VIRATOR AND ELECTROPHOTOGRAPHIC DEVELOPER, WHICH CONTAINS A AZO MAGENTA PIGMENT
The present invention relates to an elect or otográic toner and developer, based on red pigment C.I. 57: 1, as a coloring. In the electrophotographic recording procedure, a "latent load image" is used over a photoconductor. This "image of load laten + e" is revealed by the contribution of electrically charged toner, which is deposited, for example, on paper, textiles, sheets or plastics, and is fixed, for example, by means of pressure , radiation, heat or by means of solvent. Typical toners are single-component or two-component powder toners (also referred to as single-component or two-component developers); but there are also special toners, such as the magnetic toner or the liquid toner and the polymerization toner (L.B. Schem, Electrophotography and Developinent Physics, Sppnger Series in Electrophysics 14, Bprmger-Verlag,? edition, 19 ^ 2). A measure of the quality of the toner is its specific load q / rn (load per unit mass). In addition to the presentation and the high level of the electrostatic charge, the speed of the availability of the desired high load and the constancy of that charge during a prolonged activation time period are taken into account beforehand. of a firm quality criterion. Additionally, there is another valuable criterion of qualification, which is the insensitivity of the turnaround in the face of the influence of climate, for example, the temperature and the air hyrnedad. Both the chargeable toner and the negatively chargeable toner have application in photocopiers, laser printers-, LED (light emitting diodes), LC printers (liquid crystal shutter)? other digital printers, elecototropic electronic base, depending on the type of process and apparatus. In order to obtain a positively charged or negatively charged toner or electrophotographic developer, a charge regulator must be added frequently. As a color imparting component, it is typically used in toners of colored pigments of organic colors. Color pigments have outstanding advantages over color materials, due to their insolubility in the use medium, for example, they have better stability and resistance to light. Based on the principle of "subtractive color mixing", it is possible to reproduce, with the help of the three primary colors yellow, cyan and magenta, the entire spectrum of colors observable by the human o. Only the exact reproduction of a color is possible when using the corresponding primary colors that produce precisely defined color results. Otherwise, no color tone can be reproduced and the color contrast is not pure. As full color toners, the three yellow, cyan and magenta toners must be affixed exactly to each other, in addition to precisely defined color results, also with respect to their electrical properties, so that they are transferred one after the other. * ro in the same devices. It is known from colorants that the rich tpboelect charge of the toners can be partially influenced in a lasting manner (H. T. Macholdt, A. Sieber, Dyes a Pigments, 9 (1988), 119-127). Due to the different triboelectric effects of the colorants and their partially pronounced influence on the load capacity of the toner, it is not likely that the colorants are simply added to a single toner base receiver or to a single site. . On the contrary, it may be necessary that each dye has its own receiver so that any type and amount of the necessary charge carrier can be diverted. This way of proceeding is used correspondingly and does not contribute to the resolution of the disadvantages that have already been described previously in the toners for the coloring process. It is additionally important in practice that the dye has a great thermostability and a good dispersion capacity. The typical temperatures of treatment in the vitreous resin, during the use of mixers or ex-Russian, they reach 100 ° C and 200 ° C. Correspondingly, a thermostability of 200 ° C, better still, of 250 ° C would be highly advantageous. It is also important that the climate is durable over a long period of time (approximately 10 minutes) and in different systems of agglutinators. Typical toner binders are polymerization, polyaddition and polycondensation resins, such as styrene, styrene reinforcement, styrene-butadiene, acrylate, polyester, tenol-epoxide.; polulins, polyurethanes, individually or in combination, which, in addition, may contain other ingredients, such as charge regulators, waxes and flowables, or which may be added later. The magenta pigments for toner and developer1 electrophotographs are used in numerous ways. Magenta pigments typically used are the pigment ro or Cl 122 based on q? Macridone, the pigment ro or C.I. 48, the red pigment C.I. 57: 1, the red pigment C.I. 146 and the red pigment C.I. 184, of azo base, as well as the violet pigment C.I. 1 and the red pigment C.I. 8, based on triarylcarbonium. The coloring magenta pigment ro or C. I: 57: 1 is especially interesting since it corresponds to the standard color-magenta shade. An alternative to the red pigment CI 57: 1, due to its color tone, is the violet pigment CT 1, which, however, has poor resistance properties, especially its property of resistance to light, so that , in practice, it should be mixed in most cases with the pigment ro or CT 12 ?, a lot of light (2, -d? met? lqu? nacr? dona). Therefore, there is a need for a magenta pigment having the highest possible transparency, resistance to azing, good dispersion capacity and an appropriate triboelective effect, as stable as possible. For a stable appropriate triboelectric effect, it should be understood that the pigment manifests its maximum triboelectric effect on the toner after the shortest possible activation time, and that this value remains stable for as long as possible. The toner and developer, which have unstable q / rn values, that is, whose load capacity depends on the activation time, are correspondingly difficult to control. ' Transparency is of paramount importance, since during copying or printing in full color, the colors yellow, cyan and magenta are copied or printed on one another, so that the succession of colors depends on the device. If the color that is deposited on another is not sufficiently transparent, then the color that is left underneath may not appear enough and the color reproduction is distorted. Transparency is also important when copying or printing on sheets for rear projection, since then the lack of transparency can produce only a grayish color throughout the projection of the image. The purpose of the present invention is to provide a magenta dye that is as resistant as possible, transparent and resistant to blueing, with an appropriate and stable effect, with good dispersion capacity and high temperature, for use in electrophotographic toners and developers. , powders and varnishes in powder form, inkjet inks as well as in currently available electronic materials. Surprisingly, the purpose was solved by means of the azo pigment that is characterized below. The present invention provides the use of an azo pigment of the formula (1):
as a colorant in toners and electrophotographic developers, powders and powder coatings, electronic materials, as well as in ink jet inks, characterized in that the azo pigment has a specific surface area of the pigment powder of more than 70 m2 / g, preferably more of 80 m2 / g, especially more than 85 rn2g and because the azo pigment particles have a long to broad ratio on average of less than 2.8: 1, and an average particle size dso of less than 130 nrn. The pigment powder may have a specific surface < up to 200 rn2 / g, especially up to 150 rn2 / g. A pigment with the structure according to formula (I) is already known and commercially available under the designation red pigment C. I: 57: 1. However, it is novel and surprising that a red pigment 57: 1 can be obtained in the form of particles, the particle size and the specific surface according to the invention, which means a significant improvement over the red pigment C.T. 57: 1 until now, with respect to transparency and bluing resistance, for better color fastness and better dispersibility and electrostatically appropriate effect. Especially the ratio of length to width is on average less than 2.7: 1 and the particle size d2s is less than 100 nm and 7s is less than 180 nrn. The red pigment CI: 57: 1 according to the present has a strong negative electrostatic effect (JA-OS 72-71 966, P. Gregory High Technology Applications of Organic Colorants, Plenum Press, New York 1991, pages 99-102) . In EP-A-0 359 123 it is described how by the addition of the appropriate compounds of ammonium, ionium, phosphonium, arsenium or stylonium, the strong negative effect can be partially or totally counteracted, so that said addition must be effected either during the coupling reaction or during the application of the varnish or during the pigment finishing. It is further described that by special master charges, ie, high concentration pigment predispersions in selected resins, the typically appropriate effect of the red pigment C.I. 57: 1 (V. Schiosser and co-authors, Soc ety of Imaging Science and Technology, 1st Congress on Advances in Impact-Free Printing Technologies, Hilton Head, SC, USA, October 29-November 11, 1995, Proceedings, pages 110-112). In addition to the additional treatment step, this method has the disadvantage that a proportionally divided master load must be used for each filling resin, which is economically and commercially unprofitable. If the master charge is exclusively used based on the given normal resin, the toner system is contaminated with foreign resins. By using the azo pigments according to the invention, the disadvantages of said additional attachment step are remedied. The preparation of the red pigment C.I. 57: 1 is described, for example, in Ullmanns Encyklopadie der Technischen
Chernie, volume 18, pages 661-695, Verlag Chernie, leinheim, 1979; or in U. Herbst, K. Hunger Industrial Organic Pigments, VCH Ueinhei, 1993, or in Pig in Handbook, editor: T. C. Patton, 3. Wiley & Sons, New York, 1973. The preparation of the azo pigments used according to the invention is carried out in such a way that, at a desired time point during the synthesis, an auxiliary based on oxyalosilanes or non-Lonogens is added. of alcohols, fatty alcohols, phenols, alkylphenols, naphthols, alkali or fatty amines and full-oxide and / or propylene oxide, as well as block copolymers of ethylene oxide and propylene oxide; compounds with a poly (ethyleneoxy) chain or a poly (et? lenox?) - pol? - (rnet? let? lenox?) chain, which are linked by means of an oxygen atom or a nitrogen atom with radicals. following type: primary or secondary alkyl radicals, of 6 to 26 carbon atoms, especially preferably alkyl radicals with chain length of 0 to 18 carbon atoms, especially the nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl radicals , hexadecyl, heptadecyl, octadecyl, 2-butyloctyl, 2-phenyloctyl, 2-hex? ldecyl, 2-heptyl, undecyl, 2-octyldodec, 2-non? Riddle, 2 ~ dectetradec ?, 10-undecem lo, oleyl, 9-octadecenyl, linoleyl or Imolemlo; aliphatic radicals of 6 to 30 carbon atoms; aromatic radicals, such as the phenyl radical or the alkylphemyl radical, optionally substituted with up to three primary or secondary alkyl radicals, preferably the hexylphenyl, heptylphenyl, octylphemyl, nomlyl, undecylphenyl, dodecylphenyl, isononylphenyl, t-butylphenyl or dinonylphenyl radicals; the phenyl radical can be substituted with other aromatic radicals, such as the benzyl-p-phenylphenyl radical, the
naphthyl or alkylnaphthyl radicals, preferably the alpha-naphthyl or beta-naphthyl radical or the alkyl beta-naphthyl radical, with the 3 unbranched or branched alkyl groups, for example, the methyl, butyl, octyl, nonyl groups , decile, dodecilo or tet adecilo; optionally substituted alkyl radicals with alkyl, or substituted alkyl radicals with heterocyclic radicals, such as, for example, the radical 2-C- (8-heptadecen-1-1) ~ 4,5-d-hydro -l-? m? dazol? l3-et? lo. Mixtures of the compounds mentioned above and, especially, mixtures obtained by oxyalkylation with ethylene oxide and / or with propylene oxide, synthetic fatty alcohols, obtained from oxosynthesis, or fatty alcohols from raw materials can also be used. natural (after the dissociation of fat and reduction). Natural raw materials include coconut oil, palm oil, cottonseed oil, sunflower oil, soybean oil, flaxseed oil, turnip oil, tallow and oil. of fish. Also suitable are the fatty amine oxyalkylates, derived from these natural raw materials, especially coconut fatty amine, tallowamine, oleylamine or dialkylamino fatty acid, such as, for example, dirnethylcocoalkyl oxide. In addition, mention may also be made of surface-active, high molecular weight oxyalkylated auxiliaries (surfactants), such as, for example, those described in the following patents and patent documents published and open to inspection: DE-A 1-27 30 223 , DE-B2-21 56 603, DE-A1-30 26 127, DE-B2 24 21 606 and EPAl-00 17 189. Additionally it is also possible to add modern nonionic surfactants, based on reproduced raw materials such as, for example, sugar alkylate, it being also possible to use all of the aforementioned nonionic surfactants, in admixture with ammonium or cationic surfactants. Particularly interesting as ammonium surfactants are those which contain polar hydrophilic groups, sulfonic acid functions, sulfuric acid sermester, phosphoric acid partial ester or carboxylate function, such as, for example, the especially preferred rosin derivatives, their salts and their salts. derivatives, as well as abietic acid, its salts and its derivatives. In general, the cationic surfactants contain a quaternary amine function (phospho-io functions are also possible) and corresponding counter ions, such as halide, or anions derived from oxyacids of elements of the main groups. counter ions also intramolecularly (surfactants of the betaine type). The primary, secondary and tertiary amines can eventually be used, their surfactant potential is a function of the pH value during the addition. Rosin resin and abiotic acids are especially preferred in the context of the present invention. The addition of auxiliaries can be carried out before, during or after the coupling and / or before, during or after finishing the pigment. It is convenient that the auxiliary be added in such a quantity, that the ready-to-use powder pigment contains from 20 to 50% by weight, preferably from 25 to 40% by weight, of auxiliary, with respect to the total weight. By means of the preparation process which is described, the desired azo pigment is obtained in the form according to the invention, the auxiliary used on the pigment cpstalites being fixed. In addition to electro-photographic toners and developers, an electrostatically different effect of a pigment can also lead to an improvement in the electrostatic deposition of powder and varnish, especially in powder varnishes sprayed triboelectrically or electrochemically, such as those They are used for the surface coating of metal objects, plastic, ream, glass, ceramic, concrete, textile, paper or rubber. The technology of powders can be used, for example, in the lacquering of small objects, such as garden furniture, camping equipment, household appliances, vehicle parts, refrigerators and gifts, as well as in the painting of shaped pieces. complicated. The powder varnish or the powder receives its electrostatic charge in general following one or both of the following procedures: a) by means of a corona process, the powder varnish or powder is passed through a charging wheel, and thus load; b) in a tpboeléct p co or electininic procedure, is formed from the principle of the use of electricity by friction. The powder varnish or powder contains an electrostatic charge in the spray head that is contrary to the load of the friction partners, generally a hose or a sprinkler tube, for example, of polite rafluoroe + ileno . A combination of both procedures is also possible. Coating powder reams are typically used in epoxy resins, polyester resins containing carboxyl and hydroxyl groups, polyurethane and acrylic reams, together with the usual hardeners. It is also possible to use resin combinations. For example, epoxy resins are often used in combination with polyester resins containing carboxyl and hydroxyl groups. The typical components of the hardener for the epoxy resin without, for example, the acid anhydrides, the id idazole as well as the dicyanodiamide and its derivatives. For polyester resins containing * hydroxyl groups, typically the hardening components are, for example, acid anhydrides, the capped isocyanate, bisacyl urethane, phenolic resins and melamine resins. For polyester reams containing carboxyl groups, the typical hardening components are, for example, t-glycidyl isocyanurate or epoxy resins. In the case of replenishings, typical hardening agents can be used, for example: oxazole, isocyanate, tiglicyl isocyanurate or di carboxyl acids. The disadvantage of an insufficient load must be observed, first and foremost, during the pulverization of the powder and the powder varnish, which have been prepared on the basis of polyester resins, especially polyesters containing Lieho earhox groups. based on mixed powders such as those mentioned, also known as hybrid powders. Mixed powders are powder coatings whose ream base consists of a combination of epoxy resin and polyester resin containing carboxyl groups. The mixed powders form the basis for the powder varnishes represented in practice frequently. The insufficient loading of powder and powder varnish mentioned above results in. Additionally, a triboelectrically own, different effect of a pigment, can lead to the improvement of the electrical properties in colored colored (pigmented) electles, where the typical electromagnets are based on polyolefms, halogenated polyolefms, polyaphatics, polyacrylomethyl, polystyrenes or fluoropolymers, such as, for example, polyfluorides, polypropylene, polytetrafluoroethylene and perfluorinated ethylene and propylene, or based on polyesters, polycarbonates, polyamides, polynides, polyether ketones based on polyaluric sulphides, especially polyalkylene sulphides; polyacetals, cellulose esters, polyalkylene terephthalates, as well as mixtures thereof. The electronaterials have numerous uses and can be loaded by means of a corona loading or tribocharging operation (Literature: G. M. Sessier, Electret, Topics m Applied Physics, lathe 33, Springer VerLag,
New York, Heildelberg, 2a. edition, 1987). In addition, a triboelectrically appropriate effect different from a pigment can lead to improved separation performance of colored (pigmented) polymers that are separated following an electrostatic separation process (Y. Higas iyau, J. of Elect.rostatics, 30). pages 203-212, 1993, and JA Cross, Elect rostatics-Prmci feet, Problems and Applications, Adarn Hilgr, Bpsto, L987, especially chapter 5.3 Electrostatic Separation, as well as the literature cited there). Correspondingly, the triboelectrically appropriate effect of the pigments for the coloration of plastics masses is important. In the same way, the triboelectric effect is appropriate for the process / treatment steps in which it undergoes intensive friction contact, such as, for example, the centrifugation processes, the rolling processes or the molding processes. Additionally, the red pigment 57: 1 according to the invention is suitable as a dye in tmfa, aqueous and non-aqueous based ink inks, especially in those inks prepared following the hot-melt process. According to the invention, an ink-jet ink containing 0.01 to 50% by weight, preferably 0.5 to 20% by weight, of the azo pigment defined in claim 1 or 2 is provided. The main advantage of the pigment Azo according to the invention, especially in agglutinators for toner, appears when compared with red pigment CT 57: 1 hitherto normal (Permanent RubinCR) L6B02). Thus, the red pigment 57: 1 according to the invention (example 1) exhibits a substantially improved transparency (about 5 units of transparent evaluation and an increase of about 5 evaluation units in the blueing resistance), which it means a considerable improvement in practice. It is especially noteworthy that the pigment according to the invention, in comparison with the known norm, not only exhibits a smaller particle size, but that, in addition, the particle shape is improved from the shape of the needle usual in the direction of the cube shape. This improvement reinforces a clearly lighter dispersion capacity and a clearly lighter suspension capacity in polyorganic and solvent (organic) materials. The improvement in transparency obtained in practice is of great value and is also recognizable to the naked eye of the human eye. Additionally it is surprising that, despite the pronounced improvement in transparency by means of the very superior specific surface, the other coloristic, advantageous pigment properties, such as color hue, thermostability and Light firmness, do not diminish. This can be verified, for example, because in the X-ray reflection diagram, the crystal modification, as well as the position and the average amplitude of the reflection bands remain almost unchanged. Additionally, the improvement of the electrically appropriate effect of the pigment according to the invention can be checked against the current position of the art. Although in the comparative example carried out, the red pigment C.r. 57: 1 results in an unstable tribo-load charging effect, in the pigment according to the invention it is very stable, that is, the maximum load value is reached quickly and remains almost constant for more than 24 hours. Thus, a test toner is loaded with 5% of the pigment according to the invention (Example 1.3.1) and after 5 minutes at a peak value, while a comparative test toner, with a Pigment according to the state of the art (comparative example 1.3.1) does not exhibit a constant final value even after 24 hours of friction loading. The azo pigment according to the invention can be combined with numerous charge regulating means, that is, both positive control and negative control, and produce good loading capacities according to the application technique. As regulator or charge controller, which can be combined with the azo pigment according to the invention, it can be mentioned: tri fe lmetano; ammonium and ironium compounds; (iminium compounds); fluorinated ammonium and unonium compounds, biscationic acid amides, ammonium polyrnep compounds, diallyl onium compounds, aryl sulfide derivatives, phenol derivatives, phosphonium compounds and fluorinated phosphonium compounds; Calix (n) arene; oligosacap two linked, ring formers (cyclodextrin na); polyester salts, complex metal compounds, especially »cilate-salt complexes and non-metal salicylate complexes; alpha-hydroxycarboxylic acid complexes and alpha-hydroxycarboxylic acid-non-metal complexes; benzimidazolone, azine, thiazine or oxazine, which are indicated in the color index (Color Index) as pigments, solvent dyes, basic dyes or acid dyes. Especially preferred are the following charge regulators, which may be combined with the azo pigment according to the invention, individually or in combinations with each other. Triarylrnetane derivatives, such as, for example: Pigment blue Color index (CI) 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, CI solvent blue 2, 3, 4, 5, 6, 23, 43, 54, 66, 71, 72, 81, 124, 125, as well as the taryiarylmethane compounds indicated in the color index under the names acid blue and basic dye, as long as they are appropriate with respect to that? stability with temperature and its treatment capacity, such as, for example, the basic blue CI 1, 2, 5, 7, 8, Ll, 15, 18, 20, 23, 26, 36, 55, 56, 77, 81, 83, 88, 89, the basic green CI 1, 3, 4, 9, 10, especially the solvent blue C.I. 125, 66 and 124. The solvent blue C.I is especially suitable:
124 in the form of s? strongly crystalline sulfate or the tetraeloroal? ricinotp feml methyl rinnate. Especially preferred are the metal complexes with CAS Nos. 84179-66-8 (chromoazo complex), 115706-73-5 (ironazo complex) 31714-55-3 (chromoazo complex), 84030-55-7) complex of chrome salicylate) 42405-50-3 (chromium isocylate salt complex) as well as the quaternary ammonium compound CAS No. 116810-46-9. Examples of charge regulators suitable for the preparation of electric wires of the family of tpfenilmetano, the compounds described in DE-A-1 919 724 and DE-A-1, 644 619. Also described are the tpfenilmetanos that are described in US-A-5,051,585, especially those of the formula (2): wherein: R 1 and R 2 are the same or different and denote -NH 2, a mono- and dialkylamino group, whose alkyl groups have from 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms; a mono- or d? omega-hydroxyl group, the alkyl groups of which have from 2 to 4 carbon atoms, preferably 2 carbon atoms; a feml- or phenylalkyl group, optionally substituted with N-alkylamino, wherein the alkyl has from 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms, and wherein the phenylalkyl groups in the aliphatic bridges they have from 1 to 4, preferably 1 or 2 carbon atoms, and wherein the core of femlo has one or two of the following constituents: alkyl of 1 or 2 carbon atoms, alkoxy of 1 or 2 carbon atoms , and that can carry sulfonic acid groups. R2 is hydrogen or has one of the meanings given for R1 and 3; R * and R5 mean hydrogen, halogen, preferably chlorine, or a sulfonic acid group; or R * together with R5 form a ring of faith the non-condensed. Each of R6, R7, R9 and Rio means hydrogen or an alkyl radical of 1 or 2 carbon atoms, preferably me ilo; R8 is hydrogen or halogen, preferably chlorine; and X- represents a stequio-rich equivalent of an anion, especially an anion chloride, sulfate, olibdate, phosphoromolybdate or borate. Especially preferred is a charge regulator of the formula (2) wherein R 1 and R 3 are phenylene groups, R 2 is an rn-methylphenylamino group and the radicals R * to R ° are all hydrogen. Ammonium and ammonium compounds, such as those described in US-A-5,015,676, are additionally suitable. Also suitable are fluorinated ammonium and ironium compounds, such as those described in US-A-5,069, 99, especially those of the formula (3):
wherein: R 3 is perfluorinated alkyl of 5 to 11 carbon atoms;
Y?
R23? R33 R43 are the same or different and mean alkyl of 1 to 5 carbon atoms, f) reference of L or 2 carbon atoms; and Y- is a stereoquinone equivalent of anion, preferably of an anion tet ra fl uo robo rato or tet rafenilborato. Preferably, the meanings are: R13, perfluorinated alkyl of 5 to 11 carbon atoms; R23 and R33 t ethyl; and R43 methyl. In addition, the biscateic acid amides, such as those described in UO 91/10172, especially those of the formula) are suitable:
wherein: Rl *, R24 R34? Cn equal or different alkyl radicals, of 1 to 5 carbon atoms, preferably methyl; n represents an integer from 2 to 5; and 2-e represents a stoichiometric equivalent of an anion, preferably an anion te ra fen ll borate. Dialilanomer compounds, such as those described in DE-A-4 142, are also suitable.
541, especially those of the formula (5):
wherein: R15 and R25 mean the same or different alkyl groups, of 1 to 5 carbon atoms, preferably 1 or 2 carbon atoms, especially methyl groups; and A- represents an equivalent eetequiomet p co of an anion, preferably represents an anion tet rafenilbo while, as well as the polyrheric ammonium compounds derived from them, of the formula (6), such as those described in DE-A - 4 029 652 or DE-A-4 103 610:
where n has a value corresponding to molecular weights of 5,000 to 500,000. Especially preferred are those compounds of the formula (d) having molecular weights of 40,000 to 400,000. Also suitable are aplo sulfide derivatives, such as those described in DE-A-4 031 705, especially those of formula (7):
wherein: Rl7, R, R37 * 7 mean the same or different alkyl groups, of 1 to 5 carbon atoms, preferably 2 or 3 carbon atoms; and R5 is the divalent radical -S-, -S-S-, -SO- or -SO2. For example, the groups R to R * 7 are propyl groups and R5 is the group S-S-. In addition, phenol derivatives, such as those described in EP-A-0 258 651, especially those of the formula (8) are also suitable:
wherein: R and R38 are alkyl or alkenyl groups of L to 5 carbon atoms, preferably 1 to 3 carbon atoms; and R28 and 48 are hydrogen or alkyl of 1 to 3 carbon atoms, preferably methyl. As examples, mention is made of the compounds in which Rl8 to R48 < In methyl groups or in which R28 48 are hydrogen and R 8 and R 38 represent the group -CH 2 -CH-OH 2. Also suitable are fuso io compounds and fluorinated phosphonium compounds, such as those described in US-A-5,021, 473 and in US-A-5, 147, 748, especially those of the formulas (9):
in which: R19, R9 39 R "9 means identical or different alkyl groups, of 1 to 8 carbon atoms, preferably of 3 to 5 carbon atoms and R- represents a stoichiometric equivalent of an anion, of preferably a halide anion; and (10): 21 O
R 41 O where: RUO represents a strongly fluorinated alkyl radical, of 5 to 15 carbon atoms, preferably 6 to 10 carbon atoms; R io, R3io and 4 i o They are alkyl of 3 to 10 atoms of carbon or phenyl. As an example of a compound of the formula (9), tetrabutylphosphonium bromide is mentioned; Examples of compounds of the formula (10) are compounds with RUO = C8F17-CH2-CH2-, R2 or = R3io = R4io = phenyl and Eß- = PF6 ° - or the tetraphenyl orate anion. Cal? X (n) arenes are also suitable, such as those described in EP-A-0 385 580 and as described in EP-A-0 516 434, especially those of formula (11):
2 ?
wherein: R represents hydrogen, halogen, especially chloro, straight or branched chain alkyl, 1 to 12 carbon atoms, aralkyl, for example, benzyl or phenethyl, -NO2, -NH2- 0 NHR n, wherein R n means alkyl of 8 carbon atoms, optionally substituted by alkyl having 1 to 4 carbon atoms or - (0H3) 3- Further complex metal compounds, such as chromium-, cobalt- complexes, are additionally suitable. iron-, zinc- or alummium-azo, or the complexes of chromium-, cobalt-, iron-, zinc- or alu-mo-salicylic acid or -boric acid of the formulas (12), (13) and (14) :
wherein: H stands for a divalent or trivalent metal atom, preferably chromium, cobalt, iron, zinc or aluminum; or also a non-metal, such as boron or Si; YD and Zn represent aromatic double bond rings, preferably of the formulas: and rn is a number of 1 or 2;
1 wherein: M 'means a divalent or trivalent metal atom, preferably chromium, cobalt, iron; Rii3 is hydrogen, halogen, preferably Cl, nitro or amidosulfonyl; R213 is hydrogen or nitro; R313 is hydrogen, the sulfonic acid group, -C0-NH-R413, wherein R4 3 is phenyl, alkyl of 1 to 5 carbon atoms, which event is substituted by a mono-, di- or trialkylamino group; and G, in the formula (12) and in the formula (13) in each case is an opposite ion, which maintains the neutrality of the complex, preferably one or more protons, one or more alkali metal or ammonium ions .
wherein: M * is a divalent metal central atom, preferably a zinc atom; R i * and R2 14 mean the same or different alkyl groupsstraight chain or branched chain, from 1 to 8 carbon atoms, preferably from 3 to 6 carbon atoms, for example, tertiary butyl. Compounds of these classes are described in EP-A-0 152 632, U5-1-4 908 225, EP-A-0 393 479, EP-A-0 360 617, EPA-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-ñ-4 590 141 and / or characterized by the CAS numbers: 31714-55-3, 104815-18-1, 84179-68-8, 110941-75-8, 32517-36-5, 38833-00- 00, 95 692-86-7, 85414-43-3, 136709-14-3, 135534-82-6, 135534-81-5, 127800-82-2, 114803-10-0, 114803-08-6 . Examples of especially preferred metal complex compounds of the formula (13) are those given in the following Table 1:
TABLE 1
Additionally, benzunidazolones, such as those described in EP-A-0 347 695, especially those of the formula (15):
R 1 215
wherein: Rii5 is an alkyl of 1 to 5 carbon atoms and R2is is an alkyl of 1 to 12 carbon atoms and L is a stoichiometric equivalent of an anion, especially a chloride anion or tetra-1-boroborate. An example is the compound where Rus = CH3 and R 5 = C11H23. In addition, the linked oligosaccharides, such as those described in DE-A-4 418 842, especially those of the formula (16), are suitable:
where n ^ is a number between 3 and 100; R16 and R2.6 have the meaning of OH, 0R316, where R316 means alkyl of L to 18 carbon atoms, substituted or unsubstituted, aryl of 6 to 12 carbon atoms or tosyl; Y ? fi has the meaning of CH2OH or CH2COR316. it is mentioned as examples: nie = 6; RH6 and R216 = OH X16 = CH2OH; n16 = 7; RUS and R216 = OH X16 = CH2OH; n! 6 = 8; R1 and R216 _ QH X16 = CH2OH. Further suitable are polymer salts, such as those described in DE-A-4 332 170, whose anionic component is a polyester, which consists of the reaction product of the individual components a), b) e) , as well as, eventually, d) and, optionally, e): a) is a dicarboxylic acid or a reactive derivative of a dicarboxylic acid, which are free of sulfo groups. b) is a difunctional, aromatic, aliphatic or cycloaliphatic sulfo compound, which functional groups are hydroxyl or carboxyl, or hydroxyl and carboxyl;
c) is an aliphatic, cycloaliphatic or aromatic diol, a polyether diol or a polycarbonate diol; d) is a polyfunctional compound (functionality greater than 2), whose functional groups are hydroxyl or carboxyl, or hydroxyl and carboxy Lo, and e) is a monocarboxylic acid; and their cationic components are hydrogen atoms or metalium cations. The colors of the following color index numbers are also appropriate: Solvent black C.T. 5, 5: 1, 5: 2, 7, 31 and 50; black pigment C.I. 1, basic red C.I. 2 and basic black C.T: 1 and 2. It is essential that the pigment according to the invention is suitable for combinations with charge regulators (CCA) both positive and negative. Suitable for this purpose are amounts of 0.01 to 20% by weight, preferably 0.1 to 5% by weight, of charge regulator, with reference to the total weight of the toner or electrophotographic developer, powders or powder varnishes, in order to obtain the desired polarity. A clear advantage of this is the fast reach of the peak load value and its very good constancy. Because a high toner pitch resistance is necessary for a good triboelectric load (of the toner) (ie, low conductivity), the known dielectric data of the magenta pigment according to the invention are carried for good triboelectric performance (Ku / Liepins, Eléc rica! Properies of Polymers, Hanser Publishers, Mun? Ch ~ V? Ena-New
Yorl, m 7). The combination of pigment and charge regulator can be obtained later by means of physical mixing during the synthesis of the pigment, during the finishing stage or by means of a corresponding elevation on the surface of the pigment (pigment coating). In accordance with the invention, there is further provided an electrophotographic toner or developer containing a conventional toner binder, from 0.01 to 50% by weight, preferably from 0.5 to 20% by weight of the azo pigment according to the invention, and from 0 to 20% by weight, preferably from 0.1 to 5% by weight, of a charge regulator, of the class of phenyl-urethane, ammonium and ionium compounds, fluorinated ammonium and ironium compounds, amides biscatiómcae acid, polimépcos ammonium compounds, diallylammon compounds, anhydride sulfide derivatives, phenol derivatives, phosphonium compounds and fluorinated phosphonium compounds; Cal? X (n) arene, cyclodextrin, polyether salts, metal complex compounds, benzimidazolone, azine, thiazine or oxazine. Particular preference is given to electrostatic toners or developers containing a charge regulator of the formula (17): NH
or a compound of formula (3) given above; or a compound of the formula (5) given above, wherein each of R 5 and R 25 is methyl and A ° - is a tetrafer-1-borate anion; or a compound of formula (6) given above, wherein each of R s and R 5 is rnetLio, A * > - is a tetraphenyl borate anion and n has a value corresponding to molecular weights of 5,000 to 500,000; or a compound of formula (7) given backwards; or a compound of formula (13) given further back, wherein RH3 is chloro, R213 and R313 are hydrogen, N 'is chromium, cobalt or iron and G is one or two protons; or a polymeric salt mentioned above, whose ammonium component is polyester. The good use of the azo pigments according to the invention for use in powder coatings is checked at a high charge current obtainable on a nozzle printer of 3 bar (L.2 μA in example 1.3.2), on the that a load current of 1 μA is provided as a minimum condition for an effective load operation. According to this, when using the high load current, there is a good segregation share of clearly more than 70%. According to the invention there is further provided a powder or powder varnish containing an epoxide, carboxyl or polyester resin containing hydroxyl or acrylic groups, or a combination thereof, of 0.01 to 50% by weight, preferably from 0.1 to 5% by weight, of the azo pigment according to the invention, and from 0 to 20% by weight, preferably from 0.1 to 5% by weight of a charge regulator, of the class and the preferred compounds mentioned for the toner-electrophotographer co. The pigment used according to the invention is incorporated in a concentration of 0.01 to 50% by weight, preferably 0.5 to 20% by weight, especially 0.1 to 5.0% by weight, with respect to the total mixture, in the binder of the toner, developer-, the varnish, the powder varnish, the electromaterial or the polymer which is to be electrostatically separated, homogeneously, for example, by extrusion or kneading. In that way, the pigment prepared according to the present invention can be added as a dry and ground powder, as dispersion or suspension in organic or inorganic solvents, as a pressure cook, as a masterbatch, as a preparation, co or a paste thick, as well as on an appropriate carrier, such as, for example, Kieselgur, TiO2, AI2 3, co or a compound prepared in aqueous or non-aqueous solution, or in another form. It is also possible to add the pigment prepared according to the invention during the preparation of the corresponding binder, that is to say, during its polymerization, polyadicion or polycondensation. The degree of electrostatic charge of the electrophotographic toner or powder varnish, in which the pigment according to the invention is homogeneously incorporated, can not be predicted and is measured in normal test systems, under equal conditions (equal dispersion, equal particle size distribution, same particle shape) at approximately 20 ° C and 50% relative humidity. The electrostatic charge of the toner is obtained by stirring with a carrier, that is, with a standardized friction partner (3 parts by weight of toner per 97 parts by weight of carrier) in a bank of rollers (150 revolutions per shaft). The electrostatic charge is then measured on a standard q / rn meter (3. H. Dessauer, HE Clark Xerography and related Processes, Focal Press, NY, 1965, page 289. 3. F. Hughes, Electrostatic Powder-Coating, Research Studies Press Ltd., Letchworth, Hertfordshire, England, 1984, chapter 2). In the evaluation of the value q / m o of the tpbocarga of the powder varnish, the particle size has great influence so it is banned in the toner or powder varnish, obtained by sieving, large unit particle sizes. Thus, a mean particle size of 10 μrn is established for the toner, while a mean particle size of 50 μrn is practical for powder coating. The powder ribo-spray (powder varnish) is carried out with a spray device having a normal spray tube and an inner star bar, to a maximum dust production with a spray pressure of 3 bar. The object to be sprayed is hung for it in a spray booth and sprayed approximately at a distance of 20 crn, directly without additional movement of the spray apparatus. The corresponding spray powder charge is then measured with a "meter-" for measuring the riboelectric charge of powders "of the Tntec firm (Dortrnund, Germany) To measure the measuring antenna of the measuring device is kept directly in the cloud of powder that comes out of the spray apparatus The force of the electrostatic charge of the powder varnish or powder obtained is indicated in μA The separation rate is then calculated in%, establishing the difference between the sprayed powder varnish and the A powder varnish is removed The transparency of the azo pigment according to the invention is obtained in the toner agglutinator systems, as follows: It is stirred for 5 minutes, at 5,000 rpm, in 70 parts by weight of a crude varnish (consisting of 15 parts by weight of the corresponding toner ream and 85 parts by weight of ethyl acetate), 30 parts by weight of the pigmented test toner (for the preparation, see example 1.3.1) c in a solvent. The test toner varnish thus obtained is scraped off against a standard pigment varnish, obtained in a similar manner, with a hand-held applicator (Fa.RK Chemical Co., Ltd, England) on an appropriate paper (paper for printing books, by example). An appropriate size of scraper is, for example, K baria N 3 (24 μm thick scraper layer). The paper has printed, for better appreciation of transparency, a black mark, whose difference in transparency is obtained in dL values according to DIN n55 9088, or it is assessed according to the commercial pigment test text of Hoechst AG "Visual and colorimetric assessment" of 13.09-1990 (No. 1/1). The residual salt content given during the characterization of the pigment describes the specific conductivity of the extract of an aqueous suspension of pigment or (according to the commercial pigment test text, Hoechst AG No. 1/10 (2/91) "Estimation of the specific conductivity in the extract of an aqueous suspension of pigment "), the corresponding obtained pH value is calculated, according to the commercial pigment test text, Hoechst AG 1/9 (2/91)" Calculation of the value of pH in the extract of an aqueous suspension of pigment ", using in both calculation methods bidistilled water instead of the deionized water mentioned in the test document. The red pigment C.T. 57: 1 according to the invention, mentioned in Example 1 below, contains as an auxiliary abietic acid in the form of its calcium salt (CAS No. 13463-98-4) (approximately 30%). The pigment 57: 1 used in comparative example 1 is Pepnanent RubiníR >; L6B02 (Hoechst AG). In the examples that follow, parts mean parts by weight and percentages, percentages by weight.
EXAMPLE 1 SYNTHESIS
37.4 parts of 4-ammotoluene-3-sulphonic acid are dissolved in 500 parts of water and 26.1 parts of caustic soda (33%). After cooling with ice at 0 ° C, 56 parts of hydrochloric acid (31%) are added and then, for 10 minutes, at a temperature of 0 to 5 ° C, diazotized with 34.5 parts of sodium nitrite solution at room temperature. 40% 39 parts of beta-hydroxynaphthoacetic acid are dissolved in 1,000 parts of water and 70 parts of 33% caustic soda. The diazo suspension is added to this solution within 20 minutes at 20 ° C. After adding a solution of 37.8 parts of abietic acid in 380 parts of water and 15 parts of 33% caustic soda, the pH is adjusted with dilute hydrochloric acid to pH 9.0. For varnishing a solution of 35 parts of calcium chloride (77-80%) in 100 parts of water is added dropwise, during 5 minutes. The pigment suspension is heated after regulating the pH value with dilute hydrochloric acid at pH 6.0, at a temperature of 80-85 ° C, stirring for 30 minutes at that temperature, aspirating, washing with water until neutral and until it is free of salt, and dried at 80 ° C until obtaining a constant weight. 126.2 parts of a red colored varnish are obtained. 1.1 Pigment characteristics: BET surface: 90 rn2 / g Residual humidity (heating lamp): 1.0% (Karl-Fisher, 4.9%, including crystallization water) Residual salt content; 0.4 inS / crn pH 7.4. Terrnostability: An ATD (Ternodifferential analysis), heating rate 3 ° C / m? N? To, closed glass vial, indicates a thermostability clearly superior to 250 ° C. Size and shape of particle (Distribution of mass obtained by means of the electron microscope): The particle size and the particle shape were obtained by means of an electron microscope from the pigment powder. To do this, the pigment is dispersed in water for 15 minutes and then sprayed. The results show an increase in size of 13,000 and 29,000 times. Particle size: dso = 120 n; d2s = 88 nrn; d7S = 160 n. Particle shape: The long / wide ratio is calculated at 2.65: 1. Dielectric data: Q.cm: 4x1015 e: (1 kHz) 3.7 4L
so d (L l-'Hz) 4xl0 ~ 3. X-ray diffraction pattern (CuK_ radiation): 2 theta (s = strong, n = medium,? = Weak): 4.72 (s), 11.06 (w), 13.74 (w); 15.07 (m), 15.62 (), 18.34 (s), 18.? 0 (s), 19.42 (w), 21.44 (rn), 26.05 (s), 27.31 (rn).
1. 2 Transparency. It is measured in a toner resin (polyester based on bisphenol A), an improved transparency (24 μm layer thickness) using the pigmented test toner of example 1.3.1. Compared to a given standard in the comparison example, at a similar concentration of color, a transparency was found 5 units of higher valuation and a blue line 5 units of more firm valuation. Assessment of the difference in transparency according to the test text 1/1: 1 = traces, 2 = something, 3 = perceptible; 4 = marked, 5 = substantial, 6 = significantly more transparent. 1.3 Electrostatic properties 1.3.1 5 parts of pigment of Example 1.1 are treated by means of a kneader, within 45 minutes, with 95 parts of a toner binder (polyether based on bisphenol-A). It is then ground in a general purpose mill and then sorted into a centrifugal screen. The desired particle fraction (from 4 to 25 μn) is activated with a carrier, which consists of ferilized particles coated with eylicon, with a size of 50 to 200 μrn (overall density 2.75 g / cm3) (FUE 96-100; Fa. Powder 'Techn.) The measurement is carried out at a standard average value q / m. By using a screen with a mesh size of 25 μm, it is ensured that no carrier is carried with the toner spray. The measurement is carried out at 40 to 60% of relative air humidity. Depending on the activation time, the following values are obtained q / rn (μC / g):
Activation time Load (q /? N (μC / g) 5 minutes -17 10 minutes -17 30 minutes -16 2 hours -16 24 hours -15
1. 3.2 5 parts of the pigment that is described in Example 1.3.1 in 95 parts of a powder coating binder, based on a TGIC polyester, for example, Uralac (R) P 5010 (D5M), are homogeneously treated. , Holland). To assess- The separation rate, 30 g of the test powder varnish is sprayed with a defined pressure, by means of a thermocouple. By comparison difference can be calculated the amount of powder varnish released and is defined as a separation share in%, and a current flow (μA) is manipulated by means of load transfer. Pressure (barias) Current (μA) Rate of drop (%)
3 1.2 78
1. 3.3 5 parches of the magenta pigment according to the invention and 1 part of the charge regulator described in example 5 of DE-A-4 031 705, having the formula:
as described in example 1.3.1, in a binder-for toner- (polyester based on bisphenol-A). Depending on the activation time, the following values q / rn (C / g) are measured:
Activation time Load q / m (μC / g) 5 minutes -1 10 minutes +1 30 minutes + 2 2 hours +3 24 hours + 2 1.3.4 Treat and measure 5 parts of the magenta pigment according to the invention and 1 part of the charge regulator mixture described in Preparation Example L of DE-A-3 901 153, (strongly fluorinated ammonium salt, with n-2 - 5) of the formula:
C2H5 I F3C- (CF2-CF2) n-CF = CH-CH2-N-CH3f B (C6H5) 4T C2H5
such as described in example 1.3.1, in a binder-for-toner (polyester based on bisphenol-A). Depending on the activation time, the following value is measured q / rn (μC / g):
Activation time Load q / rn (μC / g) 5 minutes -14 10 minutes -18 30 minutes -20 2 hours -21 24 hours -21
1. 3.5 5 parts of pigment according to the invention and 1 part of the charge regulator mixture described in preparation example 2 of DE-A-4 103 610 (cationic polymer where x-150-800) were treated and measured. , of the formula:
as described in Example 1.3.1, in a LC) for toner (polyester based on bisphenol-A). Depending on the activation time, the following values q / m (μC / g) were measured:
Activation time Charge q / rn (μC / g) 15 5 minutes -9 10 minutes -9 30 minutes -9 2 hours -9 24 hours -9 20 COMPARATIVE EXAMPLE 1
THE red pigment C.I. 57: 1 of the invention, prepared in comparative example 1, is characterized by the following 5 properties: 1.1 Pigment characteristics:
BET Surface: 35? N2 / g Residual Moisture: 0.5% (Karl -Fisher: 3.6%, including crystallization water) Residual salt content: (3.1 mS / orn pH 7.1) Terrnostability: Decomposition temperature:> 250 ° C (DTA) Particle size: dso = 160 n; 2s - 103 n; d75 = 187 nrn Particle shape: The long / wide ratio is calculated at 2.85: 1. Dielectric data: _.cm: 3 1015 (L kHz) 4.2 tan_ (1 kHz) 3x10-2 X-ray diffraction pattern (CuK_ radiation): 2 theta (s = strong, m = medium, w = weak): 4.85 (s), 11.94 (w ), 15.09 (? N), 15.66 (m), 18.34 (s), 18.68 (s), 21.44 (rn), 26.06 (s), 27.31 (in).
COMPARATIVE EXAMPLE 1.2
The production and measurement of the test toner is obtained as described in example 1.2 COMPARATIVE EXAMPLE 1.3 ELECTROST TICAS PROPERTIES
Comparative Example 1.3.1 5 parts of pigment are treated and measured, as described in Example 1.3.1, in the toner agglutinator:
Activation time Charge q / rn (μC / g) 5 minutes ~ 7 10 minutes ~ R 30 minutes -10 2 hours -13 24 hours -23