MXPA01009590A - Crimson-colored pigment composition and the utilization thereof - Google Patents

Abstract

The invention relates to a crimson-colored pigment composition containing 1,4-diketo-2,5-dihydro-3, 6-diaryl-pyrrolo[3,4c]pyrrol and quinacridone pigments in separate crystalline phases, which show high coloring power and other excellent applicational properties. The inventive pigments can be used in printing inks, especially in printing inks for polychrome printed products. An essential component of the inventive pigment mixtures is 1,4-diketo-2,5-dihydro-3, 6-di-(4'-chlorophenyl)-pyrrolo[3,4c]pyrrol or 2,9-dichloroquinacridone, which have been subjected to kneading with a crystalline inorganic salt and a neutral organic liquid. The invention also relates to a method for producing said pigment compositions, to their use in the production of printing inks and to the printing inks themselves.

Description

Composition of purple pigments and their use The present invention relates to mixtures of purple pigments containing pigments of 1,4-diketo-2,5-dihydro-3,6-diaryl-pyrolo [3,4] pyrolone and of quinacridone in particular crystalline phases which present high color intensity along with other excellent application properties. The pigments, according to the present invention, can be used in printing inks, in particular, in printing inks for polychrome printing products. In the case of printing dyes, hue, color intensity, transparency and viscosity are important parameters. The hue must correspond to very determined values to provide along with other nuances the widest possible range of colors, generally, using purple (magenta) and bluish green (cyan), yellow and black. In addition, both the intensity of the color and the transparency must be high, but also with a viscosity within a useful range. Patent EP 337 435 describes a process for the preparation of diketopyrolipyrol pigments by wet grinding in an alcohol / base system, according to which the red pigment 254 can also be treated.

From the patent EP 277 914 it is known that quinacridones provide, together with digotopriolo [3, 4c] pyrophos, in a ratio of 5:95 to 95: 5, a solid solution whose coloristic properties differ from those of the components. These solid solutions are obtained by different methods, among others by kneading with salt in the presence of an organic solvent. The same result also provides for dry milling followed by a heat treatment in the presence of a polar solvent (EP 524 904), a simultaneous dicarboxylation of soluble derivatives (EP 654 506) and reprecipitation from alkaline dimethyl sulfoxide (EP 707 049), wherein the weight ratio between 2,9-dichlorquinacridone and 1,4-diketo -2,5-dihydro-3,6-di- (4'-chlorophenyl) -pyrol [3, 4c] pyrolone is 3: 2 according to one of the examples of the EP 707 patent 049. Finally, patent EP 737 723 describes physical mixtures of 1,4-diketo-2,5-dihydro-3,6-di- (4'-biphenylyl) -pyrol [3, 4c] irol and 2,9-dichlorquinacridone which They present a red hue and a high opacity. However, it was found that these known products for printing inks, in particular polychrome printing inks, are not yet suitable to the desired extent. The printing inks that are obtained from the known pigments have either an undesired hue or disappoint with respect to color intensity, transparency, viscosity or even with respect to several of these properties at the same time. Now, it was found that pigment compositions can be obtained which are surprisingly more suitable for printing inks if certain pigments of 1,4-diketo-2,5-dihydro-3,6-diaryl-pyrolo [3, 4c] are incorporated. ] pyrolone and quinacridone under such conditions that the crystal modification of the components is essentially retained, that is, without the formation of solid solutions or mixed crystals. In addition, 1,4-diketo-2,5-dihydro-3,6-di- (4'-chlorophenyl) -pyrol [3, 4c] pyrrole and 2,9-dichlorquinacridone surprisingly can be surface passivated by the mixing with salt, so that particles conditioned in this way no longer tend to the formation of solid solutions or mixed crystals, even if they are dispersed under the influence of high forces together with other quinacridones, that is to say, pirolo [3, 4c ] priolos, as is usual in the preparation of printing inks. Therefore, the present invention relates to a pigment composition containing pigments of the formulas wherein Ri, R2, R3 and R4 independently of each other represent hydrogen, chlorine, bromine, cyano, trifluoromethyl, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or alkylthio of 1 to 8 carbon atoms. carbon, characterized in that the pigments of the formulas (I) and (II) have separate crystalline phases of their own and because in the case of at least one pigment of the formula (I) or (II) it is a l, 4- Diketo-2, 5-dihydro-3,6-di- (4'-chlorphenyl) -pyrolo- [3,4] -pyrol or a 2,3-dichlorquinacridone kneaded with an inorganic crystalline salt and an organic neutral liquid.

Separate crystalline phases are recognized in such a way that the X-ray diffraction pattern of the pigment composition coincides with the sum in weight of the X-ray diffraction diagrams of the pure components. It is probable, however it is not proven, that the particles appear in different crystal modifications in loose form and at the same time; however, aggregates of different crystal modifications clearly correspond to the definition according to the present invention, as long as they do not have mixed phases or ranges of solid solutions. In the case of the pigment of the formula (I) it can be a uniform chemical compound or also a mixture, a solid solution or a mixed crystal of 2 to 4 compounds of the formula (I). In the case of the pigment of the formula (II) it can be a uniform chemical compound or also a mixture, a solid solution or a mixed crystal of 2 to 4 compounds of the formula (II), which can also contain from 0 to 20 mol% of the compounds of the formulas (Ha) and / or Instead of 1, 4-diketo-2, 5-dihydro-3,6-di- (4'-chlorophenyl) -pyrol [3, c] only as a kneading component, a monophasic solid solution or glass can also be used mixed, wherein the as a kneading component can also be used a monophasic solid solution or a mixed crystal, wherein the 1,4-diketo-2,5-dihydro-3,6-di- (4'-chlorphenyl) -pyrolone [3, 4c] pyrolone forms a host phase, a monophasic solid solution or a mixed crystal may also be used as a kneading component, whereby 1,4-diketo-2,5-dihydro-3,6-di- (4) '-chlorphenil) -pyrol [3, 4c] pyrolone forms a host phase. Instead of 2,9-dichlorquinacridone as the kneading component, a monophasic solid solution or a mixed crystal can also be used, wherein the 2,9-dichlorquinacridone forms a host phase. On the other hand, the use of solid solutions or mixed crystals containing at the same time compounds of the formulas (I) and (II) is not recommended. In the case where the pigments of formulas (I) and / II) are mixtures, solid solutions or mixed crystals, preference is given to the fewer components of formulas (I) and / or (II) possible, for example, 2 or 3, respectively, preferably 2, respectively, which - each individually or together - form a stable crystal modification, in particular physical mixtures or mixed crystals. In particular, preference is given to the use of a single compound of the formula (I) or a single compound of the formula (II), very particularly only one compound of the formula (I) and (II) is used, respectively. Alkyl of 1 to 8 carbon atoms represents, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, tere. -butyl, n-amyl, tere. -amyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl or 2,4,4-trimethyl-2-pentyl, preferably represents alkyl of 1 to 4 carbon atoms, in particular methyl or ethyl. Alkoxy of 1 to 8 carbon atoms means, for example, -O-alkyl of 1 to 8 carbon atoms, in particular methoxy or ethoxy. Alkylthio of 1 to 8 carbon atoms represents S-alkyl of 1 to 8 carbon atoms, preferably -S-alkyl of 1 to 4 carbon atoms, in particular methylthio or ethylthio. Ri, R2, R3 and R are preferably chlorine, bromine, cyano, alkyl of 1 to 4 carbon atoms or trifluoromethyl, particularly preferably chlorine, methyl or cyano, very particularly preferably chlorine.

Preferably, in the case of the pigment of the formula (I), it is 1,4-diketo-2,5-dihydro-3,6-di- (4'-chlorophenyl) -pyrol [3, 4c] pyrolone and in the case of the pigment of the formula (II) it is quinacridone or 2,9-dichlorquinacridone, particularly preferably 2,9-dichlorquinacridone. Of very particular preference, the preferred pigments of formulas (I) and (II) are combined with each other. The pigments of formulas (I) and (II) are known and in part can be obtained commercially. The weight ratio between the pigment of the formula (I) and the pigment of the formula (II) is, preferably, from 1.5: 1 to 1: 1.2, with particular preference of 1: 1 approximately. For the kneading of the pigments of the formula (I) or (II), the weight ratio between the inorganic crystalline salt and the pigment of the formula (I) or (II) is, preferably, from 4: 1 to 12. : 1, the ratio between the organic liquid and the inorganic crystalline salt is 1 ml: 6 g to 3 ml: 7 g, and the temperature is -20 to 100 ° C. It is advantageous that the size of the pigment particles decreases during kneading, converting a pigment, preferably with a specific surface area of 40 m2 / g, particularly preferably from 5 to 30 m / g in a pigment with a specific surface area of 40 g / g. m2 / g, particularly preferred, from 50 to 80 m2 / g. The specific surface can, for example, be determined by the nitrogen method. It is advantageous if the inorganic crystalline salt is soluble in an organic neutral liquid in an amount of 100 mg / l at a temperature of 20 ° C, preferably from 10mg / l at 20 ° C, particularly preferably insoluble at ° C. Both the inorganic salt and the neutral organic liquid are soluble in water, preferably at least 10 g / l, respectively. As the inorganic salt, preference is given to using aluminum sulphate, potassium sulfate, calcium chloride, potassium chloride or sodium chloride, which can, if necessary, contain water of crystallization. Preference is given to the use of a mono-, bis- or tris-hydroxy-alkane compound of 2 to 12 carbon atoms or a polyethylene glycol or a polypropylene glycol with 1 to 120 ether groups as an organic neutral liquid, which may be unsubstituted or substituted by 1 or 2 oxo groups or they can be etherified in one or more hydroxy groups with alkyl of 1 to 8 carbon atoms or esterified with alkylcarbonyl of 1 to 8 carbon atoms, or a mixture of these components. As examples for organic neutral liquors, alcohols of 2 to 5 carbon atoms are mentioned, as are tere. -butanol, alkylene-diols of 2 to 12 carbon atoms such as ethylene glycol, alkantriols of 3 to 12 carbon atoms such as glycerin, as well as diethylene glycol or its ethers such as monoglim or diglim, its esters such as triacetin or its oxo-substituted derivatives such as diacetone alcohol . Preferably, the temperature of the kneading is from 25 to 60 ° C. The rotational speed, if necessary under consideration of the cooling, must be adjusted in such a way that sufficient shear is generated, but without the temperature increasing beyond the upper limit of the temperature range according to the present invention. Excellent results are obtained, for example, in a mixer with a content of 5 liters with speeds of rotation of 50 to 150 rotations per minute and a mixing time of 6 to 24 hours. These data do not limit in any way and, for example, in larger devices the rotation speeds may be lower. The present invention also relates to a process for the preparation of a pigment composition containing pigments of the formulas (i) and wherein R x, R 2, R 3 and R 4 independently of each other represent hydrogen, chlorine, bromine, cyano, trichloromethyl, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or alkylthio of 1 to 8 carbon atoms. carbon, wherein pigments of the formulas (I) and (II) have their own separate crystalline phases, which includes the kneading of 1,4-diketo-2,5-dihydro-3,6-di- (4'-chlorphenyl) ) -pirol [3, 4c] pyrolone as a pigment of the formula (I) or 2,9-dichlorquinacridone as a pigment of the formula (II) with an inorganic crystalline salt and an organic neutral liquid, the rinse of the inorganic crystalline salt, as well as the organic neutral liquid, drying and mixing with the other component of the formula (II) or (I), respectively. The preferred conditions of the kneading are described in the foregoing. Preference is given to rinsing with water, in particular, with demineralized water. The drying is preferably carried out at temperatures of -20 to 250 ° C / 10"1 to 105 Pa, very particularly preferably around 80 ° C / 104 Pa. The mixing can be carried out in a common mixer, for example, a rotating drum with mixing blades, preferably using an apparatus in which the physical particles are not essentially modified.For this reason and preferably dry mills are not used, or only under very careful conditions.The mixing of the second component can performed at any time, for example, after drying the first component or also before rinsing, using in this case the mixer itself as a mixer, preferably both components of the formulas (I) and (II) are kneaded, of particular preference are kneaded according to the conditions described in the above.The pigment compositions obtained according to the present invention are characterized, in particular, by a very surprisingly high intensity. In addition, they present very attractive shades of purple color with excellent purities, good transparency and good shine. In addition, a certain shade can be obtained with a lower ratio between quinacridone and diketopyrolo [3, c] priolo than in solid solutions, which is very advantageous considering the very good general properties of application of the diketopyrolo [3, 4c] pyrobes, in particular, considering the color extraordinarily intense.

Preferably, it is printed with a nitrocellulose-based printing dye in gravure printing on standard HIFI paper (Sihl-Eica), application amount after total drying of 0.80 g / m2, of this 0.06 g / m2 is pigment from color, an angle of color tone h is 350 to 360 or 0 to 10 with a saturation C * of at least 30; Particular preference is given to an angle of the color tone h from 0 to 5 with a saturation C * of at least 33 (CIÉ 1976 Standard). In addition, the passivation supports high clamping and shearing forces. It is therefore surprisingly possible to disperse the pigment compositions that are obtained according to the present invention in ball or bead mills, obtaining their coloristic advantages. Here, the viscosity also of highly concentrated dispersions is very satisfactory, which is particularly advantageous. In addition, both components of the formulas (I) and (II) can be kneaded together, due to the extraordinarily surprising advantage of a much more efficient kneading. In this way, the kneading time to obtain a certain size of specific particles and surfaces is considerably shorter. For example, the kneading time in a 5-liter kneader of contents with rotation speeds of 50 to 120 rotations per minute can be shortened to a time of 4 to 12 hours.

Therefore, preference is given to the version of the kneading of both components together, in particular in the case of preferred combinations of pigments of the formulas (I) and (I. Therefore, the present invention also relates to a method for the preparation of pigment compositions containing pigments of the formulas wherein Ri, R2, R3 and R4 independently of each other means hydrogen, chlorine, bromine, cyano, trifluoromethyl, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or alkylthio of 1 to 8 carbon atoms, wherein the pigments of formulas (I) and (II) have their own separate crystalline phases, which includes • the kneading of 1,4-diketo-2,5-dihydro-3,6-di- (4'-chlorphenyl) ) -pirol [3, 4c] pyrolone and a pigment of the formula (II) together or the kneading of 2,9-dichloroquinacridone and a pigment of the formula (I) together, with an inorganic crystalline salt and a neutral liquid organic, • the washing of the inorganic crystalline salt, as well as the organic neutral liquid, and • the drying. In addition, the present invention also relates to a process for the preparation of a pigment dispersion in a ball or bead mill, characterized in that pigments of the formulas are used wherein R 1 t R 2, R 3 and 4 independently of each other means hydrogen, chlorine, bromine, cyano, trifluoromethyl, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or alkylthio of 1 to 8 carbon atoms, wherein the pigments of the formulas (I) and (II) have separate and separate crystalline phases and wherein in the case of at least one pigment of the formula (I) or (II) it is a 1,4-ditto 2, 5-dihydro-3,6-di- (4'-chlorphenyl) -pyrol [3, 4c] irolo or a 2, 9-dichlorquinacridone. Any common dispersion medium, for example, a solution of ethylcellulose and / or nitrocellulose and / or any other known synthetic resin in one or more solvents, for example, organic solvents such as ethoxypropanol, ethanol, can be used as the liquid phase for the dispersion. dioctylphthalate or toluene, or also water. Other common additives can also be used for the desired application. The expert is already well aware of the preparation of pigment dispersions in ball or bead mills and the liquid phases that can be used for this purpose, so no further explanation is required. The dispersions prepared, in accordance with the present invention, are particularly suitable as concentrates for the preparation of printing inks having excellent application properties and, in particular, coloristic in purple with a high color intensity.

Therefore, the present invention also relates to a printing ink or a concentrate of a printing ink containing a pigment composition, in accordance with the present invention. A printing ink comprises a liquid or pasty dispersion containing dyes, binders, as well as in some cases solvents and additives. Generally, in a liquid printing ink, the binder and, if appropriate, the additives are dissolved in the solvents. The viscosities common in the Brookfield viscometer are from 0.1 to 20 Pa's (Spindle No. 4, 10 rotations per minute). Concentrates of printing inks include compositions with which printing inks can be obtained by dilution. Ingredients and compositions of printing inks and concentrates for printing inks are known to the person skilled in the art. In addition, the present invention relates to a printing ink containing pigments of the formulas (I) and wherein R x, R 2, R 3 and R 4 independently represent hydrogen, chlorine, bromine, cyano, trifluoromethyl, alkyl of 1 to 8 carbon atoms, alkoxy of 2 to 8 carbon atoms or alkylthio of 1 to 8 carbon atoms; characterized in that the pigments of the formulas (I) and (II) have their own and separate crystalline phases and because the weight ratio between the pigment of the formula (I) and the pigment of the formula (II) is from 1.5: 1 to 1: 1.2 and the printing ink obtained with an application amount of 0.06 g / m2 color pigments on a white background after drying a color tone angle of 350 to 360 or from 0 to 10 with a saturation C * of at least 30. This printing ink preferably contains l, 4-diketo-2,5-dihydro-3,6-di- (4'-chlorphenyl) -pyrol [3, 4c] -pyrol as pigment of the formula (I) or 2,9-dichlorquinaridone as a pigment of the formula (II), particularly preferably both. Apart from the pigments of the formulas (I) and (II), as well as in any case (Ha) and / or (Hb) may be present in the pigment compositions or the pigment dispersions, according to the present invention, that is, in the processes according to the present invention other pigments can also be used, in the event that the crystal properties of the pigments of the formulas (I) and (II) are not essentially altered, which can be easily determined by X-ray cistalography. Additional pigments are any white, black or colored inorganic or organic pigment, with the exception of 1, 4-diketo-2, 5- dihydro-3,6-di- (4'-chlorphenyl) -pyrol [3,4c] -pyrol and quinacridones. Additional color pigments are used in pigment compositions or dispersions, according to the present invention, preferably in small amounts of 0 to 20% by weight, in particular 0 to 10% by weight, related to the total weight of the pigments. compounds of formulas (I), (II), (Ha) and (Hb). Of particular preference, however, no additional color pigments are used. Printing inks, according to the present invention, contain the compounds of the formulas (I), (II), (Ha) and (Hb) advantageously in a concentration from 0.01 to 75% by weight, preferably from 1 to 50% by weight, particularly from 5 to 40% by weight and of particular preference from 10 to 25% by weight, related to the total weight of the printing ink, and can, for example, be used for gravure printing, flexographic printing, screen printing, offset printing or for ink jet printing in continuous or in the form of drops on paper, cardboard, metal, wood, leather, plastic or textiles, or also in special applications according to generally known recipes, for example, in publishing houses, the technology of packaging or shipping, in logistics , advertising, security printing or also in offices for pens, markers, pens, ink pads, color tapes or cartridges for inkjet printers. Generally, for gravure and flexographic printing, a printing ink is prepared from a concentrate by dilution which is then employed according to the commonly known methods. The concentrates containing the pigment compositions, according to the present invention, are particularly suitable. The pigment compositions according to the present invention are also suitable for the preparation of liquid toners and wax transfer ribbons, as pigments in color filters or for the dyeing of organic materials with a high mass molecular weight. The organic material of high molecular weight which, according to the present invention, must be dyed may be natural or synthetic in nature and generally has a molecular weight within a range of from 103 to 108 g / mol.

It can be, for example, natural resins or drying oils, rubber or casein or modified natural materials such as chlorine rubber, oil modified alkyd resins, viscose, cellulose ether or ester such as cellulose acetate, cellulose propionate , cellulose acetate butyrate or nitrocellulose, in particular of fully synthetic organic polymers (both thermosetting and thermoplastic) as obtained by polymerization, polycondensation or polyaddition, for example polyolefins such as polyethylene, polypropylene or polyisobutylene, substituted polyolefins as polymerization products starting from vinyl chloride, vinylacetate, styrene, acnitrile of the ester of acc acid and / or ester of methacc acid or butadiene, as well as copolymerization products of the aforementioned monomers, in particular ABS or EVA.

The condensation products of formaldehyde with phenols, the so-called phenoplasts, and the condensation products of formaldehyde with urea, thiourea and melamine, the so-called aminoplasts, the polyesters used as a base, are mentioned in the series of polyadicion and polycondensation resins. varnish resins, both saturated, for example, alkyd and unsaturated resins, for example, maleinate resins, admemás linear polyesters and polyamides or silicones. The aforementioned compounds with high molecular weight can be present in the form of mixtures, plastic masses or melts, which can, if necessary, be spun for fibers. They can also be present in the form of their monomers or in their polymerized state in dissolved form as a film former or as a binder for printing inks or varnishes, such as linseed oil varnish, nitrocellulose, alkyd resins, melamine resins, urea resins. formaldehyde or acc resins. The pigmentation of organic substances with a high molecular weight with pigment compositions, according to the present invention, is carried out, for example, in such a way that, in any case, a pigment of this kind is incorporated into this substrate using rolling, mixing or grinding. Usually, the pigmented material is given its final and desired shape, calendering, pressing, extruding, applying it with a brush, pouring it or molding it by injection. It is often desired to incorporate so-called softeners into the high molecular weight compounds prior to molding for the preparation of non-rigid parts or to reduce their brittleness. As softeners, for example, the ester of phosphoric acid, phthalic acid or sebacic acid can be used. The softeners can be incorporated into the polymers during the process, according to the present invention, before or after the incorporation of the pigment dyes. In addition, it is possible, in order to obtain different shades of color, to add to the organic substances with high molecular weight apart from the pigment compositions also fillers, that is, other components that give color as white pigments, colored or blacks, as well as effect pigments in the desired quantity, respectively.

For the pigmentation of printing inks and varnishes they are finely dispersed, that is to say, the organic materials with high molecular weight and the pigment compositions are dissolved, in accordance with the present invention, optionally together with additives such as fillers, others pigments, siccatives or softeners, usually in an organic and / or aqueous solvent or a mixture of solvents. It can be carried out in such a way that the individual components are dispersed, that is, they dissolve individually or also several joints, and until then all the components are joined. Therefore, a further embodiment also relates to the masses of organic material of high molecular weight and colored containing (a) from 0.05 to 70% by weight, with reference to the sum of (a) and (b) ), of a pigment composition according to the present invention, and (b) from 99.95 to 30% by weight, with reference to the sum of (a) and (b), of an organic material with high molecular weight.

Here, it can be either a ready-to-apply composition or an object formed from this composition or a masterb, for example, in the form of a granulate. In this case, the organic material of high molecular weight and colored according to the present invention may also contain common additives, for example, stabilizers. Accordingly, another embodiment relates to a method for coloring high bulk molecular weight organic materials, characterized in that a pigment composition is used, in accordance with the present invention, for example by mixing and processing the high weight organic material molecular structure with the composition of pigments, according to the present invention, optionally in the form of a masterb, according to one of the common and known methods. This can be done, for example, in a bead mill, an extruder or a rolling apparatus of any type.

The following examples clarify the invention without limiting them in any way (unless otherwise indicated, "%" should always be understood as% by weight): Example 1: 175 g of a laboratory kneader with a capacity of 5 liters are introduced of Irgazin® DPP Red BO (Color Index Pigment Red 254, 15 m2 / g), 175 g of Cinquasia® Magenta L RT-265-D (Color Index Pigment Red 202, 21 m / g), 1400 g of sodium chloride and 350 ml of diethylene glycol and the rotations are adjusted to 50 rotations per minute. The walls of the mixer are cooled to 25 ° C, ensuring that the temperature of the dough does not exceed 30 ° C. After 12 hours, 2500 ml of deionized water are added slowly, the mixture is poured through a Büchner funnel and rinsed with water until the rinse water no longer contains salt. The product is dried at a temperature of 80 ° C / 3-103 Pa for 15 hours. Example 2: 175 g of Irgazin® DPP Red BO (Color Index Pigment Red 254, 15 m2 / g), 175 g of Cinquasia® Magenta L RT-265-D are introduced into a laboratory mixer with a capacity of 5 liters. Color Index Red Pigment 202, 21 m2 / g), 2100 g of sodium chloride and 600 ml of diacetone alcohol and the rotations are adjusted to 80 rotations per minute. The walls of the mixer are cooled to 25 ° C, ensuring that the temperature of the dough does not exceed 40 ° C.

After 10 hours, 1000 ml of deionized water are added slowly, the mixture is poured through a Büchner funnel and rinsed with water until the rinse water no longer contains salt. The product is dried at a temperature of 80 ° C / 3-103 Pa for 15 hours. Example 3: 175 g of Irgazin® DPP are introduced in a laboratory mixer with a capacity of 10 liters.

Red BO (Color Index Pigment Red 254, 15 m2 / g), 175 g of Cinquasia® Magenta L RT-265-D (Color Index Red Pigment 202, 21 m2 / g), 4200 g of water-free calcium chloride and 2000 ml of N-methyl-pyrrolidone and the rotations are adjusted to 120 rotations per minute . The walls of the mixer are cooled to 25 ° C, ensuring that the temperature of the dough does not exceed 60 ° C. After 4 hours, 5000 ml of deionized water are slowly added, the mixture is poured through a Büchner funnel and rinsed with water until the rinse water no longer contains salt. The product is dried at a temperature of 80 ° C / 3-103 Pa for 15 hours. Example 4: 210 g of Irgazin® DPP Red Bo (Color Index Pigment Red 254, 15 m2 / g), 140 g of Cinquasia® Violet NRT-201-D are introduced into a laboratory mixer with a capacity of 5 liters (Color Index Pigment Violet 19, ß-modification, 70 m2 / g), 2100 g of sodium chloride and 600 ml of diacetone alcohol and the rotations are adjusted to 80 rotations per minute. The walls of the mixer are cooled to 25 ° C, ensuring that the temperature of the dough does not exceed 50 ° C. After 8 hours, 1500 ml of deionized water are added slowly, the mixture is poured through a funnel of Büchner and rinse with water until the rinse water no longer contains salt. The product is dried at a temperature of 80 ° C / 3-103 Pa for 15 hours. Example 5: In 26.40 g of ethoxypropanol, 52.80 g of ethylacetate and 116.16 g of ethanol, 39.60 g of nitrocellulose, 15.84 g of ethylcellulose, 2.64 g of modified cetonformaldehyde resin and 10.56 g of dioctyl phthalate are dissolved. 36.00 g of the product according to example 1 are pre-dispersed with a high-speed stirrer at 6000 rotations per minute for 15 minutes. The suspension is then transferred to a 125 ml bead mill with "dissolve" attachment (Dispermat SL ™; Hediger), which has 207 g of zirconium ceramic balls with a diameter of 1.0 to 1.2 mm (Hermann Oeckel Ingenieur GmbH, D-95100 Selb). It is then dispersed for 15 minutes at 4000 rotations per minute. A usable printing ink is obtained by diluting this concentrate with a solution of 222.75 g of nitrocellulose, 98.10 g of ethylcellulose, 14.85 g of modified cetonformaldehyde resin and 59.40 g of dioctyl phthalate in 148.50 g of ethoxypropanol, 297 g of ethyl acetate and 1868.40 g of ethanol in a high speed stirrer for 15 minutes. With this printing ink and a common machine for gravure printing (Rotova ™; Rotocolor AG) is printed on standard HIFI paper (Sihl-Eica), while the fraction of solids after drying is 0.80 g / m2. A bright and transparent print is obtained in purple with the following color coordinates: L * = 67, C * = 37, h = 2. Example 6: This example is carried out analogously with respect to example 5, however, the product according to example 4 is used instead of the product according to example 1. A bright and transparent print is obtained in purple color with the following color coordinates: L * = 61, C * = 41, h = 2. Examples 7 and 8: This example is carried out analogously with respect to example 5, however, the products according to examples 2 and 3 are used instead of the product according to example 1. The results are practically identical as in example 5 (? E * < 2). Example 9: In a laboratory mixer with a capacity of 0.75 liters, 22.5 g of Irgazin® DPP Red BO (Color Index Pigment Red 254, 15 m2 / g), 22.5 g of Chromophtal® Pink PT (Color Index Pigment Red 122) are introduced. , 63.2 m2 / g), 360 g of sodium chloride and 104 ml of diacetone alcohol and the rotations are adjusted to 80 rotations per minute. The walls of the mixer are cooled to 25 ° C, ensuring that the temperature of the dough does not exceed 40 ° C.

After 10 hours, 150 ml of deionized water are slowly added, the mixture is poured through a Büchner funnel and rinsed with water until the rinse water no longer contains salt. The product is dried at a temperature of 80 ° C / 3-103 Pa for 15 hours. Example 10: In a laboratory mixer with a capacity of 0.75 liters, 27 g of Irgazin® DPP are introduced.

Red BO (Color Index Pigment Red 254, 15 m2 / g), 18 g of Chromophtal® Pink PT (Color Index Pigment Red 122, 63.2 m2 / g), 360 g of sodium chloride and 104 ml of diacetone alcohol and the rotations are adjusted to 80 rotations per minute. The walls of the mixer are cooled to 25 ° C, ensuring that the temperature of the dough does not exceed 40 ° C. After 10 hours, 150 ml of deionized water are slowly added, the mixture is poured through a Büchner funnel and rinsed with water until the rinse water no longer contains salt. The product is dried at a temperature of 80 ° C / 3-103 Pa for 15 hours. Examples 11 and 12: These examples are carried out analogously with respect to example 5, however, the products according to examples 9 and 10 are used instead of the product according to example 1. In both cases excellent coloristic results are obtained. Comparative example: This example is carried out analogously to example 5, however, Cinquasia® Brilliant Red RT-380-D (solid solution consisting of 40% by weight of 1,4-diketo-2,5-dihydro) is used. -3,6-di- (4'-chlorophenyl) -pyrol [3, 4c] pyrolone and 60% by weight of 2,9-dichlorquinaridone, 78 m2 / g) instead of the product according to example 1. According to the number of rotations, the viscosity of the concentrate in the Brookfield viscometer with spindle No. 4 is 6.8 to 9.5 times higher than that of the concentrate according to example 5. Compared with the printing ink according to example 5, a very clear flocculation is observed after 24 hours of waiting time. The viscosity of the printing ink in the container "Ford Cup" No. 4 is 2.2 times higher than the viscosity of the printing ink according to example 5. With a fraction of solid substance adjusted to 0.80 g / m2 after drying a purple print is obtained with the gravure printing, however by at least 21% less intense in its color compared to example 5. The color intensity is also at least 7% lower compared to the example 6

Claims (15)

1. Claims: 1. A pigment composition containing pigments of the formulas (I) and (ID wherein Ri, R2, R3 and R4 independently of each other represent hydrogen, chlorine, bromine, cyano, trifluoromethyl, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or alkylthio of 1 to 8 carbon atoms. carbon, characterized in that the pigments of the formulas (I) and (II) have separate and own crystalline phases and because in the case of at least one pigment of the formula (I) or (II) it is a 1, 4- Diketo-2, 5-dihydro-3,6-di- (4'-chlorphenyl) -pyrolo- [3,4] -pyrol or a 2,9-dichlorquinacridone.
2. 2. A process for the preparation of a pigment composition containing pigments of the formulas wherein Ri, R2, R3 and R4 independently of each other represent hydrogen, chlorine, bromine, cyano, trichloromethyl, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or alkylthio of 1 to 8 carbon atoms; carbon, wherein pigments of the formulas (I) and (II) have their own separate crystalline phases, which includes the kneading of 1,4-diketo-2,5-dihydro-3,6-di- (4'-chlorphenyl) ) -pirol [3, 4c] pyrolone as a pigment of the formula (I) or 2,9-dichlorquinacridone as a pigment of the formula (II) with an inorganic crystalline salt and an organic neutral liquid, the rinse of the inorganic crystalline salt, as well as organic neutral liquid, drying and mixing with the other component of the formula (II) or (I), respectively.
3. 3. A process for the preparation of a pigment composition containing pigments of the formulas wherein Ri, R2, R3 and R4 independently of each other means hydrogen, chlorine, bromine, cyano, trifluoromethyl, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or alkylthio of 1 to 8 carbon atoms, wherein the pigments of formulas (I) and (H) have their own separate crystalline phases, which includes • the mixing of 1,4-diketo-2,5-dihydro-3,6-di- (4'-chlorophenyl) ) -pirol [3, 4c] irolo and a pigment of the formula (II) together or the kneading of 2,9-dichloroquinacridone and a pigment of the formula (I) together, with an inorganic crystalline salt and a neutral liquid organic, • the washing of the inorganic crystalline salt, as well as the organic neutral liquid, and • the drying.
4. 4. A process for the preparation of a pigment dispersion in a ball or bead mill, characterized in that pigments of the formulas are used wherein R x, R 2, R 3 and R 4 independently of each other represent hydrogen, chlorine, bromine, cyano, trichloromethyl, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or alkylthio of 1 to 8 carbon atoms. carbon, wherein pigments of the formulas (I) and (II) have their own and separate crystalline phases, and where in the case of at least one pigment of the formula (I) or (II) it is a 1.4 -diceto- 2, 5-dihydro-3,6-di- (4'-chlorphenyl) -pyrol [3, 4c] pyrrole or from one 2,9-dichlorquinacridone kneaded with a crystalline inorganic salt and an organic neutral liquid.
5. 5. A printing ink or a concentrate of a printing ink containing a pigment composition, according to claim 1.
6. 6. A printing ink containing pigments of the formulas wherein Ri, R2, R3 and R4 independently of each other represent hydrogen, chlorine, bromine, cyano, trichloromethyl, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or alkylthio of 1 to 8 carbon atoms; carbon, wherein pigments of the formulas (I) and (II) have separate and crystalline crystalline phases, wherein the weight ratio between the pigment of the formula (I) and the pigment of the formula (II) is 1.5: 1 to 1: 1.2 and the printing ink presents with an application quantity of color pigments of

   0. 06 g / m2 on a white background after drying a color tone angle of 350 to 360 or from 0 to 10 with a C * saturation of at least 30.
7. 7. A pigment composition, according to claim 1, a method, according to claim 2, 3, or 4, or a printing ink or a printing ink concentrate, according to claim 5, wherein both components of the formulas (I) and (II) are kneaded.
8. 8. A pigment composition, according to claim 1, a method, according to claim 2, 3, or 4, or a printing ink or a printing ink concentrate, according to claim 5 or 6. , wherein in the case of the pigment of the formula (I) it is 1, 4-diketo-2, 5-dihydro-3,6-di- (4'-chlorphenyl) -pyrol [3, 4c] pyrolone.
9. 9. A pigment composition, according to claim 1, a method, according to claim 2, 3, or 4, or a printing ink or a printing ink concentrate, according to claim 5 or 6. , wherein in the case of the pigment of the formula (II) is quinacridone or 2,9-dichlorquinacridone, preferably, 2,9-dichlorquinacridone.
10. 10. A pigment composition, a process, a printing ink or a printing ink concentrate, according to claim 8, wherein in the case of the pigment of the formula (II) it is quinacridone or 2, 9-dichlorquinacridone, preferably 2,9-dichlorquinacridone.
11. 11. A pigment composition, according to claim 1, a process according to claim 2, 3, or 4, or a printing ink or a printing ink concentrate, according to claim 5, in where the specific surface increases during the mixing of 40 m2 / g to 40 m2 / g.
12. 12. A pigment composition, according to claim 1, a method, according to claim 2, 3, or 4, or a printing ink or a printing ink concentrate, according to claim 5, in where as inorganic salt and as organic neutral liquid a mono-, bis- or tris-hydroxy-alkane compound of 2 to 12 carbon atoms or a polyethylene glycol or a polypropylene glycol with 1 to 120 ether groups is employed, which in unsubstituted form or substituted by 1 or 2 oxo groups are etherified in one or more hydroxy groups with alkyl of 1 to 8 carbon atoms or are esterified with alkylcarbonyl of 1 to 8 carbon atoms, or a mixture of these components.
13. 13. A pigment composition, according to claim 1, a process according to claim 2, 3, or 4, or a printing ink or a printing ink concentrate, according to claim 5, in where the temperature of the kneading is -20 to 100 ° C.
14. 14. A colored material within the organic material with high molecular weight containing (a) from 0.05 to 70% by weight, with reference to the sum of (a) and (b), of a pigment composition according to claim. 1, and (b) from 99.95 to 30% by weight, with reference to the sum of (a) and (b), of an organic material with high molecular weight.
15. 15. A process for coloring high molecular weight organic material in the form of a dough, characterized in that a pigment composition is used, according to claim 1.