EP0393503A1 - Use of colourless phosphonium compounds, highly substituted by fluor, in electrophotographic recording processes - Google Patents

Use of colourless phosphonium compounds, highly substituted by fluor, in electrophotographic recording processes Download PDF

Info

Publication number
EP0393503A1
EP0393503A1 EP90106998A EP90106998A EP0393503A1 EP 0393503 A1 EP0393503 A1 EP 0393503A1 EP 90106998 A EP90106998 A EP 90106998A EP 90106998 A EP90106998 A EP 90106998A EP 0393503 A1 EP0393503 A1 EP 0393503A1
Authority
EP
European Patent Office
Prior art keywords
substituted
radicals
fluorine
atoms
alkyl
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
EP90106998A
Other languages
German (de)
French (fr)
Other versions
EP0393503B1 (en
Inventor
Jörg Dr. Gitzel
Hans-Tobias Dr. Macholdt
Wolfgang Dr. Knaup
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.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Priority to AT90106998T priority Critical patent/ATE100220T1/en
Publication of EP0393503A1 publication Critical patent/EP0393503A1/en
Application granted granted Critical
Publication of EP0393503B1 publication Critical patent/EP0393503B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/097—Plasticisers; Charge controlling agents
    • G03G9/09733—Organic compounds
    • G03G9/09766—Organic compounds comprising fluorine
    • 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

Definitions

  • the present invention relates to the use of highly fluorine-substituted phosphonium compounds as colorless charge control agents for use in toners and developers for electrophotographic recording processes.
  • a "latent charge image” is generated on a photoconductor. This is done, for example, by charging a photoconductor by means of a corona discharge and then imagewise exposing the electrostatically charged surface of the photoconductor, the exposure of the charge to the grounded base at the exposed locations being effected by the exposure.
  • the "latent charge image” thus generated is then developed by applying a toner.
  • the toner is transferred from the photoconductor to, for example, paper, textiles, foils or plastic and fixed there, for example by pressure, radiation, heat or the action of solvents.
  • the photoconductor used is then cleaned and is available for a new recording process.
  • toners The optimization of toners is described in numerous patents. a. the influence of the toner binder (variation of resin / resin components or wax / wax components), the influence of control agents or other additives or the influence of carriers (for two-component developers) and magnetic pigments (for one-component developers) were examined.
  • a measure of the toner quality is its specific charge gim (charge per unit of mass).
  • gim charge per unit of mass
  • the decisive factor in quality is the rapid achievement of the desired charge level and the constancy of this charge over a longer activation period. In practice this is of central importance insofar as the toner in the development mixture can be subjected to a considerable activation time before it is transferred to the photoconductor, since it partly remains in the developer mixture for a period of up to several thousand copies.
  • the insensitivity of the toner to climatic influences, such as temperature and humidity, is another important criterion for suitability.
  • Both positively and negatively chargeable toners are used in copiers and laser printers depending on the type of process and device.
  • charge control agents also called charge control agents
  • the extent of the control effect is important, since greater effectiveness allows a small amount to be used.
  • toner binders alone generally have a strong change in the charge from the activation time, it is the task of a charge control agent to set the sign and amount of the toner charge on the one hand and to counteract the charge drift of the toner binder on the other hand and to ensure constant toner charge.
  • Charge control agents which cannot prevent the toner or developer from showing a high charge drift (aging) over a long period of use, which can even cause the toner or developer to undergo charge reversal, are therefore unsuitable in practice.
  • Full-color copiers and laser printers work according to the trichromatic principle, which requires exact color matching of the three primary colors (yellow, cyan and magenta). The slightest color shift, even if only one of the three primary colors is required, requires a color shift of the other two colors in order to be able to produce full-color copies or prints true to the original.
  • charge control agents are absolutely particularly important absolutely without their own color.
  • the three toners yellow, cyan and magenta have to be exactly matched to each other in terms of their triboelectric properties in addition to the precisely defined color requirements.
  • This triboelectric adjustment is necessary because in the case of full-color printing or in the case of full-color copying, the three color toners (or four color toners if black is included) must be transferred in succession in the same device.
  • Colorants are known to be able to influence the triboelectric charging of toners very sustainably in some cases (H.-T. Macholdt, A. Sieber, Dyes & Pigments 9 (1988), 119-27, US-PS 4057426, EP-OS 247576 ). Because of the different triboelectric effects of colorants and the resulting, in some cases, very pronounced influence on the toner chargeability, it is not possible to add them as the exclusive colorant to a toner base formulation that has already been created. Rather, it may be necessary to create a separate recipe for each colorant, for which type and quantity, for example of the required charge control agent can be specially tailored. This procedure is correspondingly complex and, in the case of color toners for process color (trichrome), is in addition to the difficulties already described.
  • colorless charge control agents for electrophotographic toners and developers are ammonium (eg EP-OS 203532, EP-OS 242420, US-PS 4683188, US-PS 4684596, JP-OS 63-226665) and phosphonium compounds (eg US-PS 3893935, US -PS 4496643, JP-OS 63-231358), metal complexes and organyls (e.g. US-PS 4656112, DE-OS 3144017, JP-OS 61-236557 JP-OS 62-287262) as well as a number of other compounds (e.g. EP- OS 216295).
  • ammonium eg EP-OS 203532, EP-OS 242420, US-PS 4683188, US-PS 4684596, JP-OS 63-226665
  • phosphonium compounds eg US-PS 3893935, US -PS 4496643, JP-OS 63-231358
  • Positive colorless charge control agents essentially include quaternary ammonium and phosphonium compounds, as well as some tin and antimony organyls.
  • the colorless charge control agents known hitherto have a number of disadvantages which severely restrict their use in practice or in some cases even make them impossible.
  • the quaternary ammonium compounds which are suitable per se are difficult to disperse and, for reasons which have not yet been clarified, can. lead to uneven charging of the toner, and the toner charge generated by it is not stable over a longer activation time, especially at high temperature and air humidity (EP-OS 242420).
  • such compounds can be sensitive to light or mechanical influences (EP-OS 203532, US Pat. No.
  • Organotin borates as described in EP-PS 216295, and tin (JP-OS 62-287262) and antimony organyls (JP-OS 61-236557) are problematic because of their heavy metal content.
  • JP-OS 63-226665 and phosphonium compounds JP-OS 63-231358 and a number of heavy metal compounds are known as negative colorless charge control agents, namely chromium, iron, cobalt (DE-OS 3144017) and zinc -Complexes (US-PS 4656112, JP-OS 62-127754).
  • JP-OS 63-226665 and phosphonium compounds JP-OS 63-231358
  • heavy metal compounds namely chromium, iron, cobalt (DE-OS 3144017) and zinc -Complexes (US-PS 4656112, JP-OS 62-127754.
  • charge control agents are also used to coat carriers.
  • the same classes of compounds are used as for incorporation in toner resins, e.g. Ammonium (JP-OS 61-258270) and phosphonium compounds (JP-OS 61-260258) as well as heavy metal complexes and organyls (JP-OS 61-147261, JP-OS 61-259267).
  • colorless charge control agents are known in principle for both positive and negative toners, but are only partially suitable or not suitable for use in practice, or are still largely in need of improvement. This can also be seen from the fact that the ammonium and phosphonium compounds in particular have so far not been successful in practice.
  • the most highly fluorine-substituted phosphonium compounds have particularly favorable properties as colorless charge control agents for electrophotographic toners and developers. Due to their colorlessness, high effectiveness, good compatibility and dispersibility in common toner resins and chemical inertness, the compounds are particularly suitable for use in color toners or developers for full-color copiers and laser printers according to the principle of trichromatic (subtractive color mixing), but also for colored toners or developers in general and suitable for black toners or developers. It is particularly surprising that substances of one and the same class of compound, depending on the chemical modification, either as positive or as negative charge control agents are suitable (see application examples 1 to 4). The compounds are also suitable for coating carriers.
  • a great technical advantage of these readily dispersible compounds is that substances of the same class of compounds can be used either as positive or as negative control agents. Problems with incorporation into the toner binder and compatibility with the toner binder after a toner base formulation has been created are thus minimized. Both positive and negative toners can be produced using a solid toner base formulation (consisting of toner binder, colorant, flow aid and possibly other components) by incorporating the desired control agent.
  • the present invention relates to the use of highly fluorine-substituted phosphonium compounds of the general formula (I) in which R 1 to R 4 are hydrogen atoms or organic radicals, at least one of the radicals R 1 to R 4 being a straight-chain or branched, fluorine-substituted, unsaturated and / or saturated alkyl radical having 1 to 30 C atoms and 3 to 50 F atoms represents which further halogen atoms, such as fluorine, chlorine, bromine or iodine atoms, hydroxyl and / or chloromethyl and / or carboxylic acid amide and / or sulfonic acid amide and / or urethane and / or keto and / or amino and / or R 5 -OR 6 - and / or R 7 -C (O) -O-Rs groups, in which R 5 , R 6 , R 7 and Rs represent alkyl (Ci-C 3 o) radicals , or represents
  • X- as an inorganic or organic anion can be, for example Hal, such as F-, CI-, Br- or I-, further PF 6 -, sulfate, phosphate, cyanate, thiocyanate, BF 4 -, B (aryl) 4 - , such as, for example, tetraphenylborate, p-chlorotetraphenylborate, p-methyltetraphenylborate, tetranaphthylborate, also phenolate, nitrophenolate, zinc tetracyanate, zinc tetrathiocyanate, CH 3 OSO 3 - , saturated or unsaturated aliphatic or aromatic carboxylate or acylate, such as lactylate, such as lactate, such as lactylate, such as acylate, for example, 2-hydroxy-3-naphthoate, 2-hydroxy-6-naphthoate, ethyl sulfonate,
  • the phosphonium compounds of the abovementioned general formula (I) can be used on their own or in combination in toners or developers which are used for electrophotographic copying or duplication of originals and for printing electronically, optically or magnetically stored information or in color proofing.
  • these compounds can be used for the coating of carriers and in powders and lacquers for surface coating, in particular in electrokinetically sprayed powder lacquers, as charge-improving agents and are effective as dispersing assistants.
  • R 1 to R 4 is a straight-chain or branched, fluorine-substituted, unsaturated and / or saturated alkyl radical having 4 to 17 C atoms and 3 to 25 F atoms means which further halogen atoms, such as fluorine, chlorine, bromine or iodine atoms, hydroxyl and / or chloromethyl and / or carboxamide and / or urethane and / or keto and / or amino and / or R 5 -OR 6 and / or R 7 -C (O) -OR 8 groups, in which R s , R 6 , R 7 and R s represent alkyl (C 1 -C 18 ) radicals, or a fluorine-substituted aryl radical , such as phenyl, toluyl or naphthyl, or an aralkyl radical which is fluorine-
  • a toner with 1.0 percent by weight of compound (1) shows a charge of + 18.5 u.C / g after 10 minutes and of + 19.3 tlC / g after 24 hours of activation time (see application example 1 of the application examples below).
  • a toner with 1.0 percent by weight of compound (2) has a charge of -2.8 u.C / g after 10 minutes and of -2.7 tlC / g after 24 hours of activation time (application example 2).
  • the compounds of the general formula (I) mentioned can also be obtained from suitable media, e.g. Solutions, on suitable carrier materials, e.g. Silica gel, aluminum oxide, titanium dioxide.
  • suitable carrier materials e.g. Silica gel, aluminum oxide, titanium dioxide.
  • the compounds used according to the invention are generally added in a concentration of about 0.01 to about 10 percent by weight, preferably about 0.1 to about 5.0 percent by weight, in the respective carrier material in a known manner, e.g. by kneading or extruding, incorporated homogeneously.
  • the charge control agents for toners or charge-improving agents for powders and lacquers for surface coating can be used as dried and ground powders, dispersions or solutions, presscakes, masterbatches, as compounds drawn up on suitable carriers from aqueous or non-aqueous solution or in other form can be added.
  • the compounds used according to the invention can in principle also be added during the preparation of the respective binders, i.e. in the course of their polymerization or polycondensation.
  • Typical toner binders are, for example, styrene, styrene-acrylate, styrene-butadiene, acrylate, polyester, amide, amine, ammonium, ethylene, phenol and epoxy resins, individually or in combination, which also contain other ingredients, such as colorants, waxes or Flow aids, can contain or can be added afterwards.
  • Typical carrier materials (resins) for powders and lacquers for surface coating, in particular for electrokinetically sprayed powder lacquers are, for example, epoxy resins, carboxyl- and hydroxyl-containing polyester resins and acrylic resins together with hardeners, such as acid anhydrides, imidazoles, melamine or phenolic resins.
  • the level of electrostatic charging of the electrophotographic toners into which the charge control agents claimed according to the invention were homogeneously incorporated was measured on standard test systems under the same conditions (such as the same dispersion times, same particle size distribution, same particle shape) at room temperature and 50% relative atmospheric humidity.
  • the toner was activated in a two-component developer by swirling with a carrier (3 parts by weight of toner to 97 parts by weight of carrier) on a roller bench (150 revolutions per minute).
  • the electrostatic charge was then measured on a conventional q / m measuring stand (cf. J.H. Dessauer, H.E. Clark, "Xerography and related Processes", Focal Press, N.Y., 1965, page 289).
  • the particle size is of great influence in determining the q / m value, which is why strict attention was paid to uniform particle size distribution in the toner samples obtained by screening.
  • the desired particle fraction (4-25 ⁇ m) was obtained with a carrier made of 50 to 200 ⁇ m magnetite particles of the 90 ⁇ m type Xerographic Carrier coated with styrene-methacrylate copolymer 90:10 of the company Plasma Materials Inc. (Manchester, NH, USA).

Abstract

Highly fluorine-substituted phosphonium compounds of the formula (I) <IMAGE> in which R1 to R4 are hydrogen atoms or organic radicals, at least one of the radicals R1 to R4 being a fluorine-substituted, unsaturated and/or saturated alkyl radical which has 1 to 30 C atoms and 3 to 50 F atoms and can contain further substituents, or a fluorine-substituted aryl radical or an aralkyl radical fluorine-substituted on the aromatic nucleus, it being possible for the aryl radical and aralkyl radical to be additionally substituted on the aromatic nucleus, and, in the case of an aralkyl radical, the alkyl bridge between the phosphorus atom and the aromatic ring having 1 to 30 C atoms, and it being possible for at most 3 of the radicals R1 to R4 to be, independently of one another, hydrogen atoms, unsaturated or saturated, optionally substituted alkyl radicals having 1 to 30 C atoms, aryl or aralkyl radicals which can be substituted on the aromatic nucleus, and X<-> being an anion, it being possible for the radicals R1 to R4 to contain a COO<-> or SO3<-> group as a substituent, in which case X<-> becomes irrelevant, are used individually or in combination as colourless charge control agents having a positive or negative control action in toners and developers for electrophotographic recording processes.

Description

Die vorliegende Erfindung betrifft die Verwendung hochgradig fluorsubstituierter Phosphoniumverbindungen als farblose Ladungssteuermittel zum Einsatz in Tonern und Entwicklern für elektrophotographische Aufzeichnungsverfahren.The present invention relates to the use of highly fluorine-substituted phosphonium compounds as colorless charge control agents for use in toners and developers for electrophotographic recording processes.

Die erfindungsgemäßen Verbindungen besitzen durch die gezielte Einführung von fluorsubstituierten organischen Resten besonders günstige Ladungssteuereigenschaften. Bei elektrophotographischen Aufzeichnungsverfahren wird auf einem Photoleiter ein "latentes Ladungsbild" erzeugt. Dies erfolgt beispielsweise durch Aufladung eines Photoleiters durch eine Coronaentladung und anschließende bildmäßige Belichtung der elektrostatisch aufgeladenen Oberfläche des Photoleiters, wobei durch die Belichtung der Ladungsabfluß zur geerdeten Unterlage an den belichteten Stellen bewirkt wird. Anschließend wird das so erzeugte "latente Ladungsbild" durch Aufbringen eines Toners entwickelt. In einem darauffolgenden Schritt wird der Toner vom Photoleiter auf beispielsweise Papier, Textilien, Folien oder Kunststoff übertragen und dort beispielsweise durch Druck, Strahlung, Hitze oder Lösungsmitteleinwirkung fixiert. Der benutzte Photoleiter wird anschließend gereinigt und steht für einen neuen Aufzeichnungsvorgang zur Verfügung.Due to the targeted introduction of fluorine-substituted organic radicals, the compounds according to the invention have particularly favorable charge control properties. In electrophotographic recording processes, a "latent charge image" is generated on a photoconductor. This is done, for example, by charging a photoconductor by means of a corona discharge and then imagewise exposing the electrostatically charged surface of the photoconductor, the exposure of the charge to the grounded base at the exposed locations being effected by the exposure. The "latent charge image" thus generated is then developed by applying a toner. In a subsequent step, the toner is transferred from the photoconductor to, for example, paper, textiles, foils or plastic and fixed there, for example by pressure, radiation, heat or the action of solvents. The photoconductor used is then cleaned and is available for a new recording process.

In zahlreichen Patentschriften wird die Optimierung von Tonern beschrieben, wobei u. a. der Einfluß des Tonerbindemittels (Variation von Harz/Harzkomponenten oder Wachs/Wachskomponenten), der Einfluß von Steuermitteln oder anderen Zusatzstoffen oder der Einfluß von Carriern (bei Zweikomponentenentwicklern) und Magnetpigmenten (bei Einkomponentenentwicklern) untersucht wurden.The optimization of toners is described in numerous patents. a. the influence of the toner binder (variation of resin / resin components or wax / wax components), the influence of control agents or other additives or the influence of carriers (for two-component developers) and magnetic pigments (for one-component developers) were examined.

Ein Maß für die Tonerqualität ist seine spezifische Aufladung gim (Ladung pro Masseeinheit). Neben Vorzeichen und Höhe der elektrostatischen Aufladung ist vor allem das schnelle Erreichen der gewünschten Ladungshöhe und die Konstanz dieser Ladung über einen längeren Aktivierzeitraum hinweg ein entscheidendes Qualitätskriterium. In der Praxis ist dies insofern von zentraler Bedeutung, als der Toner im Entwicklungsgemisch, bevor er auf den Photoleiter übertragen wird, einer erheblichen Aktivierzeit ausgesetzt sein kann, da er teilweise für einen Zeitraum der Herstellung von bis zu mehreren tausend Kopien im Entwicklergemisch verbleibt. Darüberhinaus ist die Unempfindlichkeit des Toners gegen Klimaeinflüsse, wie Temperatur und Luftfeuchtigkeit, ein weiteres wichtiges Eignungskriterium.A measure of the toner quality is its specific charge gim (charge per unit of mass). In addition to the sign and level of the electrostatic charge, the decisive factor in quality is the rapid achievement of the desired charge level and the constancy of this charge over a longer activation period. In practice this is of central importance insofar as the toner in the development mixture can be subjected to a considerable activation time before it is transferred to the photoconductor, since it partly remains in the developer mixture for a period of up to several thousand copies. In addition, the insensitivity of the toner to climatic influences, such as temperature and humidity, is another important criterion for suitability.

Sowohl positiv als auch negativ aufladbare Toner finden Verwendung in Kopierern und Laserdruckern in Abhängigkeit vom Verfahrens- und Gerätetyp.Both positively and negatively chargeable toners are used in copiers and laser printers depending on the type of process and device.

Um elektrophotographische Toner oder Entwickler mit entweder positiver oder negativer triboelektrischer Aufladung zu erhalten, werden häufig sogenannte Ladungssteuermittel (auch Ladungskontrollmittel genannt) zugesetzt. Dabei ist neben dem Vorzeichen der Ladungssteuerung das Ausmaß des Steuereffektes von Bedeutung, da eine höhere Wirksamkeit eine geringe Einsatzmenge erlaubt.To obtain electrophotographic toners or developers with either positive or negative triboelectric charging, so-called charge control agents (also called charge control agents) are often added. In addition to the sign of the charge control, the extent of the control effect is important, since greater effectiveness allows a small amount to be used.

Da Tonerbindemittel allein in der Regel eine starke Änderung der Aufladung von der Aktivierzeit aufweisen, ist es Aufgabe eines Ladungssteuermittels, zum einen Vorzeichen und Höhe der Toneraufladung einzustellen und zum anderen der Aufladungsdrift des Tonerbindemittels entgegenzuwirken und für Konstanz der Toneraufladung zu sorgen. Ladungssteuerungsmittel, die nicht verhindern können, daß der Toner bzw. Entwickler bei längerer Gebrauchsdauer eine hohe Ladungsdrift zeigt (Alterung), die sogar bewirken kann, daß der Toner bzw. Entwickler eine Ladungsumkehr erfährt, sind daher für die Praxis ungeeignet. Vollfarbkopierer und -laserdrucker arbeiten nach dem Prinzip der Trichromie, welches eine exakte Farbtonabstimmung der drei Grundfarben (Gelb, Cyan und Magenta) erforderlich macht. Geringste Farbtonverschiebungen auch nur eines der drei Grundfarben verlangt zwingend eine Farbtonverschiebung der beiden anderen Farben, um auch dann originaltreue Vollfarbkopien bzw.- drucke produzieren zu können.Since toner binders alone generally have a strong change in the charge from the activation time, it is the task of a charge control agent to set the sign and amount of the toner charge on the one hand and to counteract the charge drift of the toner binder on the other hand and to ensure constant toner charge. Charge control agents which cannot prevent the toner or developer from showing a high charge drift (aging) over a long period of use, which can even cause the toner or developer to undergo charge reversal, are therefore unsuitable in practice. Full-color copiers and laser printers work according to the trichromatic principle, which requires exact color matching of the three primary colors (yellow, cyan and magenta). The slightest color shift, even if only one of the three primary colors is required, requires a color shift of the other two colors in order to be able to produce full-color copies or prints true to the original.

Wegen dieser in Farbtonern erforderlichen präzisen Abstimmung der Coloristik der einzelnen Farbmittel aufeinander, sind Ladungssteuermittel absolut ohne Eigenfarbe ganz besonders wichtig.Because of the precise coordination of the coloristics of the individual colorants that is required in color toners, charge control agents are absolutely particularly important absolutely without their own color.

Bei Farbtonern müssen die drei Toner Gelb, Cyan und Magenta neben den genau definierten farblichen Anforderungen auch hinsichtlich ihrer triboelektrischen Eigenschaften exakt aufeinander abgestimmt sein. Diese triboelektrische Abstimmung ist erforderlich, weil beim Vollfarbdruck bzw. bei der Vollfarbkopie aufeinanderfolgend die drei Farbtoner (bzw. vier Farbtoner, wenn Schwarz miteinbezogen wird) im selben Gerät übertragen werden müssen.In the case of color toners, the three toners yellow, cyan and magenta have to be exactly matched to each other in terms of their triboelectric properties in addition to the precisely defined color requirements. This triboelectric adjustment is necessary because in the case of full-color printing or in the case of full-color copying, the three color toners (or four color toners if black is included) must be transferred in succession in the same device.

Von Farbmitteln ist bekannt, daß sie die triboelektrische Aufladung von Tonern teilweise sehr nachhaltig beeinflussen können (H.-T. Macholdt, A. Sieber, Dyes & Pigments 9 (1988), 119-27, US-PS 4057426, EP-OS 247576). Wegen der unterschiedlichen triboelektrischen Effekte von Farbmitteln und des daraus resultierenden teilweise sehr ausgeprägten Einflusses auf die Toneraufladbarkeit ist es nicht möglich, sie in eine einmal erstellte Tonerbasisrezeptur als ausschließliches Farbmittel hinzuzufügen. Vielmehr kann es notwending werden, für jedes Farbmittel eine eigene Rezeptur zu erstellen, für welches z.B. Art und Menge des benötigten Ladungssteuermittels speziell zugeschnitten werden. Dieses Vorgehen ist entsprechend aufwendig und kommt bei Farbtonern für Prozeßfarbe (Trichromie) noch zusätzlich zu den bereits beschriebenen Schwierigkeiten hinzu.Colorants are known to be able to influence the triboelectric charging of toners very sustainably in some cases (H.-T. Macholdt, A. Sieber, Dyes & Pigments 9 (1988), 119-27, US-PS 4057426, EP-OS 247576 ). Because of the different triboelectric effects of colorants and the resulting, in some cases, very pronounced influence on the toner chargeability, it is not possible to add them as the exclusive colorant to a toner base formulation that has already been created. Rather, it may be necessary to create a separate recipe for each colorant, for which type and quantity, for example of the required charge control agent can be specially tailored. This procedure is correspondingly complex and, in the case of color toners for process color (trichrome), is in addition to the difficulties already described.

Daher sind hochwirksame farblose Ladungssteuermittel erforderlich, die imstande sind, das unterschiedliche triboelektrische Verhalten verschiedener Farbmittel zu kompensieren und dem Toner die gewünschte Aufladung zu verleihen. Auf diese Art und Weise können triboelektrisch sehr unterschiedliche Farbmittel anhand einer einmal erstellten Tonerbasisrezeptur mit ein und demselben Ladungssteuermittel in den verschiedenen erforderlichen Tonern (Gelb, Cyan, Magenta und gegebenenfalls Schwarz) eingesetzt werden.Therefore, highly effective colorless charge control agents are required which are able to compensate for the different triboelectric behavior of different colorants and to give the toner the desired charge. In this way, triboelectrically very different colorants can be used with the same charge control agent in the different required toners (yellow, cyan, magenta and possibly black) based on a toner base formulation that has been created once.

Als farblose Ladungssteuermittel für elektrophotographische Toner und Entwickler werden Ammonium-(z.B. EP-OS 203532, EP-OS 242420, US-PS 4683188, US-PS 4684596, JP-OS 63-226665) und Phosphoniumverbindungen (z.B. US-PS 3893935, US-PS 4496643, JP-OS 63-231358), Metallkomplexe und -organyle (z.B. US-PS 4656112, DE-OS 3144017, JP-OS 61-236557 JP-OS 62-287262) sowie eine Reihe anderer Verbindungen (z.B. EP-OS 216295) beansprucht.As colorless charge control agents for electrophotographic toners and developers are ammonium (eg EP-OS 203532, EP-OS 242420, US-PS 4683188, US-PS 4684596, JP-OS 63-226665) and phosphonium compounds (eg US-PS 3893935, US -PS 4496643, JP-OS 63-231358), metal complexes and organyls (e.g. US-PS 4656112, DE-OS 3144017, JP-OS 61-236557 JP-OS 62-287262) as well as a number of other compounds (e.g. EP- OS 216295).

Positive farblose Ladungssteuermittel umfassen im wesentlichen quaternäre Ammonium- und Phosphoniumverbindungen sowie einige Zinn- und Antimonorganyle. Allerdings weisen die bisher bekannten farblosen Ladungssteuermittel eine Reihe von Nachteilen auf, die den Einsatz in der Praxis stark einschränken bzw. zum Teil sogar unmöglich machen. So sind die an sich geeigneten quaternären Ammoniumverbindungen schwierig zu dispergieren, können aus bisher nicht geklärten Gründen. zu ungleichmäßiger Aufladung des Toners führen, und die durch sie erzeugte Tonerladung ist über eine längere Aktivierzeit nicht stabil, insbesondere bei hoher Temperatur und Luftfeuchte (EP-OS 242420). Ferner können derartige Verbindungen empfindlich gegen Licht oder mechanische Einwirkungen (EP-OS 203532, US-PS 4683188) und thermisch labil sein und liefern Zersetzungsprodukte, die nachteilig für die triboelektrische Aufladung der Toner sein können (US-PS 4684596). Ein Teil dieser Verbindungen ist nicht wirklich farblos und kann somit in Farbtonern nur beschränkten Einsatz finden. Darüberhinaus zeigen sie oft wachsartiges Verhalten, zum Teil Wasserlöslichkeit und geringe Wirksamkeit als Ladungssteuermittel.Positive colorless charge control agents essentially include quaternary ammonium and phosphonium compounds, as well as some tin and antimony organyls. However, the colorless charge control agents known hitherto have a number of disadvantages which severely restrict their use in practice or in some cases even make them impossible. For example, the quaternary ammonium compounds which are suitable per se are difficult to disperse and, for reasons which have not yet been clarified, can. lead to uneven charging of the toner, and the toner charge generated by it is not stable over a longer activation time, especially at high temperature and air humidity (EP-OS 242420). Furthermore, such compounds can be sensitive to light or mechanical influences (EP-OS 203532, US Pat. No. 4,683,188) and be thermally unstable and provide decomposition products which can be disadvantageous for the triboelectric charging of the toners (US Pat. No. 4,684,596). Some of these compounds are not really colorless and can therefore only be used to a limited extent in color toners. In addition, they often show waxy behavior, in part water solubility and low effectiveness as a charge control agent.

Phosphoniumsalze herkömmlicher Art besitzen außer den schon bei den Ammoniumverbindungen erwähnten Nachteilen eine geringere Wirksamkeit als Ladungssteuermittel und schlechtere Ladungskontrolleigenschaften (US-PS 4496643, EP-OS 161128) als Ammoniumverbindungen (s. Vergleichsbeispiel 1).In addition to the disadvantages already mentioned for the ammonium compounds, conventional phosphonium salts are less effective than charge control agents and have poorer charge control properties (US Pat. No. 4,496,643, EP-OS 161128) than ammonium compounds (see Comparative Example 1).

Organozinnborate, wie in EP-PS 216295 beschrieben, sowie Zinn-(JP-OS 62-287262) und Antimonorganyle (JP-OS 61-236557), sind wegen ihrer Schwermetallhaltigkeit problematisch.Organotin borates, as described in EP-PS 216295, and tin (JP-OS 62-287262) and antimony organyls (JP-OS 61-236557) are problematic because of their heavy metal content.

Als negative farblose Ladungssteuermittel sind einige Ammonium-(JP-OS 63-226665) und Phosphoniumverbindungen (JP-OS 63-231358) sowie eine Reihe von Schwermetallverbindungen bekannt, nämlich Chrom-, Eisen-, Kobalt-(DE-OS 3144017) und Zink-Komplexe (US-PS 4656112, JP-OS 62-127754). Für Ammonium- und Phosphoniumverbindungen gelten auch hier die schon oben erwähnten Nachteile bzw. Einschränkungen.Some ammonium (JP-OS 63-226665) and phosphonium compounds (JP-OS 63-231358) and a number of heavy metal compounds are known as negative colorless charge control agents, namely chromium, iron, cobalt (DE-OS 3144017) and zinc -Complexes (US-PS 4656112, JP-OS 62-127754). For ammonium and phosphonium compounds, the disadvantages and limitations mentioned above also apply here.

Neben Einarbeitung in das Tonerharz werden Ladungssteuermitel auch zur Beschichtung von Carriern eingesetzt. Dabei kommen die gleichen Verbindungsklassen wie bei Einarbeitung in Tonerharze zum Einsatz, z.B. Ammonium (JP-OS 61-258270) und Phosphoniumverbindungen (JP-OS 61-260258) sowie Schwermetallkomplexe und -organyle (JP-OS 61-147261, JP-OS 61-259267).In addition to incorporation into the toner resin, charge control agents are also used to coat carriers. The same classes of compounds are used as for incorporation in toner resins, e.g. Ammonium (JP-OS 61-258270) and phosphonium compounds (JP-OS 61-260258) as well as heavy metal complexes and organyls (JP-OS 61-147261, JP-OS 61-259267).

Grundsätzlich kann festgestellt werden, daß farblose Ladungssteuermittel sowohl für Positiv- als auch für Negativtoner im Prinzip bekannt, doch für den Einsatz in der Praxis nur bedingt oder nicht tauglich bzw. noch weitgehend verbesserungsbedürftig sind. Dies zeigt sich auch daran, daß sich insbesondere die Ammonium- und Phosphoniumverbindungen bisher in der Praxis nicht durchgesetzt haben.In principle, it can be stated that colorless charge control agents are known in principle for both positive and negative toners, but are only partially suitable or not suitable for use in practice, or are still largely in need of improvement. This can also be seen from the fact that the ammonium and phosphonium compounds in particular have so far not been successful in practice.

Ziel der vorliegenden Erfindung war es daher, verbesserte Ladungssteuermittel zu finden, die sich durch absolutes Fehlen einer Eigenfarbe auszeichnen, eine höhere Wirksamkeit besitzen, insbesondere für den Einsatz in Farbtonern geeignet sind und die elektrostatische Aufladung von Tonern und Entwicklern konzentrationsabhängig und schnell einstellen. Des weiteren sollen sie die elektrostatische Aufladung über einen längeren Aktivierzeitraum konstant halten (keine Alterung), bei hoher Luftfeuchte einwandfrei wirken und mit gängigen Tonerharzen verträglich und gut dispergierbar sein.It was therefore an object of the present invention to find improved charge control agents which are distinguished by the absolute absence of an inherent color, are more effective, are particularly suitable for use in color toners and rapidly and rapidly adjust the electrostatic charge of toners and developers. Furthermore, they should keep the electrostatic charge constant over a longer activation period (no aging), work perfectly at high atmospheric humidity and be compatible and well dispersible with common toner resins.

Überraschenderweise hat sich nun gezeigt, daß möglichst hochgradig fluorsubstituierte Phosphoniumverbindungen als farblose Ladungssteuermittel für elektrophotographische Toner und Entwickler besonders günstige Eigenschaften besitzen. Aufgrund ihrer Farblosigkeit, hohen Wirksamkeit, guten Verträglichkeit und Dispergierbarkeit in gängigen Tonerharzen und chemischen Inertheit sind die Verbindungen insbesondere für den Einsatz in Farbtonern bzw. -entwicklern für Vollfarbkopierer und -laserdrucker nach dem Prinzip der Trichromie (substraktive Farbmischung), aber auch für farbige Toner bzw. Entwickler im allgemeinen und für schwarze Toner oder Entwickler geeignet. Besonders überraschend ist, daß Substanzen ein und derselben Verbindungsklasse je nach chemischer Modifizierung entweder als positive oder auch als negative Ladungssteuermittel geeignet sind (siehe Anwendungsbeispiele 1 bis 4). Des weiteren eignen sich die Verbindungen auch für das Beschichten von Carriern.Surprisingly, it has now been shown that the most highly fluorine-substituted phosphonium compounds have particularly favorable properties as colorless charge control agents for electrophotographic toners and developers. Due to their colorlessness, high effectiveness, good compatibility and dispersibility in common toner resins and chemical inertness, the compounds are particularly suitable for use in color toners or developers for full-color copiers and laser printers according to the principle of trichromatic (subtractive color mixing), but also for colored toners or developers in general and suitable for black toners or developers. It is particularly surprising that substances of one and the same class of compound, depending on the chemical modification, either as positive or as negative charge control agents are suitable (see application examples 1 to 4). The compounds are also suitable for coating carriers.

Ein großer technischer Vorteil dieser gut dispergierbaren Verbindungen liegt darin, daß Substanzen derselben Verbindungsklasse entweder als positives oder als negatives Steuermittel eingesetzt werden können. Somit werden Probleme bei der Einarbeitung in das Tonerbindemittel und der Verträglichkeit mit dem Tonerbindemittel nach Erstellung einer Tonerbasisrezeptur minimiert. Es können so Positiv-wie auch Negativtoner anhand einer festen Tonerbasisrezeptur (bestehend aus Tonerbindemittel, Farbmittel, Fließhilfsmittel und ggfs. weiteren Komponenten) durch Einarbeitung des gewünschten Steuermittels hergestellt werden.A great technical advantage of these readily dispersible compounds is that substances of the same class of compounds can be used either as positive or as negative control agents. Problems with incorporation into the toner binder and compatibility with the toner binder after a toner base formulation has been created are thus minimized. Both positive and negative toners can be produced using a solid toner base formulation (consisting of toner binder, colorant, flow aid and possibly other components) by incorporating the desired control agent.

Die Synthese von fluorsubstituierten Phosphoniumverbindungen ist bekannt und z.B. in J. Chem. Soc., Chem. Commun. 1984, 1233-34, Chem. Ber. 114(1981), 3589-3598, J. Fluorine Chem. 23(1983), 339 und in der deutschen Offenlegungsschrift DE-OS 2936211 beschrieben. Eingesetzt werden derartige Verbindungen z.B. als Vorstufen zu Wittig-Yliden, als Vorstufen zu fluorsubstituierten Styrolen oder als oberflächenaktive Substanzen. Völlig neu ist jedoch deren Verwendung als Ladungssteuermittel in elektrophotographsichen Tonern und Entwicklern.The synthesis of fluorine-substituted phosphonium compounds is known and e.g. in J. Chem. Soc., Chem. Commun. 1984, 1233-34, Chem. Ber. 114 (1981), 3589-3598, J. Fluorine Chem. 23 (1983), 339 and in German Offenlegungsschrift DE-OS 2936211. Such connections are used e.g. as precursors to Wittig-Yliden, as precursors to fluorine-substituted styrenes or as surface-active substances. However, their use as charge control agents in electrophotographic toners and developers is completely new.

Gegenstand der vorliegenden Erfindung ist die Verwendung hochgradig fluorsubstituierter Phosphoniumverbindungen der allgemeinen Formel (I)

Figure imgb0001
in welcher R1 bis R4 Wasserstoffatome oder organische Reste bedeuten, wobei mindestens einer der Reste R1 bis R4 einen geradkettigen oder verzweigten, fluorsubstituierten, ungesättigten und/oder gesättigten Alkylrest mit 1 bis 30 C-Atomen und 3 bis 50 F-Atomen darstellt, welcher weitere Halogenatome, wie Fluor-, Chlor,- Brom- oder Jodatome, Hydroxyl- und/oder Chlormethyl- und/oder Carbonsäureamid-und/oder Sulfonsäureamid- und/oder Urethan- und/oder Keto-und/oder Amino- und/oder R5-O-R6- und/oder R7-C(O)-O-Rs-Gruppen, worin R5, R6, R7 und Rs Alkyl (Ci-C3o)-reste darstellen, enthalten kann, oder einen fluorsubstituierten Arylrest, wie beispielsweise einen Phenyl-, Toluyl- oder Naphthylrest, oder einen am aromatischen Kern fluorsubstituierten Aralkylrest, wie beispielsweise einen Benzylrest darstellt, wobei der Aryl- oder Aralkylrest am aromatischen Kern zusätzlich durch gesättigte oder ungesättigte, geradkettige oder verzweigte Alkyl(C1-C30), Alkoxy(C1-C30)-, Halogenalkyl(Ci-C30)-, bevorzugt Fluoralkyl(C1-C30)-, Halogenalkoxy(C1-C30)-, bevorzugt Fluoralkoxy(C1-C30)-, oder Hydroxylgruppen oder weitere Halogenatome, wie beispielsweise Chlor-, Brom- oder Jodatome substituiert sein kann, und im Falle eines Aralkylrestes die Alkylbrücke zwischen Phosphoratom und aromatischem Ring 1 bis 30 C-Atome enthält, und höchstens drei der Reste R1 bis R4 unabhängig voneinader Wasserstoffatome, geradkettig oder verzweigte, ungesättigte oder gesättigte, substituierte oder unsubstituierte Alkylreste mit 1 bis 30 C-Atomen, Arylreste, wie beispielsweise Phenyl-, Toluyl- oder Naphthylreste, Aralkylreste,beispielsweise Benzylreste, sind, wobei die Aryl- oder Aralkylreste am aromatischen Kern durch Alkyl(C1-C30)-, Alkoxy(C1-C30)-, Halogenalkyl(C1-C30)-, Halogenalkoxy (C1-C30)- oder Hydroxylgruppen oder Halogenatome, wie beispielsweise Fluor-, Chlor-, Brom- oder Jodatome, substituiert sein können, und X- ein organisches oder anorganisches Anion bedeutet, wobei die Reste R1 bis R4 eine COO- - oder SO3 --Gruppe als Substituent enthalten können und X- in diesem Fall gegenstandslos wird, einzeln oder in Kombination als farblose Ladungssteuermittel mit positiver oder negativer Steuerwirkung in Tonern und Entwicklern für elektrophotographische Aufzeichnungsverfahren.The present invention relates to the use of highly fluorine-substituted phosphonium compounds of the general formula (I)
Figure imgb0001
 in which R 1 to R 4 are hydrogen atoms or organic radicals, at least one of the radicals R 1 to R 4 being a straight-chain or branched, fluorine-substituted, unsaturated and / or saturated alkyl radical having 1 to 30 C atoms and 3 to 50 F atoms represents which further halogen atoms, such as fluorine, chlorine, bromine or iodine atoms, hydroxyl and / or chloromethyl and / or carboxylic acid amide and / or sulfonic acid amide and / or urethane and / or keto and / or amino and / or R 5 -OR 6 - and / or R 7 -C (O) -O-Rs groups, in which R 5 , R 6 , R 7 and Rs represent alkyl (Ci-C 3 o) radicals , or represents a fluorine-substituted aryl radical, such as a phenyl, toluyl or naphthyl radical, or an aralkyl radical which is fluorine-substituted on the aromatic nucleus, such as a benzyl radical, the aryl or aralkyl radical on the aromatic nucleus additionally being saturated or unsaturated, straight-chain or branched Alkyl (C 1 -C 30 ), alkoxy (C 1 -C 30 ) -, Haloalkyl (Ci-C 30 ) -, preferably fluoroalkyl (C 1 -C 30 ) -, haloalkoxy (C 1 -C 30 ) -, preferably fluoroalkoxy (C 1 -C 30 ) -, or hydroxyl groups or other halogen atoms, such as for example chlorine, bromine or iodine atoms, and in the case of an aralkyl radical the alkyl bridge between phosphorus atom and aromatic ring contains 1 to 30 C atoms, and at most three of the radicals R 1 to R 4 independently of one another, straight-chain or branched, unsaturated or saturated, substituted or unsubstituted alkyl radicals having 1 to 30 carbon atoms, aryl radicals, such as, for example, phenyl, toluyl or naphthyl radicals, aralkyl radicals, for example benzyl radicals, the aryl or aralkyl radicals on the aromatic nucleus being alkyl (C 1- C 30) -, alkoxy (C 1 -C 30) -, haloalkyl (C 1 -C 30) -, haloalkoxy (C 1 -C 30) - or hydroxyl groups or halogen atoms such as fluorine, chlorine, bromine or Iodine atoms, can be substituted, and X- an organic ode r means inorganic anion, where the radicals R 1 to R 4 can contain a COO - or SO 3 - group as a substituent and X- in this case becomes irrelevant, individually or in combination as a colorless charge control agent with positive or negative control action in toners and developers for electrophotographic recording processes.

X- als anorganisches oder organisches Anion kann beispielsweise sein Hal-, wie beispielsweise F-, CI-, Br- oder J-, ferner PF6-, Sulfat, Phosphat, Cyanat, Thiocyanat, BF4 -, B(Aryl)4 -, wie z.B. Tetraphenylborat, p-Chlortetraphenylborat, p-Methyltetraphenylborat, Tetranaphthylborat, ferner Phenolat, Nitrophenolat, Zinktetracyanat, Zinktetrathiocyanat, CH3OSO3 -, gesättigtes oder ungesättigtes aliphatisches oder aromatisches Carboxylat oder Sulfonat, wie beispielsweise Acetat, Lactat, Benzoat, Salicylat, 2-Hydroxy-3-naphtho- at, 2-Hydroxy-6-naphthoat, Ethylsulfonat, Phenylsulfonat, ferner perfluoriertes gesättigtes oder ungesättigtes aliphatisches oder aromatisches Carboxylat oder Sulfonat, wie beispielsweise Perfluoracetat, Perfluoralkylbenzoat, Perfluorethylsulfonat oder Perfluoralkylbenzolsulfonat.X- as an inorganic or organic anion can be, for example Hal, such as F-, CI-, Br- or I-, further PF 6 -, sulfate, phosphate, cyanate, thiocyanate, BF 4 -, B (aryl) 4 - , such as, for example, tetraphenylborate, p-chlorotetraphenylborate, p-methyltetraphenylborate, tetranaphthylborate, also phenolate, nitrophenolate, zinc tetracyanate, zinc tetrathiocyanate, CH 3 OSO 3 - , saturated or unsaturated aliphatic or aromatic carboxylate or acylate, such as lactylate, such as lactate, such as lactylate, such as acylate, for example, 2-hydroxy-3-naphthoate, 2-hydroxy-6-naphthoate, ethyl sulfonate, phenyl sulfonate, furthermore perfluorinated saturated or unsaturated aliphatic or aromatic carboxylate or sulfonate, such as for example perfluoroacetate, perfluoroalkyl benzoate, perfluoroethyl sulfonate or perfluoroalkyl benzene.

Die Phosphoniumverbindungen der vorstehend genannten allgemeinen Formel (I) können für sich allein oder in Kombination in Tonern bzw. Entwicklern, die zum elektrophotographischen Kopieren bzw. Vervielfältigen von Vorlagen sowie zum Drucken von elektronisch, optisch oder magnetisch gespeicherten Informationen oder im Colorproofing eingesetzt werden. Darüberhinaus können diese Verbindungen für die Beschichtung von Carriern und in Pulvern und Lacken zur Oberflächenbeschichtung, insbesondere in elektrokinetisch versprühten Pulverlacken, als ladungsverbessernde Mittel verwendet werden und sind wirksam als Dispergierhilfsmittel.The phosphonium compounds of the abovementioned general formula (I) can be used on their own or in combination in toners or developers which are used for electrophotographic copying or duplication of originals and for printing electronically, optically or magnetically stored information or in color proofing. In addition, these compounds can be used for the coating of carriers and in powders and lacquers for surface coating, in particular in electrokinetically sprayed powder lacquers, as charge-improving agents and are effective as dispersing assistants.

Besonders geeignet sind Verbindungen der genannten allgemeinen Formel (I), in welcher mindestens einer der Reste R, bis R4 einen geradkettigen oder verzweigten, fluorsubstituierten, ungesättigten und/oder gesättigten Alkylrest mit 4 bis 17 C-Atomen und 3 bis 25 F-Atomen bedeutet, welcher weitere Halogenatome, wie Fluor-, Chlor-, Brom- oder Jodatome, Hydroxyl- und/oder Chlormethyl- und/oder Carbonsäureamid-und/oder Urethan- und/oder Keto-und/oder Amino- und/oder R5-O-R6 und/oder R7-C(O)-O-R8-Gruppen, worin Rs, R6, R7 und Rs Alkyl(C1-C18)-reste darstellen, enthalten kann, oder einen fluorsubstituierten Arylrest, wie beispielsweise Phenyl-, Toluyl- oder Naphthylrest, oder einen am aromatischen Kern fluorsubstituierten Aralkylrest, wie beispielsweise Benzylrest, darstellt, wobei der Aryl- oder Aralkylrest am aromatischen Kern zusätzlich durch gesättigte oder ungesättigte, geradkettige oder verzweigte Alkyl(C1-C18) Alkoxy(C1-C18)-, Halogenalkyl(C1-C18)-, bevorzugt Fluoralkyl(C1-C18)-, Halogenalkoxy(C1-C18)-, bevorzugt Fluoralkoxy(C1-C18)-, oder Hydroxylgruppen oder weitere Halogenatome, wie beispielsweise Chlor-, Brom-oder Jodatome, substituiert sein kann, und im Fall eines Aralkylrestes die Alkylbrücke zwischen Phosphoratom und aromatischem Ring 1-18 C-Atome, bevorzugt 1 bis 5 C-Atome, enthält, und höchstens drei der Reste R, bis R4 unabhängig voneinander Wasserstoffatome, geradkettige oder verzweigte, ungesättigte oder gesättigte, substituierte oder unsubstituierte Alkyreste mit 1 bis 18 C-Atomen, Arylreste, wie beispielsweise Phenyl-, Toluyl- oder Naphthylreste, oder Aralkylreste, wie beispielsweise Benzylreste, wobei die Aryl- oder Aralkylreste am aromatischen Kern durch Alkyl(C1-C18)-, Alkoxy(C1-C18)-, Halogenalkyl (C1-Cis)-, Halogenalkoxy(C1-C18)- oder Hydroxylgruppen oder Fluor-, Chlor-, Brom- oder Jodatome substituiert sein können, und X- ein organisches oder anorganisches Anion darstellen, wobei die Reste R1 bis R4 eine COO- - oder S03--Gruppe als Substituent enthalten können und X- in diesem Fall gegenstandslos wird.Compounds of the general formula (I) mentioned are particularly suitable, in which at least one of the radicals R 1 to R 4 is a straight-chain or branched, fluorine-substituted, unsaturated and / or saturated alkyl radical having 4 to 17 C atoms and 3 to 25 F atoms means which further halogen atoms, such as fluorine, chlorine, bromine or iodine atoms, hydroxyl and / or chloromethyl and / or carboxamide and / or urethane and / or keto and / or amino and / or R 5 -OR 6 and / or R 7 -C (O) -OR 8 groups, in which R s , R 6 , R 7 and R s represent alkyl (C 1 -C 18 ) radicals, or a fluorine-substituted aryl radical , such as phenyl, toluyl or naphthyl, or an aralkyl radical which is fluorine-substituted on the aromatic nucleus, such as, for example, benzyl radical, the aryl or aralkyl radical on the aromatic nucleus being additionally substituted by saturated or unsaturated, straight-chain or branched alkyl (C 1 -C 18 ) Alkoxy (C 1 -C 18 ) -, haloalkyl (C 1 -C 18 ) -, be preferably fluoroalkyl (C 1 -C 18 ) -, haloalkoxy (C 1 -C 18 ) -, preferably fluoroalkoxy (C 1 -C 18 ) -, or hydroxyl groups or other halogen atoms, such as chlorine, bromine or iodine atoms can, and in the case of an aralkyl radical, the alkyl bridge between phosphorus atom and aromatic ring contains 1-18 carbon atoms, preferably 1 to 5 carbon atoms, and at most three of the radicals R to R 4 independently of one another are hydrogen atoms, straight-chain or branched, unsaturated or saturated, substituted or unsubstituted alkyl radicals having 1 to 18 carbon atoms, aryl radicals, such as, for example, phenyl, toluyl or naphthyl radicals, or aralkyl radicals, such as, for example, benzyl radicals, the aryl or aralkyl radicals on the aromatic nucleus being substituted by alkyl (C 1 -C 18 ), alkoxy (C 1 -C 18 ), haloalkyl (C 1 -Cis), haloalkoxy (C 1 -C 18 ) or hydroxyl groups or fluorine, chlorine, bromine or iodine atoms, and X- represent an organic or inorganic anion, where the radicals R 1 to R 4 can contain a COO - or S0 3 - group as a substituent and X- in this case becomes pointless.

Ganz besonders geeignet sind Verbindungen der genannten allgemeinen Formel (I), in welcher höchstens drei der Reste R1 bis R4 eine Phenylgruppe und mindestens einer der Reste R1 bis R4 eine Gruppe aus der Reihe C8F17-CH2-CH2-, und Rf-CH2-CH2- (Rf = C6F13 bis C12F25) bedeuten, und X-BF4-, Hal-, wie z.B. F-, CI-, Br-, J-, oder PF6-, (B(Aryl)4 -, wie z.B. Tetraphenylborat oder p-Chlortetraphenylborat, p-Methyltetraphenylborat oder Tetranaphthylborat, darstellt.Compounds of the general formula (I) mentioned are very particularly suitable in which at most three of the radicals R1 to R4 are a phenyl group and at least one of the radicals R 1 to R 4 is a group from the series C 8 F 17 -CH 2 -CH 2 - , and Rf-CH2-CH2- (Rf = C 6 F 13 to C 12 F 25 ), and X-BF 4 -, Hal-, such as F - , CI-, Br - , J-, or PF 6 -, (B (aryl) 4 - , such as tetraphenyl borate or p-chlorotetraphenyl borate, p-methyltetraphenyl borate or tetranaphthyl borate.

An Einzelverbindungen oder Verbindungsgemischen der genannten allgemeinen Formel (I) seien beispielsweise genannt:

Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
 Examples of individual compounds or compound mixtures of the general formula (I) mentioned are:
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017

(Auf verschiedene der vorstehend aufgeführten Verbindungen wird in einigen der Herstellungs- und Anwendungsbeispiele Bezug genommen).(Various of the compounds listed above are referenced in some of the preparation and application examples).

Beispielsweise zeigt ein Toner mit 1,0 Gewichtsprozent von Verbindung (1) eine Aufladung von + 18,5 u.C/g nach 10 Minuten und von+19,3 tlC/g nach 24 Stunden Aktivierzeit (siehe Anwendungsbeispiel 1 der nachstehenden Anwendungsbeispiele).For example, a toner with 1.0 percent by weight of compound (1) shows a charge of + 18.5 u.C / g after 10 minutes and of + 19.3 tlC / g after 24 hours of activation time (see application example 1 of the application examples below).

Ein Toner mit 1,0 Gewichtsprozent der Verbindung (2) besitzt eine Aufladung von -2,8 u.C/g nach 10 Minuten und von -2,7 tlC/g nach 24 Stunden Aktivierzeit (Anwendungsbeispiel 2).A toner with 1.0 percent by weight of compound (2) has a charge of -2.8 u.C / g after 10 minutes and of -2.7 tlC / g after 24 hours of activation time (application example 2).

Die Verbindungen der genannten allgemeinen Formel (I) können auch aus geeigneten Medien, wie z.B. Lösungen, auf geeignete Trägermaterialien, wie z.B. Kieselgel, Aluminiumoxid, Titandioxid, aufgezogen werden. Die erfindungsgemäß verwendeten Verbindungen werden in der Regel in einer Konzentration von etwa 0,01 bis etwa 10 Gewichtsprozent, vorzugsweise etwa 0,1 bis etwa 5,0 Gewichtsprozent, in das jeweilige Trägermaterial in bekannter Weise, z.B. durch Einkneten oder Extrudieren, homogen eingearbeitet. Dabei können die Ladungssteuermittel für Toner bzw. ladungsverbessernde Mitel für Pulver und Lacke zur Oberflächenbeschichtung, insbesondere für elektrokinetisch versprühte Pulverlacke, als getrocknete und gemahlene Pulver, Dispersionen oder Lösungen, Preßkuchen, Masterbatch, als auf geeignete Träger aus wäßriger oder nichtwäßriger Lösung aufgezogene Verbindungen oder in sonstiger Form zugegeben werden. Ebenso können die erfindungsgemäß eingesetzten Verbindungen grundsätzlich auch schon bei der Herstellung der jeweiligen Bindemittel zugegeben werden, d.h. im Verlauf von deren Polymerisation oder Polykondensation. Typische Tonerbindemittel sind beispielsweise Styrol-, Styrolacrylat-, Styrolbutadien-, Acrylat-, Polyester-, Amid-, Amin-, Ammonium-, Ethylen-, Phenol und Epoxidharze, einzeln oder in Kombination, die noch weitere Inhaltstoffe, wie Farbmittel, Wachse oder Fließhilfsmittel, enthalten können bzw. im Nachhinein zugesetzt bekommen können. Typische Trägermaterialien (Harze) für Pulver und Lacke zur Oberflächenbeschichtung, insbesondere für elektrokinetisch versprühte Pulverlacke, sind beispielsweise Epoxidharze, carboxyl- und hydroxylgruppenhaltige Polyesterharze und Acrylharze zusammen mit Härtern, wie beispielsweise Säureanhydride, Imidazole, Melamin- oder Phenolharze.The compounds of the general formula (I) mentioned can also be obtained from suitable media, e.g. Solutions, on suitable carrier materials, e.g. Silica gel, aluminum oxide, titanium dioxide. The compounds used according to the invention are generally added in a concentration of about 0.01 to about 10 percent by weight, preferably about 0.1 to about 5.0 percent by weight, in the respective carrier material in a known manner, e.g. by kneading or extruding, incorporated homogeneously. The charge control agents for toners or charge-improving agents for powders and lacquers for surface coating, in particular for electrokinetically sprayed powder lacquers, can be used as dried and ground powders, dispersions or solutions, presscakes, masterbatches, as compounds drawn up on suitable carriers from aqueous or non-aqueous solution or in other form can be added. Likewise, the compounds used according to the invention can in principle also be added during the preparation of the respective binders, i.e. in the course of their polymerization or polycondensation. Typical toner binders are, for example, styrene, styrene-acrylate, styrene-butadiene, acrylate, polyester, amide, amine, ammonium, ethylene, phenol and epoxy resins, individually or in combination, which also contain other ingredients, such as colorants, waxes or Flow aids, can contain or can be added afterwards. Typical carrier materials (resins) for powders and lacquers for surface coating, in particular for electrokinetically sprayed powder lacquers, are, for example, epoxy resins, carboxyl- and hydroxyl-containing polyester resins and acrylic resins together with hardeners, such as acid anhydrides, imidazoles, melamine or phenolic resins.

Die Höhe der elektrostatischen Aufladung der elektrophotographischen Toner, in welche die erfindungsgemäß beanspruchten Ladungssteuermittel homogen eingearbeitet wurden, wurde an Standardtestsystemen unter gleichen Bedingungen (wie gleiche Dispergierzeiten, gleiche Teilchengrößenverteilung, gleiche Teilchenform) bei Raumtemperatur und 50 % relativer Luftfeuchte gemessen. Die Aktivierung des Toners in einem Zweikomponentenentwickler erfolgte durch Verwirbelung mit einem Carrier (3 Gewichtsteile Toner auf 97 Gewichtsteile Carrier) auf einer Rollbank (150 Umdrehungen pro Minute). Anschließend wurde an einem üblichen q/m-Meßstand die elektrostatische Aufladung gemessen (vgl. J.H. Dessauer, H.E. Clark, "Xerography and related Processes", Focal Press, N.Y., 1965, Seite 289). Bei der Bestimmung des q/m-Wertes ist die Teilchengröße von großem Einfluß, weshalb bei den durch Sichtung erhaltenen Tonerproben streng auf einheitliche Teilchengrößenverteilung geachtet wurde.The level of electrostatic charging of the electrophotographic toners into which the charge control agents claimed according to the invention were homogeneously incorporated was measured on standard test systems under the same conditions (such as the same dispersion times, same particle size distribution, same particle shape) at room temperature and 50% relative atmospheric humidity. The toner was activated in a two-component developer by swirling with a carrier (3 parts by weight of toner to 97 parts by weight of carrier) on a roller bench (150 revolutions per minute). The electrostatic charge was then measured on a conventional q / m measuring stand (cf. J.H. Dessauer, H.E. Clark, "Xerography and related Processes", Focal Press, N.Y., 1965, page 289). The particle size is of great influence in determining the q / m value, which is why strict attention was paid to uniform particle size distribution in the toner samples obtained by screening.

Die nachstehenden Beispiele dienen zur Erläuterung der Erfindung, ohne diese darauf zu beschränken. Die angegebenen Teile bedeuten Gewichtsteile.The following examples serve to illustrate the invention without restricting it thereto. The parts given are parts by weight.

Herstellungsbeispiel 1Production Example 1

8,4 g (0,01 Mol) C8F17-CH2-CH2-P+(Phenyl)3 J- (Molekulargewicht 836, Darstellung beschrieben in J. Chem. Soc,. Chem. Commun., 1984, 1233-34) werden in 150 ml Wasser/lsopropanol (1:1 Volumenteile) gelöst und dann langsam 1,9 g (0,01 Mol) Kalium-hexa-fluorophosphat unter Rühren zugegeben. Anschließend wird mit Wasser/lsopropanol auf 400 ml aufgefüllt und 30 Minuten zum Sieden erhitzt. Der weiße Niederschlag wird heiß abgenutscht, m.t Wasser/Isopropanol gewaschen und bei 50 °C im Vakuum getrocknet.
Ausbeute 7,9 g (92,5 % d. Th.) der Verbindung (1)
Molekulargewicht: 854
Schmelzpunkt: 176-177°C
Elementaranalyse:
ber. 39,3 % C, 2,2 % H, 51,2 % F, 7,3 % P
gef. 39,1 % C, 2, 1% H, 51,7 % F, 6,9 % P
0,18 % Wasser
1 H-NMR (in DMSO-d6): 2,62 (Multiplett, 2 Methylen-H), 4,06 (Multiplett, Methylen-H), 7,85 (Multiplett, 15 Phenyl-H) ppm.8.4 g (0.01 mol) of C 8 F 17 -CH 2 -CH 2 -P + (phenyl) 3 J- (molecular weight 836, representation described in J. Chem. Soc,. Chem. Commun., 1984, 1233-34) are dissolved in 150 ml water / isopropanol (1: 1 parts by volume) and then 1.9 g (0.01 mol) potassium hexa-fluorophosphate are slowly added with stirring. The mixture is then made up to 400 ml with water / isopropanol and heated to boiling for 30 minutes. The white precipitate is filtered off with hot suction, washed with water / isopropanol and dried at 50 ° C. in vacuo.
Yield 7.9 g (92.5% of theory) of compound (1)
Molecular weight: 854
Melting point: 176-177 ° C
Elemental analysis:
calc. 39.3% C, 2.2% H, 51.2% F, 7.3% P
found 39.1% C, 2.1% H, 51.7% F, 6.9% P
0.18% water
1 H NMR (in DMSO-d6): 2.62 (multiplet, 2 methylene-H), 4.06 (multiplet, methylene-H), 7.85 (multiplet, 15 phenyl-H) ppm.

Herstellungsbeispiel 2Production Example 2

Zur Darstellung der Verbindung (2) wird wie in Herstellungsbeispielen 1 verfahren, mit dem Unterschied, daß statt Kalium-hexafluorophosphat 3,4 g (0,1 Mol) Natrium-tetra-phenylborat verwendet werden. Ausbeute: 9,3 g (90,5% d. Th.) der Verbindung (2)
Molekulargewicht: 1028
Schmelzpunkt: 169-170°C
Elementaranalyse:
ber. 60,7 % C, 3,8 % H, 3,0 % P, 1,1 % B
gef. 60,7 % C, 3,7 % H, 3,0 % P, 0,9 % B,
0,06 % Wasser
1 H-NMR (in DSMO-d6): 2,58 (Multiplett, 2 Methylen-H), 4,02 (Multiplett, 2 Methylen-H), 7,00 (Multiplett, 20 Phenyl-H des Tetraphenylboratanions), 7,83 15 Phenyl-H des Phosphoniumkations) ppm.The preparation of compound (2) is carried out as in Preparation Examples 1, with the difference that 3.4 g (0.1 mol) of sodium tetra-phenylborate are used instead of potassium hexafluorophosphate. Yield: 9.3 g (90.5% of theory) of compound (2)
Molecular weight: 1028
Melting point: 169-170 ° C
Elemental analysis:
calc. 60.7% C, 3.8% H, 3.0% P, 1.1% B
found 60.7% C, 3.7% H, 3.0% P, 0.9% B,
0.06% water
1 H-NMR (in DSMO-d6): 2.58 (multiplet, 2 methylene-H), 4.02 (multiplet, 2 methylene-H), 7.00 (multiplet, 20 phenyl-H of the tetraphenylborate anion), 7 , 83 15 phenyl-H of the phosphonium cation) ppm.

Herstellungsbeispiel 3Production Example 3

Zur Darstellung der Verbindung (3) wird wie in Herstellungsbeispiel 1 verfahren, mit dem Unterschied, daß statt Kalium-hexa-fluorophosphat 4,0 g (0,01 Mol) Natrium-tetra-p-toluylborat verwendet werden. Ausbeute: 9,7 g (89,5 % d. Th.) der Verbindung (3) Molekulargewicht: 1084 Schmelzpunkt: 189-190°C Elementaranalyse:

  • ber. 62,0 % C, 4,3 % H, 2,9 % P, 1,0 % B
  • gef. 62,1 % C, 4,2 % H, 2,4 % P, 0,9 % B,
  • 0,07 % Wasser
  • 1H-NMR (in DMSO-d6):
  • 2,14 (Singulett, 3 Toluyl-H), 2,60 (Multiplett, 2 Methylen-H), 3,99 (Multiplett, 2 Methylen-H), 6,88 (Multiplett, 16 p-Toluyl- H), 7,82 (Multiplett, 15 Phenyl-H des Phosphoniumkations) ppm.
The preparation of compound (3) is carried out as in Preparation Example 1, with the difference that 4.0 g (0.01 mol) of sodium tetra-p-toluylborate are used instead of potassium hexa-fluorophosphate. Yield: 9.7 g (89.5% of theory) of compound (3) molecular weight: 1084 melting point: 189-190 ° C elemental analysis:
  • calc. 62.0% C, 4.3% H, 2.9% P, 1.0% B
  • found 62.1% C, 4.2% H, 2.4% P, 0.9% B,
  • 0.07% water
  • 1H-NMR (in DMSO-d6):
  • 2.14 (singlet, 3 toluyl-H), 2.60 (multiplet, 2 methylene-H), 3.99 (multiplet, 2 methylene-H), 6.88 (multiplet, 16 p-toluyl-H), 7.82 (multiplet, 15 phenyl-H of the phosphonium cation) ppm.

Anwendungsbeipiel 1Application example 1

1,0 Teil der Verbindung (1) wurde mittels eines Kneters der Firma Werner & Pfleiderer (Stuttgart) 45 Minuten in 99,0 Teilen Tonerbindemittel (Dialec S 309 der Firma Diamond Shamrock, Styrol-Methacrylat-Copolymerisat 60:40) homogen eingearbeitet. Anschließend wurde auf der Laboruniversalmühle 100 LU (Firma Alpine, Augsburg) gemahlen und dann auf dem Zentrifugalsichter 100 MZR (Firma Alpine) klassifiziert. Die gewünschte Teilchenfraktion (4- 25 u.m) wurde mit einem Carrier aus mit Styrol-Methacrylat-Copolymerisat 90:10 beschichteten Magnetitteilchen der Größe 50 bis 200 um des Types 90 um Xerographic Carrier der Firma Plasma Materials Inc. (Manchester, N.H., USA) aktiviert.1.0 part of the compound (1) was homogeneously incorporated for 45 minutes into 99.0 parts of toner binder (Dialec S 309 from Diamond Shamrock, styrene-methacrylate copolymer 60:40) using a kneader from Werner & Pfleiderer (Stuttgart). Subsequently, 100 LU (Alpine, Augsburg) was ground on the laboratory universal mill and then classified on the 100 MZR centrifugal classifier (Alpine). The desired particle fraction (4-25 µm) was obtained with a carrier made of 50 to 200 µm magnetite particles of the 90 µm type Xerographic Carrier coated with styrene-methacrylate copolymer 90:10 of the company Plasma Materials Inc. (Manchester, NH, USA).

Die Messung erfolgte an einem üblichen q/m-Meßstand (Firma Epping GmbH, Neufahrn); durch Verwenden eines Siebes mit einer Maschenweite von 25 µm (Firma Gebr. Kufferath, Düren) wurde sichergestellt, daß bei den Tonerausblasungen kein Carrier mitgerissen werden konnte. In Abhängigkeit von der Aktivierdauer wurden folgende q/m-Werte (µc/g) gemessen:

Figure imgb0018
The measurement was carried out on a customary q / m measuring stand (Epping GmbH, Neufahrn); by using a sieve with a mesh size of 25 µm (from Gebr. Kufferath, Düren) it was ensured that no carrier could be entrained in the toner blowouts. The following q / m values (µc / g) were measured as a function of the activation time:
Figure imgb0018

Anwendungsbeispiel 2Example of use 2

Es wurde, wie in Anwendungsbeispiel 1 beschrieben, gearbeitet, mit dem Unterschied, daß 1,0 Teil der Verbindung (2) in 99,0 Teilen Tonerbindemittel homogen eingearbeitet wurde.

Figure imgb0019
The procedure was as described in Application Example 1, with the difference that 1.0 part of compound (2) was incorporated homogeneously in 99.0 parts of toner binder.
Figure imgb0019

Anwendungsbeispiel 3Example of use 3

Es wurde, wie in Anwendungsbeispiel 1 beschrieben, gearbeitet, mit dem Unterschied, daß 2,5 Teile der Verbindung (2) in 97,5 Teilen Tonerbindemittel homogen eingearbeitet wurden.

Figure imgb0020
The procedure was as described in Application Example 1, with the difference that 2.5 parts of compound (2) were incorporated homogeneously in 97.5 parts of toner binder.
Figure imgb0020

Anwendungsbeispiel 4Example of use 4

Es wurde, wie in Anwendungsbeipiel 1 beschrieben, gearbeitet, mit dem Unterschied, daß 0,5 Teile der Verbindung (3) in 99,5 Teilen Tonerbindemittel homogen eingearbeitet wurden.

Figure imgb0021
The procedure was as described in Application Example 1, with the difference that 0.5 part of the Compound (3) were incorporated homogeneously in 99.5 parts of toner binder.
Figure imgb0021

Vergleichsbeispiel 1Comparative Example 1

Es wurde, wie in Anwendungsbeispiel 1 beschrieben, gearbeitet, mit dem Unterschied, daß 1,0 Teil Tetramethylphosphoniumchlorid in 99.0 Teilen Tonerbindemittel homogen eingearbeitet wurde.

Figure imgb0022
The procedure was as described in Application Example 1, with the difference that 1.0 part of tetramethylphosphonium chloride was incorporated homogeneously in 99.0 parts of toner binder.
Figure imgb0022

Claims (8)

1. Verwendung hochgradig fluorsubstituierter Phosphoniumverbindungen der allgemeinen Formel (I)
Figure imgb0023
in welcher R1 bis R4 Wasserstoffatome oder organische Reste bedeuten, wobei mindestens einer der Reste R1 bis R4 einen geradkettigen oder verzweigten, fluorsubstituierten, ungesättigten und/oder gesättigten Alkylrest mit 1 bis 30 C-Atomen und 3 bis 50 F-Atomen darstellt, welcher weitere Halogenatome, Hydroxyl-und/oder Chlormethyl- und/oder Carbonsäureamid- und/oder Sulfonsäureamid- und/oder Urethan-und/oder Keto- und/oder Amino- und/oder R5-O-R6 und/oder R7-C(O)-O-R8-Gruppen, worin Rs, R6, R7 und R8 Alkyl-(Ci-Cso)-reste darstellen, enthalten kann, oder einen fluorsubstituierten Arylrest oder einen am aromatischen Kern fluorsubstituierten Aralkylrest darstellt, wobei der Aryl- oder Aralkylrest am aromatischen Kern zusätzlich durch gesättigte oder ungesättigte, geradkettige oder verzweigte Alkyl(C1-C30)-, Alkoxy(C1-C30)-, Halogenalkyl, Halogenalkoxy(C1-C30) oder Hydroxylgruppen oder weitere Halogenatome substituiert sein kann, und im Falle eines Aralkylrestes die Alkylbrücke zwischen Phosphoratom und aromatischem Ring 1 bis 30 C-Atome enthält, und höchstens drei der Reste R1 bis R4 unabhängig voneinander Wasserstoffatome, geradkettige oder verzweigte, ungesättigte oder gesättigte, substituierte oder unsubstituierte Alkylreste mit 1 bis 30 C-Atomen, Aryl-oder Aralkylreste, die am aromatischen Kern durch Alkyl(C1-C30)-, Alkoxy(C1-C30)-, Halogenalkyl(C1-C3o)-, Halogenalkoxy(C1-C30)- oder Hydroxylgruppen oder Halogenatome substituiert sein können, darstellen, und X- ein organisches oder anorganisches Anion bedeutet, wobei die Reste R1 bis R4 eine COO- oder SO3- -Gruppe als Substituent enthalten können und X- in diesem Fall gegenstandslos wird, einzeln oder in Kombination als farblose Ladungssteuermittel mit positiver oder negativer Steuerwirkung in Tonern und Entwicklern für elektrophotographische Aufzeichnungsverfahren.1. Use of highly fluorine-substituted phosphonium compounds of the general formula (I)
Figure imgb0023
 in which R 1 to R 4 are hydrogen atoms or organic radicals, at least one of the radicals R 1 to R 4 being a straight-chain or branched, fluorine-substituted, unsaturated and / or saturated alkyl radical having 1 to 30 C atoms and 3 to 50 F atoms represents which further halogen atoms, hydroxyl and / or chloromethyl and / or carboxamide and / or sulfonamide and / or urethane and / or keto and / or amino and / or R 5 -OR 6 and / or R 7 -C (O) -OR 8 groups, in which Rs, R 6 , R 7 and R 8 represent alkyl (Ci-Cso) radicals, or a fluorine-substituted aryl radical or an aralkyl radical which is fluorine-substituted on the aromatic nucleus, wherein the aryl or aralkyl radical on the aromatic nucleus is additionally saturated or unsaturated, straight-chain or branched alkyl (C 1 -C 30 ) -, alkoxy (C 1 -C 30 ) -, haloalkyl, haloalkoxy (C 1 -C 30 ) or hydroxyl groups or further halogen atoms may be substituted, and in the case of an aralkyl radical tes the alkyl bridge between phosphorus atom and aromatic ring contains 1 to 30 carbon atoms, and at most three of the radicals R 1 to R 4 independently of one another hydrogen atoms, straight-chain or branched, unsaturated or saturated, substituted or unsubstituted alkyl radicals with 1 to 30 carbon atoms, aryl or aralkyl radicals, which on the aromatic nucleus by alkyl (C 1 -C 30 ) -, alkoxy (C 1 -C 30 ) -, haloalkyl (C 1 -C 3 o) -, haloalkoxy (C 1 -C 30 ) - or hydroxyl groups or halogen atoms can be substituted, and X- represents an organic or inorganic anion, where the radicals R 1 to R 4 can contain a COO or SO 3 - group as a substituent and X- in this case becomes irrelevant, individually or in combination as a colorless charge control agent with positive or negative control effect in toners and developers for electrophotographic recording processes. 2. Verwendung hochgradig fluorsubstituierter Phosphoniumverbindungen gemäß Anspruch 1, dadurch gekennzeichnet, daß in der in Anspruch 1 genannten allgemeinen Formel (I) mindestens einer der Reste R1 bis R4 einen geradkettigen oder verzweigten, fluorsubstituierten, ungesättigten und/oder gesättigten Alkylrest mit 4 bis 17 C-Atomen und 3 bis 25 F-Atomen bedeutet, welcher weitere Halogenatome, Hydroxyl-und/oder Chlormethyl- und/oder Carbonsäureamid- und/oder Urethan-und/oder Keto- und/oder Amino-und/oder Rs-O-Rs- und/oder R7-C(O)-R8-Gruppen, worin Rs, R6, R7 und R8 Alkyl(C1-C18)-reste darstellen, enthalten kann, oder einen fluorsubstituierten Arylrest oder einen am aromatischen Kern fluorsubstituierten Aralkylrest darstellt, wobei der Aryl- und Aralkylrest am aromatischen Kern zusätzlich durch gesättigte oder ungesättigte, geradkettige oder verzweigte Alkyl(C1-C18)-, Alkoxy(C1-C18)-, Halogenalkyl(C1-C18)-, Halogenalkoxy(Ci-Cis)- oder Hydroxylgruppen oder Fluor-, Chlor-, Brom- oder Jodatome substituiert sein kann, und im Falle eines Aralkylrestes die Alkylbrücke zwischen Phosphoratom und aromatischem Ring 1 bis 18 C-Atome enthält und höchstens drei der Reste R1 bis R4 unabhängig voneinader Wasserstoffatome, geradkettige oder verzweigte, ungesättigte oder gesättigte, substituierte oder unsubstituierte Alkylreste mit 1 bis 18 C-Atomen, Aryl-oder Aralkylreste, die am aromatischen Kern durch Alkyl(C1-C18)-, Alkoxy(C1-C18)-, Halogenalkyl(C1-C18)-, Halogenalkoxy(C1-C18)- oder Hydroxylgruppen oder Fluor-, Chlor-, Brom- oder Jodatome substituierte sein können, darstellen, und X- ein organisches oder anorganisches Anion bedeutet, wobei die Reste R1 bis R4 eine COO- oder SO3 --Gruppe als Substituenten enthalten können und X- in diesem Fall gegenstandslos wird.2. Use of highly fluorine-substituted phosphonium compounds according to claim 1, characterized in that in the general formula (I) mentioned in claim 1, at least one of the radicals R 1 to R 4 is a straight-chain or branched, fluorine-substituted, unsaturated and / or saturated alkyl radical with 4 to 17 carbon atoms and 3 to 25 F atoms, which means further halogen atoms, hydroxyl and / or chloromethyl and / or carboxamide and / or urethane and / or keto and / or amino and / or R s - OR s - and / or R 7 -C (O) -R 8 groups, in which R s , R 6 , R 7 and R 8 represent alkyl (C 1 -C 18 ) radicals, or a fluorine-substituted aryl radical or represents an aralkyl radical which is fluorine-substituted on the aromatic nucleus, the aryl and aralkyl radical on the aromatic nucleus additionally being saturated or unsaturated, straight-chain or branched alkyl (C 1 -C 18 ) -, alkoxy (C 1 -C 18 ) -, haloalkyl (C 1 -C 18 ) -, Haloalkoxy (Ci-Cis) - or hydroxyl groups or fluorine, chlorine, bromine or iodine atoms, and in the case of an aralkyl radical the alkyl bridge between phosphorus atom and aromatic ring contains 1 to 18 carbon atoms and at most three of the radicals R 1 to R 4 independently of one another, straight-chain or branched, unsaturated or saturated, substituted or unsubstituted alkyl radicals with 1 to 18 carbon atoms, aryl or aralkyl radicals which are substituted on the aromatic nucleus by alkyl (C 1 -C 18 ) -, alkoxy (C 1 -C 18 ) -, haloalkyl ( C 1 -C 18 ) -, Haloalkoxy (C 1 -C 18 ) - or hydroxyl groups or fluorine, chlorine, bromine or iodine atoms can be substituted, and X- represents an organic or inorganic anion, the radicals R 1 to R 4 may contain a COO or SO 3 - group as a substituent and X- in this case becomes irrelevant. 3. Verwendung hochgradig fluorsubstituierter Phosphoniumverbindungen gemäß Anspruch 1, dadurch gekennzeichnet, daß in der in Anspruch 1 genannten allgemeinen Formel (I) X- F-, CI-, Br-, J-, PF6 -, Sulfat, Phosphat, Cyanat, Thiocyanat, BF4-, Tetraphenylborat, p-Chlortetraphenylborat, p-Methyltetraphenylborat, Tetranaphthylborat, Phenolat, Nitrophenolat, Zinktetracyanat, Zinktetrathiocyanat, CH3OSO3 -, gesättigtes oder ungesättigtes aliphatisches oder aromatisches Carboxylat oder Sulfonat, perfluoriertes gesättigtes oder ungesättigtes aliphatisches oder aromatisches Carboxylat oder Sulfonat bedeutet.3. Use of highly fluorine-substituted phosphonium compounds according to claim 1, characterized in that in the general formula (I) mentioned in claim 1, X- F-, CI-, Br-, J-, PF 6 - , sulfate, phosphate, cyanate, thiocyanate , BF 4 -, tetraphenylborate, p-chlorotetraphenylborate, p-methyltetraphenylborate, tetranaphthylborate, phenolate, nitrophenolate, zinc tetracyanate, zinc tetrathiocyanate, CH 3 OSO 3 - , saturated or unsaturated aliphatic or aromatic carboxylate or unsaturated carboxylate or sulfonate Means sulfonate. 4. Verwendung hochgradig fluorsubstituierter Phosphoniumverbindungen gemäß Anspruch 1, dadurch gekennzeichnet, daß in der in Anspruch 1 genannten allgemeinen Formel (I) höchstens drei der Reste R1 bis R4 eine Phenylgruppe und mindestens einer der Reste R1 bis R4 eine Gruppe aus der Reihe C8F17-CH2-CH2- und Rf-CH2-CH2-(Rf = C6F13 bis C12F25)
bedeuten, und X- BF4-, F-, CI-, Br- und J-, PF6-, Tetraphenylborat, p-Chlortetraphenylborat, p-Methyltetraphenylborat oder Tetranaphthylborat darstellt.4. Use of highly fluorine-substituted phosphonium compounds according to claim 1, characterized in that in the general formula (I) mentioned in claim 1, at most three of the radicals R 1 to R 4 are a phenyl group and at least one of the radicals R 1 to R 4 is a group from the Series C 8 F 17 -CH 2 -CH 2 - and Rf-CH 2 -CH 2 - (Rf = C 6 F 13 to C 12 F 25 )
mean, and X- BF 4 -, F-, CI-, Br- and J-, PF 6 -, tetraphenylborate, p-chlorotetraphenylborate, p-methyltetraphenylborate or tetranaphthylborate. 5. Verwendung von in mindestens einem der Ansprüche 1 bis 4 genannten Phosphoniumverbindungen, einzeln oder in Kombination, zur Herstellung von Tonern oder Entwicklern, die zum elektrophotographischen Kopieren oder Vervielfältigen von Vorlagen sowie zum Drucken von elektronisch, optisch oder magnetisch gespeicherten Informationen oder im Colorproofing eingesetzt werden.5. Use of phosphonium compounds mentioned in at least one of claims 1 to 4, individually or in combination, for the production of toners or developers which are used for electrophotographic copying or reproduction of originals and for printing electronically, optically or magnetically stored information or in color proofing will. 6. Verwendung von in mindestens einem der Ansprüche 1 bis 4 genannten Phosphoniumverbindungen, dadurch gekennzeichnet, daß man die Phosphoniumverbindungen, einzeln oder in Kombination, in einer Konzentration von etwa 0,01 bis etwa 10 Gewichtsprozent einsetzt.6. Use of phosphonium compounds mentioned in at least one of claims 1 to 4, characterized in that the phosphonium compounds, individually or in combination, are used in a concentration of about 0.01 to about 10 percent by weight. 7. Verwendung von im mindestens einem der Ansrüche 1 bis 4 genannten Phosphoniumverbindungen, einzeln oder in Kombination, zum Beschichten von Carriern, die in Entwicklern zum elektrophotographischen Kopieren oder Vervielfältigen von Vorlagen sowie zum Drucken von elektronisch, optisch oder magnetisch gespeicherten Informationen oder im Colorproofing eingesetzt werden.7. Use of the phosphonium compounds mentioned in at least one of claims 1 to 4, individually or in combination, for coating carriers which are used in developers for electrophotographic copying or reproduction of originals and for printing electronically, optically or magnetically stored information or in color proofing will. 8. Verwendung von in mindestens einem der Ansprüche 1 bis 4 genannten Phosphoniumverbindungen, einzeln oder in Kombination, als ladungsverbessernde Mittel in Pulvern und Lacken zur Oberflächenbeschichtung von Gegenständen aus Metall, Holz, Kunststoff, Glas, Keramik, Beton, Textilmaterial, Papier oder Kautschuk, insbesondere in elektrokinetisch versprühten Pulverlacken.8. Use of phosphonium compounds mentioned in at least one of claims 1 to 4, individually or in combination, as charge-improving agents in powders and lacquers for the surface coating of objects made of metal, wood, plastic, glass, ceramic, concrete, textile material, paper or rubber, especially in electrokinetically sprayed powder coatings.
EP90106998A 1989-04-15 1990-04-11 Use of colourless phosphonium compounds, highly substituted by fluor, in electrophotographic recording processes Expired - Lifetime EP0393503B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90106998T ATE100220T1 (en) 1989-04-15 1990-04-11 USE OF COLORLESS HIGHLY FLUORINE-SUBSTITUTED PHOSPHONIUM COMPOUNDS AS CHARGE CONTROL AGENT FOR ELECTROPHOTOGRAPHIC RECORDING PROCESSES.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3912396A DE3912396A1 (en) 1989-04-15 1989-04-15 USE OF COLORLESS HIGH GRADE FLUORATE-SUBSTITUTED PHOSPHONIUM COMPOUNDS AS LOADING AGENTS FOR ELECTROPHOTOGRAPHIC RECORDING METHODS
DE3912396 1989-04-15

Publications (2)

Publication Number Publication Date
EP0393503A1 true EP0393503A1 (en) 1990-10-24
EP0393503B1 EP0393503B1 (en) 1994-01-12

Family

ID=6378738

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90106998A Expired - Lifetime EP0393503B1 (en) 1989-04-15 1990-04-11 Use of colourless phosphonium compounds, highly substituted by fluor, in electrophotographic recording processes

Country Status (5)

Country Link
US (1) US5147748A (en)
EP (1) EP0393503B1 (en)
JP (1) JPH02293871A (en)
AT (1) ATE100220T1 (en)
DE (2) DE3912396A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992006414A1 (en) * 1990-10-06 1992-04-16 Hoechst Aktiengesellschaft Aryl and aralkyl sulfide, sulfoxide or sulphonic compounds as charge regulators
EP0718707A1 (en) * 1994-12-07 1996-06-26 Eastman Kodak Company Quaternary phosphonium trihalozincate salts as charge-control agents for toners and developers
EP1077394A1 (en) * 1999-08-12 2001-02-21 Zimmer, Michael Process for transfer of toner and toner containing vulcanizable rubber material and/ or rubber material

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5389486A (en) * 1991-03-05 1995-02-14 Nippon Kayaku Kabushiki Kaisha Electrophotographic toner
DE4447593C2 (en) * 1994-10-05 2000-12-07 Clariant Gmbh Toner for electrophotographic developers containing an azo yellow pigment
US6110588A (en) 1999-02-05 2000-08-29 3M Innovative Properties Company Microfibers and method of making
US6630231B2 (en) * 1999-02-05 2003-10-07 3M Innovative Properties Company Composite articles reinforced with highly oriented microfibers
DE19927835A1 (en) 1999-06-18 2000-12-21 Clariant Gmbh Use of improved cyan pigments in electrophotographic toners and developers, powder coatings and ink jet inks
DE19957245A1 (en) 1999-11-27 2001-05-31 Clariant Gmbh New saline structural silicates with trialkyl-perfluoroalkenyl-ethyl-ammonium cation and other saline silicates are used as charge regulator in electrophotographic toner, powder lacquer, electret material or electrostatic separation
DE10054344A1 (en) 2000-11-02 2002-05-29 Clariant Gmbh Use of coated pigment granules in electrophotographic toners and developers, powder coatings and ink-jet inks
US6420024B1 (en) 2000-12-21 2002-07-16 3M Innovative Properties Company Charged microfibers, microfibrillated articles and use thereof
US6680114B2 (en) 2001-05-15 2004-01-20 3M Innovative Properties Company Fibrous films and articles from microlayer substrates
DE10235571A1 (en) * 2002-08-03 2004-02-12 Clariant Gmbh New magnesium-aluminum hydroxide-carbonates with sebacic acid anions and use of foliated double hydroxide salt as charge regulator in electrophotographic toner or developer, powder lacquer, electret or electrostatic separation
DE10235570A1 (en) * 2002-08-03 2004-02-19 Clariant Gmbh Use of layered double hydroxide salts with an organic anion as charge control agents, e.g. in electrophotographic toners and developers, powder lacquers and electret materials
DE10251394A1 (en) * 2002-11-05 2004-05-13 Clariant Gmbh Triamino triphenylmethane compound with low primary aromatic amine content as determined by HPLC is useful as a wide application pigment and is obtained by Friedel-Crafts alkylation with steam distillation
JP5407200B2 (en) * 2007-07-13 2014-02-05 東洋インキＳｃホールディングス株式会社 Antistatic agent and its use
JP2010138234A (en) * 2008-12-10 2010-06-24 Toyo Ink Mfg Co Ltd Antistat and application thereof
KR101962406B1 (en) 2010-10-25 2019-03-26 릭 엘. 채프먼 Filtration material using fiber blends that contain strategically shaped fibers and/or charge control agents

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4496643A (en) * 1984-03-23 1985-01-29 Eastman Kodak Company Two-component dry electrostatic developer composition containing onium charge control agent
US4537848A (en) * 1984-06-18 1985-08-27 Xerox Corporation Positively charged toner compositions containing phosphonium charge enhancing additives
EP0274858A1 (en) * 1986-12-05 1988-07-20 Xerox Corporation Toner compositions with inner salt charge enhancing additives

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3893935A (en) * 1972-05-30 1975-07-08 Eastman Kodak Co Electrographic toner and developer composition
US3948654A (en) * 1974-03-25 1976-04-06 Xerox Corporation Electrophotographic Process
US4656112A (en) * 1984-09-12 1987-04-07 Orient Chemical Industries, Ltd. Toner for developing electrostatic latent images
US4683188A (en) * 1985-05-28 1987-07-28 Hodogaya Chemical Co., Ltd. Electrophotographic toner containing metal complex charge control agent
US4684596A (en) * 1986-02-18 1987-08-04 Eastman Kodak Company Electrographic toner and developer composition containing quaternary ammonium salt charge-control agent
US4840864A (en) * 1987-12-17 1989-06-20 Eastman Kodak Company New electrostatographic toners and developers containing new charge-control agents
US4837391A (en) * 1988-08-05 1989-06-06 Eastman Kodak Company Dry electrostatographic developer containing toner particles comprising a vinyl addition polymer containing a covalently bound quaternary phosphonium salt

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4496643A (en) * 1984-03-23 1985-01-29 Eastman Kodak Company Two-component dry electrostatic developer composition containing onium charge control agent
US4537848A (en) * 1984-06-18 1985-08-27 Xerox Corporation Positively charged toner compositions containing phosphonium charge enhancing additives
EP0274858A1 (en) * 1986-12-05 1988-07-20 Xerox Corporation Toner compositions with inner salt charge enhancing additives

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 10, no. 358 (P-522)(2415) 02 December 1986, & JP-A-61 156142 (RICOH CO LTD) 15 July 1986, *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992006414A1 (en) * 1990-10-06 1992-04-16 Hoechst Aktiengesellschaft Aryl and aralkyl sulfide, sulfoxide or sulphonic compounds as charge regulators
US5378571A (en) * 1990-10-06 1995-01-03 Hoechst Aktiengesellschaft Aryl and aralkyl sulfide, sulfoxide or sulfone compounds as charge regulators
EP0718707A1 (en) * 1994-12-07 1996-06-26 Eastman Kodak Company Quaternary phosphonium trihalozincate salts as charge-control agents for toners and developers
EP1077394A1 (en) * 1999-08-12 2001-02-21 Zimmer, Michael Process for transfer of toner and toner containing vulcanizable rubber material and/ or rubber material

Also Published As

Publication number Publication date
US5147748A (en) 1992-09-15
DE59004182D1 (en) 1994-02-24
EP0393503B1 (en) 1994-01-12
DE3912396A1 (en) 1990-10-25
ATE100220T1 (en) 1994-01-15
JPH02293871A (en) 1990-12-05

Similar Documents

Publication Publication Date Title
EP0367162B1 (en) Use of colourless ammonium and immonium compounds with a high level of fluoridisation as charge control agents for electrophotographic recording methods
EP0393503B1 (en) Use of colourless phosphonium compounds, highly substituted by fluor, in electrophotographic recording processes
EP0551336B1 (en) Aryl and aralkyl sulfide, sulfoxide or sulphonic compounds as charge regulators
EP0548826B1 (en) Diallyl ammonium-compounds, method for their preparation and their application
DE3144017C2 (en) Electrostatographic toner
EP0705886B1 (en) Pigments for electrophotographic toners and developers
EP0506867B1 (en) Biscationic acid amide and acid imide derivatives as charge controllers
DE2522771A1 (en) CLASSIFIED ELECTROSTATOGRAPHIC TONER MATERIAL
EP0359123B1 (en) Process to influence selectively the triboelectric effect of azopigments
EP0476647B1 (en) Polymeric ammonium compounds as charge directors
EP0609718B1 (en) Ammonium salts of cyclic diallylpolysulfones
EP0362703B1 (en) Chinaoridone with selectively imparted triboelectric effects
EP0813117B1 (en) Use of azo magenta pigment in an electrophotographic toner and developer
EP0334840B1 (en) Blue colouring agent for electrophotographic recording process with positive regulating properties
DE2922948A1 (en) DEVELOPMENT SUPPORT FOR ELECTROPHOTOGRAPHY AND A PROCESS FOR ITS PRODUCTION
DE4029653A1 (en) Use of polymeric ammonium salts - as charge controlling agents in electrophotographic toners and developers and in powders and powder lacquers
EP0230950B1 (en) Colouring agent for electrophotographic recording processes
DE4435543C2 (en) Pigment for electrophotographic toners and developers
EP0261405A2 (en) Condensation products of five-membered heterocyclic compounds with a triboelectrical effect for electrophotographical registration processes
EP0681225B1 (en) Electrostatic toner comprising phenacyl compounds
DE4209919A1 (en) Toners for electrophotography, new indole derivatives and processes for their production
DE19744097A1 (en) Pigment Yellow 155 used in electrophotographic toner or developer, powder

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT CH DE FR GB IT LI NL

17P Request for examination filed

Effective date: 19901219

17Q First examination report despatched

Effective date: 19930528

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT CH DE FR GB IT LI NL

REF Corresponds to:

Ref document number: 100220

Country of ref document: AT

Date of ref document: 19940115

Kind code of ref document: T

ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

REF Corresponds to:

Ref document number: 59004182

Country of ref document: DE

Date of ref document: 19940224

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19940321

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19950619

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19960313

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19960319

Year of fee payment: 7

Ref country code: CH

Payment date: 19960319

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19960321

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19960325

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19970101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19970411

Ref country code: AT

Effective date: 19970411

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970430

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19971101

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19970411

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19971231

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19971101

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050411