DE19804899A1 - Pigment Yellow 155 used in electrophotographic toner or developer, powder - Google Patents

Abstract

The disazo pigment C.I. Pigment Yellow 155 (I) is used as colorant in electrophotographic toners and developers, powders and powder lacquers, electret materials, color filter and ink jet inks. The disazo pigment C.I. Pigment Yellow 155 is 1,4-bis( alpha -(2,5-dimethoxycarbonylphenylazo) -acetoacetylamino)benzene of formula (I): Independent claims are also included for (a) electrophotographic toners or developers; (b) powders or powder lacquers; (c) the production of electrophotographic toners or developers, powders or powder lacquers; and (d) ink jet and hot melt ink jet inks.

Description

The present invention relates to an electrophotographic toner and Developers, powder coatings and ink jet inks based on C.I. Pigment Yellow 155 as a colorant.

In electrophotographic recording method is on a photoconductor generated "latent charge image". This "latent charge image" is applied by applying developed an electrostatically charged toner, which then, for example, on Transfer paper, textiles, films or plastic and, for example by means of Pressure, radiation, heat or solvent exposure is fixed. Typical toners are one- or two-component powder toners (also one- or two-component In addition, special toners, such as. B. magnetic or Liquid toner and polymerization toner, in use (L.B. "Electrophotography and Development Physics"; Springer Series in Electrophysics 14; Springer-Verlag, 2nd edition, 1992).

One measure of toner quality is its specific charge q / m (charge per Mass unit). In addition to sign and amount of electrostatic charge is present in particular the fast achievement of the desired charge height and the constancy this charge over a longer activation period is a crucial Quality criterion. Moreover, the insensitivity of the toner is against Climate influences, such as temperature and humidity, another important Suitability criterion.

Both positive and negatively chargeable toners find use in Photocopiers, laser printers, LED (light emitting diodes), LCS (Liquid crystal shutter) printers or other digital printers on electrophotographic Basis, depending on the process and device type.  

To electrophotographic toner or developer with either positive or to receive negative charge, charge control agents are often added. When Coloring components typically become organic in colored toners Color pigments used. Color pigments have to dyes because of their Insolubility in the application medium significant advantages, such. B. better Thermostability and lightfastness.

Building on the principle of "subtractive color mixing" can with the help of the three Primary colors yellow, cyan and magenta the whole for the human eye visible color spectrum can be reproduced. Only if the respective primary color meets the well-defined color requirements, is an exact Color reproduction possible. Otherwise, some shades may not play and the color contrast is not sufficient.

For full color toners, the three toners of yellow, cyan, and magenta must be next to the exactly defined color requirements also with regard to their triboelectric Properties must be exactly matched, as they successively in the same Device to be transmitted.

Colorants are known to be the triboelectric charge of toners partially sustainable (H.-T. Macholdt, A. Sieber, Dyes & Pigments 9 (1988), 119-127). Because of the different triboelectric effects of colorants and the resulting sometimes very pronounced Influence on the toner chargeability, it is not possible to colorants in one once created toner base recipe easy to add. Rather, it can necessary for each colorant to create its own recipe, for which type and quantity of the required charge control agent are specially tailored become. This procedure is correspondingly complicated and then comes along Color toners for process color in addition to those already described above Difficulties.

Moreover, it is important in practice that the colorants have a high Have thermal stability and a good dispersibility. typical  Incorporation temperatures for colorants in the toner resins are in use kneaders or extruders between 100 ° C and 200 ° C. Accordingly, one is Thermal stability of 200 ° C, better 250 ° C, of great advantage. It is also important, that the thermal stability over a longer period of time (about 30 minutes) and in different binder systems is guaranteed. Typical toner binders are polymerization, polyaddition and polycondensation resins, such as styrene, Styrene acrylate, styrene butadiene, acrylate, polyester, phenolic epoxy resins, Polysulfones, polyurethanes, alone or in combination, the others Ingredients such as charge control agents, waxes or flow aids can or can be added afterwards.

Basically, there is a need for a yellow pigment, the highest possible Transparency, greenness, good dispersibility and as neutral as possible possesses triboelectric intrinsic effect.

Under a neutral triboelectric intrinsic effect is understood that the Pigment should have no effect on the electrostatic self - charging of the Resin shows.

The transparency is of central importance, because when full color copying or Print the colors yellow, cyan and magenta over each other copied or printed with the order of colors depending on the device. Is now an above lying color is not transparent enough, so the underlying can not shine through sufficiently and the color reproduction is distorted. When copying or printing on overhead transparencies, transparency is even more significant here lack of transparency even one color the entire image projection gray to appear.

The present invention was based on the object of a cheapest possible, transparent and greenish Azogelb colorant with as neutral as possible triboelectric effect, good dispersibility and high thermal stability for the application in electrophotographic toners and developers, powders and Powder coatings, ink-jet inks and electret materials,  wherein the colorant should not be based on dichlorobenzidine, and none Halo, nitro, or amino groups should carry as substituents to ecotoxicologically as harmless as possible. In addition, that should Colorants should be free of additives, d. H. from the coloring component consist. The addition of additives is often necessary for colorants to optimal coloristic (color strength, transparency, etc.) and application technology (Dispersibility) properties. For electrophotographic toner, especially for liquid toners and polymerization toners, as well as ink-jet inks However, such additives disadvantageous u. a. because of their electrostatic Intrinsic effect and their detachability.

The object has surprisingly been achieved by azo pigment characterized below. The present invention relates to the use of an azo pigment of the formula (1)

as colorants in electrophotographic toners and developers, powders and Powder coatings, electret materials and in ink-jet inks.

A pigment having the structure according to formula (1) is already known and among the Designation C.I. Pigment Yellow 155 commercially. The preparation of C.I. pigment Yellow 155 is known and described, for example, in W. Herbst, K. Hunger "Industrial Organic Pigments", Verlag Chemie Weinheim 1993 "as well as in it  cited literature. New and surprising is that in itself for polyester unsuitable pigment (W. Herbst, K. Hunger "Industrial Organic Pigments", Verlag Chemie, Weinheim 1995, page 272) also in toner resins based on polyester very good properties, such as very good dispersibility and very high Transparency.

In addition, the pigment is surprisingly characterized by a neutral electrostatic inherent effect.

Moreover, it is of great advantage that the pigment has a thermal stability of greater than 300 ° C has.

Conventional azo pigments have a distinct negative electrostatic Effect (JA-OS 62-71 966, P. Gregory "High Technology Applications of Organic Colorants ", Plenum Press, New York 1991, pp 99-102.) In EP-A-0 359 123 as described by the addition of suitable ammonium, immonium, Phosphonium, Arsonium or Stiboniumverbindungen the strong negative Tribo effect can be partially or completely canceled, the said Additives either in the coupling reaction, during laking or during the Pigmentfinishs must be added.

Moreover, it has been described that by special masterbatches, i. H. highly concentrated pigment dispersions in selected resins, the triboelectric effect of pigments can be pushed back (V. Schlösser et al., Society of Imaging Science and Technology, 11th Congress on Advances in Non-Impact Printing Technologies, Hilton Head, SC, Oct. 29-November 11 1995, Proceedings pp 110-112). In addition to the additional step has this Method has the disadvantage that a tailor-made for each toner resin Masterbatch must be used, which is very costly and commercial is unprofitable. If one uses only the masterbatch based on the specified standard resin, the toner system is by foreign resin contaminated.

By using the azo pigment of the invention, the disadvantages avoided such additional steps.  

Apart from electrophotographic toners and developers, a triboelectric intrinsic effect of a pigment can also lead to an improvement in the electrostatic charging of powders and paints, especially in triboelectrically or electrokinetically sprayed powder coatings, as used for the surface coating of articles of, for example, metal, wood, plastic, glass, ceramics, Concrete, textile material, paper or rubber are used. The powder coating technology is used, for example, for painting small objects such as garden furniture, camping articles, household appliances, vehicle parts, refrigerators and shelves, as well as for painting intricately shaped workpieces. The powder coating or powder generally receives its electrostatic charge by one of the following two methods:

• a) In the corona process, the powder coating or the powder on a charged corona passed and charged,
• b) in the triboelectric or electrokinetic process is based on the principle of Frictional electricity made use of.

The powder coating or the powder receive an electrostatic in the sprayer Charging, the charge of the friction partner, generally a hose or spray tube, for example of polytetrafluoroethylene, is opposite. Also a combination of both methods is possible.

As powder coating resins are typically epoxy resins, carboxyl and hydroxyl-containing polyester resins, polyurethane and acrylic resins together with used the usual hardeners. Also find combinations of resins Use. For example, epoxy resins are often used in combination with carboxyl and hydroxyl polyester resins used. Typical hardener components for epoxy resins are, for example, acid anhydrides, Imidazoles and dicyandiamide and their derivatives. For hydroxyl-containing Polyester resins are typical hardener components such as acid anhydride, capped isocyanates, bisacylurethanes, phenolic resins and melamine resins. For carboxyl group-containing polyester resins are typical hardener components for example, triglycidyl isocyanurates or epoxy resins. Come in acrylic resins  as typical hardener components, for example, oxazolines, isocyanates, Triglycidyl isocyanurates or dicarboxylic acids for use.

The disadvantage of insufficient charging is especially in triboelectric or electrokinetically sprayed powders and powder coatings based on Polyester resins, in particular carboxyl-containing polyesters, or on the Basis of so-called mixed powders, also called hybrid powder produced have been observed. Mixed powders are powder coatings whose Resin base from a combination of epoxy resin and carboxyl group-containing Polyester resin exists. The mixed powders form the basis for the practice in the most commonly represented powder coatings. Insufficient charge of the above Powder and powder coatings causes the deposition rate and Umgriff on to coating are insufficient, it being known that under Circumstances also the triboelectric intrinsic effect of a pigment for the loss the chargeability of a per se suitable resin system may be responsible (H-T., Macholdt, "charge control agent as a concept for the triboelectric Aufladung "; EPS Series" Praxis Forum, Fachbroschüre Oberflächentechnik 27/91 "pages 102-111; Technik + Kommunikations Verlags GmbH, Berlin (1991)). The term "wraparound" is a measure of the extent to which a powder or powder coating on the workpiece to be coated on backsides, cavities, and columns especially on inner edges and corners deposits.

In addition, a changed triboelectric intrinsic effect of a pigment for improving the electret properties of colored (pigmented) Lead electret materials, with typical electret materials on polyolefins, halogenated polyolefins, polyacrylates, polyacrylonitriles, polystyrenes or Fluoropolymers such as polyethylene, polypropylene, polytetrafluoroethylene and perfluorinated ethylene and propylene, or on polyesters, polycarbonates, Polyamides, polyimides, polyether ketones, on polyarylene sulfides, in particular Polyphenylene sulfides, on polyacetals, cellulose esters, polyalkylene terephthalates as well as mixtures thereof are based. Electret materials have many Field of application and can get their charge by corona or Triboaufladung (Ref: G. M. Sessler, "Electrets", Topics in Applied Physics, Vol. New York, Heidelberg, 2nd ed., 1987).  

Furthermore, a changed triboelectric intrinsic effect of a pigment to lead to improved separation behavior of colored (pigmented) polymers, which are separated by electrostatic separation methods (Y. Higashiyau, J. of Electrostatics, 30, pp. 203-212, 1993; and yes. Cross "Electrostatics Principles, Problems and Applications ", Adam Hilger, Bristol, 1987, especially chapter 5.3 "Electrostatic Separation" and the literature cited therein). Accordingly is the triboelectric intrinsic effect of pigments also for the Plastic mass staining of importance. Likewise, the triboelectric Own effect in process / processing steps where it is too intense Frictional contact comes, of importance, such as. B. spinning processes, Foil drawing processes or further shaping processes.

The particular advantage of the CI Pigment Yellow 155 according to the invention is particularly evident in comparison to CI Pigment Yellow 180 of the formula

C.I. Pigment Yellow 180 is used in many yellow toners as a colorant and accordingly can be used as a standard for azo pigments for the toner industry not based on dichlorobenzidine, no halogen, Nitro or amino groups carry and also no heavy metal ions in the structure contain.

Thus, C.I. Pigment Yellow 155 z. B. a pronounced neutral triboelectric intrinsic effect, while C.I. Pigment Yellow 180 a recognizable shows triboelectric intrinsic effect; d. H. a toner with z. B. 5% P.Y. 155 shows electrostatically almost the same chargeability as the pure resin system without Pigment, whereas P.Y. 180 the electrostatic chargeability recognizable changed.  

In addition, P.Y. 155 more transparent or more opaque as needed to adjust.

In addition, P.Y. 155 colouristic by mixing with other pigments be nuanced.

Frequently, the task of hue in electrophotographic color toners, to nuke triboelectrically sprayable powder coatings or in ink-jet inks and to adapt to the application-specific requirements. This is possible in particular organic colored pigments, inorganic pigments and dyes on.

Preference is given to organic colored pigments in mixtures with P.Y. 155 in Concentrations between 0.01 and 50 wt .-%, preferably between 0.1 and 25 wt .-% and particularly preferably between 0.1% and 15 wt .-%, based on P.Y. 155, used to shade the color. Here, the Organic colored pigments from the group of azo pigments or polycyclic Be pigments.

In a particularly preferred variant, a greenish yellow P.Y. 155 by reddish yellow pigment types such as P.Y. 139, P.Y. 83 P.Y. 181, P.Y. 191, P.Y. 75, P.Y. 180 or P.Y. 97, in the sense of a 2-component Mix nuanced. Mixtures of several components are also suitable. Larger color steps are for example when using Orange pigments such as P.O. 62, P.O. 36, P.O. 34, P.O. 13, P.O. 43 or P.O. 5 or red / magenta pigments such as P.R. 122, P.V. 19, P.R. 57, P.R. 48, P.R. 146 P.R. 185, P.R. 184, P.R. 48 or P.V. 19 possible. A fine adjustment of the shade of P.Y. 155 is exemplified by mixtures with P.Y. 185 and P.Y. 180 possible, from an ecological point of view additionally have the advantage that all Components are chlorine-free.

The mixtures may be in the form of the powders, by blending presscake, spray-dried cake and by dispersing (extrusion, kneading, Roll mill method, bead mills, Ultraturrax) in the presence of a support material in solid or liquid form (aqueous and non-aqueous based inks) as well by flushing in the presence of a carrier material.  

In particular, to increase the brilliance and sometimes at the same time only nuancing the color, mixtures with organic dyes are suitable. As such, preferred are:
water-soluble dyes, such as. As Direct, Reactive and Acid Dyes, as well as solvent-soluble dyes such. Solvent Dyes, Disperse Dyes and Vat Dyes. As individual examples may be mentioned: CI Reactive Yellow 37, Acid Yellow 23, Reactive Red 23, 180, Acid Red 52, Reactive Blue 19, 21, Acid Blue 9, Direct Blue 199, Solvent Yellow 14, 16, 25, 56, 64, 79, 81, 82, 83: 1, 93, 98, 133, 162, 174, Solvent Red 8, 19, 24, 49, 89, 90, 91, 109, 118, 119, 122, 127, 135, 160, 195, 212, 215, Solvent Blue 44, 45, Solvent Orange 60, 63, Disperse Yellow 64, Vat Red 41.

Also, dyes and pigments with fluorescent properties, such as ® luminol (Riedel-de Haen), in concentrations of 0.0001 to 30 wt .-%, preferably from 0.001 to 15 wt .-%, most preferably between 0.001 and 5%, based on P.Y. 155, are used, for example make forgery-proof toner.

Inorganic pigments, such as TiO ₂ or BaSO ₄ , are used in bleaching mixtures. Furthermore, mixtures of PY 155 with effect pigments, such as pearlescent pigments, Fe ₂ O ₃ pigments (®Paliochrome) and pigments based on cholesteric polymers are suitable.

The invention used P.Y. 155 can also be positive with numerous or negatively controlling charge control agents, combined to good to achieve performance chargeability.

Suitable charge control agents are, for example: triphenylmethane; Ammonium and immonium compounds; iminium; fluorinated ammonium and immonium compounds; biscationic acid amides; polymeric ammonium compounds; diallylammonium compounds; Arylsulfid- derivatives; Phenol derivatives; Phosphonium compounds and fluorinated phosphonium compounds; Calix (n) arenes; ring-linked oligosaccharides (Cyclodextrins) and their derivatives, especially borate derivatives,  Interpolyelectrolyte Complexes (IPECs); Polyester salts; Metal complex compounds, in particular salicylate-metal and salicylate-nonmetal complexes, α-Hy droxycarboxylic acid metal and nonmetal complexes; benzoimidazolones; azine, Thiazines or oxazines, which are listed in the Color Index as Pigments, Solvent Dyes, Basic Dyes or Acid Dyes are listed.

Particularly preferred are the following charge control agents, the individually or in combination with each other with the azo pigment according to the invention can be combined.

Triarylmethane derivatives such as:
Color Index Pigment Blue 1, 1: 2, 2, 3, 8, 9, 9: 1, 10, 10: 1, 11, 12, 14, 18, 19, 24, 53, 56, 57, 58, 59, 61, 62, 67 or, for example, Color Index Solvent Blue 2, 3, 4, 5, 6, 23, 43, 54, 66, 71, 72, 81, 124, 125 and those in the Color Index under Acid Blue and Basic Dye listed triarylmethane compounds, provided that they are suitable in terms of their temperature stability and processability, such as Color Index Basic Blue 1, 2, 5, 7, 8, 11, 15, 18, 20, 23, 26, 36, 55, 56, 77th , 81, 83, 88, 89, Color Index Basic Green 1, 3, 4, 9, 10, again using Color Index Solvent Blue 125, 66 and 124.

Especially suitable is Color Index Solvent Blue 124 in the form of its highly crystalline sulfate or trichloro-triphenylmethyltetrachloroaluminate.

Very particular preference is given to metal complexes with the CAS numbers 84179-66-8 (Chromazo complex), 115 706-73-5 (iron azo complex), 31 714-55-3 (Chromoazo complex), 84 030-55-7 (chromium salicylate complex), 42 40 540-3 (Chromsalicylatkomplex) and the quaternary ammonium compound CAS-No. 11681046-9.

Examples of suitable for the production of electret fibers Charge control agents of the triphenylmethane series are those disclosed in DE-A-19 19 724 and DE-A-16 44 619.  

Also suitable are triphenylmethanes as described in US Pat. No. 5,051,585, especially those of the formula (2)

wherein
R ¹ and R ^{3 are the} same or different and -NH ₂ , a mono- and dialkylamino whose alkyl groups have 1 to 4, preferably 1 or 2, C atoms, a mono- or di-omega-hydroxyalkylamino group whose alkyl groups 2 to 4, preferably 2, C atoms have an optionally N-alkyl-substituted phenyl or phenalkylamino whose alkyl has 1 to 4, preferably 1 or 2, C atoms whose phenalkyl group in the aliphatic bridge 1 to 4, preferably 1 or 2 , C atoms, and whose phenyl nucleus can carry one or two of the following substituents: alkyl having 1 or 2 C atoms, alkoxy having 1 or 2 C atoms and can carry the sulfonic acid group mean
R ^{2 is} hydrogen or has one of the meanings given for R ¹ and R ³ ,
R ⁴ and R ^{5 are} hydrogen, halogen, preferably chlorine, or a sulfonic acid group or R ^{4 together} with R ⁵ forms a fused-on phenyl ring,
R ⁶ , R ⁷ , R ⁹ and R ^{10 are} each hydrogen or an alkyl radical having 1 or 2 C atoms, preferably methyl, and
R ^{8 is} hydrogen or halogen, preferably chlorine, and
X⁻ represents a stoichiometric equivalent of an anion, in particular a chloride, sulfate, molybdate, phosphomolybdate or borate anion.

Particular preference is given to a charge control agent of the formula (2) in which R ¹ and R ^{3 are} phenylamino groups, R ^{2 is} an m-methylphenylamino group and the radicals R ⁴ to R ^{10 are} all hydrogen.

Also suitable are ammonium and immonium compounds, as described in US-A-5,015,676.

Also suitable are fluorinated ammonium and immonium compounds as described in US Pat. No. 5,069,994, especially those of the formula (3)

wherein
R ¹³ perfluorinated alkyl having 5 to 11 C atoms,
R ²³ , R ³³ and R ^{43 are the} same or different and are alkyl having 1 to 5, preferably 1 to 2, C atoms and
Y⁻ is a stoichiometric equivalent of an anion, preferably a tetrafluoroborate or tetraphenylborate anion.

Preferably means
R ¹³ perfluorinated alkyl having 5 to 11 C atoms,
R ²³ and R ^{33 are} ethyl and
R ⁴³ methyl.

Also suitable are biscationic acid amides, as described in WO 91/10172, in particular those of the formula (4)

wherein
R ¹⁴ , R ²⁴ and R ^{34 are} identical or different alkyl radicals having 1 to 5 C atoms, preferably methyl,
n is an integer from 2 to 5, and
Z⁻ is a stoichiometric equivalent of an anion, preferably a tetraphenylborate anion.

Also suitable are diallylammonium compounds, as described in DE-A-41 42 541, in particular those of the formula (5)

wherein
R ¹⁵ and R ^{25 are} identical or different alkyl groups having 1 to 5, preferably 1 or 2, C atoms, but in particular are methyl and A⁻ is a stoichiometric equivalent of an anion, preferably represents a tetraphenylborate anion, and the from these obtainable polymeric ammonium compounds of the formula (6), as described in DE-A-40 29 652 or DE-A-41 03 610,

wherein n has a value of molecular weights of 5,000 to 500,000 g / mol equivalent. However, compounds of the formula (6) are particularly preferred Molecular weights from 40,000 to 400,000 g / mol.

Also suitable are aryl sulfide derivatives as described in DE-A-40 31 705, in particular those of the formula (7)

wherein
R ¹⁷ , R ²⁷ , R ³⁷ and R ^{47 are} identical or different alkyl groups having 1 to 5, preferably 2 or 3, C atoms, and
R ^{57 is} one of the divalent radicals -S-, -SS-, -SO- or -SO ₂ -.

For example, R ¹⁷ to R ^{47 are} propyl groups and R ^{57 is} the group -SS-.

Also suitable are phenol derivatives as described in EP-A-0 258 651, in particular those of the formula (8)

wherein
R ¹⁸ and R ^{38 are} alkyl or alkenyl groups having 1 to 5, preferably 1 to 3, carbon atoms, and R ²⁸ and R ^{48 are} hydrogen or alkyl having 1 to 3, preferably methyl.

Examples which may be mentioned are the compounds in which R ¹⁸ to R ^{48 are} methyl groups or in which R ²⁸ and R ^{48 are} hydrogen and R ¹⁸ and R ^{38 are} the group -CH ₂ -CH = CH ₂ .

Also suitable are phosphonium compounds and fluorinated phosphonium compounds as described in US Pat. No. 5,021,473 and in US Pat. No. 5,147,748, especially those of the formulas (9)

wherein
R ¹⁹ , R ²⁹ , R ³⁹ and R ^{49 are} identical or different alkyl groups having 1 to 8, preferably 3 to 6, carbon atoms, and E ^{θ is} a stoichiometric equivalent of an anion, preferably a halide anion;
and (10)

wherein
R ^{110 is} a highly fluorinated alkyl radical having 5 to 15, preferably 6 to 10, carbon atoms,
R ²¹⁰ , R ³¹⁰ and R ^{410 are} alkyl of 3 to 10 carbon atoms or phenyl.

As an example of a compound of formula (9) may be mentioned tetrabutyl phosphonium bromide, as examples of compounds of formula (10) may be mentioned the compounds with R ¹¹⁰ = C ₈ F ₁₇ -CH ₂ -CH ₂ -, R ²¹⁰ = R ³¹⁰ = R ⁴¹⁰ = phenyl and E ^θ = PF ₆ ^⊖ or the tetraphenylborate anion.

Also suitable are calix (n) arenes as described in EP-A-0 385 580 and as described in EP-A-0 516 434, in particular those of the formula (11a) and (11b) (Angew. Chemie (1993), 195, 1258)

wherein
n is a number from 3 to 12 and
R is hydrogen, halogen, preferably chlorine, straight-chain or branched alkyl having 1 to 12 C atoms, aralkyl, z. B. benzyl or phenethyl, -NO ₂ , -NH ₂ or NHR ¹¹¹ , wherein R ^{111 is} alkyl having 1 to 8 carbon atoms, optionally C ₁ -C ₄ -alkyl-substituted phenyl or -Si (CH ₃ ) ₃ .

Also suitable are metal complex compounds, such as chromium, cobalt, iron, zinc or aluminum azo complexes or chromium, cobalt, iron, zinc or aluminum-salicylic or boric acid complexes of the formulas (12), (13) and (14)

wherein
M is a 2- or 3-valent metal atom, preferably chromium, cobalt, iron, zinc or aluminum, or else a non-metal such as boron or Si,
Y 'and Z' for divalent aromatic rings, preferably of the formulas

and m is one of the numbers 1 or 2;

wherein
M 'is a 2- or 3-valent metal atom, preferably chromium, cobalt, iron,
R ^{113 is} hydrogen, halogen, preferably Cl, nitro or amidosulfonyl,
R ²¹³ hydrogen or nitro,
R ^{313 is} hydrogen, the sulfonic acid group, -CO-NH-R ⁴¹³ , wherein R ^{413 is} phenyl, alkyl having 1 to 5 carbon atoms, which is optionally substituted by a mono-, di- or trialkylamino group, and
G in formula (12) and (13) is in each case a counterion which produces the neutrality of the complex, preferably one or more protons, one or more alkali or ammonium ions;

wherein
M * is a bivalent metal central atom, preferably a zinc atom, R ¹¹⁴ and R ^{214 are} identical or different, straight-chain or branched alkyl groups having 1 to 8, preferably 3 to 6, C atoms, for example tert-butyl.

Such compounds are described in EP-A-0 162 632, US-A-4 908 225, EP-A-0 393 479, EP-A-0 360 617, EP-A-0 291 930, EP-A-0 280 272, EP-A-0 255 925, EP-A-0 251 326, EP-A-0 180 655, EP-A-0 141 377, US-A-4,939,061, US-A-4,623,606, US-A-4 590 141 and / or characterized by CAS numbers 31714-55-3, 104 815-18-1, 84 179-68-8, 110 941-75-8, 32 517-36-5, 38 833-00-00, 95 692-86-7, 85 414-43-3, 136 709-14-3, 135 534-82-6, 135 534-81-5, 127 800-82-2, 114 803-10-0, 114 803-08-6.

Examples of Particularly Preferred Metal Complex Compounds of Formula (13) are given in Table 1 below:

Table 1

Also suitable are benzimidazolones, as described in EP-A-0 347 695, in particular those of the formula (15)

wherein
R ¹¹⁵ is an alkyl having 1 to 5 C atoms and R ^{215 is} an alkyl having 1 to 12 C atoms and L is a stoichiometric equivalent of an anion, in particular a chloride or tetrafluoroborate anion.

As an example, the compound with R ¹¹⁵ = CH ₃ and R ²¹⁵ = C ₁₁ H _{23 may be mentioned} .

Also suitable are ring-linked oligosaccharides, as described in DE-A-44 18 842, in particular those of the formula (16)

wherein n ^{16 is} a number between 3 and 100, R ¹¹⁶ and R ²¹⁶ are OH, OR ³¹⁶ , wherein R ^{316 is} substituted or unsubstituted alkyl (C ₁ -C ₁₈ ), aryl (C ₆ -C ₁₂ ) or tosyl and X ^{16 is} CH ₂ OH or CH ₂ COR ³¹⁶ . Examples include:

n ¹⁶ = 6, R ¹¹⁶ and R ²¹⁶ = OH, X ¹⁶ = CH ₂ OH
n ¹⁶ = 7, R ¹¹⁶ and R ²¹⁶ = OH, X ¹⁶ = CH ₂ OH
n ¹⁶ = 8, R ¹¹⁶ and R ²¹⁶ = OH, X ¹⁶ = CH ₂ OH.

Also suitable are polymer salts, as described in DE-A-43 32 170, whose anionic component is a polyester consisting of the reaction product of the individual components a), b) and c) and optionally d) and optionally e), wherein

• a) a dicarboxylic acid or a reactive derivative of a dicarboxylic acid, which are free of sulfo groups,
• b) a difunctional aromatic, aliphatic or cycloaliphatic Sulfo compound whose functional groups are hydroxyl or carboxyl, or Hydroxyl and carboxyl, are  
• c) an aliphatic, cycloaliphatic or aromatic diol Polyether diol or a polycarbonate diol,
• d) a polyfunctional compound (functionality <2), whose functional Groups are hydroxyl or carboxyl, or hydroxyl and carboxyl, and
• e) is a monocarboxylic acid

and their cationic component are hydrogen atoms or metal cations.

Also suitable are cyclooligosaccharide compounds, as described for example in German Patent Application 197 11 260.9, by reacting a cyclodextrin or cyclodextrin derivative with a compound of formula

in which R ¹ and R ^{2 are} alkyl, preferably C ₁ -C ₄ -alkyl.

Also suitable are inter-polyelectrolyte complexes, as described for example in the German Patent Application 197 32 995.0 are described.

Suitable interpolyelectrolyte complexes consisting of one or more Polyanion-forming compound (s) and one or more polycations consist of forming compound (s).

Particularly suitable in this case are compounds which have a molar ratio of polymeric cationic to polymeric anionic groups from 0.9: 1.1 to 1.1: 0.9 to have.

Also suitable, especially when using P.Y. 155 in liquid toners (Handbook of Imaging Materials, 1991, Marcel Dekker, Inc. Chapter 6 Liquid Toner Technology), are surface-active, ionic compounds and so-called Metal soaps.

Particularly suitable are alkylated arylsulfonates, such as barium petronates, Calcium petronates, barium dinonylnaphthalenesulfonates (basic and neutral),  Calcium dinonylsulfonate or dodecylbenzenesulfonic acid sodium salt and Polyisobutylene succinimide (Chevron's Oloa 1200).

Also suitable are soya lecithin and N-vinylpyrrolidone polymers.

Also suitable are sodium salts of phosphated mono- and diglycerides with saturated and unsaturated substituents, AB diblock copolymers of A: Polymers of 2- (N, N) -dimethylaminoethyl methacrylate quaternized with Methyl p-toluenesulfonate, and B: poly-2-ethylhexyl methacrylate.

Further suitable, especially in liquid toners, are di- and trivalent Carboxylates, in particular aluminum tristearate, barium stearate, chromium stearate, Magnesium octrate, calcium stearate, iron naphthalite and zinc naphthalite.

Furthermore, suitable chelating charge control agents are as in EP 0 636 945 A1.

Also suitable are metallic (ionic) compounds, as in EP 0 778 501 A1.

Also suitable are phosphate metal salts as in JA 9 (1997) -106107 described.

Also suitable are azines of the following color index numbers: C.I. Solvent Black 5, 5: 1, 5: 2, 7, 31 and 50; C.I. Pigment Black 1, C.I. Basic Red 2 and C.I. basic Black 1 and 2.

Basically, C.I. Pigment Yellow 155 for combinations with positive and negative charge control agents (CCA). It is useful here Pigment concentrations of from 0.01 to 20% by weight, preferably from 0.1 to 5% by weight, to charge control agent based on the total weight of the electrophotographic toner or developer, powder or powder coating to the to set the desired polarity. A special advantage here is the fast Reaching the peak charge value and its good constancy.  

The combination of pigment and charge control agent can be postponed by physical mixing during pigment synthesis, during the Finishing process or by appropriate mounting on the pigment surface (Pigment coating).

The invention therefore also an electrophotographic toner or Developer containing a conventional toner binder, 0.1 to 60 wt .-%, preferably 0.5 to 20 wt .-%, of optionally nuanced C.I. Pigment Yellow 155, and 0 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the Total weight of the toner or developer, a charge control agent from the Class of triphenylmethanes, ammonium and immonium compounds; fluorinated Ammonium and immonium compounds; biscationic acid amides; polymeric Ammonium compounds; diallylammonium compounds; Aryl sulfide derivatives; Phenol derivatives; Phosphonium compounds and fluorinated phosphonium compounds; Calix (n) arenes; cyclodextrins; Polyester salts; Metal complex compounds; Cyclooligosaccharide Borkomplexes, Inter- Polyelectrolyte complexes; benzoimidazolones; Azines, thiazines or oxazines.

Particularly preferred are electrophotographic toners or developers which contain, as charge control agents, a compound of the formula (17)

or a compound of the above formula (3);
or a compound of the aforementioned formula (5) wherein R ¹⁵ and R ^{25 are} each methyl and A ^{θ is} a tetraphenylborate anion;
or a compound of the above formula (6) wherein R ¹⁵ and R ^{25 are} each methyl, A ^{θ is} a tetraphenylborate anion, and n has a value corresponding to molecular weights of 5,000 to 500,000 g / mol;
or a compound of the above formula (7);
or a compound of the aforementioned formula (13) wherein R ^{113 is} chloro, R ²¹³ and R ^{313 are} hydrogen, M 'is chromium, cobalt or iron and G is one or two protons;
or an above-mentioned polymer salt whose ionic component is a polyester.

The invention further relates to a powder or powder coating containing a epoxy, carboxyl or hydroxyl group-containing polyester or acrylic resin or a Combination thereof, 0.1 to 60 wt .-%, preferably 0.5 to 20 wt .-%, of optionally nuanced C.I. Pigment Yellow 155 and 0 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the total weight of the powder or powder coating, a charge control agent of the above for electrophotographic toner mentioned classes and preferred compounds.

The good suitability of the azo pigment according to the invention for the Powder coating application can be recognized by the already at 3 bar spray pressure achievable high charging current of 1.6 μA in Example 1.4.2, typically a charge current of 1 μA as a minimum requirement for a sufficient charge is seen. Along with the high charging current is a good one Separation rate of well over 50%.

The pigment used in the invention is suitably in a concentration of 0.1 to 60 wt .-%, preferably from 0.5 to 20 wt .-%, particularly preferably from 0.1 to 5.0 wt .-%, based on the Total mixture, in the binder of the respective toner (liquid or dry), developer, paint, powder coating, electret or the electrostatically separated polymer homogeneously incorporated, for example by extrusion or kneading. In this case, the pigment used according to the invention as well as the charge control agents mentioned above as dried and ground powders, dispersions or suspensions, for. In organic and / or inorganic solvents, presscake (which can be used, for example, for the so-called flushing process), spray-dried presscake, as described below, masterbatch, preparation, pasty paste, as suitable carriers, such. For example, diatomaceous earth, TiO ₂ , Al ₂ O ₃ , drawn from aqueous or non-aqueous solution compound or added in any other form. The pigment content in the presscake and masterbatch is usually between 5 and 70 wt .-%, preferably between 20 and 50 wt .-%. Moreover, the pigment used according to the invention can also be used as highly concentrated, in particular as spray-dried, presscake, in which case the pigment content is between 25 and 95% by weight, preferably between 50 and 90% by weight. The preparation of the spray-dried press cake can be done by conventional methods. For example, an aqueous, aqueous-organic or organic suspension of the pigment in a suitable apparatus at normal air inlet temperatures, preferably between 100 and 400 ° C, and customary air outlet temperatures, preferably between 50 and 200 ° C, spray-dried.

Suitable spray-drying apparatuses are, for example, direct-current dryers with centrifugal atomization, air brush, counter / DC dryer with Two-fluid nozzle atomization as well as two-point discharge of the Dry product, counter / co-current dryer with pressure nozzle atomization and Two-point discharge and devices designed for DC drying and two-nozzle Based on atomization.

The spray-dried presscake from Pigment Yellow 155 is particularly dust-free, good flowability, easy to disperse and easy to dose.

Likewise, the pigment used in the invention can in principle already be added in the preparation of the respective binders, d. H. in the course from their polymerization, polyaddition or polycondensation.

The amount of electrostatic charge of the electrophotographic toner or the powder coatings, in which the pigment according to the invention incorporated homogeneously  can not be predicted and is subject to standard test systems same conditions (same dispersion times, same particle size distribution, same particle shape) at about 20 ° C and 50% relative humidity measured. The electrostatic charging of the toner takes place by turbulence with a carrier, d. H. a standardized friction partner (3 parts by weight of toner on 97 parts by weight of carrier), on a roller table (150 revolutions per minute).

Subsequently, the electrostatic charge is applied to a standard q / m measuring stand (J.H. Dessauer, H.E. Clark, "Xerography and Related Processes", Focal Press, N.Y., 1965, page 289; J.F. Hughes, "Electrostatic Powder Coating", Research Studies Press Ltd. Letchworth, Hertfordshire, England, 1984, Chapter 2). When determining the q / m value or the tribocharging of powder coatings is the particle size of great influence, why in the obtained by sighting Toner or powder coating samples strictly for uniform particle size distribution is respected. Thus, an average particle size of 10 microns is desired for toners, while for powder coatings an average particle size of 50 microns is practicable.

The Tribover spraying of the powder (lacquer) is done with a sprayer with a Normsprührohr and a star inner rod with maximum powder throughput with a spray pressure of 3 bar. The object to be sprayed becomes suspended in a spray booth and from about 20 cm distance directly from the front sprayed without further movement of the sprayer. The respective charge of sprayed powder is then used with a "meter" to measure triboelectric charge of "powders" from Intec (Dortmund) measured. to Measurement is the measuring antenna of the meter directly into the from the sprayer exuding powder cloud held. The from the electrostatic charge of Powder coating or powder resulting current is displayed in μA. The Separation rate is then expressed in% by a differential weighing sprayed and deposited powder coating determined.

The transparency of the azo pigment according to the invention in Toner binder systems are investigated as follows: In 70 parts by weight of a Rohfirnis (consisting of 15 parts by weight of the respective toner resin and 85 parts by weight of ethyl acetate) become 30 parts by weight of the pigmented test toner  (Preparation see Example 1.4.1) stirred with a dissolver (5 min at 5000 upm).

The test toner varnish so produced is generated against one equally Standard pigment varnish with a hand coater (RK Chemical Co. Ltd, England) scrape on suitable paper (eg book printing paper). A suitable Squeegee size is z. B. K bar N 3 (= 24 microns doctor blade thickness). The paper has to better determination of transparency printed on a black bar, the Transparency differences in dL values are determined according to DIN 55 988, or according to the test specification Marketing Pigments, Hoechst AG "Visual and Colorimetric rating "dated 13.09.1990 (No. 1/1).

The residual salt content indicated in the pigment characterization describes the specific conductivity of the extract of an aqueous pigment suspension (according to Test specification Marketing Pigments, Hoechst AG No. 1/10 (2/91) "Determination of specific conductivity on the extract of an aqueous pigment suspension "), according to specified pH value is according to the test specification Marketing Pigments, Hoechst AG, 1/9 (2/91) "Determination of the pH of the Extract of a aqueous pigment suspension "determined using both methods of determination bidistilled water instead of the e-water specified in the test instructions (= deionized water) is used.

Furthermore, it was found that C.I. Pigment Yellow 155 as a colorant in ink-jet Aqueous and non-aqueous based inks, especially in such inks, which working according to the hot-melt method, is suitable. Ink-jet inks (see also: P. Gregory "Topics in Applied Chemistry: High Technology Application of Organic Colorants "Plenum Press, New York 1991, chapter Ink Jet Printing, page 175 et seq.) aqueous base could contain as cosolvents alcohols and glycols, such as. B. Diethylene glycol or N-methylpyrrolidone. Non-aqueous based inks may e.g. B. Ketones, such as methyl ethyl ketone, as a solvent. Hot-melt inks are based mostly on waxes, fatty acids, fatty alcohols or sulfonamides, which are included Room temperature and are liquid when heated, the preferred Melting range between about 60 ° C and about 130 ° C.  

The invention therefore also an ink-jet ink containing 0.01 to 50 wt .-%, preferably 0.5 to 20 wt .-%, based on the total weight of Ink, to C.I. Pigment Yellow 155.

The ink-jet inks according to the invention can be prepared by optionally nuanced C.I. Pigment Yellow 155 as a powder, as a pigment preparation, as Suspension or as press cake in the aqueous or non-aqueous medium of Ink jet ink is dispersed. The presscake can also be a highly concentrated, especially spray-dried, presscake, as described above.

In the following examples, parts are parts by weight and percent Weight.

example 1 1.1 Synthesis

a) Diazo component
In a mixture of 200 parts of water and 70 parts of HCl (31%) are added with stirring 41.8 parts Aminoterephthalsäuredimethylester and stirred for several hours.

At 10 to 15 ° C is diazotized by the addition of 35 parts of NaNO ₂ solution (40%) and stirred for 1 to 1.5 hours. The excess nitrite is destroyed with sulfamic acid. With sodium acetate solution (4N) is then adjusted to pH 4.5 with ice cooling.

b) coupling component
To 450 parts of water are added 430 parts of NaOH (33%) and dissolved under stirring, 27.6 parts of 1,4-bis (acetoacetylamino) benzene. There are added 170 parts of ice and then the coupling component is precipitated while stirring with 263 parts of glacial acetic acid.

c) coupling
The coupling suspension (b) is added in 40 minutes with stirring to the diazo component (a). It is stirred for about 2 hours and possible Diazoüberschuß coupled by adding additional coupling component.

d) Subsequently, the approach by introducing water vapor to 98 ° C. heated, stirred for 1 hour at 98 ° C and filtered off with suction. The product will washed salt-free and dried at 80 ° C in a vacuum.

The resulting 68 parts of the greenish yellow pigment P.Y. 155 will be over ground a pin mill.

1.2 Pigment Characteristics

BET surface area: 39.8 m ²

/G
Residual moisture (Ausheizbirne): 0.65%
Residual salt content: 90 μS / cm
pH: 6.5.

Thermostability: A DTA (differential thermal analysis), 3 ° C / min heating rate, closed glass ampoule, shows a thermal stability of significantly greater than 300 ° C (beginning decomposition from 310 ° C).

Particle size and shape (electron microscopic mass distribution):
Particle size and particle shape are determined by electron micrograph of the pigment powder. For this purpose, the pigment is dispersed in water for 15 minutes and then sprayed on. The images are taken at 13,000 times and 29,000 times magnification.

particle size:
d _25:50 nm; _d50: 65 nm; d _95: 83 nm.

X-ray diffraction diagram (CuK _α radiation):
2 theta (s = strong, m = medium, w = weak):

Dielectric characteristics

ε (1 KHz): 5.1
tan δ (1 KHz): 2.10 ^-2

Ω.cm: 1.10 ¹⁶

,

1.3 Transparency

In a toner resin (bisphenol A-based polyester) was improved Transparency measured (24 micron layer thickness), the pigmented test toner such prepared in Example 1.4.1.

Compared with the standard given in Comparative Example 2 is at about 50% tinting strength increased transparency by 4-5 rating units found.

Assessment of transparency differences according to test specification 1/1: 1 ≘ track, 2 ≘ something; 3 ≘ noticeable; 4 ≘ distinct; 5 ≘ essential; 6 ≘ significantly more transparent.

1.4 Electrostatic properties 1.4.1 Toner

5 parts of the pigment from Example 1.1 are homogeneously incorporated by means of a kneader within 30 minutes into 95 parts of a toner binder (polyester based on bisphenol A, ®Almacryl T500). It is then ground on a laboratory universal mill and then classified on a centrifugal separator. The desired particle fraction (4 to 25 μm) is activated with a carrier consisting of silicone-coated ferrite particles of size 50 to 200 μm (bulk density 2.75 g / cm ³ ) (FBM 96-100, Powder Techn .).

The measurement is carried out on a standard q / m measuring stand. By using a sieve with a mesh size of 25 microns ensures that no carrier is entrained in the toner blow-outs. The measurements take place at approx. 50% relative humidity. Depending on the activation time, the following q / m values [μC / g] are measured:

Activation Charge q / m [μC / g] 5 min. -14 10 minutes -14 30 min. -12 2 hours. -9 24 hours -7

1.4.2 Powder paint

5 parts of the pigment, as described in Example 1.4.1, in 95 parts of a Powder coating binder based on a TGIC polyester, z. B. ®Uralac P 5010 (DSM, Holland), homogeneously incorporated. To determine the deposition rate will be 30 g of the test powder coating with a defined pressure by a tribo pistol sprayed. By differential weighing the deposited powder coating amount can be and define a separation rate in% as well as by the Charge transfer tapping a current flow (μA).

1.4.3 Toner

5 parts of the pigment from Example 1.1 and 1 part of the charge control agent described in DE-A-39 01 153, Preparation Example 1 (highly fluorinated ammonium salt with n = 2-5) of the formula

are prepared as described in Example 1.4.1 in a polyester toner binder incorporated and measured.

Depending on the activation period, the following q / m values are measured:

Activation q / m [μC / g] 5 min. -15 10 minutes -13 30 min. -10 2 hours. -9 24 hours -9

1.4.4 Toner

5 parts of the pigment from Example 1.1 are as in Example 1.4. 1 in one Toner resin incorporated and measured, but instead of the Polyester resin a styrene-acrylate copolymer 60:40 (®Dialec S309, Fa. Diamond Shamrock) as a toner binder, and as a carrier with styrene-methacrylic copolymer (90:10) 50-200 μm Coated Magnetite Particles (90 μm Xeographic Carrier, Plasma Materials Inc., NH, USA).

Depending on the activation time, the following q / m values are measured:

Activation q / m [μC / g] 5 min. -7 10 minutes -8th 30 min. -14 2 hours. -18 24 hours -21

1.4.5 Toner

5 parts of the pigment from Example 1.1 and 1 part of the charge control agent of the formula described in DE-A-40 31 705, Example 5

are, as described in Example 1.4.4, in a styrene-acrylate toner binder incorporated and measured.

Depending on the activation time, the following q / m values are measured:

Activation q / m [μC / g] 5 min. -3 10 minutes -3 30 min. +3 2 hours. +5 24 hours +5

Example 1.4.6

5 parts of the pigment from Example 1.1 are in the form of a highly concentrated, spray-dried press cake, as described in Example 1.4.1, in 95 parts a polyester-toner binder incorporated and measured, the  Pigment content of the free-flowing and dust-free press cake was 81.3%. The pH of the presscake was determined to be 6.9. Color strength, color tone and Transparency corresponds to those described in Example 1.2 Pigment characteristics.

Depending on the activation time, the following q / m values [μC / g] measured.

Activation Charge q / m [μC / g] 5 min. -14 10 minutes -13 30 min. -13 2 hours. -9 24 hours -6

1.5 Ink-jet inks on an aqueous and non-aqueous basis 1.5.1

10 parts of a finely ground 50% pigment preparation (P.Y. 155) based on of polyvinyl chloride / polyvinyl acetate copolymer (for example ®Vinol 15/45 from Wacker or ®Vilith AS 42 Fa. Hüls), wherein the homogeneous pigment dispersion by intensive kneading in the copolymer is achieved with stirring in a mixture of 80 parts of methyl isobutyl ketone and 10 parts 1,2-propylene glycol introduced by means of a dissolver.

An ink jet ink of the following composition is obtained:
5 parts of CI Pigment Yellow 155
5 parts polyvinyl chloride / polyvinyl acetate copolymer
10 parts of 1,2-propylene glycol
80 parts of methyl isobutyl ketone.

1.5.2

To 5 parts of Pigment Yellow 155, which is in the form of a 40% ultrafine aqueous Pigment preparation is present, with stirring (paddle stirrer or dissolver)  first 75 parts deionized water and then 6 parts ®Mowilith DM 760 (acrylate dispersion), 2 parts of ethanol, 5 parts of 1,2-propylene glycol and 0.2 part of ®Mergal K7 added.

This gives an ink jet ink of the following composition:
5 parts Pigment Yellow 155
6 parts Mowilith DM 760 (acrylate dispersion)
2 parts of ethanol
5 parts of 1,2-propylene glycol
0.2 parts Mergal K7
81.8 parts deionized water.

1.5.3

To 5 parts C.I. Pigment Yellow 155, which is in the form of a 40 wt .-% ultrafine aqueous pigment preparation is present, 80 parts with stirring first deionized water, and then 4 parts ®Luviskol K30 (polyvinylpyrrolidone, BASF), 5 parts of 1,2-propylene glycol and 0.2 parts of Mergal K7 added.

An ink jet ink of the following composition is obtained:
5 parts Pigment Yellow 155
4 parts Luviskol K30 (polyvinylpyrrolidone)
5 parts of 1,2-propylene glycol
0.2 parts Mergal K7
85.8 parts deionized water.

Example 2 2.1 Synthesis

diazo
a) In a mixture of 70 parts of water, 111.5 parts of glacial acetic acid, 150 parts of hydrochloric acid (30%) and 0.3 parts of dinaphthylmethanedisulfonate sodium are added with stirring 104.5 parts Aminoterephthalsäuredimethylester and stirred for at least 4 hours. By planting an ice bath and adding 100 parts of ice, the suspension is cooled to about 0 ° C, under level with an aqueous solution (about 150 parts) of 35.2 parts of sodium nitrite, with the addition of ice for 1 hour at 0 Stirred to + 5 ° C, the suspension turns into a clear, yellow-brownish solution. Thereafter, the excess nitrite is destroyed by adding a small amount of sulfamic acid solution. For cleaning, the solution is mixed with 5 parts of commercially available filter soil, stirred, the residue is filtered off, and washed with a little water.

b) coupling component
To 500 parts of water at 10 ° C are added 93.1 parts of NaOH (30%), 69.0 parts of 1,4-bis (acetoactylamino) benzene, stirred for about 30 minutes, then adds 5.0 parts Filter earth to, stirred, the solution is filtered off and washed with a little water. Thereafter, this solution is added over 30 minutes with a solution of 400 parts of water, 400 parts of ice, 73.5 parts of glacial acetic acid and 53.2 parts of NaOH (30%).

c) coupling
For coupling, the diazonium salt solution is allowed to run in the course of 2 hours below the level of the suspension according to b), stirred for two hours at slightly increasing temperature, one hour at 40 to 45 ° C, another hour at 60 to 65 ° C and finally one hour at 80 ° C. The resulting yellow precipitate is filtered off, washed with cold water until free of salt and dried under vacuum (residual water content <1%).

d) Final treatment
71.6 parts of the crude pigment thus obtained are heated with 570 parts of dimethylformamide for 2 hours at 150 ° C, stirred for one hour at this temperature, at 80 to 100 ° C, cooled, filtered, washed with a low-boiling alcohol, dried and ground.

2.2 Pigment characteristics

BET surface area: 35 m ²

/G
Residual moisture: 0.3%
Residual salt content: 70 μS / cm
pH: 6.5
Thermostability: significantly higher than 300 ° C (incipient decomposition at approx. 330 ° C).
particle size:
d ₂₅

: 150 nm; d ₅₀

: 200 nm; d ₇₅

: 260 nm.
particle shape:
(Length-to-width ratio) approx: 3: 1.

X-ray Diffraction

Dielectric characteristics

ε (1 KHz): 5.0
tanδ (1 KHZ): 7.10 ^-2

Ωcm: 1.10 ¹⁶

,

2.3 Transparency

Compared to the standard given in Comparative Example 2 is at approx. 80% color strength increased by 5 rating units opacity significantly found greener shade.

2.4 Electrostatic properties 3.4.1

The procedure is as described in Example 1.4.1, wherein instead of 5 parts of the pigment from Example 1. 1 now 5 parts of the pigment from Example 3. 1 are incorporated. Depending on the activation time, the following q / m values are measured:

Activation Charge q / m [μC / g] 5 min. -12 10 minutes -12 30 min. -12 2 hours. -10 24 hours -9

3. Polyester resin without pigment

100 parts of the toner binder described in Example 1.4.1 (polyester on Bisphenol A base) are processed without pigment addition as in Example 1.4.1 and then measure.

Depending on the activation time, the following q / m values are measured:

Activation Charge q / m [μC / g] 5 min. -15 10 minutes -14 30 min. -14 2 hours. -14 24 hours -9

It turns out that P.Y. 155 the electrostatic inherent effect of the toner binder hardly influenced.

Comparative Example 1

A test toner is prepared and measured as described in example 1.4.1. instead of 5 parts of the pigment from Example 1.1, 5 parts of a C.I. Pigment Yellow 180 (benzimidazalon pigment, see Preparation EP 0 705 886 A2 Example 1.1) are incorporated.

Depending on the activation time, the following q / m values are measured:

Activation Charge q / m [μC / g] 5 min. 0 10 minutes 0 30 min. 0 2 hours. -7 24 hours -8th

Comparative Example 2

A test toner is prepared and measured as described in example 1.4.1. instead of 5 parts of the pigment from Example 1.1, 5 parts of a C.I. Pigment Yellow 180 (commercial ® Novoperm Yellow P-HG, Clariant GmbH, see EP 0 705 886 A2 comparative examples) are incorporated.  

Depending on the activation period, the following q / m values are measured.

Activation Charge q / m [μC / g] 5 min. -10 10 minutes -10 30 min. -10 2 hours. -20 24 hours -19

Both comparative examples show that P.Y. 180 the electrostatic inherent effect of the toner binder greatly affected.

4. Styrene-acrylate resin without pigment

The procedure is as in Example 3 except that the toner binder is the styrene Acrylate copolymer from Example 1.4.4 is used. As a carrier is also the used in Example 1.4.4 magnetite used.

Depending on the activation period, the following q / m values are measured:

Activation Charge q / m [μC / g] 5 min. -5 10 minutes -7 30 min. -11 2 hours. -16 24 hours -22

Claims (13)

1. Use of an azo pigment of the formula (1)
as colorants in electrophotographic toners and developers, powders and powder coatings, electret materials and in ink-jet inks. 2. Use according to claim 1, characterized in that the electrophotographic toner is a liquid toner or a powder toner. 3. Use according to claim 1 or 2, characterized in that the Azopigment of the formula (I) with a further pigment or dye is nuanced. 4. Use according to at least one of claims 1 to 3, characterized characterized in that optionally nuanced according to claim 2 Azo pigment of the formula (I) in combination with a charge control agent the class of triphenylmethanes, ammonium and immonium compounds; iminium; fluorinated ammonium and immonium compounds; biscationic acid amides; polymeric ammonium compounds; diallylammonium compounds; Aryl sulfide derivatives; Phenol derivatives; Phosphonium compounds and fluorinated phosphonium compounds;  Calix (n) arenes; ring-linked oligosaccharides (cyclodextrins) and their derivatives, in particular boric ester derivatives, interpolyelectrolyte complexes (IPECs); Polyester salts; Metal complex compounds, in particular Salicylate metal and salicylate nonmetal complexes, α-hydroxycarboxylic acid Metal and non-metal complexes; benzoimidazolones; Azines, thiazines or Oxazine is used. 5. An electrophotographic toner or developer containing a conventional one Toner binder, 0.1 to 60 wt .-%, preferably 0.5 to 20 wt .-%, of optionally nuanced azo pigment of the formula (1) according to claim 1 or 3 and 0 to 20 wt .-%, preferably 0.1 to 5 wt .-%, respectively based on the total weight of the toner or developer, one Charge control agent from the class of triphenylmethane, ammonium and immonium compounds; fluorinated ammonium and immonium compounds; biscationic acid amides; polymeric Ammonium compounds; diallylammonium compounds; Aryl sulfide derivatives; Phenol derivatives; Phosphonium compounds and fluorinated phosphonium compounds; Calix (n) arenes; cyclodextrins; Polyester salts; Metal complex compounds; Cyclooligosaccharide Borkomplexes, Inter- Polyelectrolyte complexes; benzoimidazolones; Azines, thiazines and oxazines. 6. Powders or powder coatings containing an epoxide, carboxyl or hydroxyl group-containing polyester or acrylic resin or a combination from 0.1 to 60% by weight, preferably from 0.5 to 20% by weight, of nuanced azo pigment of formula (1) according to claim 1 or 3 and 0 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the Total weight of the powder or powder coating, a charge control agent from the class of triphenylmethane, ammonium and immonium compounds; fluorinated ammonium and immonium compounds; biscationic acid amides; polymeric Ammonium compounds; diallylammonium compounds; Aryl sulfide derivatives; Phenol derivatives; Phosphonium compounds and fluorinated phosphonium compounds; Calix (n) arenes; cyclodextrins; Polyester salts;  Metal complex compounds; Cyclooligosaccharide Borkomplexes, Inter- Polyelectrolyte complexes; benzoimidazolones; Azines, thiazines and oxazines. 7. A method for producing an electrophotographic toner or Developer, powder or powder coating according to claim 5 or 6, characterized in that the possibly nuanced azo pigment of the formula (1) and optionally the charge control agent in the binder or resin of respective toner, developer, powder or powder coating is incorporated. 8. The method according to claim 7, characterized in that the optionally nuanced azo pigment of formula (1) and optionally the Charge control agent as dried and ground powder, as Suspension or incorporated as a press cake in the binder or resin becomes. 9. The method according to claim 8, characterized in that the press cake is a spray-dried press cake. 10. Ink jet ink containing 0.01 to 50 wt .-%, preferably 0.5 to 20 wt .-%, based on the total weight of the ink of claim 1 or 3 defined, optionally nuanced azo pigment of the formula (1). 11. ink-jet ink according to claim 10, characterized in that the ink aqueous or non-aqueous base or a hot-melt ink. 12. A process for producing an ink-jet ink according to claim 10 or 11, characterized in that optionally nuanced azo pigment of the formula (1) as Powder, as a pigment preparation, as a suspension or as a presscake in the aqueous or non-aqueous medium of the ink jet ink is dispersed. 13. The method according to claim 12, characterized in that the Optionally nuanced azo pigment of the formula (1) as a highly concentrated, preferably spray-dried, press cake is dispersed.