MXPA99006681A - Use of aluminum-azo complex dyes as ac control agents - Google Patents

Abstract

The aluminum-azo complex dyes of formula (I) or (I '), are used as charge control agents in electrophotographic toner and developers, powder coatings, electret materials, color filters, electrostatic separation procedures and inks for injection of tin

Description

USE OF COMPLEX DYES ALUM1N1O-AZO AS CARGO CONTROL AGENTS DESCRIPTIVE MEMORY The present invention rests in the technical field of charge control agents in toner and developers for electrophotographic recording processes, in powders and powder coatings for the coating of surfaces, in electret materials, especially in electret fibers, in processes of separation and in color filters. In electrophotographic recording procedures, a "latent charge image" is generated on a photoconductor. This "latent charge image" is revealed by the application of an electrostatically charged toner which can then be transferred onto paper, fabrics, sheets or plastics and fixed, for example, by pressure, irradiation, heat or solvent action. Typical toners are one- or two-component powder toner (also known as one- or two-component developers), and special toners are used, such as magnetic toner, liquid toner or polymerization toner. Polymerization toner should be understood as those toners that originate, for example, by suspension polymerization (condensation) or emulsion polymerization and lead to improved properties of the toner particles. It is also mentioned, in addition, those toner that originate basically in dispersions not watery A measure of the quality of the toner is its specific charge q / m (charge per unit mass). Together with the polarity and the level of the electrostatic charge, a decisive quality criterion is, above all, the rapid acquisition of the desired charge level and the constancy of this charge during a prolonged activation time. In addition, the toner's insensitivity to climatic actions such as temperature and humidity is another important criterion for adaptation. Both toner capable of positive loading and those capable of being negatively charged have application in copiers and laser printers, depending on the type of procedure and the device. Freight control agents are often added to obtain electrophotographic toner or developer with either positive or negative charge. Since the toner binders generally show a strong dependence of the charge with the activation time, it is the task of a load control agent, on the one hand, to adjust the polarity and the level of the toner charge and, on the other, , counteract the dropping of the load and take care of the constancy of the toner's charge. Therefore, load control agents that can not prevent the toner or developer from showing a high charge drift (aging) in extended service times, which can even cause the toner or developer to experience a reversal of the load, are unsuitable for practice.

Furthermore, it is important for the practice that the load control agents possess sufficient thermal stability and good dispersibility. The typical temperatures of incorporation of the load control agents to the toner resin, with the use of mixers or extruders, are between 100 ° C and 200 ° C. Accordingly, a thermal stability of 200 ° C is of great benefit. It is also important that the thermal stability is guaranteed for a prolonged period of time (approximately 30 minutes) and in various bonding systems. This is significant since the re-occurring matrix effects always lead to the premature decomposition of the charge control agent in the toner resin, resulting in a dark yellow or dark brown coloration of the toner resin and being lost completely or partially the load control effect. Typical toner binders are polymerization, polyaddition and polycondensation resins, such as styrene-styrene-acrylate, styrene-butadiene, acrylate, polyester, phenol-epoxy resins, as well as copolymers of cycloolefins, individually or in combination, which may also contain other ingredients, for example dyes, such as inks and pigments, waxes or flow aids or may subsequently receive the addition thereof, such as high dispersion silicas . For good dispersibility it is very advantageous that, if possible, the charge control agent shows no serious property, no stickiness and a melting or softening point of >; 150 ° C, better than > 200 ° C. A stickiness often leads to problems in the Dosing in the toner formulation, and low melting or softening points can lead to, in the dispersion, no homogeneous distribution being achieved, since the material is fused into droplets in the support material. In addition to toner and electrophotographic developers, charge control agents can also be used for improving the electrostatic charge of powders and lacquers, especially in powdered lacquers sprayed by triboelectric or electrokinetic methods, such as those used for coating of the surface of objects, for example metal, wood, plastic, glass, ceramics, concrete, textiles, paper or rubber. The powder coating technology is used, for example, in the lacquering of objects such as garden furniture, camping goods, home care appliances, vehicle parts, refrigerated cabinets and shelves, as well as in the lacquer finish. work pieces of complicated shapes. The powdered lacquer or powder acquires its electrostatic charge generally by one of the following two procedures: In the Corona process, the powder lacquer or powder is passed through a charged corona, with which it is charged, in the triboelectric process or electrokinetic is made use of the principle of electricity by rubbing. In the spray apparatus, the powder coating or the powder acquires an electrostatic charge which is opposite to the charge of the rubbing component, generally a hose or spray tube, for example of polytetrafluoroethylene.

A combination of the two procedures is also possible. As the powder coating resin, epoxy resins, polyester resins containing carboxyl and hydroxyl groups, polyurethane resins and acrylic resins are commonly used together with customary hardeners. Combinations of resins are also used. Thus, for example, epoxy resins are frequently used in combination with polyester resins containing carboxyl and hydroxyl groups. Typical hardener components for epoxy resins are, for example, acid anhydrides, imidazoles as well as dicyandiamides and their derivatives. For polyester resins containing hydroxyl groups are typical hardening components, for example, acid anhydrides, blocked isocyanates, bis-acyl urethanes, phenolic resins and melamine resins. For polyester resins containing carboxyl groups are typical hardener components, for example, triglycidyl isocyanurates or epoxy resins. In acrylic resins they have application as typical hardening components, for example, oxazolines, isocyanates, triglycidyl isocyanurates or dicarboxylic acids. The disadvantage of an insufficient load is observed, especially in the triboelectric or electrokinetic spraying of powders or powder coatings which have been prepared on the basis of polyester resins, especially of polyesters containing carboxyl groups, or on the basis of the so-called mixed powders, also called hybrid powders. Mixed powders are powder coatings whose base resin is composed of a combination of Epoxy queen and polyester resin containing carboxyl groups. Mixed powders form the basis for powder coating with more frequent representation in practice. Insufficient loading of the powders and powder coatings mentioned above leads to insufficient separation rate and coverage in the workpiece to be coated. The term "embedding" is a measure of the extent to which a powder or powder coating is deposited on the workpiece, even on the back faces, hollow spaces, slits and, above all, on the edges and inside corners. It has furthermore been found that the load control agent can considerably improve the behavior, the loading as well as the stability of the charge in electret materials, especially electret fibers (DE-A-43 21 289). Till the date, electret fibers have been described mainly in relation to the problem of the filtration of ultrafine powders. The filter materials described differ as much from the point of view of the materials of which the fibers are composed as, also, as regards the manner and manner in which the electrostatic charge is applied to the fibers. Typical electret materials are based on polyolefins, halogenated polyolefins, polyacrylates, polyacrylonitriles, polystyrenes or fluorinated polymers such as, for example, polyethylene, polypropylene, polytetrafluoroethylene and perfluorinated ethylene and propiolene, or in polyesters, polycarbonates, polyamides, polyimides, polyetherketones, in poly (its arylene furans), especially poly (phenylene sulfides), in polylacetals, cellulose esters, polyalkylene terephthalates, as well as mixtures thereof. The materials Electretes, especially electret fibers, can be used, for example, for the filtration of powders (ultrafine). The electret materials can acquire their charge in different ways, namely load by corona or tribocarga. It is also known that charge control agents can be used in electrostatic separation processes, especially in polymer separation processes. Thus, Y. Higashiyama et al. (J. Electrostatics 30, pp. 202-212 (1993)), in the example of the externally applied trimethyl-phenyl-ammonium-tetraphenylborate charge control agent, describe how polymers can be separated from one another. for recycling purposes. Without load control agent, the "low density polyethylene" (LDPE) and the "High density polyethylene" (HDPE) are charged triboelectrically in an essentially analogous manner. After the addition of the charge control agent, the LDPE acquires strongly positive charge and the HDPE strongly negative and thus can be separated well. In addition to the external application of the charge control agent, it is also conceivable to incorporate it into the polymer, for example to displace a polymer within the series of triboelectric voltages and obtain a respective separating action. In this way, other polymers can also be separated from one another, such as, for example, polypropylene (PP) and / or polyethylene terephthalate (PET) and / or polyvinyl chloride (PCV). Specially well, for example, mineral salts can also be selectively separated if there is a surface additive previously (surface conditioning) that improves the specific electrostatic charge of the substrate (A. Singewald, L. Ernst, Zeitschrift für Physikal, Chem.

Neue Folge, vol. 124, pgs. 223-248 (1981)). The load control agents are widely known in the literature. In any case, the cargo control agents known to date show a series of disadvantages that strongly limit their use in practice and even do almost entirely as, for example, insufficient thermal stability, intrinsic odor, poor dispersibility or small stability in the toner binder (decomposition, migration). A special weakness of many current load control agents in the market is the insufficient activity with regard to the polarity of the load (positive or negative charge), level of load or constancy of the desired load. It is also an important aspect that the cargo control agent must be ecotoxicologically safe. Therefore, the task of the present invention was to find load control agents that are especially active and ecotoxicologically compatible. Together with the rapid acquisition and the constancy of the load, the compounds must show a high thermal stability. In addition, they should be dispersible, well and without decomposition, in various practical toner binders such as polyesters, poly (styrene-acrylates) or poly (styrene-butadiene) / epoxy resins as well as cycloolefin copolymers. In addition, its activity should be considerably independent of the resin / support combination to enable a broad application. In addition, they should be dispersible, well and without decomposition, in powder coating binders and common electret materials such as example, polyesters (PES), epoxies, PES-epoxide hybrids, polyurethanes, acrylic systems as well as polypropylenes. Regarding their electrostatic efficiency, the load control agents should be active at the lowest possible concentration (1% or less) and the binding with carbon black or other dyes should not lose this effectiveness.

It is known that dyes can influence, in a persistent way, the triboelectric charge of toner. Surprisingly, it has now been shown that special aluminum-azo complexes possess good load-controlling properties and high thermal stability, the charge-controlling property not being lost by combination or with carbon black or other dyes. further, the compounds are well compatible with the usual binders of toner, powder coatings and electrettes and can easily be dispersed therein. The object of the present invention is the use of the dyes of aluminum-azo complexes 2: 1 of formulas (I) and (I ') below, alone or in combination, as charge control agents in toner and electrophotographic developers, as charge improvers in powder coatings, electret materials and in electrostatic separation processes, as well as inkjet inks and color filters, (i) ("'), where the A-cores, independently of one another, carry one or two substituents of the (C1-C3) alkyl, (C1-C3) alkoxy, cyano, (C1-C3) alkoxycarbonyl, benzoyl, phenoxycarbonyl, aminocarbonyl, mono-od - (C 1 -C 3) alkylaminocarbonyl, mono- or di- ((C 1 -C 3) alkoxy) - (C 2 -C 4) alkyl) aminocarbonyl, phenylaminocarbonyl, aminosulfonyl, mono- or di- (alkyl) (C? - C4)) aminosulfonyl, mono- or di- (((C? -C3) alkoxy) - (C2-C4) alkyl) aminosulfonyl and phenylaminosulfonyl; all the Ri independently of each other, mean a group of atoms, which may eventually carry substituents, necessary for the completion of a mono or binuclear aromatic ring system; the two R2, independently of each other, mean a phenyl residue, which may optionally carry substituents, or an alkyl (C? -C? 2) or ((C? -C2)) - (alkyl) (C2-C8) moiety )); and X + means a cation. Under mono- or binuclear aromatic character systems, benzene, naphthalene and heterocyclic nuclei should be especially understood. Under heterocyclic nuclei should be understood, above all, five-membered rings containing nitrogen and / or sulfur, especially pyrazolone or pyridone. As substituents in all nuclei of aromatic character, all known substituents in dye chemistry, for example, halogens, under which chlorine or bromine is to be understood, are taken into consideration unless otherwise stated. hydroxyl, (C1-C4) alkyl, (C1-C4) alkoxy, cyano, nitro, thiocyanogen, (C1-C3) alkylcarbonyl, benzoyl, (C1-C3) alkylcarbonyl, aminocarbonyl, mono- or di- (alkyl (C? -C4)) aminocarbonyl, mono- or di- (((C? -C3) alkoxy) - (C2-C3) alkyl) aminocarbonyl, (C1-C3) alkoxycarbonyl, aminosulfonyl and mono- or di- (alkyl ( C? -C4)) aminosulfonyl, mono- or di- (((C? -C3) alkoxy) - (C2-C3) alkyl) aminosulfonyl. The same substituents are also taken into consideration for R2 in the case where it is a phenyl radical. In in this case, however, halogen atoms are preferred, which is to be understood, above all, as chlorine and bromine, (C1-C4) alkyl, (C1-C4) alkoxy or acetyl. In the formulas (I) and (I '), the symbols R1 signify the groups of atoms necessary for the completion of a coupling component; in the formula (I), especially, the groups of atoms necessary for the completion of a benzene coupling component or 1-phenyl-3-methylpyrazolyl. In the formula (I '), R1 preferably means the groups of atoms necessary for the completion of a naphthalene or benzene ring. In particular, the benzene cores can optionally contain substituents, for example chlorine, bromine, alkyl (C? -C2), alkoxy (C -? - C2), carboxamide or sulfonamide. As cation X +, preference is given preferably to alkali metal ions, especially sodium or potassium ions, ammonium, mono-, di- or tri- (C 1 -C 8) alkylammonium ions and, especially, 4-amino ions, 4-hydroxy- or 4-keto-2,2,6,6-tetramethyl-piperidinium. The preferred dyes in particular correspond to the formulas (la), (Ib) and (le) (qi) et where in these formulas they mean, the two R3, with respective independence of the other substituents, hydrogen, (C1-C3) alkyl, ((C? -C2) alkoxy) - (C2-C3) alkyl or phenyl, especially methyl , ethyl, ((C? -C2) alkoxy) - (C2-C3) alkyl or phenyl, R4 hydrogen, halogen, (C? -C2) alkoxy, (C1-C2) alkyl, preferably hydrogen, chlorine or methyl , especially hydrogen, each of the two R5, respectively, a 2-ethylhexyl residue or a phenyl residue which can carry up to three substituents, including up to two of the chloro, bromo, alkyl (C? -C2), alkoxy group (C1-C3) or acetyl, preferably one or two (C1-C2) alkoxy groups and / or a chlorine or bromine atom or a methyl group, especially one or two methoxy groups, and X? + A sodium, potassium ion, ammonium or alkyl (C? -C4) ammonium, but especially a 4-amino-, 4-hydroxy- or 4-keto-2,2,6,6-tetramethyl-piperidinium ion, the two B-cores (formula la) can carry one or two substituents each, each of the halogen, hydroxyl, (C1-C2) alkyl, (C1-C3) alkoxy, acetyl, benzoyl or 4,6-bis group - (2,, 4, -dimetilfenii) -triazinyl-2, especially a hydroxyl group and an acetyl or benzoyl group each, the B-cores carry the groups of atoms necessary for the completion of a naphthalene ring, preferably attached in position 5 'and 6'. In the compounds of formulas (la), (Ib) and (le), the sulfonamido groups are preferably attached in the 4 or 5 position, respectively. The preparation of the compounds of formula (I) is known from the literature, for example from U.S. Pat. 5,731, 422, and is carried out analogously to the preparation of 2: 1 complex dyes known analogously, by coupling a diazotized amine of formula (II) with a compound of formula (III) The preparation of the dyes of formula (I ') is also carried out analogously to the preparation of complex dyes 2: 1 known analogues, by coupling a diazotized amine of formula (go) with a compound of formula (III ') H3C-CO-CH2-CO-NHR2 (III') The metallization and introduction of the cation can be carried out on the stage of the precursor products, ie of the compounds of formulas ( II), (III), (II ') or (III'), or of the final products, also in known manner. The aluminum-azo complexes used according to the invention can be exactly adapted to the respective resin / toner system. It should be added that the compounds used according to the invention have the capacity to flow and high and especially constant load control properties, good thermal stabilities and good dispersibility. Another technical advantage of these compounds consists in their inert behavior against the various binding systems and, therefore, their varied utilizability, being of special importance that they are not dissolved in the polymer matrix, but rather they are in the form of small bodies solids very finely divided. Dispersion means the distribution of one substance in another, in the sense of the invention the distribution of a charge control agent in the toner binder, powder lacquer binder or electret material. It is known that crystalline substances, in their grossest form, occur in the form of agglomerates. To achieve a homogeneous distribution in the binder, these must be divided into small aggregates or, ideally, into primary particles through the dispersion process. The charge control agent particles which are present in the binder after the dispersion process should be less than 1 μm, preferably less than 0.5 μm, a narrow distribution of the particle sizes being advantageous. For particle sizes, defined by the dso index, optimal activity ranges are found that depend on the substance. Thus, for example, coarse particles (~ 1 mm), are in part not dispersible in any way or only with a considerable consumption of time and energy, while very fine particles of the order of the submicron, imply a high risk for Safety reasons, such as the possibility of dust explosion. The sizes and shape of the particles are adjusted and modified, or through synthesis and / or subsequent treatment. Often, the required property is only made possible by selective subsequent treatment such as grinding and / or drying. For this, various grinding techniques are offered. Advantageous are, for example, air jet mills, shredding mills, hammer crusher, bead mills as well as rebound mills. In the binder systems mentioned in this invention is typically hydrophobic materials. High water contents of the charge control agent, or can oppose a wetting or favor a dispersion (flushing). Thus, the achievable moisture content is specific to the substance. The compounds according to the invention are characterized by the following physico-chemical properties: The water content, determined by the Karl-Fischer method, is between 0.1% and 30%, preferably between 1 and 25% and particularly preferably between 1 and 20%, the water being adsorbed and / or bound and its fraction adjusted by the action of the temperature up to 200 ° C and vacuum up to 10"8 Torr or by the addition of water Particle sizes, determined by evaluation by optical microscopy or by laser diffraction, and defined by the dso index, are between 0.01 μm and 1000 μm, preferably between 0.1 and 500 μm, and very particularly preferably between 0.2 and 400 μm It is especially advantageous that a narrow fraction of particle sizes results from the grinding. dso) less than 500 μm, especially less than 200 μm The aluminum-azo compounds used according to the invention can also be combined with charge control agents which control positively or negatively to achieve a good loading capacity in the technical application , the total concentration of this charge control agent being between 0.01 and 50% by weight, preferably between 0.1 and 50% by weight. % by weight, based on the total weight of the electrophotographic toner, developer, powder or powder coating. As cargo control agents, special consideration is given to: triphenylmethane, ammonium and imonium compounds, compounds Minium, fluorinated ammonium and fluorinated ammonium compounds, biscationic acid amides, polymeric ammonium compounds, diallylammonium compounds, aryl sulfide derivatives, phenol derivatives, phosphonium compounds and fluorinated phosphonium compounds, Calix (n) arene, oligosaccharides with ring links (cyclodextrins) and their derivatives, especially derivatives of boric esters, interpolyelectrolyte complexes (IPECs), polyester salts, benzimidazolones, azines, thiazines or oxazines, which are indicated in the Color Index as Pigments, Solvent Dyes, Basic Dyes or Acid Dyes. Especially preferred are the charge control agents mentioned below, which can be combined with the dye of formula (I) or (I ') individually or in combination with each other. Triarylmethane derivatives, for example: 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, as well as the triarylmethane compounds indicated in the Color Index as Acid Blue and Basic Dye, insofar as they are suitable in terms of their resistance to temperature and processability as, for example, Color Index Basic Blue 1, 2, 5, 7, 8, 11, 15, 18, 20, 23, 26, 36, 55, 56, 77, 81, 83, 88, 89, Color Index Basic Green 1, 3, 4, 9, 10, In particular, Color Index Solvent Blue 125, 66 and 124. are particularly suitable. The Color Index Solvent Blue 124 is particularly well suited in the form of its highly crystalline sulphate or trichloro-triphenylmethyltetracioroaluminate. Also suitable are triphenylmethanes as described in US-A-5 051 585, especially those of formula (2) where R1 and R3 are the same or different and mean -NH2, a mono- and dialkylamino group whose alkyl groups have from 1 to 4 C atoms, preferably 1 or 2, a mono- or di-omega-hydroxyalkylamino group whose alkyl groups have from 2 to 4 C atoms, preferably 2, a phenyl- or phenylalkylamino group, optionally N-substituted alkyl, which alkyl has from 1 to 4 C atoms, preferably 1 or 2, whose phenylalkyl group has aliphatic bridge of 1 to 4 C atoms, preferably 1 or 2, and whose phenyl nucleus can carry one or two of the following substituents: alkyl with 1 or 2 C atoms, alkoxy with 1 or 2 C atoms and can carry the sulphonic acid group, R2 is hydrogen or has one of the meanings indicated for R1 and R3, R4 and R5 denote hydrogen, halogen, preferably chlorine, or a sulfonic acid group, or R4 together with R5, form a fused phenyl ring. ñ 7 Q 10 R, R, R and R respectively represent hydrogen or an alkyl residue with 1 or 2 C atoms, preferably methyl, and R 8 is hydrogen or halogen, preferably chlorineand X "represents a stoichiometric equivalent of an anion, especially a chloride, sulfate, molybdate, phosphomolybdate or borate anion, A charge control agent of formula (2) in which R1 and R3 are phenylamino groups, R2 is especially preferred. In addition, ammonium and imonium compounds such as those described in US-A-5 015 676 are suitable. In addition fluorinated ammonium compounds and fluorinated imonium are suitable as described. in US-A-5 069 994, especially those of formula (3) wherein R13 means perfluorinated alkyl with 5 to 11 carbon atoms, R23, R33 and R43 are identical or different and mean alkyl having 1 to 5 carbon atoms, preferably 1 to 2, and Y "is a stoichiometric equivalent of an anion, preferably of a tetrafluoroborate or tetraphenylborate anion, Preferably they mean: R13 perfluorinated alkyl with 5 to 11 carbon atoms, R23 and R33 etjlo and R43 methyl. Biscaionic acid amides, such as those described in WO 91/10172, especially those of formula (4), are also suitable. in which R14, R24 and R34 are identical or different alkyl radicals having 1 to 5 carbon atoms, preferably methyl, n represents an integer from 2 to 5, and Z "represents a stoichiometric equivalent of an anion, preferably a tetraphenyl borate anion. , diallylammonium compounds are suitable as those described in DE-A-4 142 541, especially those of formula (5) 1 5 2 5? CH ^ CH \ / CHCHCHCH (5) in which 15 25 R and R mean the same or different alkyl groups with 1 to 5 C atoms, preferably 1 or 2, but especially represent methyl groups, and A "represents a stoichiometric equivalent of an anion, preferably a tetraphenyl borate anion, as well as the ammonium polymer compounds of formula (6) obtainable therefrom, such as those described in DE-A-4029 652 or DE-A-4 103 610, where n has a value corresponding to molecular weights of 5,000 to 500,000 g / moi. Especially preferred, however, are compounds of formula (6) with molecular weights of 40,000 to 400,000 g / mol. Also suitable are aryl sulfide derivatives, such as those described in DE-A-4 031 705, especially those of the formula < 7) wherein R17, R27, R37 and R47 mean the same or different alkyl groups with 1 to 5 C atoms, preferably 2 or 3, and R57 is one of the divalent residues -S-, -SS-, -SO- or - SO2-. For example, R17 to R47 are propyl groups and R57 to the group -S-S- Also suitable are phenol derivatives, such as those described in EP-A-0 258 651, especially those of formula (8) wherein R1 and R38 mean alkyl or alkenyl groups with 1 to 5 carbon atoms C, preferably 1 to 3, and R28 and R48 hydrogen or alkyl with 1 to 3 C atoms, preferably methyl. As examples, mention may be made of the compounds in which R a R are methyl groups or in which R and R are hydrogen and R and R represent the group -CH 2 -CH = CH 2. Also suitable are phosphonium compounds and fluorinated phosphonium compounds, such as those described in US-A-5 021 473 and US-A-5 147 748, especially those of formula (9) wherein R19, R29, R39 and R49 mean identical or different alkyl groups with 1 to 8 C atoms, preferably 3 to 6, and E "represents a stoichiometric equivalent of an anion, preferably a halide anion; and 00) 2 1 0 4 1 0 R where 110 R is a highly fluorinated alkyl radical with 5 to 15 C atoms, preferably 6 to 10, R 2 10, R 3 10 and R 410 alkyl having 3 to 10 C atoms or phenyl. As an example of a compound of formula (9), tetrabutylphosphonium bromide may be mentioned, as examples of compounds of formula (10) are to be mentioned compounds with R110 = C8F? -CH2-CH2-, R210 = R310 = R410 = phenyl and E * = PFβ * or the tetraphenyl borate anion. In addition, Calix (n) arene are suitable, such as those described in EP-A-0 385 580, especially those of formulas (11a) and (11b) (11 b) wherein n is a number from 3 to 12, and R means hydrogen, halogen, preferably chlorine, linear or branched alkyl having 1 to 12 carbon atoms, arylalkyl, for example benzyl or phenylethyl, -NO2, -NH2 or NHR111, R111 meaning alkyl having 1 to 8 carbon atoms, phenyl optionally substituted with (C1-C4) alkyl or -Si (CH3) 3. Further suitable are benzimidazolones, such as those described in EP-A-0 347 695, especially those of formula (12) wherein R115 is an alkyl with 1 to 5 carbon atoms and R215 is an alkyl with 1 to 12 atoms of C and L a stoichiometric equivalent of an anion, especially of a chloride anion or tetrafluoroborate. As an example, it is worth mentioning the compound with R = CH3 and R215 = CnH23. Ring-bound oligosaccharides are also suitable, such as those described in DE-A-4 418 842, especially those of formula (13) 1 R 11 R R wherein n is a number between 3 and 100, R and R have the meaning OH, OR316, meaning R316 alkyl (CrC-iß), aryl (C6-C12), substituted or unsubstituted, or tosyl, and X16 has the meaning CH2OH or CH2COR316. Examples are: n16 = 6, R116 and R216 = OH, X16 = CH2OH n16 = 7, R116 and R216 _H> ? 16 = CH20H n16 = 8, R116 and R216 = QHj? 16 = CH2oH. Also suitable are polymer salts such as those described in DE-A-4 332 170, whose anionic component is a polyester, which is composed of the reaction product of individual components a), b) and c) as well as optionally d) and optionally e), where they are: a) a dicarboxylic acid or a reactive derivative of a dicarboxylic acid, which are free of sulfo groups, b) an aromatic, aliphatic or cycloaliphatic difunctional sulfo compound, whose functional groups are hydroxyl or carboxyl, or hydroxyl and carboxyl, c) an aliphatic, cycloaliphatic or aromatic diol, a polyetherdiol 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 its cationic components are hydrogen atoms or metal cations. Also suitable are cyclo-oligosaccharide compounds, for example those described in DE-A-197 11 260, which are obtainable by reaction of a cyclodextrin or cyclodextrin derivative. on a compound of formula OR HO- B OR where R and R2 signify alkyl, preferably (C1-C4) alkyl.

Inter-polyelectrolyte complexes are also suitable, such as, for example, those described in DE-A-197 32 995.

They are also suitable, especially for liquid toner, ionic surfactants and so-called metal soaps.

Alkylated arylsulfonates are especially suitable, as barium petronate, calcium petronate, dinonylnaphthalenesulfonate barium (basic and neutral), calcium dinonyl sulfonate or dodecylbenzenesulfonate Na salt and poly (isobutylene succinimide) (Chevrons Oloa 1200).

Also suitable are soy lecithin and polymers of N-vinylpyrrolidone.

In addition, the sodium salts of mono- and phosphated diglycerides with saturated and unsaturated substituents, copolymers diblock AB of A: polymers of 2- (N, N) -di-methylaminoethyl methacrylate quaternized with methyl p-toluenesulfonate, and B: poly (2-ethylhexyl methacrylate).

They are also suitable, especially in liquid toner, di- and trivalent carboxylates, especially aluminum tristearate, barium stearate, chromium stearate, magnesium octate, calcium stearate, naphtalite of iron and zinc naphtalite. In addition, azines of the following Color Index numbers are also suitable: C.l. Solvent Black 5, 5: 1, 5: 2, 7, 31 and 50; C.l. Pigment Black 1, C.l. Basic Red 2 and C.l. Basic Black 1 and 2. The aluminum-azo complexes of formula (I) or (I ') used according to the invention and any additional charge control agents are incorporated homogenously, alone or in combination, in a concentration from 0.01 to 50% by weight, preferably from 0.5 to 20% by weight, particularly preferably from 0.1 to 5.0% by weight, based on the total mixture, to the binder of the respective toner, developer, lacquer, powder coating material, electret materials or the polymer to be electrostatically separated either from the medium of an inkjet ink or to the filtering materials, for example by extrusion or kneading, bead mills or with ultraturrax (fast stirrer). For it, the compounds used according to the invention can be added in the form of dry and ground powder, dispersions or solutions, tablets, basic mixtures, preparations, pastes, in the form of compounds in aqueous or non-aqueous solution fixed on suitable supports, for example , silica gel, T0O2, AI2? 3 or carbon black, or mixed with such supports or in other forms. Furthermore, the compounds used according to the invention can also be added substantially already in the preparation of the respective binders, that is to say, in the course of their polymerization, polyaddition or polycondensation. Another object of the present invention is a toner electrophotographic film containing a conventional binder, for example styrene, styrene-acrylate, styrene-butadiene, acrylate, acrylic, polyester or epoxy resin or a combination of the latter two, and from 0.01 to 50% by weight, preferably 0.5 to 20% by weight, particularly preferably 0.1 to 5% by weight, based on the total weight of the electrophotographic toner, of at least one aluminum-azo compound of formula (I) or (I ') , optionally in combination with one or more of the additional charge control agents described. Another object of the present invention is a powder coating containing a conventional binder, for example a urethane, acrylic, polyester or epoxy resin or a combination thereof and from 0.01 to 50% by weight, preferably 0, 5 to 20% by weight, particularly preferably 0.1 to 5% by weight, based on the total weight of the powder coating, of at least one aluminum-azo compound of formula (I) or (I '), optionally in combination with one or more of the additional charge control agents described. It was further found that the aluminum-azo compounds of formula (I) or (I ') are suitable as ink in inks for water-based (microemulsion inks) and non-aqueous ("solvent-based") inks, as well as in those inks that work by the hot melt process. The microemulsion inks are based on organic solvents, water and eventually an additional hydrotropic subst (boundary layer meter). Non-aqueous based inks contain essentially solvents organic and eventually a hydrotropic subst. Hot melt inks are mostly based on waxes, fatty acids, fatty alcohols or sulfonamides, which are solid at room temperature and become liquid upon heating, with the preferred melting range being between approximately 60 C and 140 C. approximately. Another subject of the invention is a hot melt injection ink, consisting essentially of 20 to 90% by weight of wax and 1 to 10% by weight of the aluminum-azo compound of formula (I) or (I ') . In addition, from 0 to 20% by weight of an additional polymer (as a "color diluent"), from 0 to 5% by weight of dispersion aid, from 0 to 20% by weight of viscosity modifier can be contained. , from 0 to 20% by weight of plasticizer, from 0 to 10% by weight of antiadhesive, from 0 to 10% by weight of transparency stabilizer (inhibits, for example, the crystallisation of the wax) as well as from 0 to 2 % by weight of antioxidant. Typical additives and adjuvants are described, for example, in US Pat. No. 5,560,760. Also subject of the invention are injection recording liquids, which contain one or more of the aluminum-azo compounds of formula (I) or (I '). The finished recording liquids generally contain a total of from 0.5 to 15% by weight, preferably from 1 to 5 to 8% by weight (calculated in dry form) of one or more, for example 2 or 3, of the compounds of the formula (I) or (O- Microemulsions contain 0.5 to 15% by weight, preferably from 1.5 to 8% by weight of a compound of formula (I) or (I '),. to 99% by weight of water and 0.5 to 94.5% by weight of organic solvent and / or hydrotropic compound. "Solvent-based" injection inks preferably contain 0.5 to 15% by weight of a compound of formula (I) or (I '), 85 to 94.5% by weight of organic solvents and / or hydrotropic compounds. For the preparation of the recording liquids, the water used is preferably used in the form of distilled or desalinated water. In the solvents contained in the recording liquids it can be an organic solvent or a mixture of such solvents. Suitable solvents are, for example, mono- or multivalent alcohols, their ethers and esters, for example alkanols, especially with 1 to 4 C atoms, such as, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol.; di- or trivalent alcohols, especially with 2 to 5 carbon atoms, for example ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2,6 -hexanotriol, glycerin, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, tripropylene glycol, polypropylene glycol; lower alkyl ethers of multivalent alcohols such as, for example, ethylene glycol mono-methyl-o-ethyl ether, triethylene glycol mono-methyl or o-ethyl ether; ketones and ketoalcohols such as, for example, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, cyclopentanone, cyclohexanone, diacetone alcohol; amides such as, for example, dimethylformamide, dimethylacetamide, N- methylpyrrolidone, toluene and n-hexane. As hydrotropic compounds, which optionally also serve as solvents, there can be used, for example, formamide, urea, tetramethylurea, e-caprolactam, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, butyl glycol, methyl cellosolve, glycerin, N-methylpyrrolidone, 1, 3- diethyl-2-imidazolidinone, thiodiglycol, sodium benzenesulfonate, Na xylenesulfonate, Na toluenesulfonate, sodium cumene sulphonate, Na dodecyl sulfonate, Na benzoate, Na salicylate or sodium butyl monoglycol sulfate. In addition, the recording liquids according to the invention can contain other more usual additives, for example preservatives, cationic, anionic or non-ionogenic surfactants. (surfactants and wetting substances), as well as viscosity regulating agents, for example polyvinylalcohol, cellulose derivatives, or water-soluble natural or synthetic resins such as film formers or binders for increasing the adhesion resistance and the abrasion Amines such as, for example, ethanolamine, diethanolamine, triethanolamine, N, N-dimethylethanolamine or diisopropylamine serve mainly to raise the pH value of the recording liquid. In the recording liquid, they are usually present in a concentration of 0 to 10% by weight, preferably 0.5 to 5% by weight. The injection inks according to the invention can be obtained by dispersing the aluminum-azo compound of formula (I) or (I ') in powder form, in the form of a preparation, in the form of a suspension or in the form of tablets, in the microemulsion medium or in the non-aqueous medium or in the wax for the preparation of a hot melt injection ink. The tablets can also be a highly concentrated tablet, especially spray dried. In addition, the metal complex of formula (I) and (I ') is also suitable as a colorant for color filters, both for the creation of the subtractive color and also for the additive (P. Gregory "Topics in Applied Chemistry: High Technology Application of Organic Colorants "Plenum Press, New York 1991, pp. 15-25). In the following examples, parts mean parts by weight, and percentages, percentages by weight.

EXAMPLES EXAMPLES OF PREPARATION FOR COMPLEX COMPOUNDS ALUMINUM-AZO EXAMPLE OF PREPARATION 1 26.0 parts of 2-aminophenol-4- (3'-methoxypropylaminosulfonyl) are stirred in a mixture of 200 parts of water and 70 parts of 30% HCl. After the addition of 50 parts of ice, the amine is diazotized by the addition of 26.2 parts by volume of 4N NaNO2 solution. The The resulting suspension is stirred at 0 C for 3 hours and, after that, it is allowed to slowly flow into a solution of 13.7 parts of ß-naphthol in 190 parts of water and 9.5 parts of 30% NaOH solution. By the simultaneous addition of another 70 parts of 30% NaOH solution, the pH value is maintained between 9.5 and 10. The mixture thus obtained is then stirred for 8 hours at room temperature, then adjusted with 30% HCl. at pH 1.5, the monoazoic dye originated, of formula it is filtered, washed with 4,000 parts of water and dried. 44.19 parts of the monoazo dye are suspended in a mixture of 110 parts of water and 25 parts of 30% NaOH solution, heated to 70 C and stirred for 1 hour. The pH value of the suspension is 12.3. After additional heating to 90 C, a solution of 17.1 parts of aluminum sulphate (water-free) in 340 parts of water is added over the course of 1 hour, resulting in a large suspension of the aluminum complex and lowering the pH value to 10.9. The temperature is allowed to lower, with stirring, for two hours, at 45 C, and the suspension is slowly mixed with a solution of 8.58 parts of triacetondiamine in 10 parts of water and 11.2 parts of 30% HCl. The precipitate that originates is adjusted with approximately 2.4 parts of % HCl at pH 5.4, stir at room temperature for another hour, filtered, the residue is washed with water to remove salts, dried and milled in a suitable mill. The dye of formula (la) is thus obtained in which R3 means methoxypropyl, nucleus B is naphthylene and sulphonamido groups are respectively attached in position 5. Characterization Reddish blue powder DTA: softening at 160-185 C, decomposition to from 250 C. pH: 8.7 Conductivity: 400 μS / cm Residual humidity: 5.1% (IR lamp) e (1 KHz): 6 tan d (1 KHz): 0.3 Ocm: 8 10 2 Ocm Crystallinity: crystalline, numerous sharp reflection peaks between 2 Theta 5 and 2 Theta 35 (main peaks: 21, 7 and 8.7) Particle size distribution: dso <; 10 μm EXAMPLE OF PREPARATION 2 Analogous to the procedure of the preparation example 1, equimolar amounts (12.12 parts) of 2-hydroxy-4-methylaminosulfonyl-aniline are diazotized, coupled with 10.45 parts of 1-phenyl-3-methylpyrazoline-5, transformed with aluminum sulfate, sodium hydroxide of 30% and triacetonadiamine hydrochloride to the corresponding aluminum-azo complex dye of formula (Ib), in which R3 signifies methyl and R4 hydrogen and the sulfonamido group is attached in position 4. Characterization Yellowish DTA powder: softening at 200-210 ° C, decomposition from 260 ° C. PH: 7.5 Conductivity: 500 μS / cm Residual humidity: 6.6% (IR lamp) e (1 KHz): 8.7 tan d (I KHz): 0, 2 Ocm: 2 1011 Ocm Crystallinity: crystalline, numerous sharp bands between 2 Theta 5 and 2 Theta 35 (main peaks: 11, 1 as well as 14.4 and 17.7) Particle size distribution: dso < 10 μm IR spectrum: 1587, 1568, 1474, 1303 cm "1.

EXAMPLES OF APPLICATION EXAMPLE OF APPLICATION 1.1 1 part of the compound of the preparation example 1 is homogenously incorporated in 95 parts of a toner binder (polyester based on bisphenol-A, RAlmacry! T500), by means of a kneader, in the course of 30 minutes. It is then ground in a universal laboratory mill and then classified in a centrifugal sieve. The desired particle fraction (from 4 to 25 μm) is activated with a carrier composed of ferrite particles of size between 50 and 200 μm, coated with silicone (bulk density 2.75 g / cm3). (FBM 96-100; Firma Powder Techn.). The measurement is made in a usual measuring station q / m. By using a screen with a mesh size of 25 μm, it is ensured that no carrier accompanies the blown toner. The measurements are made at approximately 50% relative humidity. Depending on the activation time, the following values are measured q / m [μC / g] EXAMPLE OF APPLICATION 1.2 The procedure is as in Application Example 1.1 where, instead of a part of the compound of Preparation Example 1, 5 parts are incorporated. Depending on the activation time, the following values are measured q / m [μC / g] EXAMPLE OF APPLICATION 1.3 One part of the compound of Preparation Example 1 is incorporated into a toner resin, as in Application Example 1.1 and is measured, but a styrene-acrylate 60 copolymer is used as the toner binder instead of the polyester resin: 40 (RDialec S309, Signature Diamond Shamrock) and, as carrier, magnetite particles of size 50-200 μm (90 μm Xerographic Carrier, Plasma Materials Inc., NH, USA) coated with copolymerized styrene-methacrylate (90:10) function of the activation time, the following values are measured q / m EXAMPLE OF APPLICATION 1.4 The procedure is as in application example 1.3, using only 0.5 parts of the compound of preparation example 1 instead of 1 part. Depending on the activation time, the following values are measured q / m EXAMPLE OF APPLICATION 1.5 The procedure is as in application example 1.3, but 5 parts of carbon black are incorporated into the compound part of preparation example 1. (Mogul L, Cabot, see comparison example A). Depending on the activation time, the following values are measured q / m EXAMPLE OF APPLICATION 1.6 1 part of the compound of Preparation Example 2 is homogenously incorporated into 99 parts of a powder coating binder based on a carboxyl-containing polyester resin, for example RCrylcoat 430 (UCB, Belgium), as described in the example of application 11. For the determination of the separation rate, 50 g of the test lacquer powder are sprayed with a pressure defined by a tribopistol. By means of differential weighing, the amount of separate powder coating can be determined and a separation rate is defined in% as well as, through the transmission of the load, a current flow [μA] is taken. Pressure [bars] Current [μA] Separation rate [%] 0.6 75 0.4 55 EXAMPLE OF COMPARISON For the determination of the separation rate of pure powder lacquer binder Crylcoat 430, proceed as described above, but without mixing an additive Pressure [bars] Current [μA] Separation rate [%] 3 0,1 5 APPLICATION EXAMPLE 1.7 Dissolve with stirring (fin agitator or dissolver), 6 parts of the compound of Preparation Example 1 in 94 parts of methyl ethyl ketone. The injection ink thus obtained has the composition: 6 parts of compound of the preparation example 1 94 parts of methyl ethyl ketone.

EXAMPLE OF APPLICATION 1.8 Dissolve with stirring, 5 parts of the compound of Preparation Example 1 in 30 parts of glycol ether (Dowanol EPh, Dow Chemical). This solution is then added, by stirring, to a solution of 50 parts of deionized water with 15 parts of xylene sulfonate. The microemulsion ink thus obtained has the composition: 30 parts of glycol ether 5 parts of compound of the preparation example 1 15 parts of xylene sulfonate (mediator of the boundary layer, hydrotropic substance) 50 parts of deionized water EXAMPLE OF APPLICATION 2.1 The procedure is as in application example 1.1 but now, instead of a part of the compound of preparation example 1, 1 part of the compound of preparation example 2 was incorporated. Depending on the activation time, the following values are measured: / m EXAMPLE OF APPLICATION 2.2 Proceed as in application example 1.3 but now, instead of a part of the compound of! Example of preparation 1, 1 part of the compound of preparation example 2 was incorporated. Depending on the activation time, the following values q / m are measured EXAMPLE OF APPLICATION 2.3 The procedure is as in Application Example 2.2 where only 0.5 parts are incorporated instead of a part of the compound of Preparation Example 2. Depending on the activation time, the following values are measured q / m EXAMPLE OF APPLICATION 2.4 The procedure is as in application example 2.2 where, in addition to the compound part of preparation example 2, 5 parts of carbon black are incorporated (Mogul L, Cabot, see comparison example A). Depending on the activation time, the following values are measured q / m EXAMPLE OF APPLICATION 2.5 The procedure is as in application example 2.2 where, in addition to the compound part of preparation example 2, 5 parts of a dye having a positive electrostatic triboelectric intrinsic effect (C. solvent blue 125, see comparison example B). Depending on the activation time, the following values are measured q / m The high positive triboelectric intrinsic effect of C.l. Solvent Blue 125 can be reversed from polarity, clearly to negative, by adding 1 part of the compound of the preparation example, where the negative charge then still shows a paradoxical good charge constancy depending on the activation time.

EXAMPLE OF APPLICATION 2.6 Dissolve 6 parts of Preparation Example 2, with stirring, in 94 parts of methyl isobutyl ketone. The injection ink thus obtained has the composition: 6 parts of compound of preparation example 2 94 parts of methyl isobutyl ketone.

EXAMPLE OF APPLICATION 2.7 3 parts of the compound of Preparation Example 2 are dissolved in 15 parts of glycol ether (Dowanol EPh) with stirring. This solution is then added, by stirring, to a solution of 74 parts of deionized water with 15 parts of xylene sulfonate (Firma Witco Surfactants, Germany). The microemulsion ink thus obtained has the composition: 15 parts of glycol ether 3 parts of compound of the preparation example 2 8 parts of xylene sulfonate 74 parts of deionized water EXAMPLE OF COMPARISON A: TO EXAMPLES OF APPLICATION 1.5 AND 2.4 The procedure is as in application example 1.3 where, instead of 1 part of the compound of preparation example 1, five parts of Mogul L. Cabot carbon black are incorporated. Depending on the activation time, the following values are measured q / m It is shown that the carbon black used displaces the negative charge to positive.

EXAMPLE OF COMPARISON B: TO EXAMPLE OF APPLICATION 2.5 The procedure is as described in application example 1.3 where, instead of a part of the compound of preparation example 1, five parts of C.l. Solvent Blue 125. Depending on the activation time, the following values are measured q / m The marked positive triboelectric intrinsic effect of blue dye is clearly recognizable.

Claims (13)

NOVELTY OF THE INVENTION CLAIMS

1. Use of the dyes of aluminum-azo complexes 2: 1 of formulas (I) and (I ') below, alone or in combination, as charge control agents in toner and electrophotographic developers, as lacquer load improvers in powder, electret materials and in electrostatic separation processes, as well as in inkjet inks and color filters, (i) ('"), where the A-cores, independently of each other, carry one or two substituents of the (C1-C3) alkyl, (C1-C3) alkoxy, cyano, (C1-C3) alkoxycarbonyl, benzoyl, phenoxycarbonyl, aminocarbonyl , mono- or di- (C 1 -C 4) alkylaminocarbonyl, mono- or di- ((C 1 -C 3) alkoxy) - (C 2 -C 4) alkyl) aminocarbonyl, phenylaminocarbonyl, aminosulfonyl, mono- or di- (C 1 -C 4) alkyl aminosulfonyl, mono- or di- ((C 1 -C 3) alkoxy- (C 2 -C 4) alkyl) aminosulfonyl and phenylaminosulfonyl; all R 1 independently together, they mean a group of atoms, which may eventually carry substituents, necessary for the completion of a mono- or binuclear aromatic ring system, the two R2s, independently of each other, mean a phenyl residue, which optionally bears substituents, or an alkyl moiety (C? -C? 2) or ((C? -C2) alkoxy) - (C2-Cs) alkyl; and X + means a cation

2. Use according to claim 1, characterized in that the colorants of aluminum complexes -azo 2: 1 has the f formulas (la), (Ib) and (le) (qi) 01 85 where in these formulas they mean, the two R's, with respective independence from the other substituents, hydrogen, (C 1 -C 3) alkyl, (C 1 -C 2) alkoxy - (C 2 -C 3) alkyl or phenyl, R 4 hydrogen , halogen, alkoxy (CrC2) or (C1-C2) alkyl, each of the two R5, respectively, a 2-ethylhexyl residue or a phenyl residue which can carry up to three substituents, including up to two of the chloro group, bromine, (C1-C2) alkyl, (C1-C3) alkoxy or acetyl, X? + a sodium, potassium, ammonium or alkyl (C? -4) ammonium ion, and where the two B-nuclei of the formula can carry it one or two substituents each, each of them from the group halogen, hydroxyl, (C1-C2) alkyl, (C1-C3) alkoxy, acetyl, benzoyl or 4,6-bis- (2 ', 4'-d) methylphenyl) -triazinyl-2, or the B-cores carry the groups of atoms necessary for the preparation of a naphthalene ring, preferably attached at the 5 'and 6' position.

3. Use according to claim 2, characterized in that the groups of formula SO2NHR3 in the compounds of formulas (la), (Ib) and (le) are in position 4 or 5.

4. Use according to at least one of claims 1 to 3, characterized in that the cation X + or X? + Is 4-amino-2,2,6,6-tetramethyl-piperidinium, 4-hydroxy-2,2,6, 6-tetramethyl-piperidinium or 4-keto-2,2,6,6-tetramethyl-piperidinium.

5. Use according to at least one of claims 1 to 4 in combination with another charge control agent that controls positively or negatively.

6. Use according to claim 5, characterized in that the other charge control agent is from the group of triphenylmethane, ammonium and imonium compounds, ammonium compounds, fluorinated ammonium and fluorinated ammonium compounds, biscationic acid amides, polymeric ammonium compounds , diallylammonium compounds, derivatives of aryl sulfides, phenol derivatives, phosphonium compounds and fluorinated phosphonium compounds, Calix (n) arene, ring-linked oligosaccharides (cyclodextrins) and their derivatives, especially boric ester derivatives, interpolyelectrolyte complexes ( IPECs), polyester salts, benzimidazolones, azines, thiazines or oxazines.

7. Use according to at least one of claims 1 to 6, characterized in that the total dye concentration of aluminum-azo complexes 2: 1 of formulas (I) or (I ') and the other charge control agents optionally added it is from 0.01 to 50% by weight, preferably from 0.1 to 5% by weight, based on the total mixture of electrophotographic toner, developer, powder coating, electret material or inkjet ink.

8. Electrophotographic toner containing an aluminum-azo compound of formula (I) or (I ') according to one or more of claims 1 to 4 and optionally one or more charge control agents, which control positively or negatively, in a concentration of 0.01 to 50% by weight, preferably 0.5 to 20% by weight, based on the total weight of the toner, as well as a usual toner binder.

9. Powdered lacquer containing an aluminum-azo compound of formula (I) or (I1) according to one or more of claims 1 to 4 and optionally one or more charge control agents, which control positively or negatively, in a concentration of 0.01 to 50% by weight, preferably of 0.5 to 20% by weight, based on the total weight of the powder coating material, as well as a conventional powder coating binder.

10. Liquid for recording by ink injection containing 0.5 to 15% by weight of an aluminum-azo compound of formula (I) or (I ') according to one or more of claims 1 to 4. 11 Liquid for recording by ink injection according to claim 10, which contains from 5 to 99% by weight of water and from 0.5 to 94.5% by weight of organic solvent and, optionally, a hydrotropic compound. 12. Liquid for recording by ink injection according to claim 10 which contains from 85 to 94.5% by weight of organic solvent and, optionally, a hydrotropic compound. 13.- Ink for hot melt injection, composed essentially of 20 to 90% by weight of wax, which melts at a temperature comprised between 60 and 140 ° C, and from 1 to 10% by weight of the aluminum-azo compound of Formula (I) or (I ') according to one or more of claims 1 to 4.