox Corporation Elektrostatographische Entwicklermischung
US4828954A (en) * 1986-08-14 1989-05-09 Fuji Xerox Co., Ltd. Toner composition with treated inorganic powder
EP0347918A1 (de) * 1988-06-24 1989-12-27 Konica Corporation Verfahren zur Herstellung elektrophotographischer Bilder

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5573999A (en) * 1991-07-27 1996-11-12 Basf Aktiengesellschaft β-substituted cinnamic acid derivative
EP0654474A1 (de) * 1993-11-24 1995-05-24 Basf Aktiengesellschaft Verdoppelte Benzimidazole und ihre Anwendung als Ladungsstabilisatoren
US5928826A (en) * 1995-09-06 1999-07-27 Hodogaya Chemical Co., Ltd. Electrostatic image developing toner
EP0803780A1 (de) * 1996-04-23 1997-10-29 Orient Chemical Industries, Ltd. Ladungssteuermittel und Toner zur Entwicklung elektrostatischer Bilder
US7309558B1 (en) 1999-11-27 2007-12-18 Clariant Produkte (Deutschland) Gmbh Use of salt-like structured silicas as charge control agents
US7749671B2 (en) * 2005-09-15 2010-07-06 Ricoh Company, Ltd. Toner for developing a latent electrostatic image, image-forming method, image-forming apparatus and process cartridge using the same
US7838193B2 (en) * 2006-02-14 2010-11-23 Ricoh Company Limited Toner and image forming method using the toner
WO2013023673A1 (en) * 2011-08-12 2013-02-21 Tetra Laval Holdings & Finance S.A. Novel marking compound
CN103619970A (zh) * 2011-08-12 2014-03-05 利乐拉瓦尔集团及财务有限公司 新型标记化合物
RU2582408C2 (ru) * 2011-08-12 2016-04-27 Тетра Лаваль Холдингз Энд Файнэнс С.А. Новое маркировочное соединение
US9375965B2 (en) 2011-08-12 2016-06-28 Adam O'Rourke Marking compound

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