MXPA99003115A - Pigment granulation - Google Patents

Abstract

The invention relates to a process for preparing organic pigment granules with a particle size from 0.5 to 4 mm, comprising a mixture of at least one organic pigment, a binder having a neutral emulsifier which does not form ions and which dissolves to give a clear solution in water or a C1-C4 alcohol. The mixture is pressed in a continuously operating apparatus consisting of at least one conveying device and a shaping section, and being constructed and operated with a throughput, such that the pressure in its shaping section does not exceed 10 bar. If desired, the cylindrical granules emerging from the dies are converted on a rotating device into ovoid or spherical granules, and the granulated product is dried at a temperature of -50 to 200°C at atmospheric pressure or under reduced pressure.

Description

PIGMENT GRANUIATION The invention relates to a novel process for granulating organic colored pigments in the presence of aqueous or alcoholic media at low pressure, and with powder-free pigment granules which can be prepared by this process. The organic pigments consist of very fine particles, of low solubility in the usual solvents, whose dimensions can fall within the submicroscopic range up to approximately 100 μm. For practical use, organic pigments that have particle sizes of approximately 0.01 to 0.1 μm for transparent forms and 0.1 to 10 μm for opaque forms have proven to be the most suitable. The physical properties of the pigment particles are very important for their use. For example, very small particles often have relatively low light resistance and environmental resistance and a strong propensity for agglomeration. Very large or irregular particles, on the other hand, give rise to undesirably low color intensities and more matt tones. In the case of physical properties, however, the distribution of particle size and agglomeration play a key part, especially with respect to the dispersibility of the pigments [see Farbe and Lack J32 / 1, 7-14 (1976)]. Therefore, it is of critical importance for pigments having a very narrow particle size distribution, which can usually be achieved by precipitation, recrystallization or heat treatment in a polar solvent, at atmospheric or above atmospheric pressure or under a high cutting force (US 4,879,380). However, all these pigments, regardless of the narrow particle size distribution, still have the great disadvantage of producing dust. Consequently, when they are used, expensive measures are necessary (for example, workplace safety, ecological nature or to ensure quality) and valuable material is lost. Up to now, a large number of methods have already been investigated to convert the pigments into a low-powder or even dust-free form. However, it has been found that improvements in pulverulent behavior can be obtained in the case of known methods only, among other disadvantages, at the expense of the physical properties of the pigment particles, and especially at the expense of dispersibility. Accordingly, the known methods described below are unable to fully satisfy what is desired for a long time for the powder-free organic pigments, which continue to have good physical properties. The known compaction methods, such as compression molding (rattling or briquetting), granulation in mixing granulators and granulating discs (Aufbereitungs-Technik JL2 (1975)) and in formers, (Chem.-Ing.-Tech. 49 / 5, 374-380 (1977)), roller granulation (DE-A 27 23 221) or pressure granulation (Powder Technology 74, 1-6 (1993)) always lead, with pure organic pigments, to highly agglomerated products which they have worse operating properties than the other powders. A common feature of these methods is that the pigment particles collide with each other with a relatively high force. Pigments for use in plastics can be incorporated into polymeric concentrates. The pigment is used as a pulverulent, dry powder. In this context, high shear forces and temperatures are required to disperse the pigment particles perfectly, and the physical properties and color properties change. The resultant polymeric grains must, in turn, be intimately mixed with colorless polymer grains for final use, again under high cutting forces, since it is necessary to effect the homogeneous distribution of the pigment particles together with the surrounding polymer completely. In addition, the concentrated polymer must be compatible with the other polymer, therefore, for a single pigment, a range of two or more products is required for different plastic applications. The pigments can also be applied to the surface of polymeric grains externally softened to give spherical particles (US 4,310,483). However, the size of such particles is difficult to control, and the fraction having the desired diameter has to be isolated by sieving. It is said that granulation aids can be used in amounts of 2-50% by weight (preferably 5-30% by weight), although it has been found that good dispersibility can be achieved with amounts of at least 15-20% in weigh. An additive that can be used in addition to the polymeric grains is a binder similar to wax, whose melting point is typically 49 to 88 ° C (US 5,455,288). In the latter case, however, the pigment content is at an unsatisfactorily low level of 5 to 50%. In both cases, the collision forces are mainly at work in the case of low shear forces, and the presence of more than 10% by weight of the substance of low melting point is disadvantageous from the point of view of operation. The pigments can also be embedded in resins. This is done by first preparing a dispersion of the pigment in an inert solvent (for example water) and a solution of the resin in an appropriate solvent and then mixing the two, and precipitating the resin from the solution, either directly in the course of mixing. or later, the pigment is enveloped by the precipitated resin. Innumerable publications have proposed, like resin, almost all known substances that have a certain resinous character, including turpentine resin. Several processes are known according to this principle, for example acid / base precipitations (CS 216 590; IN 156 867; DE-A 33 27 562) and granulations in solvent of one or two phases (US 4,055,439; US 4,208,370). The not entirely satisfactory dispersibility of such pigments embedded in resin can be improved by the use of special resin mixtures together with a very high shear force (US 4,116,924; US 4,168,180). However, the precipitation of the pigment dispersion in any case requires intensive grinding, especially when the inert solvent used is an aqueous medium, in which case the pigment, however, is comminuted in a desirable manner. Instead of the resins, it is also possible to use surfactants (EP 403 917): in this case, although the dispersion is made easier, the product is not obtained in dust-free form, but in powder form.

In the case of acid / base precipitation, control of the neutralization is a further problem that must be solved to the full satisfaction by the method described in DE 33 27 562. When precipitated with acid, in fact, the resin does not precipitate completely neutral, which in many cases causes problems for higher grade applications, such as coating operations or mass coloration of plastics. In the case of solvent granulations, on the other hand, large quantities of solvent are required, which, disadvantageously, have to be recovered from usually aqueous mixtures. Therefore, the use of acetic or propionic anhydride as solvent (EP 069 617) has been proposed, giving rise to aqueous solutions that can be used significantly in the chemical industry but which, due to lack of demand, have to be eliminated at a considerable cost. It is also known that colorants can be converted to a low-flow fluid form by spray drying or in a fluidized bed (EP 039 841, EP 670 352). The additives used there, however, are completely useless in the case of pigments that are to be used in higher grade applications, such as mass coloration of plastics or automotive finishing operations. Furthermore, in the case of spray drying or in a fluidized bed, it is hardly possible to prepare homogeneous granules having a particle size of more than 100 μ (see, for example, Chemie-Technik 2_l / 6, 72-78 (1992)). Arch. Pharm. Chemi, Sci. De. 1978/6, 189-201). Furthermore, it is not possible to fluidize all the powders in a fluidized bed (Powder Technology 57, 127-133 (1989)), so that it is not possible to make widespread use of this method. An improved variant of fluidized bed granulation is also known, especially for pigments (US 4,264,552), wherein the particle size distribution of these granules is very broad and the vast majority of the particles (approximately half by weight) are smaller than 500 μm. In addition, these granules still have an excessive propensity to produce dust. In Example 2, the. use of a mixture of 8.2 wt.% of Staybelite MR and 0.9 wt.% of hydroxypropyl cellulose (amounts based on each case in the finished product), in the form of its ammonium salts, as the anionic surfactant. The water-soluble dyes can be processed with 5 to 50% by weight of a water-soluble binder to form non-powdery cylindrical granules with a diameter of at least 1 mm (DE-A 2 317 175); according to the examples, the granules have a diameter of approximately 1 mm and a length of 5-7 mm. By means of a transport screw, the homogenous plastic mass is passed through a perforated disk (perforation diameter of 1 mm). However, water soluble binders are completely unsuitable for pigments that are intended to be used in custom plastics, and the organic pigments treated by this process are highly agglomerated and have unsatisfactory dispersibility properties. Therefore, they are not adequate enough for many applications. The same applies to the powder compression of wet pigments with water in a twin-screw extruder at pressures of 10 to 50 bar according to the known method of Journal of Powder & Bulk Solids Technology 4/4, 27-32 (1980). Fine, low-powder dye granules having a very low binder-like content similar to a wax and other foreign substances are also known (EP 424 896). Of essential importance is the use of a device in which the fed material is predominantly exposed to severe turbulence and moderate collision forces, together with declining shear stresses. This process is suitable, however, predominantly for organic pigments, and only one example of an organic pigment is described: Example 13 uses the pigment monoazo Pigmento Rojo 176, 0.72% by weight of a fatty acid mixture having a melting point of 57-61 ° C as the wax, and 50-51% by weight of water (based on each case to the fine granules). The particle size is markedly less than 1 mm, and a screening operation is necessary despite the relatively small proportions of the large particles, which are difficult to disperse, and ultrafine particles, which produce dust. Other known granules include those that exhibit a large increase in volume relative to the initial pigment as a result of the cavities that are retained with drying (EP 510 392). In this case, the training takes place exclusively by known methods; for the strand extrusion, a residual moisture content of 50 to 80% by weight was specified. These granules are said to be easily dispersible and low in powder, but they are brittle and have a low bulk density, with the result that they occupy a substantially large volume in transport and storage. In addition, it is very difficult to obtain products that have a reproducible specific weight with precision, and in the case of hydrophobic or apolar pigments this method produces unsatisfactory results. Also known, finally, it is a process in which the hydrophilic pigments are transported as aqueous agglomerates, similar to a paste (US 5,328,506). In contrast to the extruded "noodles", it is not necessary to carry out the high energy dispersion of those products subsequently. However, the process is not intended for organic pigments, but in inorganic kaolin pigments, and the presence of. Water in the stated amount of 1 to 25% has an adverse effect on, or can still completely discard, the use of organic pigments in the vast majority of fields. Furthermore, as already mentioned, the pigment preparations of large and irregular particles prepared by some of the known processes are not yet, simultaneously, satisfactorily compact, powder-free and / or easily dispersible. In addition, the desired particle size in particular has to be selected by sieving, with the particles having a size different from this desired particle size (especially the fine fraction) having to be passed back into the process. However, the recycling of the unsatisfactory pigment material causes an additional damaging alteration to these physical parameters, and, consequently, a deterioration of the performance properties as well. The main purpose of the invention was to provide large or irregular particles, extremely dust-free, highly concentrated, easily dispersible and universally applicable organic pigment granules, in which, in addition to the external appearance, the physical parameters of the pigmented particles are changed so as little as possible in relation to the initial pigment powder, unlike the known granules. It is understood that the term physical parameters has as meaning not only the properties mentioned above, but also all other technically measurable properties or relevant applications. The intention is that these pigment granules are capable as much as possible of being prepared by means of simple and universally applicable methods, in simple, inexpensive and easy to clean apparatuses, without the need for the addition of organic solvents and without the necessity of select the correct particles and recycle the rejected ones. The main objective of the invention has been achieved to a particularly surprising degree by means of the present invention. The invention also relates to a process for preparing organic pigment granules with a particle size of 0.5 to 4 mm, which consists of at least 90% by weight of at least one organic pigment with a particle size of 0.01 to 10. μ and from 0 to 10% by weight of a binder, having from 2 to 7 mol of carboxyl groups per 1000 g and from 0 to 5% by weight of a neutral emulsifier, which does not form ions and which dissolves to give an clear solution in water or an alcohol of C? ~ C4, at a concentration of at least 10 g / 100 ml, the binder and the emulsifier together contribute to more than 10% by weight and all percentages by weight are based on the amount total of pigment granules, wherein [1] the pigment is mixed with 54-92% by weight of water, a C1-C4 alcohol, a C3-C8 ketone or a mixture thereof, based on the dry pigment , with the binder and 0. 8-20 mole of ammonia or a Cx-C3 amine, per mole of carboxyl groups in the binder, and with the emulsifier; [2] This mixture is pressed in an apparatus that operates continuously through one or more openings, each of which has a size of 0.2-5.0 mm2, the apparatus consists of at least one transport device and a training section which comprises the openings, and is constructed, and operated with a passage, so that the pressure in its formation section does not exceed 10 bar; [3] if desired, the cylindrical granules emerging from the matrices are converted into a rotating device in ovoid or spherical granules, and [4] the granulated product is dried at a temperature of -50 to 200 ° C at atmospheric pressure or under reduced pressure. The granules can have any desired geometric shape; for example, they can be cylindrical, ovoid or spherical. The granules preferably have a rounded, non-angular geometric shape. Particular preference is given to the granules being essentially spherical, which can be achieved by the optional step [3]. If they are spherical, the granules generally have a particle size with a diameter of 0.5 to 4 mm. The cylindrical and ovoid granules generally have a diameter of 1 to 3 mm and a length of 1 to 10 mm. The granules preferably have a particle size with a diameter of 1 to 4 mm. With particular preference, the granules have a particle size with a diameter of 1 to 2.5 mm. If the granules are not spherical, they have a particle size with a theoretical diameter of Within the granules, the organic pigment and the binder preferably form an essentially homogeneous mixture. The organic pigment may be an individual compound of any kind of desired pigment, or it may also be a mixture of two or more compounds of the same or different kinds of pigment, and may be present in any known crystal modification, which is retained in a manner advantageous in the course of the process of the invention, or it can also be a solid solution. Examples of suitable pigment classes are diketopyrrolopyrroles, quinacridones, * perylenes, dioxazines, anthraquinones, indantrones, flavantrones, indigos, thioindigos, quinophthalones, isoindolinones, isoindolines, phthalocyanines, metal complexes and azo pigments. The preferred pigments are the diketopyrrolopyrroles, quinacridones, perylenes, dioxazines, indantrones, flavantrones, isoindolinones and phthalocyanines and also the aminoantráquinones and condensation and disazo pigments. The particularly preferred pigments are the diketopyrrolopyrroles, quinacridones and phthalocyanines. The particularly preferred pigments are the diketopyrrolopyrroles. Preferred perylenes are those of the formulas (la), (Ib), (le) or (Id), wherein Ri is hydrogen, C? -C6 alkyl, phenyl or benzyl or is phenethyl which is unsubstituted or substituted by halogen, C1-C4 alkyl or C? -C4 alkoxy. The preferred quinacridones are those of the formula wherein R 1 is hydrogen, C 1 -C 6 alkyl, phenyl or benzyl or is phenethyl which is unsubstituted or substituted by halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, and R 2 and R 3 are independently one of other hydrogen, halogen, C 1 -C 8 alkyl, C 1 -C 4 alkoxy or phenyl. The preferred dioxazines are those of the formula wherein Ri is hydrogen, C? -C6 alkyl, phenyl or benzyl or is phenethyl which is unsubstituted or substituted by halogen, C? -C alkyl or C1-C4 alkoxy, and R4 is hydrogen, halogen or Ci-Ciß alkyl »The preferred isoindolinones are those of the formula wherein R 5, R 6, R 7 and R 8 are independently of each other are hydrogen, C 1 -C β alkyl, C 1 -C 4 alkoxy, halogen or trifluoromethyl. Preferred flavantrones are those of the formula (V), wherein R 2 and R 3 are independently from each other hydrogen, halogen, Ci-Ciß alkyl, C 1 -C 4 alkoxy or phenyl. Preferred indantrones are those of the formula (VI > wherein R2 and R3 are independently from each other are hydrogen, halogen, Ci-Cie alkyl, Cx-C4 alkoxy or phenyl. Preferred phthalocyanines are those of the formula (VII), where M is H2, Zn, Cu, Ni, Fe, Ti (= 0) or V (= 0), Z is halogen and y is 0 or an integer of 1 a. The preferred pyrrolo (3, -c) pyrroles are those of the formula (VIII), wherein Ri is hydrogen, C? -C3 alkyl, phenyl or benzyl or is phenethyl which is unsubstituted or substituted by halogen, C1-C4 alkyl, or C1-C4 alkoxy, And Gi and G2 are independently from each other are from the group of formulas wherein R9 and Ri0 are independently from each other hydrogen, halogen, C? -C? 8 alkyl, Ci-Ci? alkoxy, C? -Cl8 alkylthio, Ci-Cis alkylamino, C2-Ci8 CN dialkylamino, -N02, phenyl, trifluoromethyl, C5-C6 cycloalkyl, imidazolyl, pyrazolyl, triazolyl, piperazinyl, pyrrolyl, oxazolyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, mbrolinyl, piperidinyl, pyrrolidinyl, R11 and R12 are independently from each other hydrogen, halogen, C? -C6 alkyl, C? -C6 alkoxy or -CN, R13 and Ri4 are independently from each other hydrogen, halogen or Ci-C? Alkyl L is -CH2 , -CH (CH3) -, -C (CH3) 2-, -CH = N-, -N = N-, -O-, -s-, -so-, -so2- or -NR15, and R15 is hydrogen or C? -C6 alkyl. The preferred aminoanthraquinone pigment is that of the formula (IX) (IX).

Preferred indigo derivatives are those of the formula (X), wherein R 6 is hydrogen, CN, C 1 -C 4 alkyl, C 1 -4 alkoxy or halogen. The preferred isoindolines are those of the formulas wherein R17 is hydrogen, C? -C18 alkyl, benzyl or a group R17 'is a group in which R? 8, Ria, R17' and Ris' are independently from each other hydrogen, C? -C? 8 alkyl, C? -C4 alkoxy, halogen or trifluoromethyl. Any halogen substituents are, for example, iodine, fluorine, especially bromine and preferably chlorine. C 1 -C 4 alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, in the case of C 1 -C 6 alkyl additionally, for example, n-amyl , ter-amyl or hexyl, and in the case of C? -C? 8 alkyl again additionally, for example, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl. C5-C6 cycloalkyl is, for example, cyclopentyl and, in particular, cyclohexyl. C 1 -C 4 alkoxy is, for example, methoxy, ethoxy, n-propoxy, isopropoxy or butyloxy, and C 1 -C 8 alkoxy is further, for example, hexyloxy, decyloxy, dodecyloxy, hexadecyloxy or octadecyloxy. C3-C18 alkylthio is, for example, methylthio, ethylthio, propylthio, butylthio, octylthio, decylthio, hexadecylthio or octadecylthio. Ci-Cie alkylamino is, for example, methylamino, ethylamino, propylamino, hexylamino, decylamino, hexadecylamino or octadecylamino. C2-C18 dialkylamino is, for example, dimethylamino, diethylamino, methylpropylamino, ethylhexylamino, methyl-discylamine, dioctyl or ethylhexadecylamide. The carbon atoms of both alkyl radicals are counted together. In the case of the perylenes of the formula (la) or (le), the quinacridones of the formula (II), the dioxakines of the formula (III) and the pyrrolo (3, 4-c) pyrroles of the formula (VIII), particular preference is given to those in which Ri is hydrogen. Particularly preferred quinacridones of the formula (II) are those in which Ri is hydrogen and R2 and R3 are independently of one another hydrogen, methyl, chloro or methoxy. Particularly preferred phthalocyanines of the formula (VII) are those in which M is H2, Zn or Cu, and Z is chlorine or bromine. Particularly preferred pyrrole (3, 4-c) pyrroles of the formula (VIII) are those in which Ri is hydrogen and Gi and G2 are independently from each other a group of the formula R 20 is fluorine, chlorine, cyano, nitro, trifluoromethyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylamino, or C1-C4 dialkylamino, and, of these, especially those in which R2o is chloro. Most preferred is 1, 4-diketo-3,6-di (4'-chlorophenyl) -2,5-dihydropyrrolo [3, 4-c] -pyrrole. The organic pigment used according to the invention has a particle size of 0.01 to 10 μm. This means that at least 90% by weight of the particles have that particle size. The organic pigment preferably has an average particle size of 0.2 to 2 μ. With particular preference, the organic pigment has a narrow particle size distribution, in other words, that at least 80% by weight of the particles have a particle size which is within a range whose extension is not more than one power of ten, for example between 0.5 and 5 μm, or between 0.2 and 2 μm. A narrow particle size distribution can be obtained by methods known to those skilled in the art, for example by treatment in a polar inert liquid at elevated temperature. The liquids, temperatures and appropriate durations for this treatment, which can be very different depending on the pigment, are known for all kinds of pigments and for many individual pigments. The binder has from 2 to 7 mol of carboxyl groups per 100 g of substance. The binder generally contains 30-100% by weight, preferably at least 60% by weight, of at least one organic acid, it being possible for the remainder of the binder to be neutral. The organic acid can, for example, be a pure long chain, saturated or unsaturated acid, or a mixture thereof, for example a homologous mixture. The long chain acids are those in which there is at least one linear chain consisting of 8 carbon atoms. Preference is given to abietic acid and mixtures of acid comprising at least 5% by weight of abietic acid. The neutral residue of the binder may comprise, for example, substances which usually appear as impurities in the acids used. However, it is equally possible to add relatively small amounts of a texture improver to organic acid. The texture improver, if added, is a constituent of the binder; its amount is not more than 50% by weight, more preferably not more than 10% by weight, based on the total binder. The texture improver may, for example, be an amide or a metal salt of an organic acid having at least 18 C atoms, an alkylphenol or an aliphatic alcohol, or a plasticizer or a wax. Known texture enhancers are, for example, stearamide or behenamide, magnesium stearate or magnesium behenate, stearyl alcohol, 1,2-dihydroxy aliphatic compounds having from 8 to 22 C atoms, such as 1,2- dodecanediol, dibutyl phthalate or beeswax. The binder preferably consists of a mixture of natural acids having from 8 to 30 carbon atoms and natural terpene derivatives, and can be obtained, for example, by extraction of natural woods. For example, this mixture can be Resin or Staybelite1 resin (Hercules Inc., ilmington / Delaware / USA). The binder, in a particularly preferable manner, has a melting point of 70-300 ° C and, very particularly preferably, a melting point of 90-200 ° C. The quantity of the binder depends on what is required of the granules. If granules with a very high loading capacity are required, then the amount of binder is preferably 5-10% by weight, particularly preferably 5-8% by weight. If, on the other hand, universal granules of very good compatibility are desired in as wide a range of applications as possible (for example in coatings), then the amount of binder is preferably 0.5-2% by weight. Particular preference is given to granules containing less than 0.5 wt% binder or which are still completely binder free. Although in the latter case it is not clear how the pigment particles are held together within the granules, it has surprisingly been found that even the binder-free granules prepared according to the invention have a highly remarkable mechanical stability. The neutral non-ionic emulsifier can be, for example, a copolymer of ethylene oxide and propylene oxide, a fatty alcohol ethoxylate or an alkylphenol ethoxylate, for example an emulsifier of the Emulan® series.

(BASF). The amount of emulsifier is preferable way of 0. 3-1% by weight. The binder and the emulsifier are independent of each other and both are optional. Depending on the properties of the desired granule, it is possible to use, as desired, binder, emulsifier, or binder and emulsifier, or none of the binder or emulsifier. The listed binders and emulsifiers are used in the process according to the invention, if not all, in the established concentrations, which start at zero percent by weight (corresponding to the complete absence). The preferred total amount of binder and emulsifier is preferably 0.3-5% by weight. The C? -C8 alcohol can be, if desired, for example, methanol, ethanol, n-propanol, isopropanol or butanol, and can be used in pure form or, in particular, as aqueous mixtures. Preference is given to C1-C4 alcohols, especially methanol, ethanol or isopropanol; Methanol is particularly preferred. The C3 ~ C8 ketone can be, for example, acetone, ethyl methyl ketone, methyl propyl ketone or cyclohexanone, and can be used in pure form or, in particular, as aqueous mixtures. Preference is given to C3-C6 ketones, especially acetone or ethyl methyl ketone; ethyl methyl ketone is particularly preferred. However, it is generally very particularly preferred to use in step [1] from 90 to 100% by weight of water, based on the total amount of water, C?-C8 alcohol and C3-C8 ketone, is it is possible to use, in particular, only water, which can, for example, be of a defined quality, for example, deionized water. As an exception, highly polar pigments, such as pigments having at least one primary amino group, for example the aminoanthraquinone of formula (IX), are preferably granulated at a lower concentration of water, particularly preferably 30 60% by weight of water, based on the total amount of water, C? -C8 alcohol and C3-C8 ketone. If a mixture of water, a C? -C8 alcohol and / or a C3-C8 ketone is used, it is preferably an azeotropic mixture. This makes it possible to easily reuse the mixture advantageously. The C? ~ C3 amine can, if desired, be methylamine, dimethylamine, ethylamine, trimethylamine, ethylmethylamine, n-propylamine or isopropylamine. Preference is given to C1-C3 amines having a very low boiling point, and particularly preferably to methylamine. With particular preference, however, ammonia is used instead of C1-C3 amine in step [1]. It must be understood that ammonia means gaseous ammonia. Instead of this, of course, it is also possible to use liquid ammonia - in this case, however, liquid ammonia water also counts as added water. The preferred amount of ammonia or C1-C3 amine is about 1 mole per mole of carboxyl groups in the binder, so that the binder is completely neutralized. The mixture of the pigment with water and / or C? -C8 alcohol and / or C3-C8 ketone, the emulsifier, the binder and the ammonia or d-C3 amine can be carried out in any known manner, for example, in a mixer device. Useful mixing apparatuses are those in which the pigment is subjected to a maximum pressure, which is lower than the maximum pressure that arises in step [2] of the process. A person skilled in the art knows numerous mixers that impose little mechanical effort, for example those described in Perry's Chemical Engineer's Handbook (6th edition, McGraw-Hill Book Company). Commercially available ring-bed mixers are preferred. The pigment can be used in dry form or also in the form of a wet product, for example a wet filter cake; in the latter case, the water or alcohol of C? -C8 or C3-C8 ketone present in the wet product may also count as water or alcohol or added ketone. If the wet product is sufficiently moist, it may be possible to do it entirely without additional wetting agent. For example, a pigment filtration cake with 47.9% residual moisture corresponds to the addition of 91.9% by weight, and one with 35.1% residual moisture to the addition of 54.1% by weight of water to the dry pigment. Preferably, however, a dry pigment of known specifications is employed. The binder can be used dry or in the form of a solution of the ammonium salt. In the latter case, for example, it is stirred in advance together with ammonia or C1-C3 amine in water, C? -C8 alcohol, C3-C8 ketone or a mixture thereof, at room temperature or at a temperature which is between the ambient temperature and the melting point of the binder, under atmospheric or above atmospheric pressure, until a solution is formed. The binder solutions are preferably prepared at room temperature. The form and sequence in which the ingredients are mixed is not essentially important. What is important, however, is that the mixture is substantially homogeneous after mixing. Therefore, it is preferred to employ a binder in the form of an ammonium salt solution, in which case all of the water or C1-C4 alcohol, or a portion thereof, can be used to prepare this solution. It is particularly preferred to introduce the dry pigment continuously into the inlet of the mixer and at the same time to spray an aqueous ammoniacal solution of the binder in the required amount. This process, by itself, is particularly good for complete automation by methods known per se. The mixed product can be further processed immediately or later in step [2] of the process, it is preferred to follow step [1] directly by step [2].

The pressing takes place mechanically in a continuously operating apparatus, which consists of at least one conveying device and a forming section with openings. The transport device is not subject to any particular requirement, other than that the mixture to be pressed must not be subjected to any pressure exceeding 10 bar. Conventional transport devices may be used, for example one or more rotating screws. A twin screw is the preferred transport device. The openings through which the mixture is pressed may, in principle, have any desired cross section. Openings with a non-angular cross section are preferred. This means rounded, for example elliptical or, preferably, circular openings, which have no angles. The openings preferably measure 0.5 to 2.5 mm on the shortest axis. The openings can, for example, be perforated or burned with a laser beam, while the circular openings can, moreover, and preferably, be drilled. It is preferred to have a large number of openings made at regular intervals. The preferred diameter of the circular openings depends on the binder and at 0-3% by weight, it is 0.5 to 1.5 mm, at 3-10% by weight of binder, on the other hand, from 1.0 to 2.5 mm, the forming section with the openings it has any desired shape, which is neither flat nor cylindrical. If, in fact, a planar sieve arranged at right angles to the transport device is used, then the pressure generally exceeds the maximum pressure that is critical to the invention, and the granules do not have the advantages of the invention. Therefore, it is critical for the forming section that the openings have a three-dimensional curvature, for example, of a hollow truncated cone or a hollow dome. On the other hand, the material to be formed is often pressed in a highly irregular manner if the screen is a hollow cylinder, and, in this case, the increases in pressure, which possibly exceed the maximum pressure that is critical to the invention, occur easily during short periods, and at least some of the materials likewise lack the advantages of the invention. The training section is preferably hemispherical. The preferred apparatus constructed in accordance with the features of the invention comprises radial extruders and, with particular preference, dome extruders, which are commercially obtained in numerous designs. Since the accumulation of pressure is a function of the rotational speed of the transport screw, the apparatus should be operated at a rotational speed lower than the maximum speed, which corresponds to a reduced passage, where this seems necessary, based on the maximum pressure desired. In a radial extruder, the pressure increases in the direction of the cone. In this case, it may be that the pressure at the apex of the formation section threatens to exceed 10 bar. In general, therefore, the apex of the forming section should have an additional opening, which should be designed or positioned so that the desired pressure is not exceeded. The small amount of material that emerges from this additional adjustable opening can, in fact, be recycled, but only if it has been exposed to a maximum pressure of no more than 10 bar. Recycling, however, is generally not advised. This problem does not arise in the case of the dome extruder, which is particularly preferred. The pressure in the forming section is preferably from 1 to 5 bar, particularly preferably from 1.3 to 3 bar. The cylindrical extrudate generally breaks on its own as it emerges from the forming section in two pieces, with a length of approximately 2 to 6 mm, to which, judiciously, they should not be allowed to stand for any extended period of time . The cylindrical granules are processed preferably, more directly.

The rotating device that converts the cylindrical granules into spherical granules can be, for example, a plate, a hollow cylinder or the like. The cylindrical material emerging from the extruder is preferably passed directly or approximately over the center of the rotating device, the centrifugal force sedimenting the cylindrical granules in a rotary motion, thus converting them into more or less spherical granules. The conversion into ovoid or spherical granules is optional. However, it has been found that the operating advantages of the invention are greater if the granules are ovoid or spherical. Preferably, therefore, this optional step is implemented. The granulated product is dried in a known manner at the set temperature and under the established pressure. The drying can be operated batchwise or continuously, in the latter case, the material to be dried is transported, for example, on a conveyor belt, through an oven, which is open at both ends and is at a temperature of 100-200 ° C. In the course of drying, both in water and in C1-C4 alcohol and, if present, the ammonia or the amine of C? -C3 are released, and separated if necessary. The vapors are preferably extracted by suction and condensed, with the condensate being recycled. Instead of drying in an oven, however, it is also possible to use any other drying method, for example, lyophilization. The entire process of the invention is preferably, continuously operated. The pigment granules prepared according to the invention are large and irregular, and are highly concentrated, extremely dust-free and easily dispersible. The physical parameters of the pigment particles present within the pigment granules are difficult to change, in relation to those of the pigment particles in the initial pigment powder. In general, therefore, the organic pigment present in the pigment granules in any way, has a size of 0.01 to 10 μm. The organic pigment included in the pigment granules preferably has a narrow particle size distribution. Additional preferred pigment granules include those obtained by the above mentioned embodiments of the process of the invention. The invention, therefore, also relates to pigment granules with a particle size of 0.5 to 4 mm, which consists of at least 90% by weight of at least one organic pigment and from 0 to 10% by weight of a binder having from 2 to 7 mol of carboxyl groups per 1000 g, and from 0 to 5% by weight of neutral emulsifier, which does not form ions and which dissolves to give a clear solution in water or in an alcohol of Ca-C4, at a concentration of at least 10 g / 100 ml, the binder and the emulsifier together make up no more than 10% by weight and all percentages by weight were based on the total amount of pigment granules, wherein the The pigment present in the pigment granules has essentially a particle size of 0.01 to 10 μm. To determine the particle size of the present pigment, the granules can be treated with ultrasound in a wet liquid, but do not dissolve the pigment, but can dissolve or break the other components of the granules, to give the homogeneous dispersion of the granules. pigment. The particle size distribution of the dispersed pigment can then be determined, for example, by disk centrifugation. One suitable device for this, for example, is the Joyce-Loebl DCF4 disc centrifuge. The requirements with respect to the preparation of the sample and the determination of the particle size distribution are well known to those skilled in the field of particle measurement. The techniques are also described extensively in relevant textbooks [see, for example, Terence Alien, Particle Size Measurement, (Chapman and Hall, London, New York 1981)]. In consideration of the properties highlighted above, the pigment granules of the invention are especially suitable, in an amount effective for coloring, to pigment organic materials of high molecular mass, especially plastics and coatings. Organic materials of high molecular mass for which the pigment granules of the invention can be pigmented can be of natural or synthetic origin. Organic materials of high molecular mass, usually have molecular weights of about 103 to 107 g / mol or more. They may be, for example, natural resins, drying oils, rubber or casein, or modified natural substances thereof, such as chlorinated rubber, alkyd resins modified with oil, viscose, ethers or cellulose esters, such as ethylcellulose, acetate of cellulose, cellulose propionate, cellulose acetobutyrate or nitrocellulose, but especially fully synthetic organic polymers (thermosetting or thermoplastics), such as those obtained in addition polymerization, condensation or polyaddition polymerization. Of the class of poly-resins by addition, mention should be made mainly of polyolefins, such as polyethylene, polypropylene or polyisobutylene, and substituted polyolefins, such as polymers of vinyl chloride, vinyl alcohol, vinyl acetate, butyl acetate , styrene, acrylonitrile, acrylic or methacrylic acid, acrylic or methacrylic esters or butadiene, and also copolymers of the mentioned monomers, especially ABS or EVA. From the series of polyaddition resins and condensation polymer resins, mention may be made of formaldehyde condensates with phenols, known as phenolic resins, and formaldehyde condensates with urea, thiourea and melamine, known as aminorresins, polyesters which are used as resins for paints, and, in fact, saturated resins, for example, alkyd resins and unsaturated resins, for example maleate resins and also polyesters and linear polyamides, polyurethanes or silicones. The aforementioned compounds of high molecular mass can be present individually or in mixtures, such as masses or plastic melts. They can also be in the form of their monomers or in the polymerized state in dissolved form as film formers or binders, for coating materials or printing inks, for example, linseed oil varnish, nitrocellulose, alkyd resins, melamine resins and resins of urea-formaldehyde or acrylic resins. The pigment granules of the invention can be added in any effective amount to color the organic material of high molecular mass to be pigmented. A pigmented composition judiciously contains 0.1-30% by weight, preferably 1-20% by weight, of pigment granules according to the invention, based on the organic material of high molecular mass to be pigmented. To pigment organic materials, the pigment granules of the invention can be used individually. Similarly, it is possible, however, to obtain different shades or color effects, to add other coloring constituents, such as white pigments, colored, black or with special effects, in any desired quantities to the organic substances, in addition to the granules of pigment of the invention. The pigmentation of organic substances of high molecular mass with the pigment granules of the invention takes place, for example, by mixing such pigment granules in these substrates using roller mills, mixers or milling apparatus. The pigmented material is subsequently brought to the desired final shape by techniques known per se, such as calendering, compression molding, extrusion, extension, casting or injection molding. All customary additives in the plastics industry can be incorporated, for example, plasticizers, fillers or stabilizers in the polymers in customary amounts, before or after the incorporation of the pigment. To produce non-rigid rollers or to reduce their brittleness, it is particularly desirable to incorporate plasticizers, for example, phosphoric, phthalic or sebacic acid esters, into the high molecular weight compounds, before they are formed. To pigment coating materials and printing inks, the high molecular mass organic materials and the pigment granules of the invention, alone or together with the customary additives, for example, fillers, other pigments, driers or plasticizers, are finely dispersed or dissolve in an organic solvent or solvent mixture suitable for all of them. One possible procedure here is to disperse or dissolve the individual components alone, or more than two or more of them together, and only then combine all the components. The colorations obtained, for example, in the plastics, coating materials or printing inks, preferably in the coating materials or printing inks and, with particular reference, the coating materials, are notable for their excellent properties, which are at least equal to those of the powder pigments, and in many cases, in fact, they are superior. Where the high molecular mass material to be pigmented is a coating material, this is in particular a special coating material, very particularly preferably an automotive coating material. The following examples illustrate the invention (in the examples the parts and percentages are in each case by weight): Example 1; 260 kg of 3,6-di- (4'-chlorophenyl) -2,5-dihydropyrrolo [3,4- c] pyrrol-l, 4-dione, which satisfies the pigment grade specification, was homogenously packed with 189 kg of deionized water in a conventional annular bed mixer (K-TTMR, Drais AG, Mannheim / Germany), to give a formable mass having a solids content of 58%. This wet mass was extruded through a section of hemispherical formation having perforations of 1 mm in diameter in a radial extruder (DG-L1MR, Fitzpatrick Co. Europa NV, St.-Niklaas / Belgium), at a transport speed of 40-50 rpm with a performance of approximately 120 kg / h. The cylindrical extruded particles were then formed into spheroids in a rounding step in a granulation plate, and those spheroids were dried in a convection oven at 120 ° C at a residual moisture content of < 1%. Granules were obtained, which had markedly less dust than the pigment used, even though they had a similar dispersion facility. Incorporated by conventional methods into an alkyd / melamine varnish or flexible PVC, these granules give colorations, which are essentially similar to those provided by the powdery pigment.

Example 2A: The procedure of Example 1 was repeated but using as raw material, a mixture, obtainable by analogy to IN-156'867 and US-4,264, 552, comprising 90% by weight of Pigment Red C.l. 177 [65300] and 10% Resin Staybelite1"" *. 300 parts of this dry mix were formed in a paste with 200 parts of deionized water (ie, 74.1% based on the pigment) and 9 parts of trimethylamine in an annular bed mixer, and this paste was extruded into filaments of 0.70 mm of diameter in a radial extruder, at a low extrusion pressure. The extruded particles were rounded to give spheroids of approximately 1 mm, which were dried in a vacuum oven at 100 ° C under reduced pressure. The resulting granules have very good properties.

Example 2B: The procedure of Example 2A was repeated except that filaments 1.2 mm in diameter were extruded. The extruded particles were rounded to spheroids of approximately 2 mm. The resulting granules have very good properties.

Example 2C: The procedure of Example 2B was repeated except that non-ionic process water (24 ° dh [German Hardness]) was used. The resulting granules have very good properties.

Example 3A: The procedure of Example 1 was repeated but using Pigment Red C.l. as a raw material. 220 [20055], 310 parts of this dry pigment were formed into a slurry with 190 parts of deionized water in a bed-ring mixer, and this slurry was extruded in a radial extruder at a low extrusion pressure. The extruded particles were rounded in spheroids and dried in a vacuum oven at 110 ° C under reduced pressure. The resulting granules have very good properties.

Example 3B: The procedure of Example 3A was repeated, except that 190 parts of dry pigment were formed in a paste with 143 parts of a 7% strength solution of Emulan OSN ™ (BASF, Leverkusen / Germany) in deionized water in an annular bed mixer. The resulting granules have very good properties.

Example 3C: The procedure of Example 3A was repeated, except that 195 parts of dry pigment were formed in a paste with 14 parts of a 7% strength solution of Emulan OSNMR in deionized water and 126 parts of deionized water in a mixer of annular bed. The resulting granules have very good properties.

Example 4A: The procedure of Example 1 was repeated but using as a raw material Pigmento Amarillo C.l. 93 [20710]. 300 parts of this dry pigment were formed into a paste with 200 parts of deionized water in an annular bed blender, and this paste was extruded in a radial extruder at a low extrusion pressure. The extruded particles were rounded in spheroids and dried in a vacuum oven at 100 ° C under reduced pressure. The resulting granules have very good properties.

Example 4B: The procedure of Example 4A was repeated, except that 190 parts of dry pigment were formed in a paste with 143 parts of a solution with a 7% strength of Emulan OSNm in an annular bed mixer. The resulting granules have very good properties.

Example 4C: The procedure of Example 4A was repeated, except that 195 parts of dry pigment were formed in a paste with 14 parts of a 7% strength solution of Emulan 0SNMR (BASF, Leverkusen / Germany) in deionized water and parts of deionized water in an annular bed mixer. The resulting granules have very good properties.

Example 5A: The procedure of Example 1 was repeated but using as a raw material Orange Pigment C.l. 64 [12760]. 300 parts of this dry pigment were formed into a paste with 200 parts of deionized water in an annular bed blender, and this paste was extruded in a radial extruder at a low extrusion pressure. The extruded particles were rounded in spheroids and dried in a vacuum oven at 100 ° C under reduced pressure. The resulting granules have very good properties.

Example 5B: The procedure of Example 5A was repeated, except that 195 parts of dry pigment were formed in a paste with 71 parts of a 7% strength solution of Emulan OSN ™ (BASF, Leverkusen / Germany) in deionized water and 64 parts of deionized water in an annular bed mixer. The resulting granules have very good properties.

Example 5C: The procedure of Example 5B was repeated, except that, during the formation in the ring-bed mixer, 26 parts of a solution consisting of 5 parts of Staybelite® resin, 6 parts of an aqueous solution of ammonia were added. 25% and 15 parts of deionized water The resulting granules have very good properties.

Example 6A: The procedure of Example 1 was repeated but using Pigmento Rojo C.l. as a raw material. 144 [20735]. 260 parts of this dry pigment were formed into a paste with 240 parts of deionized water in an annular bed blender, and this paste was extruded in a radial extruder at a low extrusion pressure. The extruded particles were rounded in spheroids and dried in a vacuum oven at 100 ° C under reduced pressure. The resulting granules have very good properties.

Example 6B: The procedure of Example 6A was repeated, except that the pigment was used in the form of a presscake containing water comprising 44.7% residual moisture. 372 parts of the wet press cake were formed in a paste with 24 parts of deionized water in an annular bed blender, and the dough was extruded in a radial extruder at a low extrusion pressure. The resulting granules have very good properties.

Example 7A: The procedure of Example 1 was repeated, but using as a raw material Magenta CINQUASIA B RT-343-DMR (Pigment Red C.I. 202 [73907], Ciba-Geigy AG, Basel / Switzerland). 200 parts of this dry pigment were formed into a slurry with 165 parts of deionized water in an annular bed blender, and this slurry was extruded in a radial extruder at a low extrusion pressure. The extruded particles were rounded in spheroids and dried in a vacuum oven at 100 ° C under reduced pressure. The resulting granules have very good properties.

Example 7B: The procedure of Example 7A was repeated, except that 532 parts of dry pigment were formed in a paste with 318 parts of a solution consisting of 29 parts of Staybelite ™ Resin, 198 parts of aqueous ammonia solution with a strength of 25%. % and 91 parts of deionized water in an annular bed mixer. The resulting granules have very good properties.

Example 7: The procedure of Example 7B was repeated, except that the Staybelite ™ Resin was used, not in the form of a solution, but as a fine powder and loaded directly to the annular bed mixer at the same time as the pigment, the solution Aqueous ammonia and water. The resulting granules have very good properties. 4.7 Example 8A: The procedure of Example 1 was repeated, but using as raw material Magenta CINQUASIA RT-243-D * (Pigment Red C.I. 202 [73907], Ciba-Geigy AG, Basel / Switzerland). 345 parts of this dry pigment were formed into a paste with 129 parts of deionized water in an annular bed blender, and this paste was extruded in a radial extruder at a low extrusion pressure. The extruded particles were rounded in spheroids and dried in a vacuum oven at 100 ° C under reduced pressure. The resulting granules have very good properties.

Example 8B: The procedure of Example 8A was repeated, except that 570 parts of dry pigment were formed in a paste with 251 parts of a solution consisting of 30 parts of Staybelite ™ Resin, 205 parts of aqueous ammonia solution with a strength of 25%. % and 16 parts of deionized water in an annular bed mixer. The resulting granules have very good properties.

Example 8C; The procedure of Example 8A was repeated, except that 570 parts of dry pigment were formed in a paste with 205 parts of a solution consisting of 30 parts of Staybelite® resin, 21 parts of aqueous ammonia solution with a strength of 25% and 154 parts of deionized water in an annular bed mixer. The resulting granules have very good properties.

Example 9A: The procedure of Example 1 was repeated, but using as raw material Violet CINQUASIA R RT-101-1 ™ (Pigment Violet C. I. 19 [73900], Ciba-Geigy AG, Basel / Switzerland). 335 parts of this dry pigment were formed into a paste with 295 parts of deionized water in an annular bed blender, and this paste was extruded in a radial extruder at a low extrusion pressure. The extruded particles were rounded in spheroids and dried in a vacuum oven at 100 ° C under reduced pressure. The resulting granules have very good properties.

Example 9B; The procedure of Example 9A was repeated, except that 594 parts of dry pigment were formed in a paste with 560 parts of a solution consisting of 6 parts of Staybelite "*, 41 parts of aqueous ammonia solution with a strength of 25% and 513 parts of deionized water in an annular bed mixer The resulting granules have very good properties.

Example 9C: The procedure of Example 9A was repeated, except that 594 parts of dry pigment were formed in a paste with 550 parts of a solution consisting of 6 parts of Staybelite® resin, 3 parts of aqueous ammonia solution with a strength of 25% and 541 parts of deionized water in an annular bed mixer. The resulting granules have very good properties.

Claims (16)

1. RESIGNATIONS 1. A process for preparing organic pigment granules with a particle size of 0.5 to 4 mm, which consists of at least 90% by weight of at least one organic pigment with a particle size of 0.01 to 10 μm and from 0 to 10 % by weight of a binder having from 2 to 7 mol of carboxyl groups per 1000 g and from 0 to 5% by weight of a neutral emulsifier, which does not form ions and which dissolves to give a clear solution in water or an alcohol of C1-C4 at a concentration of at least 10 g / 100 ml, the binder and the emulsifier together constitute no more than 10% by weight and all percentages by weight are based on the total amount of the pigment granules, wherein [1] the pigment is mixed with 54-92% by weight of water, a C1-C4 alcohol, a C3-C8 ketone or a mixture thereof, based on the dry pigment, with the binder and 0.8-20 mole of ammonia or a C1-C3 amine, per mole of carboxyl groups in the binder, and with the emulsifier; [2] This mixture is pressed in an apparatus that operates continuously through one or more openings, each of which has a size of 0.2-5.0 mm2, the apparatus consists of at least one transport device and a training section which comprises the openings, and is constructed, and operated with a passage, so that the pressure in its formation section does not exceed 10 bar; [3] if desired, the cylindrical granules emerging from the matrices are converted into a rotating device in ovoid or spherical granules, and [4] the granulated product is dried at a temperature of -50 to 200 ° C at atmospheric pressure or under reduced pressure.
2. 2 . The process according to claim 1, characterized in that the granules are essentially spherical and have a particle size with a diameter of 0.5 to 4 mm.
3. 3. The process according to claim 1, characterized in that the pigment is a diketopyrrolopyrrole, quinacridone, perylene, dioxacin, indantrone, flavantrone, isoindol inone, phthalocyanine, aminoanthraquinone or disazo condensation pigment. Four . The process according to claim 3, characterized in that the pigment is a pigment of diketopyrrolopyrrole, quinacridone or phthalocyanine. 5. The process according to claim 4, characterized in that the pigment is a diketopyrrolopyrrole of the formula (VIII). wherein R 1 is hydrogen, C 1 -C 6 alkyl, phenyl or benzyl or is phenethyl which is unsubstituted or substituted by halogen, C 1 -C 4 alkyl, or C 1 -C 4 alkoxy, and Gi and G 2 are independently from the other a group of the formula wherein R9 and Ri0 are independently of one another hydrogen, halogen, C? -C? 8 alkyl, Ci-C? 8 alkoxy, C? -C? alkyl, C? -C? 8 alkylamino, C2-Ci8 dialkylamino, -CN, -N02, phenyl, trifluoromethyl, C5-C6 cycloalkyl, imidazolyl, pyrazolyl, triazolyl, piperazinyl, pyrrolyl, oxazolyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, morpholinyl, piperidinyl, pyrrolidinyl, -ON- (Ci-Ciß alkyl) or Rn and R12 are independently from each other hydrogen, halogen, C? -C6 alkyl, C? -C6 alkoxy or -CN, R13 and 14 are independently from each other hydrogen, halogen or C? -C6 alkyl, L is -CH2, -CH (CHs) -, -C (CH3) 2-, -CH = N-, -N = N-, -O-, -S-, -SO-, -S02- or -NR15, and is is hydrogen or C? -C6 alkyl. 6. The process according to claim 1, characterized in that the pigment has an average particle size of 0.2 to 2 μm. The process according to claim 1, characterized in that the binder contains at least 60% by weight of at least one organic acid » 8. The process according to claim 7, characterized in that the binder contains at least 5% by weight of abietic acid. 9. The process according to claim 7, characterized in that the amount of binder is 5-8% by weight. 10. The process according to claim 7, characterized in that the amount of the agglutinant is 0.5-2% by weight. 11. The process according to claim 1, characterized in that ammonia is used. The conformance process, with claim 1, characterized in that water is used in step [1] ranging from 90 to 100% by weight, based on the total amount of water, C? -C8 alcohol and ketone of C3-C8. The process according to claim 1, characterized in that the pigment has at least one primary amino group and water of 30 to 60% by weight is used in step [1], based on the total amount of water, alcohol of C? -C8 and C3 ~ C8 ketone. 14. Pigment granules with a particle size of 0.5 to 4 mm, which consist of at least 90% by weight of at least one organic pigment and from 0 to 10% by weight of a binder having from 2 to 7 mole of carboxyl groups per 1000 g and from 0 to 5% by weight of a neutral emulsifier, which does not form ions and which dissolves to give a clear solution in water or a C1-C4 alcohol at a concentration of at least 10 g / 100 ml, the binder and emulsifier together make up no more than 10% by weight and all percentages by weight are based on the total amount of pigment granules, characterized in that the pigment present in the pigment granules essentially have a particle size from 0.01 to 10 μm. 15. A method of pigmentation an organic material with high molecular weight, characterized in that an effective amount is used for the coloration of the pigment granules according to claim 1. 16. The method according to claim 15, characterized in that they use pigment granules in an amount of 0.1-30% by weight, based on the total of the high molecular weight organic material that is pigmented. SUMMARY OF THE INVENTION The invention relates to a process for preparing organic pigment granules with a particle size of 0.5 to 4 mm, which consists of at least 90% by weight of at least one organic pigment with a particle size of 0.01 to 10 μm and from 0 to 10% by weight of a binder having from 2 to 7 moles of carboxyl groups per 1000 g and from 0 to 5% by weight of a neutral emulsifier, which does not form ions and which is dissolved to give a solution clear in water or C1-C4 alcohol at a concentration of at least 10 g / 100 ml, the binder and the emulsifier together constitute no more than 10% by weight and all percentages by weight are based on the total amount of the granules of pigment, wherein [1] the pigment is mixed with 54-92% by weight of water, a C1-C4 alcohol, a C3-C8 ketone or a mixture thereof, based on the dry pigment, with the binder and 0.8-20 mol of ammonia or a C1-C3 amine, per mol of carboxyl groups in the binder, and with the emulsifier ulsifier; [2] This mixture is pressed in an apparatus that operates continuously through one or more openings, each of which has a size of 0.2-5.0 mm2, the apparatus consists of at least one transport device and a training section which comprises the openings, and is constructed, and operated with a passage, so that the pressure in its formation section does not exceed 10 bar; [3] if desired, the cylindrical granules emerging from the matrices are converted into a rotating device in ovoid or spherical granules, and [4] the granulated product is dried at a temperature of -50 to 200 ° C at atmospheric pressure or under reduced pressure. The invention also relates to pigment granules prepared by the process of the invention, with a particle size of 0.5 to 4 mm, wherein the present pigment essentially has a particle size of 0.01 to 10 μm. The invention, finally, also relates to the pigmentation of an organic material of high molecular weight with a quantity of pigments according to the invention, which is effective for coloring.