MXPA00000166A - Process for preparing new crystal modifications of c.i. pigment red 53:2 - Google Patents

Abstract

C.I. Pigment Red 53:2 is obtained in new crystal modifications (epsilon, zeta, eta, theta, iota, kappa, lambda, nu, xi, omicron, pi and rho phases) by heating any other phase of this pigment in certain organic solvents and reprecipitating the pigment. The new crystal phases differ from one another in rheology and coloristics.

Description

PROCEDURE FOR THE PREPARATION OF NEW CRYSTALLINE MODIFICATIONS OF C.l. PIGMENT RED 53: 2 DESCRIPTION OF THE INVENTION As C.l. Pigment Red 53: 2 (hereinafter PR 53: 2) is designated the compound of the formula (1), which is formed by coupling 2-amino-5-chloro-4-methyl-benzenesulfonic acid diazotized with ß-naphthol , and subsequent reaction of the sulfonic acid formed with a calcium salt (M = V * In the solid state, the compound of the formula (1) may also be present in another tautomeric or cis / trans isomer form, and may optionally also contain ions of IC ions, water molecules and solvent molecules. part of the organic pigments exist in several different crystal modifications, also called phases.The crystalline modifications have the same chemical composition, but a Surprisingly, it was found that the C.l. Pigment Red 53: 2 can be transformed into new phases, if the pigment is heated in certain liquid media, the pigment dissolves partially or completely, and then precipitates again. Therefore, a process for the phase transformation of C.l. Pigment Red 53: 2, characterized in that C.l. Pigment Red 53: 2, dissolved in one or more organic solvents or in a mixture of these solvents with water, the water content being 90% by weight, especially 1 to 50% by weight, with the exception of solvents isopropanol, isobutanol, amyl alcohol, chlorobenzene and N-methylpyrrolidone, is heated to a temperature of 30 to 300 ° C, preferably 60 to 200 ° C, and then the pigment is precipitated again. Solvents taken from the group consisting of dimethylacetamide are preferred; methanol, ethanol, n-propanol, a C6-C6 alcohol; n-butanol; sec-butanol; acetone, butanone; xylene, trimethylbenzene, dichlorobenzene, chloronaphthalene, nitrobenzene, phenetol, pyridine, phthalic acid dimethyl ester, acetic acid ethyl ester, methyl isobutyl ketone, acetophenone; quinoline; morpholine; dimethylformamide, N-methylformamide; ethylene glycol; n-butyl ester of glycolic acid as well as dimethisulfoxide. According to the process according to the invention, crystalline modifications of P.R. 53: 2, which are distinguished by the following characteristic lines (Cu-Ka radiation, values of 2T in degrees, values of d in Á "1, relative intensity (I reí) in%): Phase e ("epsilon"): 4.48 19.7 55 .87 15.1 36 7.08 12.5 61 7.87 11.2 100 9.01 9.8 32 9.84 9.0 49 11.84 7.5 25 12.47 7.1 32 14,31 6.2 26 14.80 6.0 27 .29 5.8 26 .82 5.6 58 16.80 5.3 27 17,23 5.1 29 18.80 4.7 40 19.40 4.6 27 19.82 4.5 46 .66 4.3 33 21.44 4.1 29 21.88 4.1 36 22.69 3.9 17 23,14 3,8 19 23.85 3.7 40 24.63 3.6 34 .48 3.5 32 26.12 3.4 76 26.42 3.4 65 27,91 3,2 26 28.76 3.1 29 29.88 3.0 12 .30 2.9 9 31.68 2.8 20 31.98 2.8 13 32.36 2.8 16 32.60 2.7 17 Phase? ("zeta") 2T d Ireí 5.10 17.3 24 7.13 12.4 62 7.97 11.1 100 .09 8.8 68 14.27 6.2 54 14.67 6.0 24 .92 5.6 14 17,13 5.2 18 17.84 5.0 40 18.70 4.7 18 19.07 4.7 20 19.93 4.5 29 21, 53 4.1 26 22.76 3.9 23.58 3.8 92 24.58 3.6 28 .25 3.5 16 .95 3.4 99 27.38 3.3 29 27.95 3.2 14 28.62 3.1 48 Phase? ("eta"): 2T d I laughed 4.57 19.3 100 9.07 9.7 68 12.18 7.3 45 14.77 6.0 65 21, 09 4.2 30 26.60 3.3 96 Phase T ("theta"): 2T d I reí 5,17 17,0 26 .34 8.5 13 12.17 7.3 9 13.24 6.7 10 14.60 6.1 23 .79 5.6 15 16.63 5.3 27 17.80 5.0 28 18.04 4.9 16 19.71 4.5 13 21, 06 4.2 17 24.08 3.7 12 24.47 3.6 12 .82 3.4 100 26.67 3.4 33 27,81 3,2 10 28.52 3.1 17 Phase i ("iota") 2T d Ireí 4.20 21.1 100 8.35 10.6 93 . 86 8.1 60 11.42 7.7 35 12.37 7.2 56 13.84 6.4 32 .48 5.7 64 .94 5.6 40 16.45 5.4 43 17,05 5.2 33 17.50 5.1 31 18.59 4.8 63 19.58 4.5 47 19.86 4.5 52 .80 4.3 42 21.13 4.2 32 21,30 4,1 35 21.64 4.1 34 22.14 4.0 26 22.33 4.0 29 22.77 3.9 36 23.25 3.8 3.8 23.59 3.8 93 24.07 3.7 45 .49 3.5 64 26.46 3.4 55 26.69 3.3 35 29.49 3.0 45 Phase K ("kappa"): 2T d I laughed 6.55 13.5 32 12.62 7.0 26 12.99 6.8 28 13.73 6.4 50 14,33 6.2 36 ,01 5.9 32 .47 5.7 30 16.30 5.4 24 16.78 5.3 23 17,14 5.2 38 18.31 4.8 60 18.70 4.7 44 .39 4.4 25 24.33 3.4 22 24,70 3,6 38 .34 3.5 48 26,14 34 100 27.24 3.3 27 28.00 3.2 24 28.25 3.2 24 29.91 3.0 22 Phase? ("lambda"): 2T d I laughed .03 17.5 100 .35 16.5 57 6.88 12.8 26 9.43 9.4 23 11, 09 8.0 30 13.78 6.4 17 14,36 6.2 21 .70 5.6 15 18.25 4.9 18 18.90 4.7 19 .36 4.4 16 .68 4.3 16 21, 38 4.2 15 22.90 3.9 18 24.46 3.6 22 .00 3.6 18 26.14 3.4 28 28.54 3.1 14 Phase v ("ny"): 2T d I laughed 4.76 18.5 64 7.70 11, 5 43 9.22 9.6 24 9.50 9.3 46 11, 64 7.6 15 12.74 6.9 21 13.43 6.6 33 13.76 6.4 15 14,11 6.3 13 14.27 6.2 15 .72 5.6 16 16.26 5.4 10 17,37 5.1 12 17.73 5.0 20 18.95 4.7 20 19.91 4.5 20 .45 4.3 12 ,87 4,3 19 21, 51 4.1 13 22.79 3.9 21 23.12 3.8 28 23.44 3.8 20 24.59 3.6 17 .26 3.5 49 .96 3.4 29 26.35 3.4 100 27.05 3.3 44 28.03 3.2 14 28.72 3.1 10 29.38 3.0 8 28.89 3.0 7 31, 30 2.9 9 32,12 2,8 7 32.50 2.8 9 33.27 2.7 8 Phase? ("xi"): 4.88 18.1 approx.50 7,83 11,3 100 8,59 10,3 39 11,57 7,6 21 15,76 5,6 34 17,06 5,2 46 17,40 5 5.1 24 19.66 4.5 36 19 , 99 4,4 54 20,40 4,4 27 21,41 4,1 28 21,83 4,1 31 24,49 3,6 68 25,00 3,6 Approx.70 26,83 3,3 21 27,15 3,3 17 31,33 2,9 20 31,60 2,8 18 Phase o ("omikron"): 12,54 7,1 58 13.61 6.5 44 17,33 5,1 47 18.64 4.8 52 19.48 4.6 26 24.56 3.6 100 .43 3.5 56 Phase p ("pi"): 2T d I laugh .60 15.8 100 9.09 9.7 82 9.62 9.2 72 11, 21 7.9 27 11, 65 7.6 4 12.86 6.9 5 15.24 5.8 6 15.88 5.6 22 16,85 5.3 14 18.23 4.9 21 19.07 4.7 35 19.40 4.6 54 .82 4.3 20 22.23 4.0 24 23.02 3.9 27 23.49 3.8 23 24.79 3.6 98 26.01 3.4 41 27.66 3.2 75 28.20. 3,2 10 .12 3.0 9 .85 2.9 9 31, 34 2.9 9 31, 52 2.8 6 31, 59 2.8 6 Phase p ("rho"): 2T d I laughed 4.96 17.8 100 6.05 14.6 60 8.48 10.4 22 9.95 8.9 14 13.93 6.4 13 15.12 5.9 13 15.51 5.7 13 17.54 5.1 14 19.41 4.6 14 20.99 4.2 12 21.50 4.1 14 24 , 64 3,6 13 25,44 3,5 23 26,00 3,4 40 26,89 3,3 16 28,15 3,2 11 All the situations of the lines imply an inaccuracy of ± 0.2 °. The phases according to the invention can contain, together with Ca ions, further Na ions, Cl ions, water molecules and solvent molecules in the crystalline lattice. The new phases differ as regards their properties with respect to the known crystal modifications. They are hardly soluble and are distinguished by shades of color from orange to red, partly brown, high coloring forces and good coloristic properties.

In order to achieve a phase transformation, the starting product P.R. 53: 2 occurs in a phase that differs from the one to be prepared, preferably in the alpha phase. Phase mixtures can also be used. The P.R. 53: 2 used as a starting material can be used as a dry pigment, as a press rattan moistened with water or as an aqueous suspension. The epsilon phase is obtained if the C.l. Pigment Red 53: 2, which is presented in any other modification, either in dimethylacetamide or in a mixture of dimethylacetamide and up to 90% by weight of water, especially up to 50% by weight of water, is heated to a temperature from 40 ° C to 200 ° C, preferably from 60 ° C to the boiling point of the solvent at normal pressure, conveniently for a period of time from 1 minute to 6 hours, preferably from 10 minutes to 2 hours, passing the pigment to be partially or totally dissolved. In principle, longer heating is possible, but this does not provide any technical advantage. Then, the pigment is precipitated, for example by lowering the temperature and / or by adding water, a second solvent with a lower dissolution capacity, and / or a salt, for example NaCl, and / or by modifying the pH value. The heating can be carried out at normal pressure, with depression or under pressure. As the second solvent, for example benzene or alkanes are suitable. The modification of the pH value can be produced by the addition of acids or bases.

The zeta phase is formed in an analogous manner, if methanol, ethanol, n-propanol, or an alcohol of 6 to 16 carbon atoms are used instead of dimethylacetamide as the solvent. The eta phase is formed in an analogous manner, if solvent, 1 -butanol is used. The theta phase is formed in an analogous manner, if xylene, trimethylbenzenes, dichlorobenzenes, chloronaphthalenes, nitrobenzene, phenetol, pridine, phthalic acid dimethyl ester, acetic acid ethyl ester, methyl isobutyl ketone, butanone or acetophenone are used as solvent. . In the case of using quinoline or acetophenone a mixture of the phases T and γ is formed. The oxygen phase is formed analogously if morpholine is used as the solvent. The kappa phase is formed if N-methylformamide is used as the solvent and the pigment is completely dissolved. The lambda phase is formed in an analogous manner, if acetone is used as solvent and the pigment is used as a press cake moistened with water, in the case of treatment of a dry pigment with acetone, the theta phase is formed. Phase ny is formed in a manner analogous to the epsilon phase, if ethylene glycol is used as the solvent. The phase xi is formed in an analogous manner, if the n-butyl ester of glycolic acid is used as the solvent.

The omikron phase is formed in an analogous manner, if a mixture of N-methylformamide and from 10 to 90% by weight of water, based on the mixture of solvents, is used as the solvent, and the pigment is not completely dissolved. The pi phase is formed in a manner analogous to the epsilon phase, if dimethylsulfoxide is used as the solvent. The rho phase is formed in an analogous manner, if dimethylformamide is used as the solvent. In the preparation of the phases zeta, eta, theta, ota, lambda, ny, xi, pi and rho, the respective solvent may contain up to 90% by weight of water or water up to the saturation concentration, except in the case of the preparation of the theta phase with acetone. In all cases, it may depend on the temperatures applied, the evolution of temperatures and concentrations, as well as the possible presence of crystalline nuclei, impurities or foreign materials, which are the crystalline modifications and which are the mixtures of different crystalline modifications that are formed. The P.R. 53: 2 in the modifications or mixtures of modifications according to the invention can be isolated in hot or after cooling, for example, at room temperature in the usual way, for example, by filtration separation, or by evaporation of the solvent, eventually with application of a vacuum. It may be convenient to wash the press cake or the residue with water or an organic liquid, for example, lower alcohols such as methanol, ethanol, propanol, isopropanol, or with acetone. Depending on the range of applications desired, it may be appropriate to subject the obtained pigment to a fine mechanical division. The fine division can be carried out by dry or wet milling. The grinding can be followed by a treatment with a solvent, with water, or with a mixture of a solvent and water, in order to transform the pigment into a suitable form for use. A pure or predominantly pure phase is preferably formed, if starting from a solution in which inoculation crystals or crystal nuclei of the desired phase are already present, and if this solution is cooled so slowly or a second solvent is added an acid , a base or a salt so slowly, for example in the course of 1 to 24 hours, that the supersaturation is maintained in a range in which the growth rate of the crystals is relatively high, but the rate of formation of crystalline nuclei it is relatively small, so that the crystalline nuclei present grow with maintenance of the phase. The use of a mechanical agitator can be advantageous, since it disintegrates the present crystals of the desired phase into many fragments of smaller size, which then serve again as crystalline nuclei for the desired phase (the so-called secondary nucleation). If the supersaturation is higher, for example, since the solution has been cooled more quickly or a second solvent, an acid, a base or a salt has been added more quickly, the rate of formation of crystalline nuclei is much higher, whereby many crystalline nuclei of different phases can be formed spontaneously, in which case mixtures of different phases are preferably obtained. The preparation of a mixture of different phases can be interesting, if certain coloristic and rheological properties are desired, for example a certain shade of orange color, which is situated between the color tones of the individual phases. On the other hand, it is also possible to increase the concentration of a mixture of individual phases, in order to obtain a greater proportion of the desired modification or even a pure phase, for example by pneumatic classification, recrystallization, selective extraction by dissolution or extraction of the undesired phase, or by repeated application of process measures according to the invention, in which the formation of the desired phase is favored. Therefore, a mixture of C.l. is also object of the present invention. Pigment Red 53: 2, containing at least 10%, preferably at least 25%, especially at least 505, particularly preferably at least 75%, of the phase e, of the phase?, Of the phase ?, phase T, phase i, phase K, phase?, phase v, phase?, phase o, phase p, phase po of a mixture of these phases. It is also possible that a part (up to 50%) of the Ca ions in the crystalline lattice of the crystalline modification according to the invention is replaced by other cations, for example those of Na +, H +, K +, NH4 +, Mg2 + , Sr2 *, Ba2 +, Sn2 +, Zn2 +, Mn2 +, Fe2 +, Fe3 +, Al3 +, Si4 +, Ti4 + and TiO2 +. Such mixed crystals can be formed if, in the case of the measures described above for the preparation of the crystalline modifications according to the invention, other cations are also present, for example, Na +, NH4 +, Mg2 +, Sr2 *, Ba2 +. Sn2 + 'Zn2 +, Mn2 +, Fe2 +, Fe3 +, Al3 +, Si4 +, Ti4 + and TiO2 +. In order to facilitate the preparation of the desired modification, to stabilize the desired modification, to improve the coloristic properties and to achieve certain coloristic effects at certain points of the process, pigment dispersants, surfactants, defoamers, extenders or other additive materials can be added. Mixtures of these additive materials can also be used. The addition of the additive materials can be carried out once or in several portions. The additive materials can be added at any point of the synthesis or the different subsequent treatments, or after these subsequent treatments, the most appropriate moment must be previously determined by means of orientative experiments. The C.l. Pigment Red 53: 2 in the modifications described or in mixtures, which contain these modifications, or in the form of mixed crystals with other cations, are suitable for the pigmentation of varnishes and synthetic materials, for the production of printing inks and aqueous preparations of pigments and for the staining of seeds. The phases of P.R. 53: 2 according to the invention are suitable as coloring agents in toners (also known as toners) and electrophotographic developers, such as for example one-component or two-component powder toners (also called one-component or two-component developers), toners magnetic, liquid toners, latex toners, polymerization toners as well as special toners. Typical binding agents for toners are polymerization, polyaddition and polycondensation resins, such as styrene, styrene and acrylate resins, styrene and butadiene, acrylate, polyester, phenol and epoxide, polysulfones, polyurethanes, individually or in combination, as well as polyethylene and polypropylene, which may also contain other constituent materials, such as charge control agents, waxes or fluidity coadjuvants, or that can be modified later with these additions. For the rest, the phases of P.R. 53: 2 according to the invention are suitable as coloring agents in powders or powder coatings, especially in triboelectrically or electrokinetically projected powder coatings, which are used for the surface coating of articles based on, for example, metal, wood, material synthetic, glass, ceramic material, concrete, textile, paper or rubber. Resins for powder coatings are typically epoxy resins, polyester resins containing carboxyl and hydroxyl groups, polyurethane and acrylic resins, together with customary hardeners. They also find use of resin combinations. Thus, for example, epoxy resins are often used in combination with polyester resins containing carboxyl and hydroxyl groups. Typical hardener components (depending on the resin system) are, for example, acid anhydrides, imidazoles as well as dicyandiamide and its derivatives, capped isocyanates, bis-acyl-urethanes, phenol and melamine resins, triglycidyl isocyanurates, oxazolines and dicarboxylic acids. . For the rest, the phases of P.R. 53: 2 according to the invention are suitable as coloring agents in inks for ink jet printing (ink-jet) on an aqueous and non-aqueous basis, as well as in inks that work according to the hot melt process (hot-melt). ). In addition, the phases of P.R. 53: 2 according to the invention are also suitable as coloring agents for color filters, for both additive and subtractive color production. In the following Examples, the parts and the percentage data refer to the weight. The determination of the crystalline modification of the products obtained is carried out by X-ray powder diffractometry.

EXAMPLES A) Synthesis of P.R. 53: 2 226 parts of 2-amino-4-methyl-5-chloro-benzenesulfonic acid are mixed by stirring at room temperature together with 2500 parts of water and 150 parts of 31% hydrochloric acid. At 20-25 ° C, 173 parts of a 40% solution of NaN02 are diazotized over 30 minutes and stirring is continued at room temperature for 1 hour. 150 parts of ß-naphthol are dissolved in 1100 parts of 4% NaOH and added to the diazo suspension at room temperature within 60 minutes. The pH value of the suspension is adjusted to 8.0 with NaOH and 77 parts of CaCl2 and 500 parts of water are added. The suspension is stirred to 95 ° C for 15 minutes, it is filtered hot and the press cake is washed until it is free of salts. 1,271 g of a press cake of P.R. 53: 2 in phase a. 1) Treatment with dimethylacetamide 52 parts of this press cake are heated to boiling with 200 parts of N, N-dimethyl acetamide. The solution is cooled overnight. The pigment is precipitated with stirring by addition of 150 parts of water, and then filtered off. The residue is washed with water and dried at 60%. 15 parts of P.R. are obtained. 53: 2 in the modification e with small impurities of the sodium salt of P.R. 53 like a red-orange powder. 2) Treatment with ethanol 10 parts of P.R. are heated to boiling. 53: 2 in phase a together with 1,000 parts of ethanol. Allow to cool overnight. The pigment is separated by filtration, the residue is washed with acetone and dried at 60 ° C. 9 parts of P.R. are obtained. 53: 2 in the modification? like a red powder. 3) Treatment with 1-butanol The procedure is as in Example 2, but 1-butanol is used instead of ethanol. 8 parts of P.R. 53: 2 in the modification? with small impurities from the modification? like a reddish brown powder. 4) Acetophenone treatment The procedure is as in Example 2, but acetophenone is used instead of ethanol. 9 parts of P.R. are obtained. 53: 2 in the modification? with impurities from the modification? like a red powder.

) Treatment with morpholine 10 parts of P.R. are heated to boiling. 53: 2 in phase a together with 1,000 parts of morpholine. The solution is left to cool overnight, 1,500 parts of water are added thereto and the mixture is heated until a clear solution is obtained. The solution is allowed to cool and the precipitated pigment is separated by filtration. The residue is washed with acetone and dried at 60 ° C. 8 parts of P.R. 53: 2 in the modification i as a brown powder. 6) Treatment with N-methyl formamide The procedure is as in Example 5, but it uses N-methyl formamide instead of morpholine. 8 parts of P.R. 53: 2 in modification K with impurities from the modification? like a red-orange powder. 7) Acetone treatment 40 parts of the presscake moistened with water from Example 1 together with 1,000 parts of acetone are heated to boiling. Allow to cool overnight. The pigment is separated by filtration. The residue is washed with acetone and dried at 60 ° C. 8 parts of P.R. 53: 2 in the modification? like a red powder. 8) Treatment with ethylene glycol. The procedure is as in Example 2, but ethylene glycol is used instead of ethanol. 9 parts of P.R. are obtained. 53: 2 in the modification v as a brown powder. 9) Treatment with n-butyl ester of glycolic acid The procedure is as in Example 2, but it uses n-butyl ester of glycolic acid instead of ethanol. 9 parts of P.R. are obtained. 53: 2 in the modification? like a cloudy orange powder.

) Treatment with a mixture of NMF and water. 10 parts of P.R. are heated to boiling. 53: 2 in phase a together with a mixture of 120 parts of N-methylformamide and 80 parts of water. The suspension is allowed to cool overnight. The pigment is separated by filtration. The residue is washed with acetone and dried at 60 ° C. 9 parts of P.R. are obtained. 53: 2 in the modification or with impurities from the modification? like a red powder.11) Treatment with DMSO The procedure is as in Example 2, but dimethylsulfoxide is used instead of ethanol. 10 parts of P.R. are obtained. 53: 2 in the modification p as an orange powder. 12) Treatment with DMF 10 parts of P.R. are heated to boiling. 53: 2 in phase a together with 1,000 parts of dimethylformamide. The dimethylformamide is then evaporated in vacuo at 1000 ° C. 10 parts of P.R. are obtained. 53: 2 in the modification p as a reddish-brown powder.

Claims (15)

NOVELTY OF THE INVENTION CLAIMS

1. - Procedure for the transformation of phases of C.l. pigment

Network 53: 2, characterized because the C.l. Pigment Red 53: 2, dissolved in one or more organic solvents or in a mixture of these solvents with water, the water content being 0.90% by weight, with the exception of solvents, isopropanol, isobutanol, amyl alcohol, chlorobenzene and N-methyl-pyrrolidone is heated to a temperature of 30 to 300 ° C, and then the pigment is precipitated again. 2. Method according to claim 1, characterized in that it is heated to a temperature of 60 ° C to 200 ° C.

3. Method according to claim 1 or 2, characterized in that the pigment is precipitated by decreasing the temperature.

4. Method according to one or more of claims 1 to 3, characterized in that the pigment is precipitated by the addition of water, a solvent with a low dissolution capacity, a salt, an acid or a lye.

5. Method according to claim 1 or 2, characterized in that the pigment is precipitated by evaporation of the solvent.

6. - Method according to one or more of claims 1 to 5, characterized in that the C.l. Pigment Red 53: 2 is used in the alpha phase. 7. Method according to claim 1, wherein the organic solvent is dimethylacetamide; methanol, n-propanol, a C6-C6 alcohol; n-butanol; sec-butanol; acetone, butanone; xylene, trimethylbenzene, dichlorobenzene, chloronaphthalene, nitrobenzene, phenetol, pyridine, phthalic acid dimethyl ester, acetic acid ethyl ester, methyl isobutyl ketone, acetophenone; quinoline; morpholine; N-methyl formamide, dimethylformamide; ethylene glycol; n-butyl ester of glycolic acid or dimethyl sulfoxide. 8.- C.l. Pigment Red 53: 2 of the formula (1) or a tautomeric or cis / trans isomeric form of this wherein M is a cation, with the proviso that at least 50% of the cations must be calcium ions, characterized by the following characteristic reflections in the powder diffractogram by X-rays, measured with Cu-irradiation. Ka. Phase e ("epsilon"): 2T d Ireí 4.48 19.7 55 5.87 15.1 36 7.08 12.5 61 7.87 11.2 100 9.01 9.8 32 9.84 9.0 49 11.84 7.5 25 12.47 7.1 32 14.31 6.2 26 14.80 6.0 27 15.29 5.8 26 15.82 5.6 58 16.80 5.3 27 17.23 5.1 29 18.90 4.7 40 19.40 4.6 27 19.82 4.5 46 20.66 4.3 33 21. 44 4.1 29 21. 88 4.1 36 22. 69 3.9 17 23. 14 3.8 19 23. 85 3.7 40 24. 63 3.6 34 25. 48 3.5 32 26. 12 3.4 76 26. 42 3.4 65 24. 91 3.2 26 28. 76 3.1 29 29. 88 3.0 12 30. 30 2.9 12 31. 68 2.8 20 31. 98 2.8 13 32. 36 2.8 16 32. 60 2.7 17 Phase? ("zeta"): 2T d I laughed 5. 10 17.3 24 7. 13 12.4 62

7. 97 11.1 100 10 .09 8.8 68 14. 27 6.2 54 14. 67 6.0 24 15. 92 5.6 14 17. 13 5.2 18 17. 84 5.0 40 18. 70 4.7 18 19. 07 4.7 20 19. 93 4.5 29 21. 53 4.1 26 22. 76 3.9 56 23. 58 3.8 92 24. 58 3.6 28 25. 25 3.5 16 25. 95 3.4 99 27. 38 3.3 29 27. 95 3.2 14 28. 62 3.1 48

Phase? ("eta"): 2T d I laughed 4. 57 19.3 100

9. 7 9.7 68 12. 18 7.3 45 14. 77 6.0 65 21. 09 4.2 30 26. 60 3.3 96 Phase? ("theta"): 2T d I laughed 5. 17 17.0 26 10. 34 8.5 13 12. 17 7.3 9 13. 24 6.7 10 14. 60 6.1 23 15. 79 5.6 15 16. 63 5.3 27 17. 80 5.0 28 18. 04 4.9 16 19. 71 4.5 13 21. 06 4.2 17 24. 08 3.7 12 24. 47 3.6 12 25. 82 3.4 100 26. 67 3.4 33 27. 81 3.2 10 28. 52 3.1 17 Phase i ("iota"): 2T d I laughed 4. 20 21.1 100 8. 35 10.6 93

10. 86 8.1 60 11 .42 7.7 35 12. 37 7.2 56 13. 84 6.4 32 15. 48 5.7 64 15. 94 5.6 40 16. 45 5.4 43 17. 05 5.2 33 17. 50 5.1 31 18. 59 4.8 63 19. 58 4.5 47 19. 86 4.5 52 20. 80 4.3 42 21. 13 4.2 32 21. 30 4.1 35 21. 12. 62 7.0 26 12. 99 6.8 28 13. 73 6.4 50 14. 33 6.2 36 15. 0 5.9 32 15. 47 5.7 30 16. 30 5.4 24 16. 78 5.3 23 17. 14 5.2 38 18. 31 4.8 60 18. 70 4.7 44 20. 39 4.4 25 24. 33 3.4 22 24. 70 3.6 38 25. 34 3.5 48 26. 14 3.4 100 27. 24 3.3 24 28. 00 3.2 24 28. 25 3.2 24 29. 91 3.0 22 Phase? ("lambda"): 2T d I laughed 5. 03 17.5 100 5. 35 16.5 57 6. 88 12.8 26 9. 43 9.4 23 11. 09 8.0 30 13. 78 6.4 17 14. 36 6.2 21 15. 70 5.6 15 18. 25 4.9 18 18. 90 4.7 19 20. 36 4.4 16 20. 68 4.3 16 21. 38 4.2 15 22. 90 3.9 18 24. 46 3.6 22 25. 00 3.6 18 26. 14 3.4 28 28. 54 3.1 14 Phase v ("ny"): 2T d I laughed 4. 76 18.5 64 7. 70 11.5 43 9. 22 9.6 24 9. 50 9.3 46

11. 64 7.6 15

12. 74 6.9 21 13. 43 6.6 33

13. 76 6.4 15 14. 11 6.3 13

14. 27 6.2 15 15. 72 5.6 16 16. 26 5.4 10 17. 37 5.1 12 17. 73 5.0 20 18. 95 4.7 20 19. 91 4.5 20 20. 45 4.3 12 20. 87 4.3 19 21. 51 4.1 13 22. 79 3.9 21 23. 12 3.8 28 23. 44 3.8 20 24. 59 3.6 17 25. 26 3.5 49 25. 96 3.4 29 26. 35 3.4 100 27. 05 3.3 44 28. 03 3.2 14 28. 72 3.1 10 29. 38 3.0 8 29. 89 3.0 7 31. 30 2.9 9 32. 12 2.8 7 32. 50 2.8 9 33. 27 2.7 8 Phase? ("xi"): 4.88 18.1 approx.50 7. 83 11.3 100 8.59 10.3 39 11.57 7.6 21 15.76 5.6 34 17.06 5.2 46 17.40 5.1 24 19.66 4.5 36 19.99 4.4 54 20.40 4.4 27 21.41 4.1 28 21.83 4.1 31 24.49 3.6 68 25.00 3.6 approx.70 26. 83 3.3 21 27.15 3.3 17 31.33 2.9 20 31.60 2.8 18 Phase o ("omikron"): 2T d Ireí 12. 54 7.1 58 13. 61 6.5 44 17. 33 5.1 47 18. 64 4.8 52 19. 48 4.6 26 24. 56 3.6 100 25. 43 3.5 56 Phase p ("pi"): 5.60 15.8 100 9. 09 9.7 82 9 96666 9 9..22 72 11. 21 7.9 27 11. 65 7.6 4 12. 86 6.9 5 15. 24 5.8 6 1 155..8888 5 5..66 22 16. 85 5.3 14 18. 23 4.9 21 19. 07 4.7 35 19. 40 4.6 54 20. 82 4.3 20 22. 23 4.0 24 23. 02 3.9 27 23. 49 3.8 23 24. 79 3.6 98 26. 01 3.4 41 27. 66 4.2 75 28. 20 3.2 10 3 300..1122 3 3..00 9 30. 85 2.9 9 31. 34 2.9 9 31. 52 2.8 6 31. 59 2.8 6 F Faassee pp (("" oommiikkrroonn "")) :: 4.96 17.8 100 6. 05 14.6 60 8 8..4488 1 100..44 22 9. 95 8.9 14 13. 93 6.4 13 15. 12 5.9 13

15. 51 5.7 13 17.54 5.1 14 19.41 4.6 14 20.99 4.2 12 21.50 4.1 14 24.64 3.6 13 25.44 3.5 23 26.00 3.4 40 26.89 3.3 16 28.15 3.2 11 or a mixture of these. 9. Mixture or mixed crystal of C.l. Pigment Red 53: 2, which contains at least 10% by weight, preferably at least 25% by weight, especially at least 50% by weight, particularly preferably at least 75% by weight of one or more of the phases defined in the claim. 10.- Use of C.l. Pigment Red 53: 2 according to claim 8 or 9, for the pigmentation of varnishes, synthetic materials, printing inks, toners and electrophotographic developers, powder varnishes, inks for ink-jet printing (Ink-Jet), filters chromatic as well as for the production of aqueous preparations of pigments and for the staining of seeds.