EP0284000A2 - Sel d'ammonium quaternaire et toner électrophotographique - Google Patents

Sel d'ammonium quaternaire et toner électrophotographique Download PDF

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Publication number
EP0284000A2
EP0284000A2 EP88104495A EP88104495A EP0284000A2 EP 0284000 A2 EP0284000 A2 EP 0284000A2 EP 88104495 A EP88104495 A EP 88104495A EP 88104495 A EP88104495 A EP 88104495A EP 0284000 A2 EP0284000 A2 EP 0284000A2
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EP
European Patent Office
Prior art keywords
group
acid ion
carbon atoms
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.)
Granted
Application number
EP88104495A
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German (de)
English (en)
Other versions
EP0284000B1 (fr
EP0284000A3 (en
Inventor
Nobuo Hodogaya Chemical Co Suzuki
Genpei Hodogaya Chemical Co. Sugiyama
Susumu Hodogaya Chemical Co. Suzuka
Hiromitsu Hodogaya Chemical Co. Tomiyama
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hodogaya Chemical Co Ltd
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Hodogaya Chemical Co Ltd
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Filing date
Publication date
Application filed by Hodogaya Chemical Co Ltd filed Critical Hodogaya Chemical Co Ltd
Publication of EP0284000A2 publication Critical patent/EP0284000A2/fr
Publication of EP0284000A3 publication Critical patent/EP0284000A3/en
Application granted granted Critical
Publication of EP0284000B1 publication Critical patent/EP0284000B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • G03G9/09733—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
    • G03G9/09783—Organo-metallic compounds

Definitions

  • the present invention relates to a novel quaternary ammonium salt and an electrophotographic toner.
  • electrophotography it is common that an electrostatic latent image is formed on a photo­conductive layer containing a photoconductive material, and the latent image is then developed with a powder developing agent to a visible image, which is then fixed by means of heat or a solvent.
  • a mixture which comprises fine powder called a toner composed of a coloring agent and a resin, and fine glass beads or iron powder called a carrier.
  • the photoconductive layer can be electrified positively or negatively, so that when it is exposed under an original, an electrostatic image electrified either positively or negatively will be formed.
  • an electrostatic image electrified either positively or negatively will be formed.
  • a negatively electrified electrostatic latent image is developed with a positively electrified toner, a positive image of the original will be obtained.
  • a toner is a fine powder of a mixture of a synthetic resin and a coloring agent such as a dyestuff or a pigment.
  • the electrification property of the toner is governed by the resin as the major component thereof. However, it is usually possible to obtain a desired frictional electrification property by an incorporation of a charge-controlling agent.
  • Conventional charge-controlling agents include pigments and dyestuffs such as oil black, Nigrosine (Japanese Examined Patent Publication No. 25669/1973), aniline black, crystal violet or metal-containing azodyestuffs. Further, as colorless charge-controlling agents, quaternary ammonium salts (Japanese Unexamined Patent Publication No. 119364/1982) and metal soaps are known.
  • charge-controlling agents have disadvantages such that they are likely to be decomposed or modified by humidity, heat, light or mechanical shock, and when they are incorporated in toners, the electrification properties are subject to change due to the change of the environment or during the use for a long period of time, whereby they are likely to give adverse effects to developed images.
  • the present invention provides an electrophotographic toner containing a quaternary ammonium salt having the formula: wherein each of R1 and R2 is a long chain alkyl group having from 8 to 22 carbon atoms, R3 is an alkyl group having from 1 to 4 carbon atoms, R4 is an alkyl group having from 1 to 4 carbon atoms or a benzyl group and A ⁇ is an anion.
  • the compound of the formula 1 is characterized in that it has two long alkyl groups, whereby the properties of the toner have been substantially improved.
  • the long alkyl group for R1 and R2 in the formula 1 includes an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an eicosyl group, a docosyl group, an oleyl group, a linolyl group and a hexadecenyl group. Particularly preferred among them is a long chain alkyl group having from 12 to 18 carbon atoms.
  • R3 includes a methyl group, an ethyl group, a propyl group, a butyl group and a ⁇ -hydroxyethyl group.
  • R4 includes a methyl group, an ethyl group, a propyl group, a butyl group, a ⁇ -hydroxyethyl group and a benzyl group.
  • the anion A ⁇ includes inorganic anions which contain a molybdenum or tungsten atom, such as a molybdic acid ion, a tungstic acid ion, a phosphomolybdic acid ion, a silicomolybdic acid ion, a phosphotungstic acid ion, a silicotungstic acid ion, a phosphotungsten-molybdic acid ion, a silicotungsten-molybdic acid ion and a chromium-molybdic acid ion, and a chlorine ion, a bromine ion, an iodine ion, a nitric acid ion, a sulfuric acid ion, a perchrolic
  • the compound of the formula 1 is novel when A ⁇ molybdic acid ion or a tungstic acid ion and provided that when each of R3 and R4 is a methyl group, R1 and R2 are not simultaneously dodecyl groups or octadecyl groups.
  • the toner of the present invention contains a binder resin and a coloring agent in addition to the quaternary ammonium salt of the formula 1.
  • binder resin suitable for use for the toner of the present invention there may be mentioned a homopolymer of styrene or substituted styrene such as a polystyrene or a polyvinyl toluene, a styrene-substituted styrene copolymer, a styrene-acrylate copolymer, a styrene-methacrylate copolymer, a styrene-acrylonitrile copolymer, a polyvinyl chloride, a polyethylene, a silicon resin, a polyester, a polyurethane, a polyamide, an epoxy resin, a modified rosin or a phenol resin.
  • a homopolymer of styrene or substituted styrene such as a polystyrene or a polyvinyl toluene, a styrene-substituted
  • coloring agent there may be employed, for example, C.I. pigment yellow-12, C.I. solvent yellow 16, 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 toner of the present invention may be prepared by melt-mixing the compound of the formula 1 to the synthetic resin in a weight ratio within a range of from 1 to 50%, solidifying the mixture, and then pulverizing it by a ball mill or by other pulverizers. Otherwise, it may be prepared by adding a polymerization initiator to the synthetic resin monomer, then adding the compound of the formula 1 in a weight ratio within a range of from 1 to 50% relative to the monomer, and polymerizing the mixture while suspending it in water. During the preparation, other coloring agents or carbon black may be added as the dyestuff.
  • the toner thus prepared provides an electric charge suitable for the development of the static latent image, and even when the development is repeated, the electric charge can be maintained at a predetermined level.
  • the charge distribution is uniform, and will be maintained at a constant state.
  • the carrier there may be employed a carrier prepared by coating iron powder or magnetic cores with a styrene-methyl methacrylate copolymer, a silicon resin, a resin mixture of a styrene-methyl methacrylate copolymer and a silicon resin or a tetrafluoroethylene polymer.
  • the charge controlling agent of the present invention presents excellent electrification properties also when used for a so-called one component toner containing a magnetic powder.
  • the magnetic material for the magnetic powder may be a fine powder of a metal such as iron, nickel or cobalt, an alloy of a metal such as iron, cobalt, copper, aluminum, nickel or zinc, a metal oxide such as aluminum oxide, iron oxide or titanium oxide, a ferrite of e.g. iron, manganese, nickel, cobalt or zinc, a nitride such as vanadium nitride or chromium nitride, a carbide such as tungsten carbide or silicon carbide or a mixture thereof. The most preferred among them is magnetite.
  • a metal such as iron, nickel or cobalt
  • an alloy of a metal such as iron, cobalt, copper, aluminum, nickel or zinc
  • a metal oxide such as aluminum oxide, iron oxide or titanium oxide
  • a nitride such as vanadium nitride or chromium nitrid
  • a toner was prepared in the same manner as in Example 1 except that instead of the quaternary ammonium salt used in Example 1, N,N,N-trimethyl-N-hexadecylammonium molybdate was used. Namely, the quaternary ammonium salt used in this Comparative Example is different from the one used in Example 1 in that one of the two long chain alkyl groups (hexadecyl groups) of the quaternary ammonium salt used in Example 1 was substituted by a lower alkyl group (methyl group).
  • the toners of Example 1 and Comparative Example 1 were put in polypropylene containers, respectively, and stirred at a speed of about 100 rpm, and the triboelectric charges of the toners were measured as time passed.
  • a toner was prepared in the same manner as in Example 2 except that instead of the quaternary ammonium salt used in Example 2, N,N,N-trimethyl-N-tetradecylammonium molybdate was used. Namely, the quaternary ammonium salt used in this Comparative Example is different from the one used in Example 2 in that one of the two long chain alkyl groups (tetradecyl groups) of the quaternary ammonium salt used in Example 2 was substituted by a lower alkyl group (methyl group).
  • the toners of Example 2 and this Comparative Example were put in propylene containers, respectively, and stirred at a speed of about 100 rpm, and the triboelectric charges of the toners were measured as the time passed.
  • Toners were prepared in the same manner as in Example 1 except that the quaternary ammonium salt was changed. The results are shown in Table 1.
  • N,N-dimethyl-N,N-dioctadecylammonium chrolide and 5 parts of carbon black were kneaded with 100 parts of a styrene-n-butyl methacrylate copolymer under heating. After cooling, the mixture was pulverized by a hammer mill, then finely pulverized by a jet pulverizer and classified to obtain a powder having a particle size of from 10 to 12 ⁇ m.
  • the black powder thus obtained was mixed with an iron powder carrier in a weight ratio of 5 : 150, and the mixture was shaked.
  • the toner was positively electrified, and the electric charge was 22 ⁇ C/g.
  • a toner was prepared in the same manner as in Example 24 except that instead of the quaternary ammonium salt used in Example 24, N,N,N-trimethyl-N-octadecylammonium chloride was used.
  • the quaternary ammonium salt used in this Comparative Example is different from the one used in Example 24 in that one of the two long chain alkyl groups (octadecyl groups) of the quaternary ammonium salt used in Example 24 was substituted by a lower alkyl group (methyl group).
  • the toners of Example 24 and Comparative Example 3 were put in polypropylene containers, respectively, and stirred at a speed of about 100 rpm, and the triboelectric charges of the toners were measured as time passed.
  • Example 24 the increase of the electric charge is quick from the initial stage of stirring, whereas in Comparative Example 3, the increase of electric charge is slow at the initial stage of stirring.
  • the toner of the present invention i.e. the toner containing a quaternary ammonium salt having two long chain alkyl groups, is superior.
  • a toner was prepared in the same manner as in Example 25 except that instead of the quaternary ammonium salt used in Example 25, N,N,N-trimethyl-N-octadecylammonium molybdate was used. Namely, the quaternary ammonium salt used in this Comparative Example is different from the one used in Example 25 in that one of the two long chain alkyl groups (octadecyl groups) of the quaternary ammonium salt used in Example 25 was substituted by a lower alkyl group (methyl group).
  • Example 25 The toners of Example 25 and this Comparative Example were put in propylene containers, respectively, and stirred at a speed of about 100 rpm, and the triboelectric charges of the toners were measured as the time passed. The results are shown in Figure 4. From this Figure, it is apparent that in Example 25, the increase of electric charge is quick from the initial stage of stirring, whereas in Comparative Example 4, the increase of electric charge is slow at the initial stage of stirring. Also in this respect, the toner of the present invention i.e. the toner containing a quaternary ammonium salt having two long chain alkyl groups, is superior.
  • N,N-dimethyl-N,N-­dioctadecylammonium chloride N,N-dimethyl-N,N-di-­hardened beef tallow alkyl ammoni
  • This toner was positively charged, and the charge was 33 ⁇ C/g.
  • an image was reproduced by a commercially available photocopying machine, whereby copies with an excellent image quality were obtained not only at the initial stage but also after the reproduction of 10,000 copies.
  • Toners were prepared in the same manner as in Example 24 except that the quaternary ammonium salt was changed. The results are shown in Table 2.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP88104495A 1987-03-25 1988-03-21 Sel d'ammonium quaternaire et toner électrophotographique Expired - Lifetime EP0284000B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP6876587 1987-03-25
JP68765/87 1987-03-25

Publications (3)

Publication Number Publication Date
EP0284000A2 true EP0284000A2 (fr) 1988-09-28
EP0284000A3 EP0284000A3 (en) 1990-01-03
EP0284000B1 EP0284000B1 (fr) 1992-09-02

Family

ID=13383157

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88104495A Expired - Lifetime EP0284000B1 (fr) 1987-03-25 1988-03-21 Sel d'ammonium quaternaire et toner électrophotographique

Country Status (4)

Country Link
EP (1) EP0284000B1 (fr)
JP (1) JP2624755B2 (fr)
KR (1) KR930006193B1 (fr)
DE (1) DE3874176T2 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0488742A1 (fr) * 1990-11-28 1992-06-03 Mita Industrial Co., Ltd. Toner électrophotographique pour charger négativement
EP0488741A1 (fr) * 1990-11-28 1992-06-03 Mita Industrial Co., Ltd. Toner électrophotographique pour charger négativement
EP0488744A1 (fr) * 1990-11-28 1992-06-03 Mita Industrial Co., Ltd. Toneur électrophotographique pour charger négativement
EP0488743A1 (fr) * 1990-11-28 1992-06-03 Mita Industrial Co., Ltd. Toner électrophotographique pour charger négativement
EP0548826A3 (en) * 1991-12-21 1993-11-10 Hoechst Ag Diallyl ammonium-compounds, method for their preparation and their application
US5318872A (en) * 1993-04-02 1994-06-07 Xerox Corporation Toner and developer compositions with fluorophosphate charge enhancing additives
WO2006061230A1 (fr) * 2004-12-09 2006-06-15 Lonza Inc. Sels d'ammonium quaternaires utilises en tant que revetement de conversion ou en tant qu'additif anticorrosion dans des peintures
WO2013023673A1 (fr) * 2011-08-12 2013-02-21 Tetra Laval Holdings & Finance S.A. Nouveau composé marqueur
WO2016195914A1 (fr) 2015-06-04 2016-12-08 Delphi Technologies, Inc. Sélection de règle de commande de véhicule automatisé en fonction de l'état d'attention de l'opérateur

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4937157A (en) * 1989-08-21 1990-06-26 Xerox Corporation Toner and developer compositions with charge enhancing additives
US4904762A (en) * 1989-08-21 1990-02-27 Xerox Corporation Toner compositions with charge enhancing additives
JP2025075866A (ja) * 2023-10-31 2025-05-15 東京応化工業株式会社 ポリ酸塩又はその混合物

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3346604A (en) * 1962-06-11 1967-10-10 American Cyanamid Co Quaternary ammonium complexes with heteropolyanions
CA1219270A (fr) * 1982-07-28 1987-03-17 William J. Kroenke Molybdates d'amine
US4410463A (en) * 1982-07-28 1983-10-18 The B. F. Goodrich Company Tetrapentylammonium molybdates
JPS6253944A (ja) * 1985-05-28 1987-03-09 Hodogaya Chem Co Ltd 電子写真用トナー
US4683188A (en) * 1985-05-28 1987-07-28 Hodogaya Chemical Co., Ltd. Electrophotographic toner containing metal complex charge control agent

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0488742A1 (fr) * 1990-11-28 1992-06-03 Mita Industrial Co., Ltd. Toner électrophotographique pour charger négativement
EP0488741A1 (fr) * 1990-11-28 1992-06-03 Mita Industrial Co., Ltd. Toner électrophotographique pour charger négativement
EP0488744A1 (fr) * 1990-11-28 1992-06-03 Mita Industrial Co., Ltd. Toneur électrophotographique pour charger négativement
EP0488743A1 (fr) * 1990-11-28 1992-06-03 Mita Industrial Co., Ltd. Toner électrophotographique pour charger négativement
EP0548826A3 (en) * 1991-12-21 1993-11-10 Hoechst Ag Diallyl ammonium-compounds, method for their preparation and their application
US5475119A (en) * 1991-12-21 1995-12-12 Hoechst Aktiengesellschaft Diallylammonium compounds, processes for their preparation and their use
US5563016A (en) * 1991-12-21 1996-10-08 Hoechst Ag Diallylammonium compounds, processes for their preparation and their use
US5318872A (en) * 1993-04-02 1994-06-07 Xerox Corporation Toner and developer compositions with fluorophosphate charge enhancing additives
WO2006061230A1 (fr) * 2004-12-09 2006-06-15 Lonza Inc. Sels d'ammonium quaternaires utilises en tant que revetement de conversion ou en tant qu'additif anticorrosion dans des peintures
EA014610B1 (ru) * 2004-12-09 2010-12-30 Лонца Инк. Четвертичные аммониевые соли как конверсионные покрытия или как противокоррозионная добавка для красок
US8580154B2 (en) 2004-12-09 2013-11-12 Lonza, Inc. Quaternary ammonium salts as a conversion coating or coating enhancement
WO2013023673A1 (fr) * 2011-08-12 2013-02-21 Tetra Laval Holdings & Finance S.A. Nouveau composé marqueur
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
US20140147392A1 (en) * 2011-08-12 2014-05-29 Tetra Laval Holdings & Finance S.A. Novel marking compound
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
WO2016195914A1 (fr) 2015-06-04 2016-12-08 Delphi Technologies, Inc. Sélection de règle de commande de véhicule automatisé en fonction de l'état d'attention de l'opérateur

Also Published As

Publication number Publication date
JPS6454A (en) 1989-01-05
JP2624755B2 (ja) 1997-06-25
EP0284000B1 (fr) 1992-09-02
DE3874176D1 (en) 1992-10-08
DE3874176T2 (de) 1993-04-08
KR880011075A (ko) 1988-10-26
EP0284000A3 (en) 1990-01-03
KR930006193B1 (ko) 1993-07-08

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