EP0247576A2 - Magenta dye for electrophotographic recording processes - Google Patents
Magenta dye for electrophotographic recording processes Download PDFInfo
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- EP0247576A2 EP0247576A2 EP87107650A EP87107650A EP0247576A2 EP 0247576 A2 EP0247576 A2 EP 0247576A2 EP 87107650 A EP87107650 A EP 87107650A EP 87107650 A EP87107650 A EP 87107650A EP 0247576 A2 EP0247576 A2 EP 0247576A2
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/09—Colouring agents for toner particles
- G03G9/0906—Organic dyes
- G03G9/092—Quinacridones
Definitions
- the present invention relates to an improved magenta colorant for multi-color electrophotographic recording processes, the magenta colorant being a mixed crystal of 2,9-dimethylquinacridone and unsubstituted quinacridone in a specific mixing ratio.
- the toner is the colorant-containing component which gives color in the recording process
- its triboelectric chargeability is essential, the sign and the amount of the chargeability being of fundamental importance.
- the present invention was based on the need to find a magenta colorant which improves the triboelectric chargeability of the toner and at the same time has the required color shade and transparency.
- a "latent charge image” is generated on a photoconductor drum. This is achieved by charging the photoconductor drum with a corona discharge and then imagewise exposing the electrostatic charged surface of the photoconductor drum, 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 drum to, for example, paper, textiles, foils or plastic and is 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.
- Electrophotographic multi-color reproduction can be achieved, for example, by three successive recording processes with three toners of the respective primary colors magenta, yellow and cyan.
- a measure of the toner quality is its specific chargeability Q / M (charge per unit mass).
- the color shade of toners for monochrome recordings is essentially determined from an aesthetic point of view; transparency and color location are decisive for multi-pass reproduction based on the principle of "subtractive color mixing".
- mixtures of pigments have proven to be suitable for setting the desired shade (JA-OS 59/219756, JA-OS 59/220750).
- pigment mixtures Compared to systems with only 1 pigment component, pigment mixtures have the disadvantage that they are cloudy and show a lower transparency. It also results in the application
- the disadvantage of pigment mixtures is that the already complex toner formulations have to be expanded by at least 1 component, which in turn means that pigment compatibility, mixing problems and deviating color shades have to be taken into account.
- a toner composition color-coordinated by a pigment mixture also has the required triboelectric chargeability, so that a charge control agent, which in turn is usually colored itself, must also be added, which again raises problems of the deviating color shade or incompatibilities leads.
- the chargeability of the toner is described in US Pat. No. 4,057,426, such as using a complex carrier consisting of polymer-coated steel particles, the polymer in turn containing a certain proportion of copper tetra-4- (octadecylsulfonamido) phthalocyanine needs to be improved.
- magenta toners which contain 2,9-dimethylquinacridone as colorants
- a "nickel berry” carrier nickel particles with a special knot-shaped surface
- US Pat. Nos. 3,909,259 and 3,804,619 a special combination of carrier and toner could ensure perfect toner transfer. Since no uniform carrier is available for the three toner colors due to the use of a special nickel carrier for the magenta toner, the recording process becomes more complex, especially since the use of nickel is inherently problematic because of its toxicological concern.
- magenta toners Another approach to improving the poor chargeability of magenta toners is to optimize the resin in terms of its tribolelectric properties as described in DE-OS 2 447 083.
- a resin optimized in this way for its triboelectric properties now often shows problems, for example with regard to its fixing and offset behavior, its glass point and its dispersibility.
- the three color toners or developers in the multicolor copier do not differ in terms of pigments, but also in terms of toner binders.
- the aim is that in a multi-color copier the respective components for toner and carrier or developer are as uniform as possible and differ only in terms of the colorants used for yellow, cyan and magenta.
- the present invention has surprisingly shown that it is possible to give the toner a significantly improved triboelectric chargeability by means of suitable mixed crystals of 2,9-dimethylquinacridone, without significantly changing the color shade of the 2,9-dimethylquinacridone.
- the chargeability thus improves from -23.0 ⁇ C / g (toner example 4, with 2,9-dimethylquinacridone) to up to -40.5 ⁇ / g (toner example 3, mixed crystal 3 parts of 2,9-dimethylquinacridone, 1 Part of unsubstituted quinacridone).
- toners with mixed crystals of 2,9-dimethylquinacridone and unsubstituted quinacridone show a similarly good charge profile as those with 2,9-dimethylquinacridone alone.
- the color shade of the toner colored with the colorant (mixed crystal) according to the invention corresponds to the color shade of toners with 2,9-dimethylquinacridone known to be suitable.
- a mere pigment mixture of 2,9-dimethylquinacridone and quinacridone in a ratio of, for example, 3: 1, incorporated into the toner does not give the required shade and transparency.
- magenta toners with the colorants (mixed crystals) used according to the invention have the necessary transparency.
- the triboelectric chargeability of mixed crystals of the same composition can vary, for example, between -31.1 ⁇ / g (toner example 1) and -40.5 ⁇ C / g (toner example 4).
- the present invention thus relates to improved magenta colorants for electrophotographic multi-color recording processes consisting of mixed crystals with 95 to 60 parts of a compound of the formula I below and 5 to 40 parts of a compound of the formula II below the use thereof for the production of toners which are used for electrophotographic copying or duplication of originals and for the printing of electronically, optically or magnetically stored information, and the use of toners or developers which have been produced using the abovementioned magenta colorants for magenta reproduction in multi-color electrophotographic recording.
- the preparation of the mixed crystal pigments mentioned is possible in a manner known per se, for example by jointly redissolving the mixed crystal components from sulfuric acid or another suitable solvent and subsequent solvent treatment, as described in US Pat. No. 3,160,510, or by salt grinding the mixed crystal components and subsequent solvent treatment ( DE-AS 1 217 333) or by cyclizing the correspondingly substituted diamino-terephthalic acid mixtures and subsequent solvent treatment, as indicated, for example, in DE-AS 1 217 333.
- either dried and ground pigment or, for example, an aqueous pigment dispersion or a pigment press cake can be used to incorporate the mixed crystal into the toner binder.
- the amount of electrostatic charging of the toner using mixed crystals of compounds of the above formulas (I) and (II) in the specified mixing ratio or on the comparison system with C.I. Pigment Red 122 (formula (I)) was measured on standard systems under the same conditions (such as the same dispersion times, same particle size distribution, same particle shape) at 23 ° C. and 50% relative atmospheric humidity.
- the toner is activated in a two-component developer by swirling the toner with a carrier (3 parts toner to 97 parts carrier) for 30 minutes on a roller bench (150 revolutions per minute).
- the particle size distribution of the sighted toner powder was determined using a Cilas 715 granulator from Cilas.
- the average particle sizes for the toners listed in the examples were between 7.4 ⁇ m and 7.9 ⁇ m.
- the mixed crystal pigments A, B and C are mixed crystals of 3 parts of the compound of the formula I and 1 part of the compound of the formula II mentioned, for the preparation of mixed crystal A (cf. Example 1) the hydrolysis from polyphosphoric acid was carried out in an aqueous medium at 50 ° C. and an aftertreatment in alcoholic solvent was carried out at 125 ° C. for 5 hours; of mixed crystal B (cf. Example 2) the hydrolysis from polyphosphoric acid was carried out in an aqueous medium at 50 ° C. and an aftertreatment in alcoholic solvent was carried out at 150 ° C. for 5 hours; of mixed crystal C (cf. Example 3), the hydrolysis from polyphosphoric acid was carried out in an aqueous medium at 70 ° C. and an aftertreatment in alcoholic solvent was carried out at 120 ° C. for 5 hours.
- the mixed crystals labeled A, B and C are characterized by three strong lines at 16.21; 8.43 and 3.28 ⁇ , two moderate lines at 8.06 and 3.51 ⁇ and other weak lines in the X-ray diffraction spectrum.
- the 2,9-dimethylquinacridone listed in Comparative Example 4 is the CI Pigment Red 122 (®Hostaperm-Rosa E).
- the desired particle fraction was activated with a carrier composed of magnetite particles of size 50 to 200 ⁇ m of the type 90 ⁇ m Xerographic Carrier from Plasma Materials Inc., coated with styrene methacrylate 90:10.
- the measurement is carried out on a standard Q / M measuring stand [cf. J.H. Dessauer, H.E. Clark “Xerography and related Processes", Focal Press, N.Y. 1965, page 289]; by using a sieve with a mesh size of 25 ⁇ m (508 mesh per inch), from Gebrüder Kufferath, Düren, it was ensured that no carrier can be entrained in the toner blowouts.
- the Q / M value was determined to be -31.1 ⁇ C / g.
- the Q / M value was determined to be -36.8 ⁇ C / g.
- the Q / M value was determined to be -40.5 ⁇ C / g.
- the Q / M value was determined to be -23.0 ⁇ C / g.
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Abstract
Verbessertes Magentafarbmittel für elektrophotographische Mehrfarbaufzeichnungsverfahren bestehend aus Mischkristallen mit 95 bis 60 Teilen einer Verbindung der nachstehenden Formel I und 5 bis 40 Teilen einer Verbindung der nachstehenden Formel II
Description
Die vorliegende Erfindung betrifft ein verbessertes Magentafarbmittel für elektrophotographische Mehrfarbaufzeichnungsverfahren, wobei das Magentafarbmittel ein Mischkristall aus 2,9-Dimethylchinacridon und unsubstituiertem Chinacridon eines bestimmten Mischungsverhältnisses ist.The present invention relates to an improved magenta colorant for multi-color electrophotographic recording processes, the magenta colorant being a mixed crystal of 2,9-dimethylquinacridone and unsubstituted quinacridone in a specific mixing ratio.
Aufbauend auf dem Prinzip der "subtraktiven Farbmischung" kann mit Hilfe der drei Primärfarben Gelb, Cyan, Magenta das gesamte für das menschliche Auge sichtbare Farbspektrum wiedergegeben werden. Nur wenn die jeweiligen Primärfarbe den genau definierten farblichen Anforderungen genügt, ist eine exakte Farbwiedergabe möglich. Andernfalls können einige Farbtöne nicht wiedergegeben werden und der Farbkontrast ist nicht ausreichend.Building on the principle of "subtractive color mixing", the entire color spectrum visible to the human eye can be reproduced with the help of the three primary colors yellow, cyan and magenta. An exact color reproduction is only possible if the respective primary color meets the precisely defined color requirements. Otherwise, some colors cannot be reproduced and the color contrast is insufficient.
Bei elektrophotographischen Aufzeichnungsverfahren ist zusätzlich zur richtigen Farbnuance des Toners (der Toner ist die das Farbmittel enthaltende, im Aufzeichnungsverfahren farbgebende Komponente) dessen triboelektrische Aufladbarkeit unabdingbar, wobei das Vorzeichen und die Höhe der Aufladbarkeit von grundsätzlicher Bedeutung sind.In electrophotographic recording processes, in addition to the correct color shade of the toner (the toner is the colorant-containing component which gives color in the recording process), its triboelectric chargeability is essential, the sign and the amount of the chargeability being of fundamental importance.
Der vorliegenden Erfindung lag das Bedürfnis zugrunde, ein Magentafarbmittel zu finden, welches die triboelektrische Aufladbarkeit des Toners verbessert und zugleich die benötigte Farbnuance und Transparenz besitzt.The present invention was based on the need to find a magenta colorant which improves the triboelectric chargeability of the toner and at the same time has the required color shade and transparency.
Bei elektrophotographischen Aufzeichnungsverfahren wird beispielsweise auf einer Photoleitertrommel ein "latentes Ladungsbild" erzeugt. Dies gelingt durch Aufladung der Photoleitertrommel durch eine Corona-Entladung und anschließende bildmäßige Belichtung der elektrostatisch aufgeladenen Oberfläche der Photoleitertrommel, 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 electrophotographic recording processes, for example, a "latent charge image" is generated on a photoconductor drum. This is achieved by charging the photoconductor drum with a corona discharge and then imagewise exposing the electrostatic charged surface of the photoconductor drum, 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 einem darauffolgenden Schritt wird der Toner von der Photoleitertrommel 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.In a subsequent step, the toner is transferred from the photoconductor drum to, for example, paper, textiles, foils or plastic and is 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.
Die elektrophotographische Mehrfarbwiedergabe läßt sich beispielsweise durch drei nacheinander erfolgende Aufzeichnungsvorgänge mit drei Tonern der jeweiligen Primärfarben Magenta, Gelb und Cyan erreichen.Electrophotographic multi-color reproduction can be achieved, for example, by three successive recording processes with three toners of the respective primary colors magenta, yellow and cyan.
Neuere Entwicklungen bei der Erstellung von Tonern betreffen Farbmittel, die neben der Farbgebung auch eine Verbesserung der triboelektrischen Aufladbarkeit zum Ziel haben.Recent developments in the production of toners concern colorants which, in addition to the coloring, also aim to improve the triboelectric chargeability.
Ein Maß für die Tonerqualität ist seine spezifische Aufladbarkeit Q/M (Ladung pro Masseeinheit).A measure of the toner quality is its specific chargeability Q / M (charge per unit mass).
Die Farbnuance von Tonern für einfarbige Aufzeichnungen wird im wesentlichen von ästhetischen Gesichtspunkten bestimmt; für die Mehrfahrbewiedergabe nach dem Prinzip der "substraktiven Farbmischung" sind Transparenz und Farbort entscheidend.The color shade of toners for monochrome recordings is essentially determined from an aesthetic point of view; transparency and color location are decisive for multi-pass reproduction based on the principle of "subtractive color mixing".
Zur Einstellung der gewünschten Farbnuance haben sich in einigen Fällen Mischungen von Pigmenten als geeignet erwiesen (JA-OS 59/219756, JA-OS 59/220750). Pigmentmischungen weisen aber gegenüber Systemen mit nur 1 Pigmentkomponente den Nachteil auf, daß sie trüber sind und eine geringere Transparenz zeigen. Zudem ergibt sich bei der Anwendung von Pigmentmischungen der Nachteil, daß die ohnehin komplexen Tonerrezepturen um mindestens 1 Bestandteil erweitert werden müssen, wodurch wiederum Pigmentverträglichkeiten, Mischungsprobleme und abweichende Farbnuancen mit in Betracht gezogen werden müssen. Zudem ist nicht zu erwarten, daß eine durch eine Pigmentmischung farblich abgestimmte Tonerkomposition auch die benötigte triboelektrische Aufladbarkeit besitzt, so daß zusätzlich ein Ladungssteuermittel, welches wiederum in der Regel selbst farbig ist, zugegeben werden muß, was erneut Probleme der abweichenden Farbnuance aufwirft oder zu Unverträglichkeiten führt.In some cases, mixtures of pigments have proven to be suitable for setting the desired shade (JA-OS 59/219756, JA-OS 59/220750). Compared to systems with only 1 pigment component, pigment mixtures have the disadvantage that they are cloudy and show a lower transparency. It also results in the application The disadvantage of pigment mixtures is that the already complex toner formulations have to be expanded by at least 1 component, which in turn means that pigment compatibility, mixing problems and deviating color shades have to be taken into account. In addition, it is not to be expected that a toner composition color-coordinated by a pigment mixture also has the required triboelectric chargeability, so that a charge control agent, which in turn is usually colored itself, must also be added, which again raises problems of the deviating color shade or incompatibilities leads.
Die grundsätzliche Eignung von 2,9-Dimethylchinacridon, C.I. Pigment Red 122, als Magentafarbmittel für elektrophotographische Aufzeichnungsverfahren wird beispielsweise in den US-PS 4 057 426, 3 804 619 und 3 909 259 beschrieben, wonach das 2,9-Dimethylchinacridon hinsichtlich seiner Farbnuance und seiner Transparenz gut geeignet sei. Hinsichtlich der triboelektrischen Aufladbarkeit des Toners bestehen beim 2,9-Dimethylchinacridon jedoch gewisse Mängel.The basic suitability of 2,9-dimethylquinacridone, C.I. Pigment Red 122, as a magenta colorant for electrophotographic recording processes, is described, for example, in US Pat. Nos. 4,057,426, 3,804,619 and 3,909,259, according to which the 2,9-dimethylquinacridone is well suited with regard to its color shade and its transparency. However, there are certain shortcomings with 2,9-dimethylquinacridone in terms of the triboelectric chargeability of the toner.
Da die drei Toner, Gelb, Cyan, Magenta aufeinanderfolgend im selben Gerät übertragen werden müssen, die Aufladbarkeiten der drei Toner also untereinander abgestimmt sein müssen, werden in einem "Dreifarbengerät" besonders hohe Anforderungen an den Wert und die Stabilität der Aufladung sowie der tolerierbaren Abweichung der vorgegebenen Werte gestellt.Since the three toners, yellow, cyan, magenta have to be transmitted successively in the same device, ie the chargeability of the three toners must be coordinated with one another, in a "three-color device" particularly high demands are placed on the value and stability of the charge and the tolerable deviation of the specified values.
So wird beispielsweise in der US-PS 4 057 426 beschrieben, wie durch Verwendung eines aufwendigen Carriers, bestehend aus polymerbeschichteten Stahlteilchen, wobei im Polymer wiederum ein bestimmter Anteil Kupfer-tetra-4-(octadecylsulfonamido)phthalocyanin enthalten sein muß, die Aufladbarkeit des Toners verbessert werden muß.For example, the chargeability of the toner is described in US Pat. No. 4,057,426, such as using a complex carrier consisting of polymer-coated steel particles, the polymer in turn containing a certain proportion of copper tetra-4- (octadecylsulfonamido) phthalocyanine needs to be improved.
Gleichzeitig wird in der genannten Patentschrift noch einmal darauf verwiesen, daß Magentatoner (die 2,9-Di-methylchinacridon als Farbmittel enthalten) bisher nur mit einem "Nickel-berry"-Carrier (Nickelteilchen mit einer speziellen knotenförmigen Oberfläche) erfolgreich eingesetzt werden konnten (US-PS 3 909 259 und 3 804 619), weil nur durch eine besondere Kombination von Carrier und Toner einer einwandfreie Tonerübertragung erreicht werden konnte.
Da für die drei Tonerfarben durch die Verwendung eines speziellen Nickel-Carriers für den Magentatoner kein einheitlicher Carrier zur Verfügung steht, wird der Aufzeichnungsprozeß um einen weiteren Parameter komplexer, zumal die Verwendung von Nickel wegen seiner toxikologischen Bedenklichkeit schon von sich aus problematisch ist.At the same time, the patent mentioned again refers to the fact that magenta toners (which contain 2,9-dimethylquinacridone as colorants) have so far only been used a "nickel berry" carrier (nickel particles with a special knot-shaped surface) could be used successfully (US Pat. Nos. 3,909,259 and 3,804,619), because only a special combination of carrier and toner could ensure perfect toner transfer.
Since no uniform carrier is available for the three toner colors due to the use of a special nickel carrier for the magenta toner, the recording process becomes more complex, especially since the use of nickel is inherently problematic because of its toxicological concern.
Eine andere Herangehensweise zur Verbesserung der mangelhaften Aufladbarkeit von Magentatonern besteht in der Optimierung des Harzes in Bezug auf seine tribolelektrischen Eigenschaften wie in DE-OS 2 447 083 beschrieben. Ein solchermaßen auf seine triboelektrischen Eigenschaften optimiertes Harz zeigt nun häufig Probleme beispielsweise hinsichtlich seines Fixier- und Offset-Verhaltens, seines Glaspunktes und seines Dispergiervermögens. Hinzu kommt, daß dann im Mehrfarbkopiergerät die drei Farbtoner bzw. Entwickler sich nicht zur hinsichtlich der Pigmente, sondern auch hinsichtlich der Tonerbindemittel unterscheiden. Angestrebt wird jedoch, daß in einem Mehrfarbkopierer die jeweiligen Komponenten für Toner und Carrier bzw. Entwickler möglichst einheitlich sind und sich nur bezüglich der eingesetzten Farbmittel für Gelb, Cyan und Magenta unterscheiden.Another approach to improving the poor chargeability of magenta toners is to optimize the resin in terms of its tribolelectric properties as described in DE-OS 2 447 083. A resin optimized in this way for its triboelectric properties now often shows problems, for example with regard to its fixing and offset behavior, its glass point and its dispersibility. In addition, the three color toners or developers in the multicolor copier do not differ in terms of pigments, but also in terms of toner binders. However, the aim is that in a multi-color copier the respective components for toner and carrier or developer are as uniform as possible and differ only in terms of the colorants used for yellow, cyan and magenta.
Die vorliegende Erfindung hat überraschenderweise gezeigt, daß es möglich ist, durch geeignete Mischkristalle aus 2,9-Dimethylchinacridon dem Toner eine deutlich verbesserte triboelektrische Aufladbarkeit zu geben, ohne die Farbnuance des 2,9-Dimethylchinacridons wesentlich zu ändern.The present invention has surprisingly shown that it is possible to give the toner a significantly improved triboelectric chargeability by means of suitable mixed crystals of 2,9-dimethylquinacridone, without significantly changing the color shade of the 2,9-dimethylquinacridone.
So verbessert sich die Aufladbarkeit von -23,0 µC/g (Toner Beispiel 4, mit 2,9-Dimethylchinacridon) auf bis zu -40,5 µ/g (Toner Beispiel 3, Mischkristall 3 Teile 2,9-Dimethylchinacridon, 1 Teil unsubstituiertes Chinacridon). Einhergehend mit der verbesserten Aufladbarkeit zeigen Toner mit Mischkristallen aus 2,9-Dimethylchinacridon und unsubstituiertem Chinacridon ein ähnlich gutes Ladungsprofil wie solche mit 2,9-Dimethylchinacridon allein.The chargeability thus improves from -23.0 μC / g (toner example 4, with 2,9-dimethylquinacridone) to up to -40.5 μ / g (toner example 3, mixed crystal 3 parts of 2,9-dimethylquinacridone, 1 Part of unsubstituted quinacridone). Along with the improved chargeability, toners with mixed crystals of 2,9-dimethylquinacridone and unsubstituted quinacridone show a similarly good charge profile as those with 2,9-dimethylquinacridone alone.
Die Farbnuance des mit dem erfindungsgemäßen Farbmittel (Mischkristall) eingefärbten Toners entspricht der als geeignet bekannten Farbnuance von Tonern mit 2,9-Dimethylchinacridon. Dagegen ergibt eine bloße Pigmentmischung von 2,9-Dimethylchinacridon und Chinacridon im Verhältnis von beispielsweise 3 : 1, eingearbeitet im Toner, nicht die benötigte Farbnuance und Transparenz.The color shade of the toner colored with the colorant (mixed crystal) according to the invention corresponds to the color shade of toners with 2,9-dimethylquinacridone known to be suitable. In contrast, a mere pigment mixture of 2,9-dimethylquinacridone and quinacridone in a ratio of, for example, 3: 1, incorporated into the toner, does not give the required shade and transparency.
Die Magentatoner mit den erfindungsgemäß eingesetzten Farbmitteln (Mischkristallen) besitzen - wie die Toner mit 2,9-Dimethylchinacridon - die notwendige Transparenz.Like the toners with 2,9-dimethylquinacridone, the magenta toners with the colorants (mixed crystals) used according to the invention have the necessary transparency.
In Abhängigkeit von der Temperaturführung bei der Mischkristallherstellung und Nachbehandlung läßt sich die triboelektrische Aufladbarkeit von Mischkristallen gleicher Zusammensetzung beispielsweise zwischen -31,1 µ/g (Toner Beispiel 1) und -40,5 µC/g (Toner Beispiel 4) variieren.Depending on the temperature control during mixed crystal production and aftertreatment, the triboelectric chargeability of mixed crystals of the same composition can vary, for example, between -31.1 μ / g (toner example 1) and -40.5 μC / g (toner example 4).
Gegenstand der vorliegenden Erfindung sind somit verbesserte Magentafarbmittel für elektrophotographische Mehrfarbaufzeichnungsverfahren bestehend aus Mischkristallen mit 95 bis 60 Teilen einer Verbindung der nachstehenden Formel I und 5 bis 40 Teilen einer Verbindung der nachstehenden Formel II
Die Herstellung der angeführten Mischkristallpigmente ist in an sich bekannter Weise möglich, beispielsweise durch gemeinsames Umlösen der Mischkristallkomponentnen aus Schwefelsäure oder einem anderen geeigneten Lösungsmittel und anschließende Lösungsmittelbehandlung, wie in der US-PS 3 160 510 beschrieben, oder durch Salzvermahlung der Mischkristallkomponenten und anschließende Lösungsmittelbehandlung (DE-AS 1 217 333) oder durch Cyclisieren der entsprechend substituierten Diamino-terephthalsäure-Gemische und anschließende Lösungsmittelbehandlung, wie beispielsweise in der DE-AS 1 217 333 angegeben.The preparation of the mixed crystal pigments mentioned is possible in a manner known per se, for example by jointly redissolving the mixed crystal components from sulfuric acid or another suitable solvent and subsequent solvent treatment, as described in US Pat. No. 3,160,510, or by salt grinding the mixed crystal components and subsequent solvent treatment ( DE-AS 1 217 333) or by cyclizing the correspondingly substituted diamino-terephthalic acid mixtures and subsequent solvent treatment, as indicated, for example, in DE-AS 1 217 333.
Toner mit den erfindungsgemäß als Magentafarbmittel beanspruchten Mischkristallen aus 2,9-Dimethylchinacridon und unsubstituiertem Chinacridon besitzen, bei geeigneter Farb nuance und Transparenz, eine deutlich verbesserte triboelektrische Aufladbarkeit.Have toners with the mixed crystals of 2,9-dimethylquinacridone and unsubstituted quinacridone claimed according to the invention as magenta colorants, with a suitable color nuance and transparency, a significantly improved triboelectric chargeability.
Im Falle einer völligen Verzichtbarkeit des Zusatzes eines gesonderten Steuermittels bei den erfindungsgemäßen Farbmitteln, welches als dritter Bestandteil bei der Tonerherstellung zugesetzt werden müßte, können die Probleme, die bei Zusatz eines Steuermittels auftreten können, wie unerwünschte Beeinflussung des Farbtons durch Eigenfarbe oder inhomogene Verteilung des Steuermittels im Toner oder allmähliches Auswandern des Steuermittels aus dem Toner, grundsätzlich vermieden werden.If it is completely unnecessary to add a separate control agent to the colorants according to the invention, which would have to be added as a third constituent in the production of toner, the problems which can occur when a control agent is added, such as undesirable influence on the color tone by the inherent color or inhomogeneous distribution of the control agent in the toner or gradual migration of the control agent out of the toner, be avoided in principle.
Zur Einarbeitung des Mischkristalls in das Tonerbindemittel können grundsätzlich entweder getrocknetes und gemahlenes Pigment oder eine beispielsweise wäßrige Pigmentdispersion oder ein Pigmentpreßkuchen verwendet werden.In principle, either dried and ground pigment or, for example, an aqueous pigment dispersion or a pigment press cake can be used to incorporate the mixed crystal into the toner binder.
Die Höhe der elektrostatischen Aufladung des Toners unter Verwendung von Mischkristallen aus Verbindungen der vorstehend genannten Formeln (I) und (II) im angegebenen Mischungsverhältnis bzw. am Vergleichssystem mit C.I. Pigment Red 122 (Formel (I)) wurde an Standardsystemen unter gleichen Bedingungen (wie gleiche Dispergierzeiten, gleiche Teilchengrößenverteilung, gleiche Teilchenform) bei 23°C und 50 % relativer Luftfeuchtigkeit gemessen. Die Aktivierung des Toners in einem Zweikomponentenentwickler erfolgt durch Verwirbelung des Toners mit einem Carrier (3 Teile Toner auf 97 Teile Carrier) 30 Minuten auf einer Rollbank (150 Umdrehungen pro Minute).The amount of electrostatic charging of the toner using mixed crystals of compounds of the above formulas (I) and (II) in the specified mixing ratio or on the comparison system with C.I. Pigment Red 122 (formula (I)) was measured on standard systems under the same conditions (such as the same dispersion times, same particle size distribution, same particle shape) at 23 ° C. and 50% relative atmospheric humidity. The toner is activated in a two-component developer by swirling the toner with a carrier (3 parts toner to 97 parts carrier) for 30 minutes on a roller bench (150 revolutions per minute).
Bei der Bestimmung des Q/M-Wertes ist die Teilchengröße von großem Einfluß. Es wurde daher streng darauf geachtet, daß die bei den Sichtungen erhaltenen und in den nachstehenden 4 Beispielen aufgeführten Tonerproben bezüglich der Teilchengrößenverteilung einheitlich waren.When determining the Q / M value, the particle size is of great influence. Care was therefore taken to ensure that the toner samples obtained from the sightings and listed in the 4 examples below were uniform in terms of particle size distribution.
Die Teilchengrößenverteilung des gesichteten Tonerpulvers wurde mit einem Cilas-Granulometer 715 der Fa. Cilas bestimmt.
Die Mittelwerte der Teilchengrößen für die in den Beispielen aufgeführten Toner lagen zwischen 7,4 µm und 7,9 µm.The particle size distribution of the sighted toner powder was determined using a Cilas 715 granulator from Cilas.
The average particle sizes for the toners listed in the examples were between 7.4 μm and 7.9 μm.
Die Mischkristallpigmente A, B und C , wie sie in den nachstehenden Beispielen 1 bis 3 verwendet werden, stellen Mischkristalle aus 3 Teilen der Verbindung der genannten Formel I und 1 Teil der Verbindung der genannten Formel II dar, wobei zur Herstellung
des Mischkristalles A (vgl. Beispiel 1) die Hydrolyse aus Polyphosphorsäure in wäßrigem Medium bei 50°C erfolgte und eine Nachbehandlung in alkoholischem Lösungsmittel bei 125°C über 5 Stunden durchgeführt wurde;
des Mischkristalls B (vgl. Beispiel 2) die Hydrolyse aus Polyphosphorsäure in wäßrigem Medium bei 50°C erfolgte und eine Nachbehandlung in alkoholischem Lösungsmittel bei 150°C über 5 Stunden durchgeführt wurde;
des Mischkristalls C (vgl. Beispiel 3) die Hydrolyse aus Polyphosphorsäure in wäßrigem Medium bei 70°C erfolgte und eine Nachbehandlung in alkoholischem Lösungsmittel bei 120°C über 5 Stunden durchgeführt wurde.The mixed crystal pigments A, B and C, as used in Examples 1 to 3 below, are mixed crystals of 3 parts of the compound of the formula I and 1 part of the compound of the formula II mentioned, for the preparation
of mixed crystal A (cf. Example 1) the hydrolysis from polyphosphoric acid was carried out in an aqueous medium at 50 ° C. and an aftertreatment in alcoholic solvent was carried out at 125 ° C. for 5 hours;
of mixed crystal B (cf. Example 2) the hydrolysis from polyphosphoric acid was carried out in an aqueous medium at 50 ° C. and an aftertreatment in alcoholic solvent was carried out at 150 ° C. for 5 hours;
of mixed crystal C (cf. Example 3), the hydrolysis from polyphosphoric acid was carried out in an aqueous medium at 70 ° C. and an aftertreatment in alcoholic solvent was carried out at 120 ° C. for 5 hours.
Die mit A, B und C bezeichneten Mischkristalle zeichnen sich durch drei starke Linien bei 16,21; 8,43 und 3,28 Å, zwei mittelstarke Linien bei 8,06 und 3,51 Å sowie weitere schwache Linien im Röntgenbeugungsspektrum aus.The mixed crystals labeled A, B and C are characterized by three strong lines at 16.21; 8.43 and 3.28 Å, two moderate lines at 8.06 and 3.51 Å and other weak lines in the X-ray diffraction spectrum.
Das im Vergleichsbeispiel 4 aufgeführte 2,9-Dimethylchinacridon (siehe auch Formel (I) weiter oben) ist das C.I. Pigment Red 122 (®Hostaperm-Rosa E).The 2,9-dimethylquinacridone listed in Comparative Example 4 (see also formula (I) above) is the CI Pigment Red 122 (®Hostaperm-Rosa E).
Die nachstehenden Beispiele dienen zur Erläuterung der Erfindung, ohne sie darauf zu beschränken. Die angegebenen Teile bedeuten Gewichtsteile.The following examples serve to illustrate the invention without restricting it. The parts given are parts by weight.
5 Teile Mischkristallpigment des Typs A wurden mittels eines Kneters der Firma Werner & Pfleiderer (Stuttgart) 60 Minuten in 95 Teilen Tonerbindemittel(®Dialec S 309 der Firma Diamond Shamrock (Styrol-Methacryl-Copolymer)) dispergiert. Anschließend wurde auf der Laboruniversalmühle 100 LU (Firma Alpine, Augsburg) gemahlen und dann auf dem Zentrifugalsichter 100 MZR (Firma Alpine) klassifiziert.5 parts of mixed crystal pigment type A were dispersed for 60 minutes in 95 parts of toner binder (®Dialec S 309 from Diamond Shamrock (styrene-methacrylic copolymer)) 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).
Die gewünschte Teilchenfraktion wurde mit einem Carrier aus mit Styrol-Methacrylat 90 : 10 beschichteten Magnetit-Teilchen der Größe 50 bis 200 µm des Typs 90 µm Xerographic Carrier der Firma Plasma Materials Inc. aktiviert.The desired particle fraction was activated with a carrier composed of magnetite particles of size 50 to 200 μm of the type 90 μm Xerographic Carrier from Plasma Materials Inc., coated with styrene methacrylate 90:10.
Die Messung erfolgt an einem üblichen Q/M-Meßstand [vgl. hierzu J.H. Dessauer, H.E. Clark "Xerography and related Processes", Focal Press, N.Y. 1965, Seite 289]; durch Verwenden eines Siebes mit einer Maschenweite von 25 µm (508 Mesh per inch), Fa. Gebrüder Kufferath, Düren, wurde sichergestellt, daß bei den Tonerausblasungen kein Carrier mitgerissen werden kann.The measurement is carried out on a standard Q / M measuring stand [cf. J.H. Dessauer, H.E. Clark "Xerography and related Processes", Focal Press, N.Y. 1965, page 289]; by using a sieve with a mesh size of 25 µm (508 mesh per inch), from Gebrüder Kufferath, Düren, it was ensured that no carrier can be entrained in the toner blowouts.
Der Q/M-Wert wurde zu -31,1 µC/g bestimmt.The Q / M value was determined to be -31.1 µC / g.
Es wurde, wie in Beispiel 1 beschrieben, gearbeitet mit dem Unterschied, daß statt des Mischkristallpigmentes A das Mischkristallpigment B eingesetzt wurde.The procedure was as described in Example 1, with the difference that the mixed crystal pigment B was used instead of the mixed crystal pigment A.
Der Q/M-Wert wurde zu -36,8 µC/g bestimmt.The Q / M value was determined to be -36.8 µC / g.
Es wurde, wie in Beispiel 1 beschrieben, gearbeitet mit dem Unterschied, daß statt des Mischkristallpigmentes A das Mischkristallpigment C eingesetzt wurde.The procedure was as described in Example 1, with the difference that the mixed crystal pigment C was used instead of the mixed crystal pigment A.
Der Q/M-Wert wurde zu -40,5 µC/g bestimmt.The Q / M value was determined to be -40.5 μC / g.
Es wurde, wie in Beispiel 1 beschrieben, gearbeitet mit dem Unterschied, daß statt des Mischkristallpigments die Komponente der genannten Formel I (C.I. Pigment Red 122) eingesetzt wurde.The procedure was as described in Example 1, with the difference that instead of the mixed crystal pigment, the component of the formula I mentioned (C.I. Pigment Red 122) was used.
Der Q/M-Wert wurde zu -23,0 µC/g bestimmt.The Q / M value was determined to be -23.0 µC / g.
Claims (3)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3618214 | 1986-05-30 | ||
DE19863618214 DE3618214A1 (en) | 1986-05-30 | 1986-05-30 | IMPROVED MAGNETIC COLOR FOR ELECTROPHOTOGRAPHIC RECORDING METHODS |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0247576A2 true EP0247576A2 (en) | 1987-12-02 |
EP0247576A3 EP0247576A3 (en) | 1989-06-28 |
EP0247576B1 EP0247576B1 (en) | 1993-01-20 |
Family
ID=6301944
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87107650A Expired - Lifetime EP0247576B1 (en) | 1986-05-30 | 1987-05-26 | Magenta dye for electrophotographic recording processes |
Country Status (4)
Country | Link |
---|---|
US (1) | US4777105A (en) |
EP (1) | EP0247576B1 (en) |
JP (1) | JP2610618B2 (en) |
DE (2) | DE3618214A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0362703A2 (en) * | 1988-10-01 | 1990-04-11 | Hoechst Aktiengesellschaft | Chinaoridone with selectively imparted triboelectric effects |
EP0827039A1 (en) * | 1996-09-02 | 1998-03-04 | Canon Kabushiki Kaisha | Magenta toner for developing electrostatic images and process for production thereof |
EP0890883A1 (en) * | 1997-07-08 | 1999-01-13 | Canon Kabushiki Kaisha | Magenta toner for developing electrostatic images and process for production thereof |
US6251553B1 (en) | 1998-11-26 | 2001-06-26 | Clariant Gmbh | Use of mixed-crystal pigments of the quinacridone series in electrophotographic toners and developers, powder coatings and inkjet inks |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01303448A (en) * | 1988-06-01 | 1989-12-07 | Tomoegawa Paper Co Ltd | Positively chargeable magenta toner |
JPH01303449A (en) * | 1988-06-01 | 1989-12-07 | Tomoegawa Paper Co Ltd | Positively chargeable magenta toner |
US5275905A (en) * | 1991-05-28 | 1994-01-04 | Xerox Corporation | Magenta toner compositions |
US5707769A (en) * | 1994-07-21 | 1998-01-13 | Minolta Co., Ltd. | Yellow toner and magenta toner and image forming apparatus and method using same |
DE69725938T2 (en) * | 1996-08-02 | 2004-09-02 | Canon K.K. | Magenta toner, manufacturing process therefor, and color imaging process herewith |
DE19733642A1 (en) * | 1997-08-04 | 1999-02-11 | Clariant Gmbh | Mixed crystal pigments of the quinacridone series |
DE19901060A1 (en) * | 1999-01-14 | 2000-07-20 | Clariant Gmbh | Quinacridone mixed crystal pigments of the gamma phase |
JP4387613B2 (en) | 2000-07-10 | 2009-12-16 | キヤノン株式会社 | Magenta toner |
US6667140B2 (en) | 2000-09-01 | 2003-12-23 | Canon Kabushiki Kaisha | Toner and image forming method |
US6855471B2 (en) | 2002-01-15 | 2005-02-15 | Canon Kabushiki Kaisha | Toner and image-forming method |
DE60310456T2 (en) | 2002-01-18 | 2007-09-27 | Canon K.K. | Color toner and multi-color image forming method |
CN1333020C (en) | 2002-11-01 | 2007-08-22 | 精工爱普生株式会社 | Ink set, recording method, recording device, recording system, and recorded object |
JP4492069B2 (en) * | 2003-09-11 | 2010-06-30 | 富士ゼロックス株式会社 | Toner for developing electrostatic image, image forming apparatus, image forming method, and method for producing toner for developing electrostatic image |
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US4057426A (en) * | 1975-09-29 | 1977-11-08 | Xerox Corporation | Magenta toner with a coated carrier |
GB2059618A (en) * | 1979-10-01 | 1981-04-23 | Xerox Corp | Developer for electrostatic latent images |
EP0046398A2 (en) * | 1980-08-18 | 1982-02-24 | Xerox Corporation | Electrostatographic developer composition |
JPS58189652A (en) * | 1982-04-28 | 1983-11-05 | Canon Inc | Magnetic color toner |
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DE1217333B (en) * | 1959-04-29 | 1966-05-26 | Ici Ltd | Color pigments |
GB896916A (en) * | 1959-04-29 | 1962-05-23 | Ici Ltd | New pigments and pigment compositions of the quinacridone series |
US3160510A (en) * | 1960-04-25 | 1964-12-08 | Du Pont | Quinacridone pigment compositions |
US3804619A (en) * | 1972-12-18 | 1974-04-16 | Xerox Corp | Color electrophotographic imaging process |
US3909259A (en) * | 1973-12-17 | 1975-09-30 | Xerox Corp | Color electrophotographic imaging process utilizing specific carrier-toner combinations |
US4698289A (en) * | 1984-08-15 | 1987-10-06 | Halomet Inc. | Process for making ferrite spherical particulate toner core from raw fly ash |
-
1986
- 1986-05-30 DE DE19863618214 patent/DE3618214A1/en not_active Withdrawn
-
1987
- 1987-05-26 EP EP87107650A patent/EP0247576B1/en not_active Expired - Lifetime
- 1987-05-26 DE DE8787107650T patent/DE3783654D1/en not_active Expired - Lifetime
- 1987-05-27 JP JP62128508A patent/JP2610618B2/en not_active Expired - Lifetime
- 1987-05-28 US US07/055,347 patent/US4777105A/en not_active Expired - Lifetime
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US4057426A (en) * | 1975-09-29 | 1977-11-08 | Xerox Corporation | Magenta toner with a coated carrier |
GB2059618A (en) * | 1979-10-01 | 1981-04-23 | Xerox Corp | Developer for electrostatic latent images |
EP0046398A2 (en) * | 1980-08-18 | 1982-02-24 | Xerox Corporation | Electrostatographic developer composition |
JPS58189652A (en) * | 1982-04-28 | 1983-11-05 | Canon Inc | Magnetic color toner |
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CHEMICAL ABSTRACTS, Band 101, Nr. 23, 3. Dezember 1984, Seiten 540-541, Zusammenfassung Nr. 219719d, Columbus, Ohio, US; & JP-A-58 189 652 (CANON K.K.) 05-11-1983 * |
DYES AND PIGMENTS, Band 9, 1988, Seiten 119-127, Elsevier Applied Science Publishers Ltd, GB; H.-T. MACHOLDT et al.: "Charging effects of organic pigments in electrophotographic toners" * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0362703A2 (en) * | 1988-10-01 | 1990-04-11 | Hoechst Aktiengesellschaft | Chinaoridone with selectively imparted triboelectric effects |
EP0362703A3 (en) * | 1988-10-01 | 1990-10-24 | Hoechst Aktiengesellschaft | Chinaoridone with selectively imparted triboelectric effects |
EP0827039A1 (en) * | 1996-09-02 | 1998-03-04 | Canon Kabushiki Kaisha | Magenta toner for developing electrostatic images and process for production thereof |
EP0890883A1 (en) * | 1997-07-08 | 1999-01-13 | Canon Kabushiki Kaisha | Magenta toner for developing electrostatic images and process for production thereof |
US6251553B1 (en) | 1998-11-26 | 2001-06-26 | Clariant Gmbh | Use of mixed-crystal pigments of the quinacridone series in electrophotographic toners and developers, powder coatings and inkjet inks |
Also Published As
Publication number | Publication date |
---|---|
JPS62291669A (en) | 1987-12-18 |
DE3783654D1 (en) | 1993-03-04 |
DE3618214A1 (en) | 1987-12-03 |
JP2610618B2 (en) | 1997-05-14 |
US4777105A (en) | 1988-10-11 |
EP0247576B1 (en) | 1993-01-20 |
EP0247576A3 (en) | 1989-06-28 |
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