Pigment preparation

Abstract

The invention relates to a pigment preparation. In particular, the invention relates to novel pigment formulations based on metal azo pigments and aliphatic C10-22 monocarboxylic acids, to a method for the production thereof and to the use thereof as yellow pigments for coloring plastics, and to the use of aliphatic C10-22 monocarboxylic acids for improving the filtration properties of the pigment formulations while improving the color strength.

Description

Technical Field

[0001] The present invention relates to a method for preparing a metal azo pigment and an aliphatic C 10-22 New pigment preparations of monocarboxylic acids, methods for their production and their use as yellow pigments for coloring plastics, and aliphatic C 10-22 Use of monocarboxylic acids for improving the filtration properties of pigment preparations while simultaneously improving the color strength. Background Art

[0002] Metal complexes of azobarbituric acid and nickel salts and their use as yellow pigments have been widely described in the literature such as W. Herbst, K. Hunger, Industrial Organic Pigments [Industrial Organic Pigments], 3rd edition 2004, pages 390-397. It is also known that these products can further react, for example, with melamine or melamine derivatives to improve the performance characteristics of these pigments, especially in plastics and lacquers and in the coloring of color filters for LCDs (liquid crystal displays). In the literature, it is also described that these metal azo complexes can also contain at least one other salt of different metals in addition to nickel salts in order to adapt to the color characteristics. EP-A 1 591 489 discloses metal complexes of azo compounds based on alkali metals, alkaline earth metals, lanthanides, aluminum, scandium, titanium, vanadium, chromium, manganese, cobalt, copper, nickel and zinc. The pigment according to EP-A1 591 489 has a different color position compared to pure nickel-azobarbituric acid complexes. The color position describes the position of a measured or selected color in a color space and is usually defined by coordinates, preferably by the coordinates L*, a* and b* in the CIELAB color space. The quantity of all color positions in a color space is called the gamut or color gamut; see: https: / / de.wikipedia.org / wiki / Farbraum. Although EP-A 1 591 489 contains statements about the color strength of the adhesive determined according to Bayer Farben Revue [Bayer Color Review], Special Issue 3 / 2 D, Farbmessung [Colour measurement] (color measurement) 1986, there are no statements about filterability or the determination of the filter pressure value FPV according to DIN EN ISO 23900-5:2019-01.

[0003] The literature also discloses treating the surface of the pigment with an auxiliary agent. For example, the dispersion characteristics of the pigment will be improved by such surface coverage. However, increasing the coverage of the pigment surface is also always associated with a loss of color intensity. Such surface treatments of azo pigments are known, for example, from "W. Herbst, K. Hunger, Industrial Organic Pigments (Production, Properties, Applications), 3rd Edition Complete Revised (2004), Wiley-VCH-Verlag, pp. 202-203".

[0004] Pigments based on metal azobarbituric acid and melamine, which contain copper and nickel ions and optionally further metal ions, are known from EP-A 3 072 932 and EP-A 3 222 680. These pigments are noteworthy for their improved dispersion properties and increased color strength. However, EP-A 3 072 932 and EP-A 3 222 680 do not contain any statements about filterability or determination of the filter pressure value FPV according to DIN EN ISO 23900-5:2019-01.

[0005] Pigments based on metal azobarbituric acids and melamine, which contain copper and nickel ions and optionally further metal ions and are surface-coated with specific fatty acid derivatives, are known from EP-A 3 981 840. These products are distinguished by improved thermal stability and, presumably, high color strength, but no more precise information is available on the latter.

[0006] Among other things, EP-A 1 612 246 discloses five nickel azobarbiturate-melamine pigments with improved dispersibility. EP-A 1 612 246 contains no statements about relative color strength, nor about filterability or determination of the filter pressure value FPV according to DIN EN ISO 23900-5:2019-01.

[0007] The metal azo pigments known from the prior art are insufficient with regard to their performance characteristics, and there is therefore a need for improved metal azo pigments, in particular with regard to filter properties and at least retention of color strength. Summary of the invention

[0008] It has now been found that, surprisingly, when 100 to 250 g of aliphatic C 10-22 Monocarboxylic acid per mole of all metal azo compounds contained in the metal azo pigment, based on at least two zinc-based and nickel-based metal azo compounds and at least one aliphatic C 10-22Pigment preparations of monocarboxylic acid combinations have improved filter properties and at the same time have improved color strength.

[0009] The subject of the invention is a pigment preparation consisting of

[0010] i) Metallic azo pigments A) containing

[0011] a) at least two metal azo compounds of formula (I) which differ at least in the metal ion Me, or tautomeric forms thereof,

[0012] (I)

[0013] in

[0014] R 1 and R 2 Each independently is OH, NH2 or NHR 5 ,

[0015] R 3 and R 4 Each independently is O or NR 5 ,

[0016] R 5 is hydrogen or alkyl, preferably C1-C4 alkyl, and

[0017] Me in the first metal azo compound is the metal ion Me 1 And in the second metal azo compound it is the metal ion Me 2 ,

[0018] in

[0019] Me 1 Zn 2+ and Ni 2+ and the molar ratio of Zn to Ni metal ions is 97:3 to 3:97, and

[0020] Me 2 It's Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 、Co 2+ 、Co 3+ 2 / 3 ,La 3+ 2 / 3 、Ce 3+ 2 / 3 , Pr 3+ 2 / 3 -、Nd 2+ 、Nd 3+ 2 / 3、Sm 2+ 、Sm 3+ 2 / 3 、Eu 2+ 、Eu 3+ 2 / 3 , Gd 3+ 2 / 3 , Tb 3+ 2 / 3 、Dy 3+ 2 / 3 、Ho 3+ 2 / 3 , Yb 2+ , Yb 3+ 2 / 3 , Er 3+ 2 / 3 、Tm 3+ 2 / 3 Mg 2+ , Ca 2+ , Sr 2 + , Mn 2+ , Y 3+ 2 / 3 Sc 3+ 2 / 3 、Ti 2+ 、Ti 3+ 2 / 3 , Nb 3+ 2 / 3 、Mo 2+ 、Mo 3+ 2 / 3 、V 2+ 、V 3+ 2 / 3 、Zr 2+ 、Zr 3+ 2 / 3 、Cd 2+ Cr 3+ 2 / 3 , Pb 2+ Or Ba 2+ ,

[0021] Provided that, based in each case on one mole of all compounds of the formula (I), the metal ion Me 1 The amount of is 97 to 100 mol % in total, and the amount of metal ions selected from the Me² series is 0 to 3 mol %, and

[0022] b) at least one compound having the formula (II)

[0023] (II)

[0025] in

[0026] R6 is independently in each case hydrogen or alkyl, preferably C1-C4-alkyl, which may be optionally substituted one or more times by OH,

[0027] or a reaction product of (I) and (II), preferably a reaction product of (I) and melamine,

[0028] as well as

[0029] (ii) per mol of all metal azo compounds (I) contained in the metal azo pigment A), 100 to 250 g of at least one aliphatic C 10-22 Monocarboxylic acids B).

[0030] However, the present invention also relates to at least one aliphatic C 10-22 Use of monocarboxylic acids B) for simultaneously improving the filter pressure value FPV determined by filter press test according to DIN EN ISO 23900-5:2019-01 and the color strength determined according to DIN 55986 of pigment preparations containing metal azo pigments A) consisting of:

[0031] a) at least two metal azo compounds of formula (I) which differ at least in the metal ion Me, or tautomeric forms thereof,

[0032] (I)

[0033] in

[0034] R 1 and R 2 Each independently is OH, NH2 or NHR 5 ,

[0035] R 3 and R 4 Each independently is O or NR 5 ,

[0036] R 5 is hydrogen or alkyl, preferably C1-C4 alkyl, and

[0037] Me in the first metal azo compound is the metal ion Me 1 And in the second metal azo compound it is the metal ion Me 2 ,

[0038] in

[0039] Me 1 Zn 2+ and Ni 2+ and the molar ratio of Zn to Ni metal ions is 97:3 to 3:97, and

[0040] Me 2 It's Al 3+ 2 / 3 、Fe 2+ 、Fe 3+ 2 / 3 、Co 2+ 、Co 3+ 2 / 3 、La 3+ 2 / 3 、Yes 3+ 2 / 3 、Pr 3+ 2 / 3 -、Nd 2+ 、Nd 3+ 2 / 3 、Sm 2+ 、Sm 3+ 2 / 3 、Eu 2+ 、Eu 3+ 2 / 3 、Gd 3+ 2 / 3 、Tb 3+ 2 / 3 、Dy 3+ 2 / 3 、Ho 3+ 2 / 3 、Yb 2+ 、Yb 3+ 2 / 3 、Er 3+ 2 / 3 、Tm 3+ 2 / 3 、Mg 2+ 、Ca 2+ 、Sr 2 + 、Mn 2+ 、Y 3+ 2 / 3 、Sc 3+ 2 / 3 、Ti 2+ 、Ti 3+ 2 / 3 、Nb 3+ 2 / 3 、Mo 2+ 、Mo 3+ 2 / 3 、V 2+ 、V 3+ 2 / 3 、Zr 2+ 、Zr 3+ 2 / 3 ,CD 2+ 、Cr 3+ 2 / 3 、Pb 2+ Or Ba2+ ,

[0041] Provided that, based in each case on one mole of all compounds of the formula (I), the metal ion Me 1 The amount of is 97 to 100 mol % in total, and the amount of metal ions selected from the Me² series is 0 to 3 mol %, and

[0042] b) at least one compound having the formula (II)

[0043] (II)

[0045] in

[0046] R 6 is independently in each case hydrogen or alkyl, preferably C1-C4-alkyl, which may be optionally substituted one or more times by OH,

[0047] or the reaction product of (I) and (II), preferably the reaction product of (I) and melamine,

[0048] Provided that 100 to 250 g of aliphatic C are used per mole of all metal azo compounds (I) contained in the metal azo pigment A). 10-22 Monocarboxylic acids B).

[0049] The present invention also relates to a method for simultaneously improving the filter pressure value FPV determined by a filter press test according to DIN EN ISO 23900-5:2019-01 and the color strength determined according to DIN 55986 of a pigment preparation containing a metal azo pigment A) consisting of:

[0050] a) at least two metal azo compounds of formula (I) which differ at least in the metal ion Me, or tautomeric forms thereof,

[0051] (I)

[0052] in

[0053] R 1 and R 2 Each independently is OH, NH2 or NHR 5 ,

[0054] R 3 and R 4 Each independently is O or NR 5 ,

[0055] R 5 is hydrogen or alkyl, preferably C1-C4 alkyl, and

[0056] Me in the first metal azo compound represents Me 1 And Zn 2+ and Ni 2+ , wherein the molar ratio of Zn to Ni metal ions is 97:3 to 3:97,

[0057] and

[0058] Me in the second metal azo compound represents Me 2 And it is Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 、Co 2+ 、Co 3+ 2 / 3 ,La 3 + 2 / 3 、Ce 3+ 2 / 3 , Pr 3+ 2 / 3 -、Nd 2+ 、Nd 3+ 2 / 3 、Sm 2+ 、Sm 3+ 2 / 3 、Eu 2+ 、Eu 3+ 2 / 3 , Gd 3+ 2 / 3 , Tb 3+ 2 / 3 、Dy 3+ 2 / 3 、Ho 3+ 2 / 3 , Yb 2 + , Yb 3+ 2 / 3 , Er 3+ 2 / 3 、Tm 3+ 2 / 3 Mg 2+ , Ca 2+ , Sr 2+ , Mn 2+ or Y 3+ 2 / 3 Sc 3+ 2 / 3 、Ti 2+ 、Ti 3+ 2 / 3 , Nb 3+ 2 / 3 、Mo 2+ 、Mo3 + 2 / 3 、V 2+ 、V 3+ 2 / 3 、Zr 2+ 、Zr 3+ 2 / 3 、Cd 2+ Cr 3+ 2 / 3 , Pb 2+ Or Ba 2+ ,

[0059] Provided that, based in each case on one mole of all compounds of the formula (I), the metal ion Me 1 The amount of is 97 to 100 mol % in total, and the amount of metal ions selected from the Me² series is 0 to 3 mol %, and

[0060] b) at least one compound having the formula (II)

[0061] (II)

[0063] in

[0064] R 6 is independently in each case hydrogen or alkyl, preferably C1-C4-alkyl, which may be optionally substituted one or more times by OH,

[0065] or the reaction product of (I) and (II), preferably the reaction product of (I) and melamine,

[0066] The method comprises using 100 to 250 g of at least one aliphatic C per mole of all metal azo compounds (I) contained in the metal azo pigment A). 10-22 Monocarboxylic acids B).

[0067] In formula (I), if Me is a trivalent metal ion, the charge is in each case balanced by an equivalent of an anionic building block having formula (Ia)

[0068] (Ia)

[0069] Where R 1 , R 2 , R 3 and R 4 has the meaning indicated for formula (I).

[0070] For the sake of clarity, it should be noted that the scope of the present invention encompasses all definitions and parameters in any desired combination cited in a general sense or in a preferred range. This also applies to the amount used in the method and use claimed in the present application. The standards cited in the context of the present application relate to the current version on the filing date of the present invention. Unless otherwise stated, the reported percentages are weight percentages. The substituents in the meaning of alkyl refer to straight or branched hydrocarbon groups, preferably C1-C6 alkyl, particularly preferably C1-C4 alkyl, which can be optionally replaced by the same or different substituents, particularly by chlorine, bromine, fluorine,-OH,-CN,-NH2 or C1-C6 alkoxy substituted one or more times.

[0071] Color strength is a colorimetric quantity that describes the coloring power of a colorant. A distinction is made between absolute and relative color strength. Color strength is the most important property of a pigment; see: https: / / de.wikipedia.org / wiki / Farbstärke.

[0072] In the context of the present invention, relative color strength is determined in accordance with DIN 55986. In the production of pigments, it is common not to use absolute color strength but relative color strength measured relative to a standard. For this purpose, each batch to be tested is dispersed and used for coloring under the same conditions as the standard. The quotient of the K / S value (Kubelka-Munk) (sample / standard) represents a measure of the light absorption of the entire system, is called relative color strength and is expressed as a percentage:

[0073]

[0074] A value of 100% means that the sample has the same color strength as the standard; larger values ​​mean higher color strength, meaning that less pigment is needed to convey a given hue.

[0075] The filter pressure value FPV is determined within the scope of the present invention by means of a filter press test in accordance with DIN EN ISO 23900-5:2019-01 (determination of the pressure increase / option 2). This standard specifies a method for determining the dispersion of colorants in thermoplastics. The method is suitable for testing colorants in the form of color concentrates in all plastics used for extrusion and melt spinning processes. The filter pressure value determined by this method is only valid for the equipment used, the conditions and the plastic to be tested. The use of test conditions other than those specified may lead to different results. The production of color concentrates is not described in this part of ISO 23900. Therefore, the test results of individual colorants are only comparable if the color concentrates are produced using the same method. According to DIN EN ISO 23900-5:2019-01, the corresponding pigment preparation to be tested is thoroughly mixed into a polyamide 6 (with 1% titanium dioxide added) in the form of Durethan® B30S from LANXESS Deutschland GmbH, Cologne on a tumble mixer. The mixture obtained in this way is then extruded on a Leistritz ZSE 18HP twin-screw extruder at a speed of 225 ° C and 700 rpm, and the resulting granular material is filtered through a 25 μm filter at a temperature of 238 ° C, and the pressure increase that occurs is measured. The pressure difference between the initial pressure and the maximum pressure is used to calculate the filter pressure value FPV. The lower the pressure increase measured in bar / gram, the better the filtering characteristics of the pigment preparation to be tested in the context of the present invention.

[0076] Preferably, the component a) contained in the metal azo pigment used in the present invention forms a so-called adduct together with the component b), wherein an adduct according to the present invention means a "complex molecule". The bonding between the molecules of such an adduct preferably occurs via intermolecular interactions, via Lewis acid-base interactions or via coordination bonds. According to the present invention, the term "adduct" generally includes all types of intercalation compounds or addition compounds.

[0077] The term "intercalation compound" or "addition compound" within the meaning of the present invention is to be understood in particular as meaning a compound which is formed by intermolecular interactions such as van der Waals interactions or Lewis acid-base interactions. How the intercalation takes place depends not only on the chemical nature of the component to be intercalated, but also on the chemical nature of the host lattice. Such compounds are also often referred to as intercalation compounds. In the chemical sense, this refers to the incorporation of molecules, ions and sometimes even atoms into a compound.

[0078] Furthermore, the term "adduct" also includes inclusion compounds, so-called clathrates. These represent compounds of two substances in which a guest molecule is incorporated into a lattice or cage consisting of a host molecule.

[0079] The term "intercalation compound" or "addition compound" within the meaning of the present invention also includes mixed intercalation crystals or interstitial compounds. These are chemical, non-stoichiometric, crystalline compounds of at least two elements.

[0080] Furthermore, the term "intercalation compound" or "addition compound" is also understood in the context of the present invention to mean a compound formed on the basis of a coordination bond or a complex bond. Such compounds are particularly referred to as mixed substitution crystals or mixed replacement crystals, in which at least two substances form common crystals and the atoms of the second component are located at regular lattice sites of the first component.

[0081] Compounds suitable for forming adducts as defined above with the metal azo compounds of formula (I) may be both organic and inorganic compounds. These compounds are referred to hereinafter as adduct formers.

[0082] Suitable adduct formers are in principle from the most diverse classes of compounds. For practical reasons only, preference is given to such compounds which are liquid or solid under standard conditions (25° C., 1 bar). Among liquid substances, preference is generally given to those having a boiling point of 100° C. or higher, preferably greater than or equal to 150° C., at 1 bar. Suitable adduct formers are generally acyclic and cyclic organic compounds, preferably aliphatic or aromatic hydrocarbons, which may be substituted, in particular by OH, COOH, NH2, substituted NH2, CONH2, substituted CONH2, SO2NH2, substituted SO2NH2, SO3H, halogen, NO2, CN, -SO2-alkyl, -SO2-aryl, -O-alkyl, -O-aryl, -O-acyl.

[0083] Carboxamides and sulfonamides are a group of preferred adduct formers. Also particularly suitable are ureas and substituted ureas, such as phenylurea, dodecylurea, etc., and also polycondensates thereof with aldehydes, in particular formaldehyde; but also heterocycles, preferably barbituric acid, benzimidazolone, benzimidazolone-5-sulfonic acid, 2,3-dihydroxyquinoxaline, 2,3-dihydroxyquinoxaline-6-sulfonic acid, carbazole, carbazole-3,6-disulfonic acid, 2-hydroxyquinoline, 2,4-dihydroxyquinoline, caprolactam, melamine, 6-phenyl-1,3,5-triazine-2,4-diamine, 6-methyl-1,3,5-triazine-2,4-diamine, cyanuric acid.

[0084] The polymer, preferably a water-soluble polymer, in particular an ethylene oxide-propylene oxide block polymer, preferably has an M greater than or equal to 1000, in particular from 1000 to 10 000 g / mol. n , polyvinyl alcohol, poly(meth)acrylic acid, modified celluloses, preferably carboxymethylcellulose, hydroxyethylcellulose and hydroxypropylcellulose, methylhydroxyethylcellulose and ethylhydroxyethylcellulose are likewise suitable as adduct formers.

[0085] According to the invention, the adduct formers used are those of the formula (II). According to the invention, melamine is particularly preferred. DETAILED DESCRIPTION

[0086] Preferred embodiments of the present invention

[0087] A preferred subject of the invention is a pigment preparation consisting of

[0088] i) Metallic azo pigments A) containing

[0089] a) at least two metal azo compounds of formula (I) which differ at least in the metal ion Me, or tautomeric forms thereof,

[0090] (I)

[0091] in

[0092] R 1 and R 2 Each independently is OH, NH2 or NHR 5 ,

[0093] R 3 and R 4 Each independently is O or NR 5 ,

[0094] R 5 is hydrogen or alkyl, preferably C1-C4 alkyl, and

[0095] Me in the first metal azo compound is the metal ion Me 1 And in the second metal azo compound it is the metal ion Me 2 ,

[0096] in

[0097] Me 1 Zn 2+ and Ni 2+ and the molar ratio of Zn to Ni metal ions is 97:3 to 3:97, and

[0098] Me 2It's Al 3+ 2 / 3 、Fe 2+ 、Fe 3+ 2 / 3 、Co 2+ 、Co 3+ 2 / 3 、La 3+ 2 / 3 、Yes 3+ 2 / 3 、Pr 3+ 2 / 3 -、Nd 2+ 、Nd 3+ 2 / 3 、Sm 2+ 、Sm 3+ 2 / 3 、Eu 2+ 、Eu 3+ 2 / 3 、Gd 3+ 2 / 3 、Tb 3+ 2 / 3 、Dy 3+ 2 / 3 、Ho 3+ 2 / 3 、Yb 2+ 、Yb 3+ 2 / 3 、Er 3+ 2 / 3 、Tm 3+ 2 / 3 、Mg 2+ 、Ca 2+ 、Sr 2 + 、Mn 2+ 、Y 3+ 2 / 3 、Sc 3+ 2 / 3 、Ti 2+ 、Ti 3+ 2 / 3 、Nb 3+ 2 / 3 、Mo 2+ 、Mo 3+ 2 / 3 、V 2+ 、V 3+ 2 / 3 、Zr 2+ 、Zr 3+ 2 / 3 ,CD 2+ 、Cr 3+ 2 / 3 、Pb 2+ Or Ba 2+ ,

[0099] Provided that, based in each case on one mole of all compounds of the formula (I), the metal ion Me 1 The amount of is 97 to 100 mol % in total, and the amount of metal ions selected from the Me² series is 0 to 3 mol %, and

[0100] b) at least one compound having the formula (II)

[0101] (II)

[0103] in

[0104] R 6 is independently in each case hydrogen or alkyl, preferably C1-C4-alkyl, which may be optionally substituted one or more times by OH,

[0105] as well as

[0106] (ii) per mol of all metal azo compounds (I) contained in the metal azo pigment A), 100 to 250 g of at least one aliphatic C 10-22 Monocarboxylic acids B).

[0107] Preferably, in the metal azo pigment A), the ratio of the metal azo compound (I) to the compound of formula (II) is 1 mol: 0.05 to 4 mol, more preferably 1 mol: 0.5 to 2.5 mol and especially preferably 1 mol: 1.0 to 2.0 mol.

[0108] In one embodiment, the metal azo compound A) contained in the pigment preparation according to the invention is a physical mixture of adducts of a) at least two metal azo compounds of formula (I) and b) at least one compound of formula (II). Preferably, they are physical mixtures of adducts of pure Ni-azo compounds with melamine and pure Zn-azo compounds with melamine.

[0109] However, it is particularly preferred that the metal azo pigments A) contained in the pigment preparations according to the invention are chemically mixed compounds of adducts of a) at least two metal azo compounds of formula (I) and b) at least one compound of formula (II). These chemically mixed compounds are compounds in which Ni and Zn atoms and optionally also other metal ions Me are added. 2 Adducts of metal azo compounds incorporated into common crystal lattices.

[0110] A preferred subject of the invention is a pigment preparation consisting of

[0111] i) Metallic azo pigments A) containing

[0112] a) at least two metal azo compounds having the formula (I)

[0113] (I)

[0114] Where R 1 and R 2 Yes OH,

[0115] R 3 and R 4 It's O.

[0116] Me in the first metal azo compound represents Me 1 And Zn 2+ and Ni 2+ , wherein the molar ratio of Zn to Ni metal ions is 97:3 to 3:97, and Me in the second metal azo compound represents Me 2 And Me 2 It's Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 、Co 2+ 、Co 3+ 2 / 3 ,La 3+ 2 / 3 、Ce 3+ 2 / 3 , Pr 3+ 2 / 3 -、Nd 2+ 、Nd 3+ 2 / 3 、Sm 2+ 、Sm 3+ 2 / 3 、Eu 2+ 、Eu 3+ 2 / 3 , Gd 3+ 2 / 3 , Tb 3+ 2 / 3 、Dy 3+ 2 / 3 、Ho 3+ 2 / 3 , Yb 2+ , Yb 3+ 2 / 3 , Er 3+ 2 / 3 、Tm 3+ 2 / 3 Mg 2+ , Ca 2+ , Sr 2+, Mn 2+ or Y 3+ 2 / 3 、Ti 2+ 、Ti 3+ 2 / 3 , Nb 3+ 2 / 3 、Mo 2+ 、Mo 3+ 2 / 3 、V 2+ 、V 3+ 2 / 3 、Zr 2+ 、Zr 3+ 2 / 3 、Cd 2+ Cr 3+ 2 / 3 , Pb 2+ Or Ba 2+ ,

[0117] Provided that, based in each case on one mole of all compounds of the formula (I), the metal ion Me 1 The amount of total is 97 mol% to 100 mol%, and the metal ion Me 2 The amount of is 0 mol% to 3 mol% in total, and

[0118] b) melamine (2,4,6-triamino-1,3,5-triazine, CAS No. 108-78-1), or alternatively the reaction product of formula (I) with melamine,

[0119] as well as

[0120] ii) 100 to 250 g of at least one aliphatic C per mol of all metal azo compounds (I) contained in the metal azo pigment A) 10-22 Monocarboxylic acids B).

[0121] The present invention particularly preferably relates to a pigment preparation consisting of

[0122] i) Metallic azo pigments A) containing

[0123] a) at least two metal azo compounds having the formula (I)

[0124] (I)

[0125] Where R 1 and R 2 Yes OH,

[0126] R 3 and R 4 It's O.

[0127] Me in the first metal azo compound represents Me 1 And Zn 2+ and Ni 2+ , wherein the molar ratio of Zn to Ni metal ions is 90:10 to 30:70, and

[0128] Me in the second metal azo compound represents Me 2 And it is Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 、Co 2+ 、Co 3+ 2 / 3 、Ce 3 + 2 / 3 Mg 2+ , Ca 2+ , Sr 2+ ,La 3+ 2 / 3 Mg 2+ , Mn 2+ 、Nd 2+ 、Nd 3+ 2 / 3 、Ti 2+ 、Ti 3+ 2 / 3 , Nb 3+ 2 / 3 、Mo 2+ 、Mo 3+ 2 / 3 、V 2+ 、V 3 + 2 / 3 、Zr 2+ 、Zr 3+ 2 / 3 、Cd 2+ Cr 3+ 2 / 3 , Pb 2+ , Ca 2+ Or Ba 2+ ,

[0129] Provided that, based in each case on one mole of all compounds of the formula (I), the metal ion Me 1 The amount of metal ions Me 2 The amount of is 0 mol% to 1 mol% in total, and

[0130] b) melamine (2,4,6-triamino-1,3,5-triazine, CAS No. 108-78-1), or alternatively the reaction product of (I) and melamine,

[0131] as well as

[0132] i) per mol of all metal azo compounds (I) contained in the metal azo pigment A) 100 to 250 g of at least one aliphatic C 10-22 Monocarboxylic acids B).

[0133] The present invention particularly preferably relates to a pigment preparation consisting of

[0134] i) Metallic azo pigments A) containing

[0135] a) at least two metal azo compounds having the formula (I)

[0136] (I)

[0137] Where R 1 and R 2 Yes OH,

[0138] R 3 and R 4 It's O.

[0139] Me in the first metal azo compound represents Me 1 And Zn 2+ and Ni 2+ , wherein the molar ratio of Zn to Ni metal ions is 40:80 to 20:60, and

[0140] Me in the second metal azo compound represents Me 2 And it is Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 , Ca 2+ 、Co 2+ 、Co 3+ 2 / 3 ,La 3+ 2 / 3 Mg 2+ 、Nd 2+ or Nd 3+ 2 / 3 ,

[0141] Provided that, based in each case on one mole of all compounds of the formula (I), the metal ion Me 1 The amount of total is 97 mol% to 100 mol%, and the metal ion Me2 The amount of is 0 mol% to 3 mol% in total, and

[0142] b) melamine (2,4,6-triamino-1,3,5-triazine, CAS No. 108-78-1), or alternatively the reaction product of (I) and melamine,

[0143] as well as

[0144] ii) 100 to 250 g of at least one aliphatic C per mol of all metal azo compounds (I) contained in the metal azo pigment A) 10-22 Monocarboxylic acids B).

[0145] Preferably, zinc and nickel are present in an amount of 3 to 97 mol% Zn, 3 to 97 mol% Ni and 3 to 0 mol% Me. 2 The ratio of is present in at least two metal azo compounds of the metal azo pigment of the present invention.

[0146] Zinc and nickel are particularly preferably present in a ratio of 30 to 90 mol % Zn, 70 to 10 mol % Ni and 3 to 0 mol % Me. 2 The ratio of is present in at least two metal azo compounds of the metal azo pigment of the present invention.

[0147] Particularly preferably, zinc and nickel are mixed in an amount of 80 to 40 mol% Zn, 60 to 20 mol% Ni and 3 to 0 mol% Me. 2 The ratio of is present in at least two metal azo compounds of the metal azo pigment of the present invention.

[0148] More particularly preferably, zinc and nickel are mixed in an amount of 80 to 40 mol% Zn, 60 to 20 mol% Ni and 0 mol% Me 2 The ratio of is present in at least two metal azo compounds of the metal azo pigment of the present invention.

[0149] The metal azo pigments A) contained in the pigment preparations according to the invention preferably have a specific surface area BET (determination of the specific surface area of ​​solids by gas adsorption according to Brunauer, Emmett and Teller (BET)) determined in accordance with DIN 66131 of 50 to 200 m² / g, particularly preferably 80 to 160 m² / g and especially preferably 100 to 150 m² / g.

[0150] The metal azo pigments A) contained in the pigment preparations according to the invention are known in principle. In this respect, reference may be made to EP-A 3 072 932 or EP-A 3 222 680 and to the production methods described therein.

[0151] Preferably, the metal azo pigment A) is obtainable by reacting

[0152] a) at least two metal azo compounds of formula (I) which differ at least in the metal ion Me, or tautomeric forms thereof,

[0153] (I)

[0154] in

[0155] R 1 and R 2 Each independently is OH, NH2 or NHR 5 ,

[0156] R 3 and R 4 Each independently is O or NR 5 ,

[0157] R 5 is hydrogen or alkyl, preferably C1-C4 alkyl, and

[0158] Me is the metal ion Me 1 or Me 2 ,

[0159] The Me in the first metal azo compound (I) 1 Zn 2+ and Ni 2+ , and the molar ratio of Zn to Ni metal ions is 97:3 to 3:97, and

[0160] Me in the second metal azo compound (I) 2 It's Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 、Co 2+ 、Co 3+ 2 / 3 ,La 3+ 2 / 3 、Ce 3 + 2 / 3 , Pr 3+ 2 / 3 -、Nd 2+ 、Nd 3+2 / 3 、Sm 2+ 、Sm 3+ 2 / 3 、Eu 2+ 、Eu 3+ 2 / 3 , Gd 3+ 2 / 3 , Tb 3+ 2 / 3 、Dy 3+ 2 / 3 、Ho 3+ 2 / 3 , Yb 2+ , Yb 3 + 2 / 3 , Er 3+ 2 / 3 、Tm 3+ 2 / 3 Mg 2+ , Ca 2+ , Sr 2+ , Mn 2+ or Y 3+ 2 / 3 、Ti 2+ 、Ti 3+ 2 / 3 , Nb 3+ 2 / 3 、Mo 2+ 、Mo 3+ 2 / 3 、V 2+ 、V 3+ 2 / 3 、Zr 2+ 、Zr 3+ 2 / 3 、Cd 2+ Cr 3+ 2 / 3 , Pb 2+ Or Ba 2 ,

[0161] Provided that, based in each case on one mole of all compounds of the formula (I), the metal ion Me 1 The amount of is 97 to 100 mol % in total, and the amount of metal ions selected from the Me² series is 0 to 3 mol %, and

[0162] b) at least one compound having the formula (II)

[0163] (II)

[0165] in

[0166] R 6is hydrogen or alkyl, preferably C1-C4 alkyl, which may be optionally substituted one or more times by OH.

[0167] The metal azo compound (I) can be obtained by reacting an alkali metal salt having the formula (III),

[0168] (III)

[0169] in

[0170] X is an alkali metal ion, preferably a sodium or potassium ion,

[0171] R 1 and R 2 Each independently is OH, NH2 or NHR 5 ,

[0172] R 3 and R 4 Each independently is O or NR 5 ,

[0173] and

[0174] R 5 Hydrogen or alkyl, preferably C1-C4 alkyl,

[0175] or a tautomer thereof, preferably a sodium or potassium salt,

[0176] and nickel and zinc salts and optionally one or more Me from the series 2 Metal salt: Al 3+ 2 / 3 , Fe 2+ , Fe 3 + 2 / 3 、Co 2+ 、Co 3+ 2 / 3 ,La 3+ 2 / 3 、Ce 3+ 2 / 3 , Pr 3+ 2 / 3 -、Nd 2+ 、Nd 3+ 2 / 3 、Sm 2+ 、Sm 3+ 2 / 3 、Eu 2+ 、Eu 3+ 2 / 3 , Gd 3+ 2 / 3 , Tb 3 + 2 / 3 、Dy3+ 2 / 3 、Ho 3+ 2 / 3 , Yb 2+ , Yb 3+ 2 / 3 , Er 3+ 2 / 3 、Tm 3+ 2 / 3 Mg 2+ , Ca 2+ , Sr 2+ , Mn 2+ or Y 3+ 2 / 3 、Ti 2+ 、Ti 3+ 2 / 3 , Nb 3 + 2 / 3 、Mo 2+ 、Mo 3+ 2 / 3 、V 2+ 、V 3+ 2 / 3 、Zr 2+ 、Zr 3+ 2 / 3 、Cd 2+ Cr 3+ 2 / 3 , Pb 2+ Or Ba 2+ Salt,

[0177] Per mole of compound of formula (III), 0.001 to 0.999 mol of at least one nickel salt, 0.001 to 0.999 mol of at least one zinc salt and 0.03 to 0 mol of at least one metal salt from the Me² metal salt series are used.

[0178] For the synthesis of the metal azo compound (I), preferably 0.03 to 0.97 mol of at least one nickel salt and 0.97 to 0.03 mol of at least one zinc salt and 0.03 to 0 mol of at least one metal salt from the Me² metal salt series are used per mole of compound of the formula (III) in the context of the invention.

[0179] For the synthesis of the metal azo compound (I), it is particularly preferred to use 0.1 to 0.7 mol of at least one nickel salt and 0.9 to 0.3 mol of at least one zinc salt and 0.03 to 0 mol of at least one metal salt from the Me² metal salt series per mole of compound of the formula (III) in the context of the invention.

[0180] For the synthesis of the metal azo compound (I), it is particularly preferred to use 0.2 to 0.6 mol of at least one nickel salt and 0.8 to 0.4 mol of at least one zinc salt and 0.03 to 0 mol of at least one metal salt from the salt series of the Me² metal salts per mole of the compound of the formula (III) in the context of the present invention.

[0181] For the synthesis of the metal azo compound (I), it is very particularly preferred to use 0.2 to 0.6 mol of at least one nickel salt and 0.4 to 0.4 mol of at least one zinc salt per mole of compound of the formula (III) in the context of the invention.

[0182] Preferably, the ratio of the components in the metal azo pigment A) is 1 mol of the compound of formula (I): 0.05 to 4 mol of the compound of formula (II), more preferably 1 mol of the compound of formula (I): 0.5 to 2.5 mol of the compound of formula (II), and particularly preferably 1 mol of the compound of formula (I): 1.0 to 2.0 mol of the compound of formula (II).

[0183] The process for producing the metal azo pigments A) is preferably carried out at a temperature of 60° C. to 95° C. in aqueous solution at a pH below 7. The nickel and zinc salts to be used and optionally the further Me 2 The metal salts can be used individually or as a mixture with one another, preferably in the form of aqueous solutions. The compounds of the formula (II) can likewise be added individually or as a mixture with one another, preferably in the form of solids.

[0184] Preferably, the process for producing the metal azo pigments A) is carried out such that initially an azo compound of formula (III) is introduced, preferably as a Na or K salt, one or more compounds of formula (II) to be inserted or added (in particular melamine) are added, and then simultaneously or successively with at least one nickel salt and at least one zinc salt and optionally one or more Me 2 The metal salts, preferably in the form of aqueous solutions of these salts, react preferably at a pH value of less than 7. Suitable substances for adjusting the pH are sodium hydroxide solution, potassium hydroxide solution, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate.

[0185] Suitable nickel and zinc salts are preferably their water-soluble salts, in particular chlorides, bromides, acetates, formates, nitrates, sulfates, etc. Preferably used nickel and zinc salts have a water solubility of more than 20 g / l, in particular more than 50 g / l at 20° C.

[0186] Suitable for Me 2 The metal salt is preferably a water-soluble Me 2 Salt, especially preferably Me 2 Chloride, Me 2 Bromide, Me 2 Acetate, Me 2 Nitrate and Me 2 Sulfate, more particularly Me 2 chloride.

[0187] The metal azo pigment A) obtained in this way can then be isolated by filtering its aqueous suspension as an aqueous filter cake. The filter cake can then be dried by conventional drying methods, preferably after washing with hot water. Suitable drying methods are in particular paddle drying or spray drying of the corresponding aqueous slurry. Finally, the pigment can be ground again.

[0188] The metal azo pigments A) contained in the pigment preparation according to the invention can also be obtained by 2+ The adduct of a metal azo compound having the formula (I) with wherein Me represents Zn 2+ The adduct of a metal azo compound having the formula (I), and optionally with wherein Me represents a metal ion Me 2 The invention is produced by mixing one or more adducts of a metal azo compound having the formula (I).

[0189] The aliphatic C 10-22 The monocarboxylic acid B) may be saturated or monounsaturated or polyunsaturated. Preferably, the aliphatic C 10-22 The monocarboxylic acids B) are saturated or mono- to triunsaturated carboxylic acids. The aliphatic C 10-22 The monocarboxylic acids B) are saturated or mono- or diunsaturated carboxylic acids.

[0190] Particularly preferably, at least one aliphatic C from the following series is used. 10-22 Monocarboxylic acid B): n-decanoic acid (CAS No. 334-48-5, decanoic acid, C 10 H 20 O2), undecyl-10-enoic acid (CAS No. 112-38-9, undecylenic acid, C 11 H 20 O2), dodecanoic acid (CAS No. 143-07-7, lauric acid, C 12 H 24 O2), tetradecanoic acid (CAS No. 544-63-8, myristic acid, C 14 H 28O2), hexadecanoic acid (CAS No. 57-10-3, palmitic acid, C 16 H 32 O2), octadecanoic acid (CAS No. 57-11-4, stearic acid, C 18 H 36 O2), (9Z)-octadec-9-enoic acid (CAS No. 112-80-1, oleic acid, C 18 H 34 O2) and n-docosanoic acid (CAS No. 112-85-6, behenic acid, C 22 H 44 O2).

[0191] With very particular preference, the aliphatic monocarboxylic acids B) comprised in the pigment preparations according to the invention are those which contain 14 to 18 carbon atoms and are saturated or monounsaturated.

[0192] Very particularly preferably, the aliphatic monocarboxylic acids B) contained in the pigment preparation according to the invention are tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid) and (9Z)-octadec-9-enoic acid (oleic acid).

[0193] The aliphatic C 10-22 The monocarboxylic acids B) may be present in pure form or as a mixture.

[0194] Preferably, the mixture of aliphatic monocarboxylic acids B) contained in the pigment preparation according to the invention is a mixture containing at least one saturated or monounsaturated aliphatic monocarboxylic acid having 14 carbon atoms, at least one saturated or monounsaturated aliphatic monocarboxylic acid having 16 carbon atoms and at least one saturated or monounsaturated aliphatic monocarboxylic acid having 18 carbon atoms.

[0195] Preferably, the mixture of aliphatic monocarboxylic acids B) used according to the invention contains 0.5 to 5% by weight, particularly preferably 1 to 3% by weight, of at least one saturated or monounsaturated aliphatic monocarboxylic acid having 14 carbon atoms, 25 to 60% by weight, preferably 30 to 50% by weight, of at least one saturated or monounsaturated aliphatic monocarboxylic acid having 16 carbon atoms and 40 to 75% by weight, preferably 45 to 65% by weight, of at least one saturated or monounsaturated aliphatic monocarboxylic acid having 18 carbon atoms.

[0196] The mixture of aliphatic monocarboxylic acids B) contained in the pigment preparation according to the invention is particularly preferably a mixture containing myristic acid, palmitic acid and stearic acid, and particularly preferably within the preferred amount ranges indicated above.

[0197] Such mixtures are known as commercial products of the company Unichema under the trade name "Pristerene®", wherein the different chemical and quantitative compositions of these mixtures are characterized by a four-digit code. Pristerene® 4910 contains a mixture of 2% by weight of myristic acid, 30% by weight of palmitic acid and 64% by weight of stearic acid, Pristerene® 4911 contains a mixture of 2% by weight of myristic acid, 45% by weight of palmitic acid and 52% by weight of stearic acid, Pristerene® 4922 contains a mixture of 0.7% by weight of myristic acid, 30% by weight of palmitic acid and 66% by weight of stearic acid, and Pristerene® 9429.

[0198] The pigment preparation according to the invention preferably contains 100 to 250 g of at least one aliphatic monocarboxylic acid B), based on 1 mol of all metal azo compounds (I) contained in the metal azo pigment A).

[0199] Particularly preferably, the pigment preparations according to the invention contain 100 to 180 g, particularly preferably 120 to 160 g, of at least one aliphatic monocarboxylic acid B), based in each case on 1 mol of all metal azo compounds (I) contained in the metal azo pigment A).

[0200] The pigment preparations according to the invention can be produced by mixing at least one metal azo pigment A) with at least one aliphatic monocarboxylic acid B). The mixing can be carried out mechanically, for example and preferably by stirring with the aid of suitable stirring devices such as slow-running stirrers, in particular blade, rod or planetary stirrers or centrifugal mixers, or fast-running stirrers, in particular propeller, turbine, disk or impeller stirrers. The mixing can also be carried out hydraulically by continuous pumping of the reactor contents, in particular with the aid of a centrifugal pump.

[0201] The metal azo pigment A) is preferably mixed in the form of an aqueous suspension with at least one aliphatic monocarboxylic acid B). To produce such an aqueous suspension, at least one dry and optionally ground metal azo pigment A) is mixed with sufficient water to produce a complete suspension of the metal azo pigment.

[0202] However, the metal azo pigments A) can also preferably be used directly in the form of the aqueous reaction mixture as it occurs in the synthesis of the metal azo pigments A).

[0203] In order to produce the pigment preparation according to the invention, an aqueous pigment suspension containing at least one metal azo pigment A) is mixed with at least one aliphatic monocarboxylic acid B) under stirring, preferably at a temperature in the range of 60° C. to 95° C., preferably in a time of 10 to 60 minutes, and the mixture prepared in this way is preferably stirred for 60 to 240 minutes. The pH of the mixture is then adjusted to a value in the range of 3 to 7, and the pigment preparation is separated via a suction filter or a filter press. The pigment preparation obtainable in this way can be dried by means of a common drying method. A suitable drying method is preferably paddle drying or spray drying of the corresponding aqueous slurry. The pigment preparation can then be ground again.

[0204] The pigment preparation according to the invention may also contain one or more auxiliary agents and / or adjuvants. Preferably, all conventional auxiliary agents and adjuvants for pigment preparations are suitable as auxiliary agents or adjuvants. It is particularly preferred to use at least one auxiliary agent or adjuvant from the surfactant series, in particular dispersants, surfactants, wetting agents, emulsifiers, alkalis and acids.

[0205] Therefore, in a preferred embodiment, the present invention further provides a process for producing a pigment preparation according to the invention, wherein at least one metal azo pigment A) is reacted with at least one aliphatic C 10-22 A monocarboxylic acid B) and optionally one or more auxiliaries and / or adjuvants are mixed.

[0206] Due to the surprisingly good filterability, which is determined by means of a filter press test based on the filter pressure value FPV according to DIN EN ISO 23900-5:2019-01, and the high color strength determined according to DIN 55986, the pigment preparations according to the invention are ideally suitable for all pigment applications. In particular, the pigment preparations according to the invention are suitable for the bulk coloring of synthetic, semisynthetic or natural macromolecular substances, in particular polyvinyl chloride, polystyrene, polyamide, polyethylene or polypropylene, and for the spin dyeing of natural, regenerated or synthetic fibers, such as cellulose, polyester, polycarbonate, polyacrylonitrile or polyamide fibers, and for the printing of textiles and paper.

[0207] Therefore, the present invention also relates to 10-22 Monocarboxylic acids B) Use of pigment preparations improved in terms of filterability and color strength for the overall coloring of synthetic, semisynthetic or natural macromolecular substances, in particular polyvinyl chloride, polystyrene, polyamide, polyethylene or polypropylene, and for the spin dyeing of natural, regenerated or synthetic fibers, such as cellulose, polyester, polycarbonate, polyacrylonitrile or polyamide fibers, and for printing on textiles and paper.

[0208] Preferred Uses

[0209] The present invention preferably relates to at least one aliphatic C 10-22 Use of monocarboxylic acids B) for simultaneously improving the filter pressure value FPV determined by filter press test according to DIN EN ISO 23900-5:2019-01 and the color strength determined according to DIN 55986 of pigment preparations containing metal azo pigments A) consisting of:

[0210] a) at least two metal azo compounds having the formula (I)

[0211] (I)

[0212] Where R 1 and R 2 Yes OH,

[0213] R 3 and R 4 It's O.

[0214] Me in the first metal azo compound (I) 1 Zn 2+ and Ni 2+ , and the molar ratio of Zn to Ni metal ions is 97:3 to 3:97, and

[0215] Me in the second metal azo compound (I) 2 It's Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 、Co 2+ 、Co 3+ 2 / 3 ,La 3+ 2 / 3 、Ce 3 + 2 / 3 , Pr 3+ 2 / 3 -、Nd 2+ 、Nd 3+ 2 / 3 、Sm 2+ 、Sm 3+ 2 / 3 、Eu 2+ 、Eu 3+ 2 / 3 , Gd 3+ 2 / 3 , Tb 3+ 2 / 3 、Dy 3+ 2 / 3 、Ho 3+2 / 3 , Yb 2+ , Yb 3 + 2 / 3 , Er 3+ 2 / 3 、Tm 3+ 2 / 3 Mg 2+ , Ca 2+ , Sr 2+ , Mn 2+ or Y 3+ 2 / 3 、Ti 2+ 、Ti 3+ 2 / 3 , Nb 3+ 2 / 3 、Mo 2+ 、Mo 3+ 2 / 3 、V 2+ 、V 3+ 2 / 3 、Zr 2+ 、Zr 3+ 2 / 3 、Cd 2+ Cr 3+ 2 / 3 , Pb 2+ Or Ba 2+ Salt,

[0216] Provided that, based in each case on one mole of all compounds of the formula (I), the metal ion Me 1 The amount of total is 97 mol% to 100 mol%, and the metal ion Me 2 The amount of is 0 mol% to 3 mol% in total, and

[0217] b) melamine (2,4,6-triamino-1,3,5-triazine, CAS No. 108-78-1), or melamine obtainable by reaction of components a) and b).

[0218] The present invention particularly preferably relates to at least aliphatic C 10-22 Use of monocarboxylic acids B) for simultaneously improving the filter pressure value FPV determined by filter press test according to DIN EN ISO 23900-5:2019-01 and the color strength determined according to DIN 55986 of pigment preparations containing metal azo pigments A) consisting of:

[0219] a) at least two metal azo compounds having the formula (I)

[0220] (I)

[0221] Where R 1 and R 2 Yes OH,

[0222] R 3 and R 4 It's O.

[0223] Me in the first metal azo compound 1 Zn 2+ and Ni 2+ , wherein the molar ratio of Zn to Ni metal ions is 90:30 to 10:70, and

[0224] Me in the second metal azo compound (I) 2 It's Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 、Co 2+ 、Co 3+ 2 / 3 ,La 3+ 2 / 3 、Ce 3 + 2 / 3 , Pr 3+ 2 / 3 -、Nd 2+ 、Nd 3+ 2 / 3 、Sm 2+ 、Sm 3+ 2 / 3 、Eu 2+ 、Eu 3+ 2 / 3 , Gd 3+ 2 / 3 , Tb 3+ 2 / 3 、Dy 3+ 2 / 3 、Ho 3+ 2 / 3 , Yb 2+ , Yb 3 + 2 / 3 , Er 3+ 2 / 3 、Tm 3+ 2 / 3 Mg 2+ , Ca 2+ , Sr 2+ , Mn 2+ or Y 3+ 2 / 3 、Ti 2+ 、Ti 3+ 2 / 3, Nb 3+ 2 / 3 、Mo 2+ 、Mo 3+ 2 / 3 、V 2+ 、V 3+ 2 / 3 、Zr 2+ 、Zr 3+ 2 / 3 、Cd 2+ Cr 3+ 2 / 3 , Pb 2+ Or Ba 2+ Salt,

[0225] Provided that, based in each case on one mole of all compounds of the formula (I), the metal ion Me 1 The amount of total is 97 mol% to 100 mol%, and the metal ion Me 2 The amount of is 0 mol% to 3 mol% in total, and

[0226] b) melamine (2,4,6-triamino-1,3,5-triazine, CAS No. 108-78-1), or alternatively melamine obtainable by reaction of components a) and b).

[0227] The present invention particularly preferably also relates to at least one aliphatic C 10-22 Use of monocarboxylic acids B) for simultaneously improving the filter pressure value FPV determined by filter press test according to DIN EN ISO 23900-5:2019-01 and the color strength determined according to DIN 55986 of pigment preparations containing metal azo pigments A) consisting of:

[0228] a) at least two metal azo compounds having the formula (I)

[0229] (I)

[0230] Where R 1 and R 2 Yes OH,

[0231] R 3 and R 4 It's O.

[0232] Me in the first metal azo compound 1 Zn 2+ and Ni 2+ , and the molar ratio of Zn to Ni metal ions is 40:80 to 20:60, and

[0233] Me in the second metal azo compound (I)2 is Al 3+ 2 / 3 、Fe 2+ 、Fe 3+ 2 / 3 、Co 2+ 、Co 3+ 2 / 3 、La 3+ 2 / 3 、Ce 3 + 2 / 3 、Pr 3+ 2 / 3 -、Nd 2+ 、Nd 3+ 2 / 3 、Sm 2+ 、Sm 3+ 2 / 3 、Eu 2+ 、Eu 3+ 2 / 3 、Gd 3+ 2 / 3 、Tb 3+ 2 / 3 、Dy 3+ 2 / 3 、Ho 3+ 2 / 3 、Yb 2+ 、Yb 3 + 2 / 3 、Er 3+ 2 / 3 、Tm 3+ 2 / 3 、Mg 2+ 、Ca 2+ 、Sr 2+ 、Mn 2+ or Y 3+ 2 / 3 、Ti 2+ 、Ti 3+ 2 / 3 、Nb 3+ 2 / 3 、Mo 2+ 、Mo 3+ 2 / 3 、V 2+ 、V 3+ 2 / 3 、Zr 2+ 、Zr 3+ 2 / 3 、Cd 2+ 、Cr 3+ 2 / 3 、Pb 2+ or Ba 2+ salt,

[0234] Provided that, based in each case on one mole of all compounds of the formula (I), the metal ion Me 1 The amount of total is 97 mol% to 100 mol%, and the metal ion Me 2 The amount of is 0 mol% to 3 mol% in total, and

[0235] b) melamine (2,4,6-triamino-1,3,5-triazine, CAS No. 108-78-1), or alternatively melamine obtainable by reaction of components a) and b).

[0236] In the context of these uses, it is particularly preferred to use at least one aliphatic C from the following series: 10-22 Monocarboxylic acid B): n-decanoic acid (CAS No. 334-48-5, decanoic acid, C 10 H 20 O2), undecyl-10-enoic acid (CAS No. 112-38-9, undecylenic acid, C 11 H 20 O2), dodecanoic acid (CAS No. 143-07-7, lauric acid, C 12 H 24 O2), tetradecanoic acid (CAS No. 544-63-8, myristic acid, C 14 H 28 O2), hexadecanoic acid (CAS No. 57-10-3, palmitic acid, C 16 H 32 O2), octadecanoic acid (CAS No. 57-11-4, stearic acid, C 18 H 36 O2), (9Z)-octadec-9-enoic acid (CAS No. 112-80-1, oleic acid, C 18 H 34 O2) and n-docosanoic acid (CAS No. 112-85-6, behenic acid, C 22 H 44 O2).

[0237] With very particular preference, the aliphatic monocarboxylic acids B) comprised in the pigment preparations according to the invention are those which contain 14 to 18 carbon atoms and are saturated or monounsaturated.

[0238] Very particularly preferably, the aliphatic monocarboxylic acids B) contained in the pigment preparation according to the invention are tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid) and (9Z)-octadec-9-enoic acid (oleic acid).

[0239] In the context of the use of the present invention, the aliphatic C 10-22The monocarboxylic acid B) may be present in pure form or as a mixture. Such mixtures are known as commercial products of the company Pristerene® under the trade name of Liqkama, wherein the different chemical and quantitative compositions of these mixtures are characterized by a four-digit code. Preferred according to the invention are Pristerene® 4910 containing a mixture of 2% by weight of myristic acid, 30% by weight of palmitic acid and 64% by weight of stearic acid, Pristerene® 4911 containing a mixture of 2% by weight of myristic acid, 45% by weight of palmitic acid and 52% by weight of stearic acid, Pristerene® 4922 containing a mixture of 0.7% by weight of myristic acid, 30% by weight of palmitic acid and 66% by weight of stearic acid and Pristerene® 9429.

[0240] Preferred method

[0241] The present invention preferably relates to a method for simultaneously improving the filter pressure value FPV determined by a filter press test according to DIN EN ISO 23900-5:2019-01 and the color strength determined according to DIN 55986 of a pigment preparation containing a metal azo pigment A) comprising:

[0242] a) at least two metal azo compounds having the formula (I)

[0243] (I)

[0244] Where R 1 and R 2 Yes OH,

[0245] R 3 and R 4 It's O.

[0246] Me in the first metal azo compound (I) 1 Zn 2+ and Ni 2+ , and the molar ratio of Zn to Ni metal ions is 97:3 to 3:97,

[0247] and

[0248] Me in the second metal azo compound (I) 2 It's Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 、Co 2+ 、Co 3+ 2 / 3 ,La 3+2 / 3 、Ce 3 + 2 / 3 , Pr 3+ 2 / 3 -、Nd 2+ 、Nd 3+ 2 / 3 、Sm 2+ 、Sm 3+ 2 / 3 、Eu 2+ 、Eu 3+ 2 / 3 , Gd 3+ 2 / 3 , Tb 3+ 2 / 3 、Dy 3+ 2 / 3 、Ho 3+ 2 / 3 , Yb 2+ , Yb 3 + 2 / 3 , Er 3+ 2 / 3 、Tm 3+ 2 / 3 Mg 2+ , Ca 2+ , Sr 2+ , Mn 2+ or Y 3+ 2 / 3 、Ti 2+ 、Ti 3+ 2 / 3 , Nb 3+ 2 / 3 、Mo 2+ 、Mo 3+ 2 / 3 、V 2+ 、V 3+ 2 / 3 、Zr 2+ 、Zr 3+ 2 / 3 、Cd 2+ Cr 3+ 2 / 3 , Pb 2+ Or Ba 2+ Salt,

[0249] Provided that, based in each case on one mole of all compounds of the formula (I), the metal ion Me 1 The amount of total is 97 mol% to 100 mol%, and the metal ion Me 2 The amount of is 0 mol% to 3 mol% in total, and

[0250] b) melamine (2,4,6-triamino-1,3,5-triazine, CAS No. 108-78-1), or alternatively melamine obtainable by reaction of components a) and b),

[0251] The method comprises using 100 to 250 g of at least one aliphatic C per mole of all metal azo compounds (I) contained in the metal azo pigment A). 10-22 Monocarboxylic acids B).

[0252] The present invention particularly preferably relates to a method for simultaneously improving the filter pressure value FPV determined by the filter press test according to DIN EN ISO 23900-5:2019-01 and the color strength determined according to DIN 55986 of a pigment preparation containing a metal azo pigment A) comprising:

[0253] a) at least two metal azo compounds having the formula (I)

[0254] (I)

[0255] Where R 1 and R 2 Yes OH,

[0256] R 3 and R 4 It's O.

[0257] Me in the first metal azo compound 1 Zn 2+ and Ni 2+ , and the molar ratio of Zn to Ni metal ions is 90:10 to 30:70, and

[0258] Me in the second metal azo compound (I) 2 It's Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 、Co 2+ 、Co 3+ 2 / 3 ,La 3+ 2 / 3 、Ce 3 + 2 / 3 , Pr 3+ 2 / 3 -、Nd 2+ 、Nd 3+ 2 / 3 、Sm 2+ 、Sm 3+ 2 / 3 、Eu2+ 、Eu 3+ 2 / 3 , Gd 3+ 2 / 3 , Tb 3+ 2 / 3 、Dy 3+ 2 / 3 、Ho 3+ 2 / 3 , Yb 2+ , Yb 3 + 2 / 3 , Er 3+ 2 / 3 、Tm 3+ 2 / 3 Mg 2+ , Ca 2+ , Sr 2+ , Mn 2+ or Y 3+ 2 / 3 、Ti 2+ 、Ti 3+ 2 / 3 , Nb 3+ 2 / 3 、Mo 2+ 、Mo 3+ 2 / 3 、V 2+ 、V 3+ 2 / 3 、Zr 2+ 、Zr 3+ 2 / 3 、Cd 2+ Cr 3+ 2 / 3 , Pb 2+ Or Ba 2+ Salt,

[0259] Provided that, based in each case on one mole of all compounds of the formula (I), the metal ion Me 1 The amount of total is 97 to 100 mol%, and the metal ion Me 2 The amount is 0 to 3 mol% in total, and

[0260] b) melamine (2,4,6-triamino-1,3,5-triazine, CAS No. 108-78-1), or alternatively melamine obtainable by reaction of components a) and b).

[0261] The method comprises using 100 to 250 g of at least one aliphatic C per mole of all metal azo compounds (I) contained in the metal azo pigment A). 10-22 Monocarboxylic acids B).

[0262] The present invention particularly preferably relates to a method for simultaneously improving the filter pressure value FPV determined by the filter press test according to DIN EN ISO 23900-5:2019-01 and the color strength determined according to DIN 55986 of a pigment preparation containing a metal azo pigment A) comprising:

[0263] a) at least two metal azo compounds having the formula (I)

[0264] (I)

[0265] Where R 1 and R 2 Yes OH,

[0266] R 3 and R 4 It's O.

[0267] Me in the first metal azo compound 1 Zn 2+ and Ni 2+ , and the molar ratio of Zn to Ni metal ions is 40:80 to 20:60, and

[0268] Me in the second metal azo compound (I) 2 It's Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 、Co 2+ 、Co 3+ 2 / 3 ,La 3+ 2 / 3 、Ce 3+ 2 / 3 , Pr 3+ 2 / 3 -、Nd 2+ 、Nd 3+ 2 / 3 、Sm 2+ 、Sm 3+ 2 / 3 、Eu 2+ 、Eu 3+ 2 / 3 , Gd 3+ 2 / 3 , Tb 3+ 2 / 3 、Dy 3+ 2 / 3 、Ho 3+ 2 / 3 , Yb 2+ , Yb 3+ 2 / 3 , Er3+ 2 / 3 、Tm 3+ 2 / 3 Mg 2+ , Ca 2+ , Sr 2+ , Mn 2+ or Y 3+ 2 / 3 、Ti 2+ 、Ti 3+ 2 / 3 , Nb 3+ 2 / 3 、Mo 2+ 、Mo 3+ 2 / 3 、V 2+ 、V 3+ 2 / 3 、Zr 2+ 、Zr 3+ 2 / 3 、Cd 2+ Cr 3+ 2 / 3 , Pb 2+ Or Ba 2+ Salt,

[0269] Provided that, based in each case on one mole of all compounds of the formula (I), the metal ion Me 1 The amount of metal ions Me 2 The amount of is 0 mol% to 1 mol% in total, and

[0270] b) melamine (2,4,6-triamino-1,3,5-triazine, CAS No. 108-78-1), or alternatively melamine obtainable by reaction of components a) and b),

[0271] The method comprises using 100 to 250 g of at least one aliphatic C per mole of all metal azo compounds (I) contained in the metal azo pigment A). 10-22 Monocarboxylic acids B).

[0272] In the context of the process according to the invention, it is particularly preferred to use at least one aliphatic C from the following series: 10-22 Monocarboxylic acid B): n-decanoic acid (CAS No. 334-48-5, decanoic acid, C 10 H 20 O2), undecyl-10-enoic acid (CAS No. 112-38-9, undecylenic acid, C 11 H 20 O2), dodecanoic acid (CAS No. 143-07-7, lauric acid, C 12 H24 O2), tetradecanoic acid (CAS No. 544-63-8, myristic acid, C 14 H 28 O2), hexadecanoic acid (CAS No. 57-10-3, palmitic acid, C 16 H 32 O2), octadecanoic acid (CAS No. 57-11-4, stearic acid, C 18 H 36 O2), (9Z)-octadec-9-enoic acid (CAS No. 112-80-1, oleic acid, C 18 H 34 O2) and n-docosanoic acid (CAS No. 112-85-6, behenic acid, C 22 H 44 O2).

[0273] With very particular preference, the aliphatic monocarboxylic acids B) comprised in the pigment preparations according to the invention are those which contain 14 to 18 carbon atoms and are saturated or monounsaturated.

[0274] Very particularly preferably, the aliphatic monocarboxylic acids B) contained in the pigment preparation according to the invention are tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid) and (9Z)-octadec-9-enoic acid (oleic acid).

[0275] In the context of the method of the present invention, the aliphatic C 10-22 The monocarboxylic acid B) may be present in pure form or as a mixture. Such mixtures are known as commercial products of the company Levitra under the trade name "Pristerene®", wherein the different chemical and quantitative compositions of these mixtures are characterized by a four-digit code. Preferred according to the invention are Pristerene® 4910 containing a mixture of 2% by weight of myristic acid, 30% by weight of palmitic acid and 64% by weight of stearic acid, Pristerene® 4911 containing a mixture of 2% by weight of myristic acid, 45% by weight of palmitic acid and 52% by weight of stearic acid, Pristerene® 4922 containing a mixture of 0.7% by weight of myristic acid, 30% by weight of palmitic acid and 66% by weight of stearic acid and Pristerene® 9429.

[0276] The following examples are intended to explain the present invention, but the present invention is not limited thereto.

[0277] Examples

[0278] I. Production of Metal-azobarbituric Acid Melamine Pigments A to W According to the Prior Art

[0279] Example 1:Nickel azobarbituric acid melamine pigment preparation according to Example 2 of EP-A 26 82 435 (Pigment A) (not according to the invention)

[0280] a) Production of crude pigments

[0281] 154.1 g (1.0 mol) of diazobarbituric acid and 128.1 g (1.0 mol) of barbituric acid are introduced into 3670 g of distilled water at 85° C. Subsequently, a pH of 5 is established using an aqueous potassium hydroxide solution and the reaction mixture is stirred for 90 minutes. 5000 g of distilled water are added to the azobarbituric acid (1.0 mol) thus prepared at 82° C. Subsequently, a pH of 2 to 2.5 is established by dropwise addition of 33 g of 30% hydrochloric acid and 264.8 g (2.1 mol) of melamine are added. Subsequently, 1.0 mol of nickel chloride is added dropwise in the form of an approximately 25% solution. After 3 hours at 82° C., a pH of about 5.5 is established by addition of potassium hydroxide.

[0282] b) Reprocessing

[0283] For this purpose, the product was diluted with about 330 g of distilled water at 90° C. 70 g of 30% hydrochloric acid were then added dropwise, and the reaction mixture was stirred for 12 hours at 90° C. The pH of the reaction mixture was then adjusted to about 5 with aqueous potassium hydroxide solution.

[0284] c) Post-processing

[0285] The pigment preparation obtainable from reprocessing b) was separated on a suction filter, washed, dried in a vacuum drying oven at 80° C. and ground in a conventional laboratory grinder for about 2 minutes. (Pigment A)

[0286] Examples 2 to 23: Metal-azobarbituric acid melamine pigments B to W

[0287] Pigments B to W of Examples 2 to 23 listed in Table 1 below were produced analogously to Example 1, but 1.0 mol of nickel chloride was replaced by nickel chloride and zinc chloride and optionally a third metal chloride (Me 2 ) were replaced in the molar amounts as indicated in Table 1.

[0288] For Pigments A to W, the color strength and filter pressure values ​​were determined as described in Protocols 1 and 2 indicated below. The values ​​can be found in Table 1.

[0289] Table 1: Pigments A to W

[0290]

[0291] Examples 24 to 28: Nickel azobarbituric acid melamine pigment preparation according to EP-A 1 612 246 (not according to the invention)

[0292] Initial Phase 1

[0293] 63 g of 35% hydrochloric acid is stirred into 150 g of water. 30 g of aminoguanidine bicarbonate is introduced into the mixture. After complete dissolution, the mixture is cooled to 0 ° C. After this, 19 g of sodium nitrite is added in 30 min, and then stirred at 0 ° C to 15 ° C for 30 min. Then sulfamic acid is added until no more color reaction occurs with potassium iodide starch test paper. Subsequently, 25.6 g of barbituric acid is added, and the mixture is heated to 55 ° C and then stirred for 2 hours. Then 25.6 g of barbituric acid is added, and the mixture is heated to 80 ° C and adjusted to pH 5 with sodium hydroxide. After 3 hours, the temperature is reduced to 70 ° C. Then the obtained reaction product is separated and washed with hot water, and the filter cake is dried at 80 ° C. Yield: 61.4 g of azobarbituric acid disodium salt.

[0294] Initial Phase 2

[0295] 63 g of 35% hydrochloric acid is stirred into the water of 150 g. 38.7 g of benzenesulfonyl hydrazide is introduced into the mixture. The mixture is cooled to below 0 ° C with ice. After this, 19 g of sodium nitrite is added in 30 min, and then stirred at 0 ° C to 15 ° C for 30 min. Then sulfamic acid is added until no more color reaction occurs with potassium iodide starch test paper. Then with sodium hydroxide, pH is adjusted to 7.0 to 9.0, 25.6 g of barbituric acid is added, and the mixture is heated to 50 ° C and stirred for 2 hours subsequently. Then another 25.6 g of barbituric acid is added, the mixture is heated to 80 ° C and the pH of the mixture is adjusted to 5 with hydrochloric acid. After 3 hours, the temperature is reduced to 70 ° C, and the obtained reaction product is separated and washed with hot water. The filter cake obtained is slurried in the water of 1200 g and stirred for 2 hours at 80 ° C. Thereafter, it was separated off and washed with 2000 g of water at 80° C. until free of benzenesulfonamide, and dried at 80° C. Yield: 61.0 g of azobarbituric acid disodium salt.

[0296] Example 24

[0297] 25 g of disodium azobarbituric acid from preliminary stage 1 and 0.5 g of oleic acid are introduced into 600 g of water and stirred evenly. The pH is then adjusted to 1.0 and the mixture is heated to 95°C. Then 19.2 g of melamine is added to the mixture and 18.6 g of nickel chloride hexahydrate (preliminarily dissolved in 115 g of water) is added dropwise over a period of 5 min. After 1.5 hours at 90°C, the pH of the mixture is adjusted to 5.5 and stirring is continued for 4 hours. The reaction product is then separated and washed with hot water until free of salt and melamine. The filter cake is dried at 80°C to a residual water content of less than 1.5%. Yield: 42 g of pigment.

[0298] Example 25

[0299] 25 g of disodium azobarbituric acid salt from preliminary stage 1 and 0.5 g of oleic acid were introduced into 600 g of water and stirred evenly. The pH was then adjusted to 8.5 and the mixture was heated to 95°C. Then 19.2 g of melamine was added to the mixture. After stirring for 5 minutes, the pH of the mixture was adjusted to 5.0 with hydrochloric acid. Thereafter, stirring was then performed for 5 minutes, and then 18.6 g of nickel chloride hexahydrate (preliminarily dissolved in 115 g of water) was added dropwise during 10 min. After 1.5 hours at 90°C, the pH of the mixture was adjusted to 5.5 and stirring was continued for 4 hours. The reaction product was then separated and washed with hot water until free of salt and melamine. The filter cake was dried at 80°C to a residual water content of less than 1.5%. Yield: 42 g of pigment.

[0300] Example 26

[0301] 25 g of disodium azobarbituric acid salt from preliminary stage 1 and 0.5 g of linoleic acid were introduced into 600 g of water and stirred evenly. The pH was then adjusted to 8.5 and the mixture was heated to 95°C. Then 19.2 g of melamine was added to the mixture. After stirring for 5 minutes, the pH of the mixture was adjusted to 5.0 with hydrochloric acid. The mixture was stirred for another 5 minutes, and then 18.6 g of nickel chloride hexahydrate (pre-dissolved in 115 g of water) was added dropwise during 10 min. After 1.5 hours at 90°C, the pH of the mixture was adjusted to 5.5 and continued to stir for 4 hours. The reaction product was then separated and washed with hot water until free of salt and melamine. The filter cake was dried at 80°C to a residual water content of less than 1.5%. Yield: 41.8 g of pigment.

[0302] Example 27

[0303] 25 g of disodium azobarbituric acid from preliminary stage 1 and 0.5 g of alpha-linolenic acid (α-linolenic acid; CAS number 463-40-1) are introduced into 600 g of water and stirred evenly. The pH is then adjusted to 8.5 and the mixture is heated to 95°C. 19.2 g of melamine are then added to the mixture. After subsequent stirring for 5 minutes, the pH of the mixture is adjusted to 5.0 with hydrochloric acid, the mixture is stirred for a further 5 minutes, and then 18.6 g of nickel chloride hexahydrate (previously dissolved in 115 g of water) is added dropwise over the course of 10 minutes. After 1.5 hours at 90°C, the pH of the mixture is adjusted to 5.5 and stirring is continued for 4 hours. The reaction product is then separated and washed with hot water until free of salt and melamine. The filter cake is dried at 80°C to a residual water content of less than 1.5%. Yield: 42 g of pigment.

[0304] Example 28

[0305] 25 g of disodium azobarbituric acid from preliminary stage 2 and 0.5 g of oleic acid (CAS No. 112-80-1) are introduced into 600 g of water and stirred evenly. The pH is then adjusted to 1.0 and the mixture is heated to 95°C. 19.2 g of melamine are then added to the mixture and 18.6 g of nickel chloride hexahydrate (previously dissolved in 115 g of water) are added dropwise over the course of 5 minutes. After 1.5 hours at 90°C, the pH of the mixture is adjusted to 5.5 and the mixture is stirred for a further 4 hours. The reaction product is then separated and washed with hot water until free of salt and melamine. The filter cake is dried at 80°C to a residual water content of less than 1.5%. Yield: 41.4 g of pigment.

[0306] Table 2:

[0307]

[0308] Color strength compared to Example 1

[0309] II. Production of pigment preparations

[0310] Example 29: Production of Pigment Preparation A-1 (Not According to the Invention)

[0311] The aqueous suspension of pigment A obtained after step c) of Example 1 was mixed with 100 g of Pristerene® 4910 and stirred for 60 minutes. Subsequently, a pH of 5 was established using aqueous potassium hydroxide solution. The pigment preparation was then separated on a suction filter, washed, dried in a vacuum drying oven at 80° C. and ground in a conventional laboratory grinder for about 2 minutes. (= Pigment preparation A-1)

[0312] Examples 30 to 45: Production of Pigment Preparations A-2 to A-17 (Not According to the Invention)

[0313] Analogously to Example 29, pigment preparations A-2 to A-17 not according to the invention were produced in Examples 30 to 45. In each case, an aqueous suspension of pigment A as obtained after step c) of Example 1 was mixed with different aliphatic carboxylic acids B) or mixtures thereof in different amounts as indicated in Table 2.

[0314] Determination of color strength and filter pressure values

[0315] For pigment preparations A-1 to A-17, the color strength and filter pressure values ​​compared to pigment A were determined according to protocols 1 and 2 indicated below. The values ​​can also be found in Table 3.

[0316] Table 3: Pigment preparation with pigment A

[0317]

[0318] Example 46: Production of Pigment Preparation B-1 (Not According to the Invention)

[0319] The aqueous suspension of pigment B obtained after step c) of Example 2 was mixed with 50 g of Pristerene® 4910 and stirred for 60 minutes. Subsequently, a pH of 5 was established using aqueous potassium hydroxide solution. The pigment preparation was then separated on a suction filter, washed, dried in a vacuum drying oven at 80° C. and ground in a conventional laboratory grinder for about 2 minutes. (= Pigment preparation B-1)

[0320] Examples 47 to 93: Production of Pigment Preparations B-2 to B-48 (Not According to the Invention)

[0321] Analogously to Example 46, pigment preparations B-2 to B-48 not according to the invention were produced in Examples 47 to 93. In each case, an aqueous suspension of the pigment B as obtained after step c) of Example 2 was mixed with different aliphatic carboxylic acids B) or mixtures thereof in different amounts as indicated in Table 4.

[0322] Determination of color strength and filter pressure values

[0323] For pigment preparations B-1 to B-48, the color strength and filter pressure values ​​compared to Pigment B were determined according to Protocols 1 and 2 indicated below. The values ​​can also be found in Table 4.

[0324] Table 4: Pigment preparation with pigment B

[0325]

[0326] Example 94: Production of Pigment Preparation C-1 (Not According to the Invention)

[0327] The aqueous suspension of pigment C obtained after step c) of Example 3 was mixed with 70 g of Pristerene® 4910 and stirred for 60 minutes. Subsequently, a pH of 5 was established using aqueous potassium hydroxide solution. The pigment preparation was then separated on a suction filter, washed, dried in a vacuum drying oven at 80° C. and ground in a conventional laboratory grinder for about 2 minutes. (= Pigment preparation C-1)

[0328] Examples 95 to 136: Production of Pigment Preparations C-2 to C-44 (Not According to the Invention)

[0329] Analogously to Example 94, pigment preparations C-2 to C-44 not according to the invention were produced in Examples 95 to 137. In each case, an aqueous suspension of pigment C as obtained after step c) of Example 3 was mixed with different aliphatic carboxylic acids B) or mixtures thereof in different amounts as indicated in Table 5.

[0330] Determination of color strength and filter pressure values

[0331] For pigment preparations C-1 to C-44, the color strength and filter pressure values ​​compared to pigment C were determined according to protocols 1 and 2 indicated below. The values ​​can also be found in Table 5.

[0332] Table 5: Pigment preparation with pigment C

[0333]

[0334] Example 138: Production of Pigment Preparation D-1 (Not According to the Invention)

[0335] The aqueous suspension of pigment D obtained after step c) of Example 4 was mixed with 70 g of Pristerene® 4910 and stirred for 60 minutes. Subsequently, a pH of 5 was established using aqueous potassium hydroxide solution. The pigment preparation was then separated on a suction filter, washed and dried in a vacuum drying oven at 80° C. and ground in a conventional laboratory grinder for about 2 minutes. (= Pigment preparation D-1)

[0336] Examples 139 to 171: Production of Pigment Preparations D-2 to D-34 (Not According to the Invention and According to the Invention)

[0337] Analogously to Example 138, pigment preparations according to the invention and not according to the invention were produced in Examples 139 to 171. In each case, an aqueous suspension of the pigment D as obtained after step c) of Example 4 was mixed with different aliphatic carboxylic acids B) or mixtures thereof in different amounts as indicated in Table 5.

[0338] Determination of color strength and filter pressure values

[0339] For pigment preparations D-1 to D-34, the color strength and filter pressure values ​​compared to pigment D were determined according to the following protocols 1 and 2. The values ​​can also be found in Table 6.

[0340] Table 6: Pigment preparation with pigment D

[0341]

[0342] Example 172: Production of Pigment Preparation E-1 (Not According to the Invention)

[0343] The aqueous suspension of pigment E obtained after step c) of Example 5 was mixed with 70 g of Pristerene® 4910 and stirred for 60 minutes. Subsequently, a pH of 5 was established using aqueous potassium hydroxide solution. The pigment preparation was then separated on a suction filter, washed, dried in a vacuum drying oven at 80° C. and ground in a conventional laboratory grinder for about 2 minutes. (= Pigment preparation E-1)

[0344] Examples 173 to 240: Production of Pigment Preparations E-2 to E-70 (Not According to the Invention and According to the Invention)

[0345] Analogously to Example 172, pigment preparations E-2 to E-81 according to the invention and not according to the invention were produced in Examples 173 to 240. In each case, an aqueous suspension of pigment E as obtained after step c) of Example 5 was mixed with different aliphatic carboxylic acids B) or mixtures thereof in different amounts as indicated in Table 7.

[0346] Determination of color strength and filter pressure values

[0347] For pigment preparations E-1 to E-70, the color strength and filter pressure values ​​compared to Pigment E were determined according to Protocols 1 and 2 indicated below. The values ​​can also be found in Table 7.

[0348] Table 7: Pigment preparation with pigment E

[0349]

[0350] Example 241: Production of Pigment Preparation F-1 (Not According to the Invention)

[0351] The aqueous suspension of pigment F obtained after step c) of Example 6 was mixed with 70 g of Pristerene 4910 and stirred for 60 minutes. Subsequently, a pH of 5 was established using an aqueous potassium hydroxide solution. The pigment preparation was then separated on a suction filter, washed, dried in a vacuum drying oven at 80° C. and ground in a conventional laboratory grinder for about 2 minutes. (= Pigment preparation F-1)

[0352] Examples 242 to 274: Production of Pigment Preparations F-2 to F-33 (Not According to the Invention and According to the Invention)

[0353] Analogously to Example 242, pigment preparations F-2 to F-33 according to the invention and not according to the invention were produced in Examples 242 to 274. In each case, an aqueous suspension of the pigment F as obtained after step c) of Example 6 was mixed with different aliphatic carboxylic acids B) or mixtures thereof in different amounts as indicated in Table 8.

[0354] Determination of color strength and filter pressure values

[0355] For pigment preparations F-1 to F-33, the color strength and filter pressure values ​​compared to pigment F were determined according to protocols 1 and 2 indicated below. The values ​​can also be found in Table 8.

[0356] Table 8: Pigment preparation with pigment F

[0357]

[0358] Example 275: Production of Pigment Preparation G-1 (Not According to the Invention)

[0359] The aqueous suspension of pigment G obtained after step c) of Example 7 was mixed with 70 g of Pristerene® 4910 and stirred for 60 minutes. Subsequently, a pH of 5 was established using aqueous potassium hydroxide solution. The pigment preparation was then separated on a suction filter, washed, dried in a vacuum drying oven at 80° C. and ground in a conventional laboratory grinder for about 2 minutes. (= Pigment preparation G-1)

[0360] Examples 276 to 355: Production of Pigment Preparations G-2 to G-81 (Not According to the Invention and According to the Invention)

[0361] Analogously to Example 275, pigment preparations G-2 to G-81 according to the invention and not according to the invention were produced in Examples 276 to 355. In each case, an aqueous suspension of the pigment G as obtained after step c) of Example 7 was mixed with different aliphatic carboxylic acids B) or mixtures thereof in different amounts as indicated in Table 9.

[0362] Determination of color strength and filter pressure values

[0363] For pigment preparations G-1 to G-81, the color strength and filter pressure values ​​compared to pigment G were determined according to protocols 1 and 2 indicated below. The values ​​can also be found in Table 9.

[0364] Table 9: Pigment preparation with pigment G

[0365]

[0366] Example 356: Production of Pigment Preparation H-1 (Not According to the Invention)

[0367] The aqueous suspension of pigment H obtained after step c) of Example 8 was mixed with 70 g of Pristerene® 4910 and stirred for 60 minutes. Subsequently, a pH of 5 was established using aqueous potassium hydroxide solution. The pigment preparation was then separated on a suction filter, washed, dried in a vacuum drying oven at 80° C. and ground in a conventional laboratory grinder for about 2 minutes. (= Pigment preparation H-1)

[0368] Examples 357 to 436: Production of Pigment Preparations H-2 to H-81 (Not According to the Invention and According to the Invention)

[0369] Analogously to Example 356, pigment preparations H-2 to H-81 according to the invention and not according to the invention were produced in Examples 357 to 436. In each case, an aqueous suspension of the pigment H as obtained after step c) of Example 8 was mixed with different aliphatic carboxylic acids B) or mixtures thereof in different amounts as indicated in Table 10.

[0370] Determination of color strength and filter pressure values

[0371] For pigment preparations H-1 to H-81, the color strength and filter pressure values ​​compared to pigment H were determined according to protocols 1 and 2 indicated below. The values ​​can also be found in Table 10.

[0372] Table 10: Pigment preparation with pigment H

[0373]

[0374] Example 437: Production of Pigment Preparation I-1 (Not According to the Invention)

[0375] The aqueous suspension of pigment I obtained after step c) of Example 9 was mixed with 70 g of Pristerene® 4910 and stirred for 60 minutes. Subsequently, a pH of 5 was established using aqueous potassium hydroxide solution. The pigment preparation was then separated on a suction filter, washed, dried in a vacuum drying oven at 80° C. and ground in a conventional laboratory grinder for about 2 minutes. (= Pigment preparation I-1)

[0376] Examples 438 to 468: Production of Pigment Preparations I-2 to I-32 (Not According to the Invention and According to the Invention)

[0377] Analogously to Example 437, pigment preparations I-2 to I-32 according to the invention and not according to the invention were produced in Examples 438 to 468. In each case, an aqueous suspension of the pigment I as obtained after step c) of Example 9 was mixed with different aliphatic carboxylic acids B) or mixtures thereof in different amounts as indicated in Table 11.

[0378] Determination of color strength and filter pressure values

[0379] For pigment preparations I-1 to I-32, the color strength and filter pressure values ​​compared to pigment I were determined according to the following protocols 1 and 2. The values ​​can also be found in Table 11.

[0380] Table 11: Pigment preparation with pigment I

[0381]

[0382] Example 469: Production of Pigment Preparation J-1 (Not According to the Invention)

[0383] The aqueous suspension of pigment J obtained after step c) of Example 10 was mixed with 70 g of Pristerene® 4910 and stirred for 60 minutes. Subsequently, a pH of 5 was established using aqueous potassium hydroxide solution. The pigment preparation was then separated on a suction filter, washed, dried in a vacuum drying oven at 80° C. and ground in a conventional laboratory grinder for about 2 minutes. (= Pigment preparation J-1)

[0384] Examples 470 to 500: Production of Pigment Preparations J-2 to J-32 (Not According to the Invention and According to the Invention)

[0385] Analogously to Example 469, pigment preparations J-2 to J-32 according to the invention and not according to the invention were produced in Examples 469 to 500. In each case, an aqueous suspension of the pigment J as obtained after step c) of Example 10 was mixed with different aliphatic carboxylic acids B) or mixtures thereof in different amounts as indicated in Table 2.

[0386] Determination of color strength and filter pressure values

[0387] For pigment preparations J-1 to J-32, the color strength and filter pressure values ​​compared to Pigment I were determined according to the following protocols 1 and 2. The values ​​can also be found in Table 12.

[0388] Table 12: Pigment preparation with pigment J

[0389]

[0390] Example 501: Production of Pigment Preparation K-1 (Not According to the Invention)

[0391] The aqueous suspension of pigment K obtained after step c) of Example 11 was mixed with 70 g of Pristerene® 4910 and stirred for 60 minutes. Subsequently, a pH of 5 was established using aqueous potassium hydroxide solution. The pigment preparation was then separated on a suction filter, washed, dried in a vacuum drying oven at 80° C. and ground in a conventional laboratory grinder for about 2 minutes. (= Pigment preparation K-1)

[0392] Examples 502 to 532: Production of Pigment Preparations K-2 to K-32 (Not According to the Invention and According to the Invention)

[0393] Analogously to Example 501, pigment preparations K-2 to K-32 according to the invention and not according to the invention were produced in Examples 502 to 532. In each case, an aqueous suspension of pigment K as obtained after step c) of Example 11 was mixed with different aliphatic carboxylic acids B) or mixtures thereof in different amounts as indicated in Table 13.

[0394] Determination of color strength and filter pressure values

[0395] For pigment preparations K-1 to K-32, the color strength and filter pressure values ​​compared to pigment K were determined according to protocols 1 and 2 indicated below. The values ​​can also be found in Table 13.

[0396] Table 13: Pigment preparation with pigment K

[0397]

[0398] Example 533: Production of Pigment Preparation L-1 (Not According to the Invention)

[0399] The aqueous suspension of pigment L obtained after step c) of Example 12 was mixed with 70 g of Pristerene® 4910 and stirred for 60 minutes. Subsequently, a pH of 5 was established using aqueous potassium hydroxide solution. The pigment preparation was then separated on a suction filter, washed, dried in a vacuum drying oven at 80° C. and ground in a conventional laboratory grinder for about 2 minutes. (= Pigment preparation L-1)

[0400] Examples 534 to 563: Production of Pigment Preparations L-2 to L-32 (Not According to the Invention)

[0401] Analogously to Example 530, pigment preparations L-2 to L-32 not according to the invention were produced in Examples 531 to 561. In each case, an aqueous suspension of the pigment L as obtained after step c) of Example 12 was mixed with different aliphatic carboxylic acids B) or mixtures thereof in different amounts as indicated in Table 14.

[0402] Determination of color strength and filter pressure values

[0403] For pigment preparations L-1 to L-32, the color strength and filter pressure values ​​compared to pigment L were determined according to protocols 1 and 2 indicated below. The values ​​can also be found in Table 14.

[0404] Table 14: Pigment preparation with pigment L

[0405]

[0406] Example 565: Production of Pigment Preparation M-1 (Not According to the Invention)

[0407] The aqueous suspension of pigment M obtained after step b) of Example 13 was mixed with 70 g of Pristerene® 4910 and stirred for 60 minutes. Subsequently, a pH of 5 was established using an aqueous potassium hydroxide solution. The pigment preparation was then separated on a suction filter, washed, dried in a vacuum drying oven at 80° C. and ground in a conventional laboratory grinder for about 2 minutes. (= Pigment preparation M-1)

[0408] Examples 566 to 593: Production of Pigment Preparations M-2 to M-32 (Not According to the Invention)

[0409] Analogously to Example 565, pigment preparations M-2 to M-32 according to the invention and not according to the invention were produced in Examples 563 to 593. In each case, an aqueous suspension of the pigment M as obtained after step b) of Example 13 was mixed with different aliphatic carboxylic acids B) or mixtures thereof in different amounts as indicated in Table 15.

[0410] Determination of color strength and filter pressure values

[0411] For pigment preparations M-1 to M-32, the color strength and filter pressure values ​​compared to pigment M were determined according to protocols 1 and 2 indicated below. The values ​​can also be found in Table 15

[0412] Table 15: Pigment preparation with pigment M

[0413]

[0414] Example 594: Production of Pigment Preparation N-1 (Not According to the Invention)

[0415] The aqueous suspension of pigment N obtained after step b) of Example 14 was mixed with 70 g of Pristerene® 4910 and stirred for 60 minutes. Subsequently, a pH of 5 was established using aqueous potassium hydroxide solution. The pigment preparation was then separated on a suction filter, washed, dried in a vacuum drying oven at 80° C. and ground in a conventional laboratory grinder for about 2 minutes. (= Pigment preparation N-1)

[0416] Examples 595 to 597: Production of Pigment Preparations N-2 to N-32 (Not According to the Invention)

[0417] Analogously to Example 594, pigment preparations N-2 to N-32 according to the invention and not according to the invention were produced in Examples 595 to 625. In each case, an aqueous suspension of the pigment N as obtained after step b) of Example 14 was mixed with different aliphatic carboxylic acids B) or mixtures thereof in different amounts as indicated in Table 16.

[0418] Determination of color strength and filter pressure values

[0419] For pigment preparations N-1 to N-32, the color strength and filter pressure values ​​compared to Pigment N were determined according to Protocols 1 and 2 indicated below. The values ​​can also be found in Table 16.

[0420] Table 16: Pigment preparation with pigment N

[0421]

[0422] Example 626: Production of Pigment Preparation O-1 (Not According to the Invention)

[0423] The aqueous suspension of pigment O obtained after step b) of Example 11 was mixed with 70 g of Pristerene® 4910 and stirred for 60 minutes. Subsequently, a pH of 5 was established using aqueous potassium hydroxide solution. The pigment preparation was then separated on a suction filter, washed, dried in a vacuum drying oven at 80° C. and ground in a conventional laboratory grinder for about 2 minutes. (= Pigment preparation O-1)

[0424] Examples 627 to 657: Production of Pigment Preparations O-2 to O-32 (Not According to the Invention)

[0425] Analogously to Example 626, pigment preparations O-2 to O-32 according to the invention and not according to the invention were produced in Examples 627 to 657. In each case, an aqueous suspension of pigment O as obtained after step b) of Example 15 was mixed with different aliphatic carboxylic acids B) or mixtures thereof in different amounts as indicated in Table 17.

[0426] Determination of color strength and filter pressure values

[0427] For pigment preparations O-1 to O-32, the color strength and filter pressure values ​​compared to pigment O were determined according to protocols 1 and 2 indicated below. The values ​​can also be found in Table 17.

[0428] Table 17: Pigment preparation with pigment O

[0429]

[0430] Example 658: Production of Pigment Preparation P-1 (Not According to the Invention)

[0431] The aqueous suspension of pigment P obtained after step b) of Example 16 was mixed with 70 g of Pristerene® 4910 and stirred for 60 minutes. Subsequently, a pH of 5 was established using aqueous potassium hydroxide solution. The pigment preparation was then separated on a suction filter, washed, dried in a vacuum drying oven at 80° C. and ground in a conventional laboratory grinder for about 2 minutes. (= Pigment preparation P-1)

[0432] Examples 659 to 689: Production of Pigment Preparations P-2 to P-32 (Not According to the Invention and According to the Invention)

[0433] Analogously to Example 658, pigment preparations P-2 to P-32 according to the invention and not according to the invention were produced in Examples 659 to 689. In each case, an aqueous suspension of the pigment P as obtained after step b) of Example 16 was mixed with different aliphatic carboxylic acids B) or mixtures thereof in different amounts as indicated in Table 18.

[0434] Determination of color strength and filter pressure values

[0435] For pigment preparations P-1 to P-32, the color strength and filter pressure values ​​compared to pigment P were determined according to protocols 1 and 2 indicated below. The values ​​can also be found in Table 18.

[0436] Table 18: Pigment preparation with pigment P

[0437]

[0438] Example 690: Production of Pigment Preparation Q-1 (Not According to the Invention)

[0439] The aqueous suspension of pigment Q obtained after step b) of Example 17 was mixed with 70 g of Pristerene® 4910 and stirred for 60 minutes. Subsequently, a pH of 5 was established using an aqueous potassium hydroxide solution. The pigment preparation was then separated on a suction filter, washed, dried in a vacuum drying oven at 80° C. and ground in a conventional laboratory grinder for about 2 minutes. (= Pigment preparation Q-1)

[0440] Examples 691 to 721: Production of Pigment Preparations Q-2 to Q-32 (Not According to the Invention and According to the Invention)

[0441] Analogously to Example 690, pigment preparations Q-2 to Q-32 according to the invention and not according to the invention were produced in Examples 691 to 721. In each case, an aqueous suspension of the pigment Q as obtained after step b) of Example 17 was mixed with different aliphatic carboxylic acids B) or mixtures thereof in different amounts as indicated in Table 19.

[0442] Determination of color strength and filter pressure values

[0443] For pigment preparations Q-1 to Q-32, the color strength and filter pressure values ​​compared to pigment Q were determined according to protocols 1 and 2 indicated below. The values ​​can also be found in Table 19.

[0444] Table 19: Pigment preparation with pigment Q

[0445]

[0446] Example 722: Production of Pigment Preparation R-1 (Not According to the Invention)

[0447] The aqueous suspension of pigment R obtained after step b) of Example 18 was mixed with 70 g of Pristerene® 4910 and stirred for 60 minutes. Subsequently, a pH of 5 was established using aqueous potassium hydroxide solution. The pigment preparation was then separated on a suction filter, washed, dried in a vacuum drying oven at 80° C. and ground in a conventional laboratory grinder for about 2 minutes. (= Pigment preparation R-1)

[0448] Examples 723 to 753: Production of Pigment Preparations R-2 to R-32 (Not According to the Invention and According to the Invention)

[0449] Analogously to Example 722, pigment preparations R-2 to R-32 according to the invention and not according to the invention were produced in Examples 723 to 753. In each case, an aqueous suspension of the pigment R as obtained after step b) of Example 18 was mixed with different aliphatic carboxylic acids B) or mixtures thereof in different amounts as indicated in Table 20.

[0450] Determination of color strength and filter pressure values

[0451] For pigment preparations R-1 to R-32, the color strength and filter pressure values ​​compared to pigment R were determined according to protocols 1 and 2 indicated below. The values ​​can also be found in Table 20.

[0452] Table 20: Pigment preparation with pigment R

[0453]

[0454] Example 754: Production of Pigment Preparation S-1 (Not According to the Invention)

[0455] The aqueous suspension of pigment S obtained after step b) of Example 19 was mixed with 70 g of Pristerene® 4910 and stirred for 60 minutes. Subsequently, a pH of 5 was established using aqueous potassium hydroxide solution. The pigment preparation was then separated on a suction filter, washed, dried in a vacuum drying oven at 80° C. and ground in a conventional laboratory grinder for about 2 minutes. (= Pigment preparation S-1)

[0456] Examples 754 to 784: Production of Pigment Preparations S-2 to S-32 (Not According to the Invention and According to the Invention)

[0457] Analogously to Example 727, pigment preparations S-2 to S-32 according to the invention and not according to the invention were produced in Examples 754 to 784. In each case, an aqueous suspension of the pigment S as obtained after step b) of Example 19 was mixed with different aliphatic carboxylic acids B) or mixtures thereof in different amounts as indicated in Table 21.

[0458] Determination of color strength and filter pressure values

[0459] For pigment preparations S-1 to S-32, the color strength and filter pressure values ​​compared to pigment S were determined according to protocols 1 and 2 indicated below. The values ​​can also be found in Table 21.

[0460] Table 21: Pigment preparation with pigment S

[0461]

[0462] Example 785: Production of Pigment Preparation T-1 (Not According to the Invention)

[0463] The aqueous suspension of pigment T obtained after step b) of Example 20 was mixed with 70 g of Pristerene® 4910 and stirred for 60 minutes. Subsequently, a pH of 5 was established using aqueous potassium hydroxide solution. The pigment preparation was then separated on a suction filter, washed, dried in a vacuum drying oven at 80° C. and ground in a conventional laboratory grinder for about 2 minutes. (= Pigment preparation T-1)

[0464] Examples 786 to 816: Production of Pigment Preparations T-2 to T-32 (Not According to the Invention and According to the Invention)

[0465] Analogously to Example 785, pigment preparations T-2 to T-32 according to the invention and not according to the invention were produced in Examples 785 to 816. In each case, an aqueous suspension of the pigment T as obtained after step b) of Example 20 was mixed with different aliphatic carboxylic acids B) or mixtures thereof in different amounts as indicated in Table 22.

[0466] Determination of color strength and filter pressure values

[0467] For pigment preparations T-1 to T-32, the color strength and filter pressure values ​​compared to pigment T were determined according to protocols 1 and 2 indicated below. The values ​​can also be found in Table 22.

[0468] Table 22: Pigment preparation with pigment T

[0469]

[0470] Example 817: Production of Pigment Preparation U-1 (Not According to the Invention)

[0471] The aqueous suspension of pigment U obtained after step b) of Example 21 was mixed with 70 g of Pristerene® 4910 and stirred for 60 minutes. Subsequently, a pH of 5 was established using an aqueous potassium hydroxide solution. The pigment preparation was then separated on a suction filter, washed, dried in a vacuum drying oven at 80° C. and ground in a conventional laboratory grinder for about 2 minutes. (= Pigment preparation U-1)

[0472] Examples 817 to 848: Production of Pigment Preparations U-2 to U-32 (Not According to the Invention and According to the Invention)

[0473] Analogously to Example 793, pigment preparations U-2 to U-32 according to the invention and not according to the invention were produced in Examples 817 to 848. In each case, an aqueous suspension of the pigment U as obtained after step b) of Example 21 was mixed with different aliphatic carboxylic acids B) or mixtures thereof in different amounts as indicated in Table 23.

[0474] Determination of color strength and filter pressure values

[0475] For pigment preparations U-1 to U-32, the color strength and filter pressure values ​​compared to pigment U were determined according to protocols 1 and 2 indicated below. The values ​​can also be found in Table 23.

[0476] Table 23: Pigment preparation with pigment U

[0477]

[0478] Example 849: Production of Pigment Preparation V-1 (Not According to the Invention)

[0479] The aqueous suspension of pigment U obtained after step b) of Example 22 was mixed with 70 g of Pristerene® 4910 and stirred for 60 minutes. Subsequently, a pH of 5 was established using an aqueous potassium hydroxide solution. The pigment preparation was then separated on a suction filter, washed, dried in a vacuum drying oven at 80° C. and ground in a conventional laboratory grinder for about 2 minutes. (= Pigment preparation V-1)

[0480] Examples 850 to 880: Production of Pigment Preparations V-2 to V-32 (Not According to the Invention and According to the Invention)

[0481] Analogously to Example 849, pigment preparations V-2 to V-32 according to the invention and not according to the invention were produced in Examples 850 to 880. In each case, an aqueous suspension of the pigment V as obtained after step b) of Example 22 was mixed with different aliphatic carboxylic acids B) or mixtures thereof in different amounts as indicated in Table 24.

[0482] Determination of color strength and filter pressure values

[0483] For pigment preparations V-1 to V-32, the color strength and filter pressure values ​​compared to pigment V were determined according to protocols 1 and 2 indicated below. The values ​​can also be found in Table 24.

[0484] Table 24: Pigment preparation with pigment V

[0485]

[0486] Example 881: Production of Pigment Preparation W-1 (Not According to the Invention)

[0487] The aqueous suspension of pigment W obtained after step b) of Example 23 was mixed with 70 g of Pristerene® 4910 and stirred for 60 minutes. Subsequently, a pH of 5 was established using an aqueous potassium hydroxide solution. The pigment preparation was then separated on a suction filter, washed, dried in a vacuum drying oven at 80° C. and ground in a conventional laboratory grinder for about 2 minutes. (= Pigment preparation W-1)

[0488] Examples 882 to 913: Production of Pigment Preparations W-2 to W-32 (Not According to the Invention and According to the Invention)

[0489] Analogously to Example 881, pigment preparations W-2 to W-32 according to the invention and not according to the invention were produced in Examples 882 to 913. In each case, an aqueous suspension of the pigment W as obtained after step b) of Example 23 was mixed with different aliphatic carboxylic acids B) or mixtures thereof in different amounts as indicated in Table 25.

[0490] Determination of color strength and filter pressure values

[0491] For pigment preparations W-1 to W-32, the color strength and filter pressure values ​​compared to pigment W were determined according to protocols 1 and 2 indicated below. The values ​​can also be found in Table 25.

[0492] Table 25: Pigment preparation with pigment W

[0493]

[0494] Table 26 Reactants

[0495]

[0496]

[0497] The pigments produced according to Examples 1 to 22 and the pigment preparations produced according to Examples 23 to 913 were each subjected to determination of the color strength according to DIN 55986 (see Option 1) and to determination of the filtration pressure value according to DIN EN ISO 23900-5:2019-01 (see Option 2).

[0498] Determination of color strength in PVC: Option 1

[0499] A plasticized PVC compound was produced as test medium by homogenizing 67.5% Vestolit® E7004 (Vestolit GmbH), 29.0% Hexamoll® DINCH (BASF), 2.25% Baerostab UBZ 770 (Baerlocher GmbH) and 1.25% Isocolor white pigment paste (ISL-Chemie) in a laboratory dissolver.

[0500] On a laboratory roller mill, 100 g of the PVC compound was applied at 150 °C to two -1 and 18min -1 The rolled sheet was then placed on a roller with a diameter of 150 mm rotating under a pressure of 200 °C. Together with 0.10 g of pigment, a rolled sheet was produced by rotation and then passed through a roller gap of 0.10 mm eight times. The uniformly colored rolled sheet was then removed after passing through a roller gap of 0.8 mm and laid smoothly on a metal surface. The cooled rolled sheet was then applied through a roller gap of 0.2 mm to two rollers that were placed on a plate at 26 min. -1 and 24 min -1 The rolled sheet was then rolled eight times on a non-heated 110 mm diameter roller rotating at 150°C. To make the surface smooth, the rolled sheet was again applied to a roller at 150°C, removed at 0.8 mm and laid on a smooth surface to cool. A sample of this rolled sheet was used to determine the relative color strength.

[0501] The relative color intensity is calculated according to DIN 55986 after reflectance measurement of the test specimen against a white background using a spectrophotometer with a measuring geometry of d / 8 under standard illuminant D65 and a 10° observer using the sum of the K / S values ​​in the visible spectrum in the range 400 nm-700 nm.

[0502] Determination of the filtration pressure value (FPV) by filter pressure test according to DIN EN ISO 23900-5:2019-01 (determination of the pressure increase): Option 2

[0503] 1950 g of polyamide 6 (Durethan® B30S from LANXESS Germany GmbH, Cologne) with 1% titanium dioxide added were thoroughly mixed with 50 g of the pigment to be tested on a tumble mixer for one hour. The mixture was extruded on a Leistritz ZSE 18HP twin-screw extruder at 225°C and a speed of 700 rpm. 200 g of the granular material produced in this way was filtered through a 25 µm filter at a temperature of 238°C and the resulting pressure increase was measured. The pressure difference between the initial pressure and the maximum pressure was used to calculate the filter pressure value FPV. The lower this pressure increase measured in bar / g, the better the filtering properties of the pigment preparation to be tested.

[0504] Conclusion: From the measurement results as listed in Tables 1 to 25 it can be seen that only the pigment preparations according to the invention have both improved filter properties and improved color strength compared to pigment preparations not according to the invention.

Claims

1. A pigment preparation consisting of the following i) Metallic azo pigments A) containing a) at least two metal azo compounds of formula (I) which differ at least in the metal ion Me, or tautomeric forms thereof, (I) in R 1 and R 2 Each independently is OH, NH2 or NHR 5 , R 3 and R 4 Each independently is O or NR 5 , R 5 is hydrogen or alkyl, preferably C1-C4 alkyl, and Me in the first metal azo compound is the metal ion Me 1 And in the second metal azo compound it is the metal ion Me 2 , in Me 1 Zn 2+ and Ni 2+ and the molar ratio of Zn to Ni metal ions is 97:3 to 3:97, and Me 2 It's Al 3+ 2 / 3 、Fe 2+ 、Fe 3+ 2 / 3 、Co 2+ 、Co 3+ 2 / 3 、La 3+ 2 / 3 、Yes 3+ 2 / 3 、Pr 3+ 2 / 3 -、Nd 2+ 、Nd 3+ 2 / 3 、Sm 2+ 、Sm 3+ 2 / 3 、Eu 2+ 、Eu 3+ 2 / 3 、Gd 3+ 2 / 3 、Tb 3+ 2 / 3 、Dy 3+ 2 / 3 、Ho 3+ 2 / 3 、Yb 2+ 、Yb 3+ 2 / 3 、Er 3+ 2 / 3 、Tm 3+ 2 / 3 、Mg 2+ 、Ca 2+ 、Sr 2+ 、Mn 2+ 、Y 3+ 2 / 3 、Sc 3+ 2 / 3 、Ti 2+ 、Ti 3+ 2 / 3 、Nb 3+ 2 / 3 、Mo 2+ 、Mo 3+ 2 / 3 、V 2+ 、V 3+ 2 / 3 、Zr 2+ 、Zr 3+ 2 / 3 ,CD 2+ 、Cr 3+ 2 / 3 、Pb 2+ Or Ba 2+ , Provided that, based in each case on one mole of all compounds of the formula (I), the metal ion Me 1 The amount of is 97 to 100 mol % in total, and the amount of metal ions selected from the Me² series is 0 to 3 mol %, and b) at least one compound having the formula (II) (II) in R 6 is independently in each case hydrogen or alkyl, preferably C1-C4-alkyl, which may be optionally substituted one or more times by OH, or the reaction product of (I) and (II), as well as (ii) 100 to 250 g of at least one aliphatic C per mol of all metal azo compounds (I) contained in the metal azo pigment A) 10-22 Monocarboxylic acids B).

2. The pigment preparation according to claim 1, characterized in that In the metal azo pigment A), the ratio of the metal azo compound (I) to the compound having the formula (II) is 1 mol: 0.05 to 4 mol, preferably 1 mol: 0.5 to 2.5 mol, more preferably 1 mol: 1.0 to 2.0 mol.

3. The pigment preparation according to claim 1 or 2, characterized in that In formula (I), R 1 and R 2 Yes OH, R 3 and R 4 is O, and Me in the first metal azo compound represents Me 1 And Zn 2+ and Ni 2+ , wherein the molar ratio of Zn to Ni metal ions is 90:10 to 30:70, and Me in the second metal azo compound represents Me 2 And Me 2 It's Al 3+ 2 / 3 , Fe 2 + , Fe 3+ 2 / 3 、Co 2+ 、Co 3+ 2 / 3 、Ce 3+ 2 / 3 Mg 2+ , Ca 2+ , Sr 2+ ,La 3+ 2 / 3 Mg 2+ , Mn 2+ 、Nd 2+ 、Nd 3+ 2 / 3 、Ti 2+ 、Ti 3+ 2 / 3 , Nb 3 + 2 / 3 、Mo 2+ 、Mo 3+ 2 / 3 、V 2+ 、V 3+ 2 / 3 、Zr 2+ 、Zr 3+ 2 / 3 、Cd 2+ Cr 3+ 2 / 3 , Pb 2+ , Ca 2+ Or Ba 2+ , and b) is melamine or a reaction product of formula (I) and melamine.

4. The pigment preparation according to one or more of claims 1 to 3, characterized in that The aliphatic C 10-22 The monocarboxylic acid B) is a saturated or mono- to triunsaturated carboxylic acid, preferably at least one from the series C 10-22 Monocarboxylic acids: capric acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid.

5. The pigment preparation according to claim 4, characterized in that The aliphatic C 10-22 The monocarboxylic acids B) are present in pure form or as mixtures, preferably mixtures containing myristic acid, palmitic acid or stearic acid.

6. At least one aliphatic C 10-22 Use of monocarboxylic acids B) for simultaneously improving the filter pressure value FPV determined by filter press test according to DIN EN ISO 23900-5:2019-01 and the color strength determined according to DIN 55986 of pigment preparations containing metal azo pigments A) consisting of: a) at least two metal azo compounds of formula (I) which differ at least in the metal ion Me, or tautomeric forms thereof, (I) in R 1 and R 2 Each independently is OH, NH2 or NHR 5 , R 3 and R 4 Each independently is O or NR 5 , R 5 is hydrogen or alkyl, preferably C1-C4 alkyl, and Me in the first metal azo compound is the metal ion Me 1 And in the second metal azo compound it is the metal ion Me 2 , in Me 1 Zn 2+ and Ni 2+ and the molar ratio of Zn to Ni metal ions is 97:3 to 3:97, and Me 2 It's Al 3+ 2 / 3 、Fe 2+ 、Fe 3+ 2 / 3 、Co 2+ 、Co 3+ 2 / 3 、La 3+ 2 / 3 、Yes 3+ 2 / 3 、Pr 3+ 2 / 3 -、Nd 2+ 、Nd 3+ 2 / 3 、Sm 2+ 、Sm 3+ 2 / 3 、Eu 2+ 、Eu 3+ 2 / 3 、Gd 3+ 2 / 3 、Tb 3+ 2 / 3 、Dy 3+ 2 / 3 、Ho 3+ 2 / 3 、Yb 2+ 、Yb 3+ 2 / 3 、Er 3+ 2 / 3 、Tm 3+ 2 / 3 、Mg 2+ 、Ca 2+ 、Sr 2+ 、Mn 2+ 、Y 3+ 2 / 3 、Sc 3+ 2 / 3 、Ti 2+ 、Ti 3+ 2 / 3 、Nb 3+ 2 / 3 、Mo 2+ 、Mo 3+ 2 / 3 、V 2+ 、V 3+ 2 / 3 、Zr 2+ 、Zr 3+ 2 / 3 ,CD 2+ 、Cr 3+ 2 / 3 、Pb 2+ Or Ba 2+ , Provided that, based in each case on one mole of all compounds of the formula (I), the metal ion Me 1 The amount of is 97 to 100 mol % in total, and the amount of metal ions selected from the Me² series is 0 to 3 mol %, and b) at least one compound having the formula (II) (II) in R 6 is independently in each case hydrogen or alkyl, preferably C1-C4-alkyl, which may be optionally substituted one or more times by OH, or alternatively the reaction product of (I) and (II), Provided that 100 to 250 g of aliphatic C are used per mole of all metal azo compounds (I) contained in the metal azo pigment A). 10-22 Monocarboxylic acids B).

7. The use according to claim 6, characterized in that In the metal azo pigment A), the ratio of the metal azo compound (I) to the compound having the formula (II) is 1 mol: 0.05 to 4 mol, preferably 1 mol: 0.5 to 2.5 mol, more preferably 1 mol: 1 mol: 1.0 to 2.0 mol.

8. The use according to claim 6 or 7, characterized in that In formula (I), R 1 and R 2 Yes OH, R 3 and R 4 is O, and Me in the first metal azo compound represents Me 1 And Zn 2+ and Ni 2+ , wherein the molar ratio of Zn to Ni metal ions is 90:10 to 30:70, and Me in the second metal azo compound represents Me 2 And Me 2 It's Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 、Co 2+ 、Co 3+ 2 / 3 、Ce 3+ 2 / 3 Mg 2+ , Ca 2+ , Sr 2+ ,La 3+ 2 / 3 Mg 2+ , Mn 2+ 、Nd 2+ 、Nd 3+ 2 / 3 、Ti 2+ 、Ti 3+ 2 / 3 , Nb 3 + 2 / 3 、Mo 2+ 、Mo 3+ 2 / 3 、V 2+ 、V 3+ 2 / 3 、Zr 2+ 、Zr 3+ 2 / 3 、Cd 2+ Cr 3+ 2 / 3 , Pb 2+ , Ca 2+ Or Ba 2+ , and b) is melamine or a reaction product of formula (I) and melamine.

9. Use according to one or more of claims 6 to 8, characterized in that The aliphatic C 10-22 The monocarboxylic acid B) is a saturated or mono- to triunsaturated carboxylic acid, preferably at least one from the series C 10-22 Monocarboxylic acids: capric acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and behenic acid.

10. The use according to claim 9, characterized in that The aliphatic C 10-22 The monocarboxylic acids B) are present in pure form or as mixtures, preferably mixtures containing myristic acid, palmitic acid or stearic acid.

11. A method for simultaneously improving the filter pressure value FPV determined by filter press test according to DIN EN ISO 23900-5:2019-01 and the color strength determined according to DIN 55986 of a pigment preparation containing a metal azo pigment A) consisting of: a) at least two metal azo compounds of formula (I) which differ at least in the metal ion Me, or tautomeric forms thereof, (I) in R 1 and R 2 Each independently is OH, NH2 or NHR 5 , R 3 and R 4 Each independently is O or NR 5 , R 5 is hydrogen or alkyl, preferably C1-C4 alkyl, and The Me in the first metal azo compound represents Me 1 And Zn 2+ and Ni 2+ , wherein the molar ratio of Zn to Ni metal ions is 97:3 to 3:97, and Me in the second metal azo compound represents Me 2 And it is Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 、Co 2+ 、Co 3+ 2 / 3 ,La 3 + 2 / 3 、Ce 3+ 2 / 3 , Pr 3+ 2 / 3 -、Nd 2+ 、Nd 3+ 2 / 3 、Sm 2+ 、Sm 3+ 2 / 3 、Eu 2+ 、Eu 3+ 2 / 3 , Gd 3+ 2 / 3 , Tb 3+ 2 / 3 、Dy 3+ 2 / 3 、Ho 3+ 2 / 3 , Yb 2 + , Yb 3+ 2 / 3 , Er 3+ 2 / 3 、Tm 3+ 2 / 3 Mg 2+ , Ca 2+ , Sr 2+ , Mn 2+ or Y 3+ 2 / 3 Sc 3+ 2 / 3 、Ti 2+ 、Ti 3+ 2 / 3 , Nb 3+ 2 / 3 、Mo 2+ 、Mo 3 + 2 / 3 、V 2+ 、V 3+ 2 / 3 、Zr 2+ 、Zr 3+ 2 / 3 、Cd 2+ Cr 3+ 2 / 3 , Pb 2+ Or Ba 2+ , Provided that, based in each case on one mole of all compounds of the formula (I), the metal ion Me 1 The amount of is 97 to 100 mol % in total, and the amount of metal ions selected from the Me² series is 0 to 3 mol %, and b) at least one compound having the formula (II) (II) in R 6 is independently in each case hydrogen or alkyl, preferably C1-C4-alkyl, which may be optionally substituted one or more times by OH, or alternatively the reaction product of (I) and (II), The method comprises using 100 to 250 g of at least one aliphatic C per mole of all metal azo compounds (I) contained in the metal azo pigment A). 10-22 Monocarboxylic acids B).

12. The method according to claim 11, characterized in that In the metal azo pigment A), the ratio of the metal azo compound (I) to the compound having the formula (II) is 1 mol: 0.05 to 4 mol, preferably 1 mol: 0.5 to 2.5 mol, more preferably 1 mol: 1 mol: 1.0 to 2.0 mol.

13. The method according to claim 11 or 12, characterized in that: In formula (I), R 1 and R 2 Yes OH, R 3 and R 4 is O, and Me in the first metal azo compound represents Me 1 And Zn 2+ and Ni 2+ , wherein the molar ratio of Zn to Ni metal ions is 90:10 to 30:70, and Me in the second metal azo compound represents Me 2 And Me 2 It's Al 3+ 2 / 3 , Fe 2 + , Fe 3+ 2 / 3 、Co 2+ 、Co 3+ 2 / 3 、Ce 3+ 2 / 3 Mg 2+ , Ca 2+ , Sr 2+ ,La 3+ 2 / 3 Mg 2+ , Mn 2+ 、Nd 2+ 、Nd 3+ 2 / 3 、Ti 2+ 、Ti 3+ 2 / 3 , Nb 3 + 2 / 3 、Mo 2+ 、Mo 3+ 2 / 3 、V 2+ 、V 3+ 2 / 3 、Zr 2+ 、Zr 3+ 2 / 3 、Cd 2+ Cr 3+ 2 / 3 , Pb 2+ , Ca 2+ Or Ba 2+ , and b) is melamine or a reaction product of formula (I) and melamine.

14. Method according to one or more of claims 11 to 13, characterized in that The aliphatic C 10-22 The monocarboxylic acid B) is a saturated or mono- to triunsaturated carboxylic acid, preferably at least one from the series C 10-22 Monocarboxylic acids: capric acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and behenic acid.

15. The method according to claim 14, characterized in that The aliphatic C 10-22 The monocarboxylic acids B) are present in pure form or as mixtures, preferably mixtures containing myristic acid, palmitic acid or stearic acid.

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