Universal pigment preparations for point-of-sale use Description The present invention relates to aqueous pigment preparations, the production thereof, and their use for the coloring of paints, inks or renders, preferably in metering systems at the point of sale (POS) or in in-plant tinting systems.

BACKGROUND OF THE INVENTION

Liquid systems, such as coating materials, varnishes, emulsion paints, and printing inks, are customarily pigmented using pigment preparations which comprise water, organic solvent or combinations thereof. In addition to anionic, cationic, nonionic or amphoteric dispersants, these pigment preparations must generally be admixed with further auxiliaries, such as humectants, agents for increasing the freeze resistance, thickeners for stabilization, biocides, and defoamers.

Such pigment preparations are employed as tinting pastes in retail stores and professional decorating businesses, and, using metering and tinting systems, are added to aqueous and solventborne inks and paints in order to set customer-specific shades. For the precise setting of a particular shade, the tinting pastes are generally metered volumetrically.

In order to comply with the guidelines for awarding of various eco labels, inks and paints have for some time advantageously been given low-VOC (volatile organic compounds) or VOC-free formulations. The same standards are also desired for the pigment preparations which are mixed in at the point of sale to the low-VOC or VOC- free inks and paints. US-A-5,340,394 teaches VOC-free pigment concentrates based on linear polyethylene glycol polyethers with molecular weights of 190 to 700 and nonionic alkyl glycosides for use at the point of sale. The pigment concentrates are described as being especially suitable for latex paints and alkyd paints, and additionally these pigment concentrates are said to be blocking-resistant.

US-A-2006/0207476 and US-A-2010/01 13685 describe low-VOC universal pigment pastes which are stable, which have favorable rheology, and which are suitable for aqueous emulsion paints and for solventborne alkyd paints. The pastes may be provided in closed containers which allow simple metering in controlled quantities. These pastes contain not only solvent-compatible surfactants but also latex-compatible surfactants, such as alkyl polyethylene glycol ethers, secondary alcohol ethoxylates, difunctional propylene oxide/ethylene oxide block polymers (with secondary OH groups), ethylene oxide/propylene oxide block copolymers, alkylaryl polyglycol ethers, or amine salts of hydrophilic copolymers of polycarboxylic acids.

WO-A-2014/000842 teaches aqueous universal pigment preparations based on fatty acid condensation products and nonionic surfactants. The pigment preparations are described as being stable in their viscosity, foam, and sedimentation behavior after storage at 60°C for one week.

WO-A-201 1/151277 teaches low-VOC aqueous universal pigment preparations which are described as being suitable for preventing the drying of the preparations in open nozzles of the paint-mixing systems, and also for producing coatings of certain hardness. The pigment preparations comprise stabilizers, examples being ethoxylated fatty acid monoethanolamides, anionic surfactants based on tristyrylphenol-polyglycol ether phosphate esters, or phospholipid-based surfactants, rheological additives based on clay minerals, and also nonvolatile, organic solvents such as polyethylene glycols PEG 200 or PEG 400.

US-A-2012/0316273 describes a point-of-sale system for aqueous emulsion paints that is composed of a plurality of liquid pigment preparations which are described as being suitable for preventing the drying of the preparations in open nozzles of the metering systems. The pigment preparations comprise a polyalkylene glycol as humectant, an ethoxylated surfactant, and filler.

DE-A-102006062441 describes modified comb copolymers based on styrene units and maleic anhydride units, which may further contain Ν,Ν-disubstituted amino groups or substituted ammonium groups. The possible uses of the copolymers include the production of solids concentrates, such as pigment concentrates.

Despite the proposals in the prior art of a multiplicity of compounds as additives for universal pigment preparations, there continues to be a need for effective additive combinations for such pigment preparations, satisfying the requirements of precise volumetric metering and at the same time the desired color properties.

Moreover, environmentally objectionable substances and also sensitizing substances ought largely to be avoided.

European directives and laws are requiring not only ever-lower VOC contents of less than 1000 ppm but also low SVOC contents (i.e., low levels of semivolatile organic compounds). Analytically, the VOC contents and SVOC contents are determined by means of GC-MS in accordance with DIN ISO 1 1890-2 (in-can measurement in ppm).

This therefore necessitates an entirely new assessment of the additives, since many additives undergo decomposition under the ISO 1 1890-2 conditions, starting at about 200°C to 367°C (387°C: boiling point of C22H46 (n-docosane)), and therefore simulate a VOC and/or SVOC content.

Further requirements of European directives and laws call for the absence of additives which have an environmental hazard potential in accordance with the CLP Regulation (EC) No. 1272/2008 concerning the Classification, Labeling and Packaging of substances and mixtures. Additives with H400 hazard statements are approved only with very great restrictions for use in paints. Alkylphenyl ethoxylates (APEOs) are likewise no longer approved in EU Directive 2003/53/EC.

Furthermore, the use of the customary surfactants based on fatty alcohol alkoxylates with less than 20 alkylene oxide units, or on amino compounds, is restricted.

Surfactants with H318 classification can no longer be used in the quantities needed. Moreover, compounds having H317 classification, which may give rise to allergic skin reactions, can be used only at a maximum of 0.1 wt%.

It was an object of the present invention, therefore, to provide stable universal pigment preparations which are distinguished by ultimately advantageous performance properties, especially high color strength or easy dispersibility (capacity for stirred incorporation) in a very wide variety of application media, and/or which, over a prolonged period, exhibit no drying either in the containers or in the metering system, especially in nozzles. The pigment preparations ought also to exhibit no rubout, in the context of the coloring of the various emulsion paints and coatings.

A further object of the invention was to provide aqueous universal pigment preparations which pose a low environmental hazard, in other words preparations which are low in VOC and low in SVOC and which also contain largely no environmentally objectionable substances and sensitizing substances, in other words containing no substances liable for labeling in accordance with various eco labels, as for example in accordance with the CLP Regulation (EC) No. 1272/2008.

SUMMARY OF THE INVENTION It has now been found that pigment preparations which comprise a combination of a copolymer having a nitrogen-containing pigment-affinic group, and an additive based on a phosphoric or phosphonic ester, and having the desired properties, can be obtained. The present invention accordingly provides a pigment preparation comprising, based in each case on the total weight of the preparation,

(A) 1 to 80 wt% of a pigment component which comprises a pigment and optionally a filler; (B) 0.01 to 10 wt% of a water-soluble, nonionic, surface-active additive comprising a copolymer formed from at least one vinyl monomer and from an ethylenically unsaturated monomer selected from the group consisting of monocarboxylic esters, dicarboxylic esters, monocarboxamides, and dicarboxamides,

the vinyl monomer and/or the ethylenically unsaturated monomer containing an

N-containing group with pigment affinity;

(C) 0.01 to 8 wt% of a phosphoric ester and/or phosphonic ester;

(D) 0 to 20 wt% of further additives customary for aqueous pigment preparations; and

(E) water,

where the sum of the percentages by weight of components (A) to (E) makes 100 wt%.

Further provided is a method for producing a pigment preparation of the invention, where first of all components (A) to (C) and at least part of component (D) are introduced into water, the resulting suspension is subjected to wet comminution, and optionally the remaining amount of component (D) is subsequently added to the suspension.

A further subject of the present invention relates to the use of the pigment preparation of the invention for coloring paints, inks, and renders, preferably in metering systems at the point of sale or in in-plant tinting systems.

DETAILED DESCRIPTION OF THE INVENTION

The term "low-VOC" denotes a concentration of the volatile organic compounds as per DIN ISO 1 1890-2 of less than 1000 ppm.

The term "low-SVOC" denotes a concentration of the semivolatile organic compounds as per DIN ISO 1 1890-2 of less than 5000 ppm. The term "(meth)acryl..." encompasses acryl... and/or methacryl....

The terms "a/an", "the", "at least one", and "one or more" are used interchangeably; in other words, a pigment component comprising "a" pigment also encompasses a pigment component comprising "one or more pigments".

Essential constituents of the pigment preparations of the invention are the pigment component (A), a water-soluble, nonionic, surface-active additive (B), a phosphoric ester and/or phosphonic ester (C), and water. Present optionally are further additives (D) customary for the production of aqueous pigment preparations, examples being humectants, rheological additives like thickeners, further dispersants, for example nonionic additives based on polyethers, and defoamers, foam suppressants, stabilizers, such as biocides or fungicides, antiflocculants, buffer substances, pH regulators, and pigment synergists. Components (D) are different from components (B) and (C). All of the constituents add up to 100 wt% of the pigment preparation.

As component (A), organic or inorganic pigments may be present in the pigment preparations of the invention. The pigment preparations may of course also comprise combinations of different organic or different inorganic pigments, or combinations of organic and inorganic pigments. The same applies to fillers and combinations of pigment(s) and filler(s). Component (A) preferably comprises at least one pigment and at least one filler.

The pigments and fillers are customarily in finely divided form. The pigments accordingly generally have an average particle size of 0.1 to 5 μηη. The particle size may be determined in accordance with DIN 13320.

The organic pigments are customarily organic chromatic and black pigments. Inorganic pigments may likewise be color pigments (chromatic, black and white pigments) and also luster pigments, and the inorganic pigments used customarily as fillers. Organic pigments may be selected from the class of the monoazo pigments, disazo pigments, disazo condensation pigments, anthanthrone pigments, anthraquinone pigments, anthrapyrimidine pigments, quinacridone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, dithioketopyrrolopyrrole pigments, dioxazine pigments, flavanthrone pigments, indanthrone pigments, isoindoline pigments, isoindolinone pigments, isoviolanthrone pigments, metal complex pigments, perinone pigments, perylene pigments, phthalocyanine pigments, pyranthrone pigments, pyrazoloquinazolone pigments, indigo pigments, thioindigo pigments, triarylcarbonium pigments, and combinations thereof. The following examples of suitable organic color pigments are given below:

- Monoazo pigments: C.I. Pigment Yellow 1 , 3, 62, 65, 73, 74, 97, 183 and 191 ; C.I.

Pigment Orange 5, 38, and 64; C.I. Pigment Red 1 , 2, 3, 4, 5, 23, 48:1 , 48:2, 48:3, 48:4, 49, 49:1 , 51 , 51 :1 , 52:1 , 52:2, 53, 53:1 , 53:3, 57:1 , 58:2, 58:4, 63, 1 12, 146, 148, 170, 184, 187, 191 :1 , 210, 245, 247, and 251 ;

- Disazo pigments: C.I. Pigment Yellow 12, 13, 14, 16, 17, 81 , 83, 106, 1 13, 126, 127, 155, 170, 174, 176, and 188; C.I. Pigment Orange 16, 34, and 44;

- Disazo condensation pigments: C.I. Pigment Yellow 93, 95, and 128; C.I. Pigment Red 144, 166, 214, 220, 221 , 242, and 262; C.I. Pigment Brown 23, and 41 ;

- Anthanthrone pigments: C.I. Pigment Red 168;

- Anthraquinone pigments: C.I. Pigment Yellow 147 and 199; C.I. Pigment Red 177;

- Anthrapyrimidine pigments: C.I. Pigment Yellow 108; - Benzimidazolone pigments: C.I. Pigment Yellow 120, 151 , 154, 180, 181 ; C.I.

Pigment Orange 36, and 72, C.I. Pigment Red 175, 185, 208; C.I. Pigment

Brown 25; C.I. Pigment Violet 32;

- Quinacridone pigments: C.I. Pigment Orange 48 and 49; C.I. Pigment Red 122, 202, 206, and 209; C.I. Pigment Violet 19;

- Quinophthalone pigments: C.I. Pigment Yellow 138;

- Diketopyrrolopyrrole pigments: C.I. Pigment Orange 71 , 73, and 81 ; C.I. Pigment Red 254, 255, 264, 270, and 272;

- Dioxazine pigments: C.I. Pigment Violet 23;

- Flavanthrone pigments: C.I. Pigment Yellow 24;

- Indanthrone pigments: C.I. Pigment Blue 60 and 64;

- Isoindoline pigments: C.I. Pigment Yellow 139 and 185; C.I. Pigment Orange 61 and 69, C.I. Pigment Red 260;

- Isoindolinone pigments: C.I. Pigment Yellow 109, 1 10, and 173;

- Isoviolanthrone pigments: C.I. Pigment Violet 31 ;

- Metal complex pigments: C.I. Pigment Red 257; C.I. Pigment Yellow 1 17, 129, 150, 153, and 177; C.I. Pigment Green 8;

- Perinone pigments: C.I. Pigment Orange 43; C.I. Pigment Red 194;

- Perylene pigments: C.I. Pigment Red 123, 149, 178, 179, and 224; C.I. Pigment Violet 29; C.I. Pigment Black 31 and 32;

- Phthalocyanine pigments: C.I. Pigment Blue 15, 15:1 , 15:2, 15:3, 15:4, 15:6, 16;

C.I. Pigment Green 7, 36;

- Pyranthrone pigments: C.I. Pigment Orange 51 ; C.I. Pigment Red 216;

- Pyrazoloquinazolone pigments: C.I. Pigment Orange 67 and C.I. Pigment Red 216; - Thioindigo pigments: C.I. Pigment Red 88 and 181 ; C.I. Pigment Violet 38;

- Triarylcarbonium pigments: C.I. Pigment Red 81 , 81 :1 , and 169; C.I. Pigment Violet 1 , 2, 3, and 27; C.I. Pigment Blue 1 , 61 , and 62; C.I. Pigment Green 1 ;

- C.I. Pigment Black 1 (aniline black);

- C.I. Pigment Yellow 101 (aldazine yellow);

- C.I. Pigment Brown 22.

Examples of suitable inorganic color pigments are as follows:

- white pigments: titanium dioxide (C.I. Pigment White 6), zinc white, pigment-grade zinc oxide; zinc sulfide, lithopone;

- black pigments: black iron oxide (C.I. Pigment Black 1 1 ), iron manganese black, spinel black (C.I. Pigment Black 27); carbon black (C.I. Pigment Black 7); graphite (C.I. Pigment Black 10); chromium iron oxide black (P. Brown 29);

- chromatic pigments: chromium oxide, chromium oxide hydrate green; chromium green (C.I. Pigment Green 48); cobalt green (C.I. Pigment Green 50); ultramarine green; cobalt blue (C.I. Pigment Blue 28 and 36; C.I. Pigment Blue 72); ultramarine blue; manganese blue; ultramarine violet; cobalt violet and manganese violet; red iron oxide (C.I. Pigment Red 101 ); cadmium sulfoselenide (C.I. Pigment Red 108); cerium sulfide (C.I. Pigment Red 265); molybdate red (C.I. Pigment Red 104); ultramarine red; brown iron oxide (C.I. Pigment Brown 6 and 7), mixed brown, spinel phases and corundum phases (C.I. Pigment Brown 29, 31 , 33, 34, 35, 37, 39, and 40), chromium titanium yellow (C.I. Pigment Brown 24), chromium orange; cerium sulfide (C.I. Pigment Orange 75); yellow iron oxide (C.I. Pigment Yellow 42); nickel titanium yellow (C.I. Pigment Yellow 53; C.I. Pigment Yellow 157, 158, 159, 160, 161 , 162, 163, 164, and 189); spinel phases (C.I. Pigment Yellow 1 19); cadmium sulfide and cadmium zinc sulfide (C.I. Pigment Yellow 37 and 35); chromium yellow (C.I. Pigment Yellow 34); bismuth vanadate (C.I. Pigment Yellow 184). Examples of suitable fillers are inorganic pigments, such as transparent silicon dioxide, finely ground quartz, aluminum oxide, aluminum hydroxide, natural and synthetic micas, talc, kaolin, calcium carbonate, such as natural and precipitated chalk, and barium sulfate. The luster pigments are platelet-shaped pigments which have a monophasic or polyphasic construction and a color play which is marked by the interplay of

interference, reflection, and absorption phenomena. Examples include aluminum platelets, and aluminum, iron oxide, glass and mica platelets bearing one or more coating layers, in particular of metal oxides.

The amount of the pigment component (A) is 1 to 80 wt%, based on the total weight of the aqueous pigment preparation, preferably 5 to 70 wt%.

Where there is a combination of pigment and filler, the weight ratio of pigment to filler may be in the range from 1 :20 to 20:1.

As component (B), the pigment preparations of the invention comprise at least one water-soluble, nonionic, surface-active additive comprising a copolymer which is formed from at least one vinyl monomer and from at least one ethylenically unsaturated monomer selected from the group consisting of monocarboxylic esters, dicarboxylic esters, monocarboxamides, and dicarboxamides,

the vinyl monomer or the ethylenically unsaturated monomer containing an

N-containing group with pigment affinity. The additives (B) are in nonionic form in the aqueous pigment preparation, which in general has a pH of about 6 to 10.

Depending on the pH of the application medium, the N-containing groups with pigment affinity in the monomer may also be present in cationic/protonated form.

Examples of the ethylenically unsaturated monomers and the vinyl monomers include the following:

- vinylaromatics, such as styrene, methylstyrene, chlorostyrene, and vinyltoluene; - a-C2-C22-(1 -alkenes), such as ethylene, propylene, isobutene, diisobutene, butadiene, 1-hexadecene, 1-octadecene, 1-eicosene, and 1-docosene;

- vinyl ethers, such as polyalkylene glycol monovinyl ethers and alkyl or aryl

derivatives thereof, e.g., polyethylene glycol monovinyl ether, polypropylene glycol monovinyl ether, polyethylene glycol methyl vinyl ether (mPEG vinyl ether) or polypropylene glycol methyl vinyl ether;

- vinyl esters of linear or branched monocarboxylic acids, such as vinyl acetate and vinyl propionate;

- alkyl esters and aryl esters of ethylenically unsaturated monocarboxylic acids, especially acrylic and methacrylic esters, for example Ci-C22-alkyl esters

(meth)acrylic acid, such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, cyclohexyl, 2-ethylhexyl, nonyl, isobornyl, lauryl (meth)acrylate, and hydroxyethyl (meth)acrylate and also phenyl, naphthyl, and benzyl (meth)acrylate;

- dialkyl esters of ethylenically unsaturated dicarboxylic acids, such as dimethyl, diethyl, dipropyl, diisopropyl, dibutyl, dipentyl, dihexyl, di-2-ethylhexyl, dinonyl, dilauryl, and di-2-hydroxyethyl maleate and fumarate;

- ethylenically unsaturated monocarboxylic acids, especially acrylic or methacrylic acid, which are esterified with polyether alcohols or derivatives thereof, examples being polypropylene glycol monomethyl (meth)acrylate, polyethylene glycol monomethyl (meth)acrylate, or EO-PO monomethyl (meth)acrylate.

Particularly suitable for the esterification of the ethylenically unsaturated

monocarboxylic acids, in particular acrylic or methacrylic acid, are the polyether alcohols themselves, preferably polyethylene glycols and polypropylene glycols, and also their unilaterally endgroup-capped derivatives, especially the corresponding monoethers, such as monoaryl ethers, e.g., monophenyl ethers, and especially mono- Ci-C26-alkyl ethers, examples being ethylene glycols and propylene glycols etherified with fatty alcohols, and the polyetheramines, which are preparable, for example, by conversion of a terminal OH group of the corresponding polyether alcohols or by polyaddition of alkylene oxides with preferably primary aliphatic amines. Preferred here are polyethylene glycols, polyethylene glycol monoethers, and polyetheramines. The average molecular weights M _n of the polyether alcohols and their derivatives that are used are customarily 200 to 10 000 g/mol. Preferred vinyl monomers are styrene, vinyltoluene, isobutene, diisobutene,

1-hexadecene, 1-octadecene, 1-eicosene, (meth)acrylic acid Ci-C22-alkyl esters, hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, polyethylene glycol monovinyl ether, polyethylene glycol methyl vinyl ether, (meth)acrylic acid, which are esterified with polyether alcohols or derivatives, and also combinations of these monomers.

More preferably the additives comprise at least one monomer which in the side chain contains a polyether alcohol group or a derivative thereof. In a preferred pigment preparation, therefore, the vinyl monomer and/or the

ethylenically unsaturated monomer in the copolymer of component (B) comprise a polyether alcohol group or a derivative thereof, more particularly from the group of the polyethylene glycol monovinyl ethers, the polypropylene glycol monovinyl ethers, the (meth)acrylic acids which are esterified with polyether alcohols, and the (meth)acrylic acids which are esterified with a monoether derivative of polyether alcohols.

Examples of monomers which comprise an N-containing group with pigment affinity include the following:

- acrylamide or methacrylamide;

- (meth)acryl-(Ci-C4-alkyl)i-2amides, such as N-methyl(meth)acrylamide,

N,N-dimethyl(meth)acrylamide, N-ethyl(meth)acrylamide or N,N-diethyl(meth)- acrylamide;

- maleimide and N-Ci-C4-alkylmaleimides, such as N-methyl- or N-ethylmaleimide, or N-arylmaleimides, such as N-phenylmaleimide;

- aminostyrene or (Ci-C4-alkyl)i-2amino-substituted styrene, such as 4-aminostyrene or 4-dimethylaminostyrene;

- N-mono-(Ci-C4-alkyl)i-2amino-C2-C4-alkyl(meth)acrylamides and N,N-di(Ci-C4- alkyl)i-2amino-C2-C4-alkyl(meth)acrylamides, such as 2-N-tert-butylamino- or 2-N,N-dimethylaminoethyl(meth)acrylamide or 2-N-tert-butylamino- or

2-N,N-dimethylaminopropyl(meth)acrylamide;

- vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylcaprolactam or Ci-C4-alkyl- substituted derivatives, e.g., 4-vinylpyridine, 2-vinylpyridine, 1 -vinylimidazole or 2-methyl-N-vinylimidazole;

- monomers of formula CH ₂ =C(-R ¹ )-C(=0)-R ² (II),

in which R ¹ is hydrogen or methyl, and

R ² is amino-substituted C2-Cis-alkoxy, selected from the group consisting of amino- C2-C4-alkoxy, Ci-C4-alkylamino-C2-C4-alkoxy, di-Ci-C4-alkylamino-C2-C4-alkoxy, hydroxy-C2-C4-alkylamino-C2-Ci8-alkoxy, and Ci-C4-alkyl(hydroxy-C2-C4- alkyl)amino-C2-C4-alkoxy.

Particularly suitable examples of the monomers having an N-containing group with pigment affinity are as follows:

- 4-aminostyrene, 4-dimethylaminostyrene;

- aminoalkyl (meth)acrylates (N-(Ci-C4-alkylamino)-Ci-C6-alkyl (meth)acrylates or N,N-di(Ci-C4-alkylamino)-Ci-C6-alkyl (meth)acrylates), selected from the group consisting of 2-dimethylaminoethyl acrylate (DMAEA), 2-dimethylaminoethyl methacrylate (DMAEMA), 2-diethylaminoethyl acrylate (DEAEA), 2-diethylamino- ethyl methacrylate (DEAEMA), 2-tert-butylaminoethyl acrylate (t-BAEA), 2-tert-butyl- aminoethyl methacrylate (t-BAEMA);

- 3-dimethylaminopropylmethacrylamide (DMAPMA),

- 4-vinylpyridine, 2-vinylpyridine, and 1-vinylimidazole. The amount of the monomers having an N-containing group with pigment affinity in the copolymer (B) is generally 2 to 55 mol%, preferably 2 to 50 mol%, more particularly 5 to 40 mol%. The copolymers of component (B) may be composed of two or more monomers, more particularly two to 8 different monomers. There may be random copolymers, alternating copolymers, block copolymers, comb polymers, and graft copolymers. The copolymers may be prepared by conventional methods of polymerization, as for example by radical polymerization or by controlled free radical polymerization, as described in

WO-A-2006/074969, for example.

Preferred copolymers are constructed from

(1 ) a monomer having an N-containing group of pigment affinity, selected from the group consisting of 4-aminostyrene, 4-dimethylaminostyrene, N-(Ci-C4-alkylamino)- Ci-C6-alkyl (meth)acrylates, N,N-di(Ci-C4-alkylamino)-Ci-C6-alkyl (meth)acrylates; 3-dimethylaminopropylmethacrylamide, 4-vinylpyridine, 2-vinylpyridine, and 1 -vinyl- imidazole;

(2) a monomer containing in the side chain a polyether alcohol group or a derivative thereof; and

(3) at least one further monomer from the group of the vinylaromatics and (meth)acrylic acid Ci-C22-alkyl esters.

The copolymers of component (B) customarily have average molecular weights M _w of 900 to 250 000 g/mol. The molecular weight ranges particularly suitable for the individual polymers are of course dependent on their composition. The copolymers (B) preferably have average molecular weights of approximately 900 to 20 000 g/mol.

The amount of component (B) is preferably 1 to 8 wt%, based on the total weight of the aqueous pigment preparation.

Component (C) of the pigment preparations of the invention is formed by additives based on lecithins and/or anionic additives based on phosphoric esters and/or phosphonic esters of polyalkylene oxides or of reaction products of alkylene oxides or aryl-substituted alkylene oxides, as for example phenyl-substituted ethylene oxide, with aliphatic alcohols, phenol or naphthol, each of which may also be substituted, with aliphatic or aromatic amines, aliphatic carboxylic acids or carboxamides, or the salts of these esters. Additives of these kinds are described for example in WO-A-2004/00903.

By reaction with phosphoric acid, phosphorus pentoxide or phosphonic acid, the alkoxylation products/polyether alcohol derivatives can be converted into the phosphoric monoesters and diesters or phosphonic esters, respectively. The anionic esters are preferably in the form of water-soluble salts, more particularly alkali metal salts, especially sodium salts, potassium salts, ammonium salts or organic ammonium salts. They may, however, also be used in the form of the free acids.

The polyether alcohol derivatives may be prepared by polyaddition of alkylene oxides with starter molecules, such as aliphatic or aromatic alcohols. It is usual to use 1 to 300 mol, preferably 3 to 150 mol, more particularly 3 to 50 mol of alkylene oxide per mole of starter molecule. The alcohols are reacted by known methods, with acidic or alkaline catalysis, for example. Suitable aliphatic alcohols contain generally 6 to 26 C atoms, preferably 8 to 18 C atoms, and may be straight-chain or branched in construction, and may also be unsaturated.

Examples of saturated alcohols are hexyl alcohol, heptyl alcohol, octyl alcohol (caprylyl alcohol), nonyl alcohol, decyl alcohol, isodecyl alcohol, undecyl alcohol, dodecyl alcohol (lauryl alcohol), 2-butyloctyl alcohol, tridecyl alcohol, isotridecyl alcohol, tetradecyl alcohol (myristyl alcohol), pentadecyl alcohol, hexadecyl alcohol (cetyl alcohol), 2-hexyldecyl alcohol, heptadecyl alcohol, octadecyl alcohol (stearyl alcohol), nonadecyl alcohol, eicosyl alcohol, docosyl alcohol, hydrated tallow alcohol, and combinations thereof.

Particularly suitable are alcohols of natural origin, such as capryl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosyl alcohol, oleyl alcohol, linoleyl alcohol, linolenoyl alcohol, ricinol alcohol, and combinations thereof.

Also particularly suitable are the saturated or unsaturated fatty alcohols obtained by lipolysis and reduction from natural raw materials, examples being fatty alcohols from coconut oil or palm kernel oil, as for example cocoyl alcohol or palm kernel oil alcohol. Also particularly suitable are the synthetic alcohols from the oxo process (also referred to as "oxo-process alcohols" or "oxo alcohols"). Oxo alcohols are linear and have no more than one branching point, examples being iso-Ci3-oxo alcohols and C13-C15-OXO alcohols. Suitable aromatic alcohols are phenol, 1 -naphthol, and 2-naphthol, which may be substituted by Ci-Ci2-alkyl, preferably Ci-C4-alkyl or C4-Ci2-alkyl, or by styryl, which may be substituted by methyl.

The polyether alcohol derivatives comprise unmixed polyalkylene oxides, preferably C2-C ₄ -alkylene oxides and phenyl-substituted C2-C ₄ -alkylene oxides, more particularly polyethylene oxide (PO), polypropylene oxide, and poly(phenylethylene oxide), block copolymers such as ethylene oxide/propylene oxide block copolymers and ethylene oxide/phenylethylene oxide block copolymers, or random copolymers of these alkylene oxides.

Suitable phosphoric and phosphonic esters are derived in particular from alkoxylated, more particularly ethoxylated, fatty alcohols, oxo alcohols, or substituted phenols.

Preferred are phosphoric esters of alkoxylated fatty alcohols, oxo alcohols, or phenols, such as phosphoric esters of the formula

[RO-(C ₂ -C ₃ -alkylene oxide) _y ]x-PO(OH) ₃ -x (I) in which

the radical R independently at each occurrence is linear or branched Cs-C22-alkyl, Cs- C22-alkenyl or phenyl which may be substituted one or more times by Ci-Ci2-alkyl, styryl or methyl-substituted styryl,

the (C2-C3-alkylene oxide) group is ethylene oxide and/or propylene oxide,

x = 1 or 2, and

y = 1 -100.

The group (C2-C3-alkylene oxide) _y is constructed preferably of -(CH2-CH2O)- and/or -(CH2 -CH(CH ₃ )0)-. In the case of mixed alkylene oxide units -(CH2-CH ₂ 0)m-(CH2- CH(CH3)0)n-, when m > 1 and n > 1 , more particularly m > 3 and n > 3 these may be of random or blockwise construction.

The group (C ₂ -C ₃ -alkylene oxide) _y is preferably -(CH2-CH20)m-(CH2-CH(CH ₃ )0)n- in which

m = 0-50; and n = 0-50;

with the proviso that m + n is at least 1 , more particularly at least 3.

The group (C2-C3-alkylene oxide) _y is more particularly -(CH2-CH20) _m -(CH2- CH(CH ₃ )0) _n - in which

m = 3-20; and n = 3-20;

with the proviso that m + n is at least 3.

Particularly preferred are phosphoric esters of the formula

[RO-(CH ₂ -CH ₂ 0) _m ]x-PO(OH)3-x (I) in which m = 3-20 and x = 1 or 2. Further preferred are phosphoric esters of the formula (I) in which the group (C2-C3- alkylene oxide) _y is a polyethylene oxide having 3 to 20, more particularly 5 to 20, units.

Further preferred are phosphoric esters of the formula (I) in which the group (C2-C3- alkylene oxide) _y comprises an ethylene oxide/propylene oxide block copolymer having in each case at least one ethylene oxide block of 3 to 20 units and at least one propylene oxide block of 3 to 20 units. Further preferred are phosphoric esters of the formula (I) in which the group (C2-C3- alkylene oxide) _y is a random copolymer of 3 to 20 ethylene oxide units and of 3 to 20 propylene oxide units. Particularly preferred are phosphoric esters of the formula

[RO-(C ₂ -C ₃ -alkylene oxide) _y ]x-PO(OH) ₃ -x (I) in which

the radical R independently at each occurrence is C8-C22-alkyl, C8-C22-alkenyl, distyrylphenyl, tristyrylphenyl, dibutylphenyl or tributylphenyl. Anionic surface-active additives of these kinds are known and are available commercially for example under the names Crodafos ^® (Croda), Rhodafac ^® (Rhodia), Maphos ^® (BASF), Dispex ^® (BASF), Empicol ^® (Albright & Wilson), Matexil ^® (ICI), Soprophor ^® (Rhodia) and Lutensit ^® (BASF), Strodex (Dexter), Hostphat ^® (Clariant). In one preferred embodiment, accordingly, the present invention relates to a pigment preparation where component (C) is a phosphoric ester of the formula

[RO-(C ₂ -C ₃ -alkylene oxide) _y ]x-PO(OH) ₃ -x (I) in which

the radical R independently of each occurrence is linear or branched Cs-C22-alkyl, Cs- C22-alkenyl or phenyl, which may be substituted one or more times by Ci-Ci2-alkyl, styryl or methyl-substituted styryl,

the (C2-C ₃ -alkylene oxide) group is ethylene oxide and/or propylene oxide, x = 1 or 2, and

y = 1 -100. Especially preferred is a pigment preparation where component (C) is a phosphoric ester of the formula

[RO-(C ₂ -C ₃ -alkylene oxide)y] _x -PO(OH) ₃ - _x (I) in which

the radical R independently of each occurrence is Cs-C22-alkyl, Cs-C22-alkenyl, distyrylphenyl, tristyrylphenyl, dibutylphenyl or tributylphenyl,

the (C2-C ₃ -alkylene oxide) group is ethylene oxide and/or propylene oxide, x = 1 or 2, and

y = 3-50.

With particular preference, furthermore, lecithins are part of component (C). Lecithins are phospholipids which are composed of fatty acids, glycerol, phosphoric acid, and choline. In this case the fatty acids may be saturated or unsaturated. The lecithins are generally in amphoteric form. Component (C) more preferably comprises lecithin or soylecithin. Preferred accordingly is a pigment preparation where component (C) comprises lecithins. As component (C) it is possible likewise to use combinations of lecithins and anionic phosphoric and phosphonic esters, more particularly phosphoric esters of the formula

(I)- The amount of component (C) is preferably 0.5 to 8 wt%, based on the total weight of the aqueous pigment preparation.

The optional component (D) is formed from various additives which are used customarily in aqueous pigment preparations for inks, paints, and renders. These additives may comprise, for example, humectants, rheological additives like thickeners, further dispersants, for example nonionic additives based on polyethers, and defoamers, foam suppressants, stabilizers such as biocides or fungicides,

antiflocculants, buffers, pH regulators, and pigment synergists. Additions of this kind are known for aqueous pigment preparations to the skilled person.

In one preferred embodiment, the invention relates to a pigment preparation where component (D) comprises 0 to 20 wt%, more particularly 0.1 to 20 wt%, of further additives customary to the production of aqueous pigment preparations, selected from humectants, rheological additives, dispersants other than (B) and (C), defoamers, foam suppressants, biocides, fungicides, antiflocculants, buffers, pH regulators, and pigment synergists.

Suitable humectants (component D1 ) are, for example, water-soluble polyethylene glycols, polyglycerols, glycerol alkoxylates, and alkoxylation products prepared by addition reaction of ethylene oxide(s) and/or propylene oxide(s) with polyhydric alcohols.

Suitable water-soluble polyethylene glycols are those having molecular weights of about 300 g/mol, 400 g/mol, 600 g/mol or the like, or polypropylene glycols having molecular weights of about 300 g/mol, 400 g/mol, 600 g/mol or the like.

Examples of polyglycerols are di-, tri- and tetraglycerols or combinations thereof.

Glycerol alkoxylates may for example be glycerol ethoxylates having a molecular weight of about 200 to about 1000 g/mol.

Alkoxylation products prepared by addition reaction of ethylene oxide(s) and/or propylene oxide(s) with polyhydric alcohols may be, for example, trimethylol alkoxylates or pentaerythritol alkoxylates having a molecular weight of about 200 to about 1000 g/mol.

The humectants are added generally in an amount of 0.01 to 15 wt%, preferably 3 to 12 wt%, based on the total weight of the pigment preparation. Figures for molecular weight of the polymers are based fundamentally on their number- average molecular weight. Molecular weights are to be determined by GPC against polyethylene glycol as standard.

Dispersants (component D2) are preferably nonionic dispersants based on polyethers, as described for example in WO-A-2004/046251 as component (C). The polyethers more particularly are polyalkylene oxides or reaction products of alkylene oxides or aryl-substituted alkylene oxides, especially phenyl-substituted ethylene oxides, with alcohols, amines, aliphatic carboxylic acids or aliphatic carboxamides. Alkylene oxide adducts of this kind may be formed, for example, with monofunctional amines and alcohols, but also with amines and alcohols having a functionality of at least two.

Additives which may be used as component (D2) are known commercially, for example, under the Tetronic ^® , Rhodoline ^® or Lutensol ^® designation.

Preference is given to using ethylene oxide/propylene oxide block copolymers, fatty alcohol ethoxylates, and fatty alcohol-ethylene oxide/propylene oxide adducts as further dispersants. The amount of nonionic dispersant (D2) is preferably up to 5 wt%, based on the total weight of the aqueous pigment preparation.

As further dispersants it is also possible for water-soluble anionic surface-active additives (D3) from the group of the homo- and copolymers of ethylenically unsaturated monocarboxylic acids and/or ethylenically unsaturated dicarboxylic acids, which further comprise, in copolymerized form, vinylmonomers containing no acid function, and of the salts of these homo- and copolymers to be included.

Examples of the carboxyl-containing monomers and the vinylmonomers are the above monomers which form component (B).

Preferred copolymers include styrene/acrylic acid, acrylic acid/maleic acid, acrylic acid/methacrylic acid, butadiene/acrylic acid, isobutene/maleic acid, diisobutene/maleic acid, styrene/maleic acid, and polyethylene glycol monovinyl ether/maleic acid copolymers, each of which may comprise, as additional monomer constituents, acrylic esters, maleic esters and/or 1-alkenes such as 1 -hexadecene, 1 -octadecene, or 1 - eicosene.

Defoamers may be included in the preparation in small amounts (0.01 to 0.2 wt%, based on the total weight of the pigment preparation, from the companies Tego, Byk, and Borchers, for example). Suitable defoamers are preferably mineral oil defoamers, polyether-modified polysiloxanes, silicones, polysiloxanes, vegetable oils, polymer- based defoamers such as modified fatty acids, polyethers, polyacrylates, silicon oils, or modified amides. Foam suppressants as well, known for example commercially under the Degressal ^® name, may be included in an amount up to about 5 wt%, based on the total weight of the pigment preparation.

The pigment preparations may further comprise biocides, including fungicides, in small amounts (0.01 to 0.5 wt%, based on the total weight of the pigment preparation), from the companies Thor, and Rohm & Haas, for example.

Rheological additives may be added in an amount of about 0.01 to 2 wt%, based on the total weight of the pigment preparation. Preference is given to adding thickeners, such as organophyllosilicates, cellulose derivatives, polyurethane thickeners, hydrated castor oil, polyamides, sulfonates, or silica.

Pigment synergists may likewise be present in the pigment preparation, examples being compounds which comprise a pigment chromophore wholly or partly in their molecular structure and preferably have acidic or basic groups, as for example those disclosed in WO-A-2010/057864. The structure of the pigment synergist need not be the same as the structure of the pigment employed. Where a pigment synergist is present, the amount may be in the range from 0.01 to 5 wt%, preferably 0.1 to 3 wt%, based on the total weight of the pigment preparation.

The pigment preparations present are preferably substantially free from surface-active agents based on alkylphenol ethoxylates. These surface-active agents are commonly prepared from reaction products of branched nonylphenol or octylphenol with ethylene oxide. The term "substantially free from alkylphenol ethoxylates" means that the amount of alkylphenol ethoxylates is less than about 0.1 wt%, based on the total weight of the pigment preparation. With further preference the pigment preparations are free from alkylphenol ethoxylates.

The pigment preparation of the invention is preferably in the form of a paste. It is further preferred for the pigment composition of the invention to be fluid and pumpable. The present pigment preparation preferably has a viscosity of less than 3000 mPa.s, measured using a cone/plate rheometer (e.g., Rheo Stress RS 600, from Thermo) at a shear rate of 20 sec ^-1 . The amount of water in the present pigment preparation may be up to 60 wt%, more particularly from 10 to 50 wt%.

Subject matter of the present invention, furthermore, is a method for producing the present pigment preparation,

where first of all components (A) to (C) and at least part of component (D) are introduced into water, the resulting suspension is subjected to wet comminution, and optionally the remaining amount of component (D) is subsequently added to the suspension. With preference, in succession, the components (B), (C), and at least part of the additives (D), such as defoamers and biocides, are introduced into water and subsequently the pigment component (A) is added.

In the method, component (A) may be used in the form of dry powder or as a presscake. With preference an aftertreated product is used, meaning that the primary particle size of the pigment component has already been set to the value desired for the application. This aftertreatment is advisable especially in the case of organic pigments, since the as-synthesized crude pigment is generally not suitable directly for the application. In the case of inorganic pigments, as with oxide pigments and bismuth vanadate pigments, for example, the primary particle size may also be set during pigment synthesis, and so the pigment suspensions obtained can be used directly in the method of the invention.

Since the aftertreated pigment component (A) frequently undergoes reagglomeration again in the course of drying and/or on the filter assembly, it is subjected to wet comminution, such as to grinding in a stirred ball mill, for example, in aqueous suspension.

The wet comminution ought to be carried out with at least some of the additive (D) comprised in the completed pigment preparation; it is preferable to add defoamers, fractions of biocides, and nonionic dispersants prior to wet comminution. Remaining additives (D) such as biocides, fungicides, pigment synergists, humectants, antiflocculants or rheological additives may also be added only after the grinding.

Thickeners may be added in during wet grinding, and also after the grinding, in order to set the viscosity desired for the pigment preparation. A further subject of the present invention is the use of the pigment preparation as mentioned above for coloring paints, inks, and renders, preferably in metering systems and tinting apparatus at the point of sale, or in in-plant tinting systems.

The pigment preparations of the invention are notable for outstanding performance properties, in particular for high color strength and ready dispersibility in application media of different kinds. They are suitable especially as universal pigment

preparations, meaning that they are compatible both with aqueous emulsion paints, for example even with very alkaline hydrophilic silicate paints, and with solventborne paints. The resulting solventborne paints and emulsion paints do not show any color change in the rubout test as described in DE-A-2202527.

The preparations are low in VOC and in SVOC and meet all of the requirements of customary eco labels. Furthermore, in the tinting of the emulsion paints and solventborne paints, they exhibit high accuracy in metering, even at very small amounts of 0.1 ml, and also directly after introduction into the metering-system containers, allowing the usual waiting time of around one day to be done away with.

The pigment preparations are stable and do not dry on the inner walls of the containers or in the metering system, such as in open nozzles, for example, thereby ensuring consistent coloristic performance.

Examples

Production of the pigment preparation

A suspension of pigment component (A), additives (B), (C), and (D) in water (in the case of pH levels < 7, adjusted to a pH of 7-9 by addition of aqueous sodium hydroxide solution (25 wt% strength solution)) was ground in a ball mill to a dso of < 1 μηη. The pigment preparations contain ingredients as below, based in each case on the total weight of the preparation.

Ingredients of the exemplary pigment preparations

In the examples, the amount of component (B) and (C) is based on each of the components used, in the form of solutions.

Component A

I rgalite ^® Yellow L 1254 HD (C.I. Pigment Yellow 74)

Bayferrox ^® 943 (C.I. Pigment Yellow 42)

Bayferrox ^® 130 (C.I. Pigment Red 101 )

Furnace black (C.I. Pigment Black 7)

Filler: talc

Component B

B-1 aqueous solution (50 wt%) of a random copolymer of 62 wt% methacrylic acid mPEG ester (M„ 350); 10 wt% ethylhexyl acrylate, 10 wt% vinylimidazole, 9 wt% vinyltoluene, and 9 wt% hydroxyethyl methacrylate.

B-2 aqueous solution (50 wt%) of a copolymer, prepared as per example A6 from

WO-A-2006/074969 Component C

C-1 : potassium salt of a phosphoric ester based on an ethoxylated C12/C14 fatty alcohol

(12 EO) (25 wt% aqueous solution)

C-2: potassium salt of a phosphoric ester based on an ethoxylated tristyrylphenol (16

EO) (25 wt% aqueous solution)

Lecithin

Example 1

45 wt% Irgalite Yellow L 1254 HD 5 wt% B-1

10 wt% C-1

1 wt% foam suppressant 10 wt% PEG 400

0.4 wt% biocide

0.5 wt% defoamer

remainder water

Example 2

45 wt% Irgalite Yellow L 1254 HD 10 wt% B-1

5 wt% C-1

1 wt% foam suppressant 10 wt% PEG 400

0.4 wt% biocide

0.5 wt% defoamer

remainder water

Example 3

45 wt% Irgalite Yellow L 1254 HD 10 wt% B-1

10 wt% C-2

3 wt% lecithin

1 wt% foam suppressant 10 wt% PEG 400

0.4 wt% biocide

0.5 wt% defoamer

remainder water

Example 4

45 wt% Irgalite Yellow L 1254 HD 5 wt% B-1

5 wt% C-2

3 wt% lecithin

1 wt% foam suppressant 10 wt% PEG 400

0.4 wt% biocide

0.5 wt% defoamer

remainder water

Example 5

45 wt% Irgalite Yellow L 1254 HD 10 wt% B-1 3 wt% lecithin

1 wt% foam suppressant

10 wt% PEG 400

0.4 wt% biocide

0.5 wt% defoamer

remainder water

Examples 1a to 5a

The compositions of examples 1 a to 5a correspond to those of examples 1 to 5 apart from the fact that they contain the same amount of B-2 instead of B-1.

Example 6

55 wt% Bayferrox 943

5 wt% B-2

4 wt% C-1

3 wt% lecithin

1 wt% foam suppressant

10 wt% PEG 400

0.4 wt% biocide

0.5 wt% defoamer

remainder water

Example 7

55 wt% Bayferrox 943

5 wt% B-2

4 wt% C-1

1 wt% foam suppressant

10 wt% PEG 400

0.4 wt% biocide

0.5 wt% defoamer

remainder water

Examples 6a and 7a

The compositions of examples 6a and 7a correspond to those of examples 6 and 7 apart from the fact that they contain the same amount of C-2 instead of C-1.

Examples 6b and 7b

The compositions of examples 6b and 7b correspond to those of examples 6 and 7 apart from the fact that they contain 60 wt% Bayferrox 130 (C.I. Pigment Red 101 ) instead of 55 wt% Bayferrox 943. Examples 6c and 7c

The compositions of examples 6c and 7c correspond to those of examples 6a and 7a apart from the fact that they contain 60 wt% Bayferrox 130 (C.I. Pigment Red 101 ) instead of 55 wt% Bayferrox 943.

Example 8

8 wt% Furnace black

30 wt% talc

8 wt% B-1

8 wt% C-1

2 wt% Lecithin

1 wt% foam suppressant

10 wt% PEG 400

0.4 wt% biocide

0.5 wt% defoamer

remainder water

Example 9

8 wt% Furnace black

30 wt% talc

12 wt% B-1

12 wt% C-1

3 wt% Lecithin

1 wt% foam suppressant

10 wt% PEG 400

0.4 wt% biocide

0.5 wt% defoamer

remainder water Examples 8a and 9a

The compositions of examples 8a and 9a correspond to those of examples 8 and 9 apart from the fact that they contain the same amount of C-2 instead of C-1.

Application systems:

(1 ) Waterborne emulsion paint based on styrene/acrylate, with a white pigment content of 16.4 wt% (Ti0 ₂ , Kronos 2043) (test binder 00-1067, BASF)

(2) Aromatics-free, air-drying white alkyd gloss paint (60-69 wt% solids fraction), aliphatic solvents (Rubbol; Akzo Nobel)

(3) Water-repellant spreadable silicate-based masonry paint (Granital ^® , Keim), T1O2 pigment content 15.2 wt%

(4) low-VOC/SVOC emulsion paint based on Acronal DS 6282X (pigment volume concentration 41 %) The pigment preparations of examples 1 to 9a were added to the test systems (1 ) to (3) in each case in a dispenser (Corob D410):

Dispenser: Corob D410, minimum metering quantity of 0.1 ml; pump accuracy 0.01 ml Test 1 : Calibration of the 0.1 ml metering directly after introduction

Even after direct metering of 0.1 ml after introduction, deviations only of 10% at most were found by measurement. This figure is frequently not achieved until after a waiting time of 1 day. Test 2: Reproducibility

Even after 8 weeks, the accuracy of the 0.1 ml metering remained < 10%. Under the storage conditions of the dispenser and in the containers, the paste remained unchanged. No change was observed in the rheology, and no sedimentation of the pigment component; the coloristic properties remained unchanged (change in color strength after 8 weeks ΔΕ < 0.5).

The color strength of the pigment preparations was determined by colorimetry as a white reduction (Datacolor SF600; standard illuminant D65). For this purpose, a mixture of 2.5 of each of examples 1 to 7 and 50 g of application system 1 was homogenized in a plastic beaker, using a high-speed stirrer at 1500 rpm, for 3 minutes. The paint obtained was then drawn down using a 100 μηη coil blade onto black/white test cardboard, and dried for 30 min.

Test 3: Conditioning of the dispenser as a whole at 35°C

The metering properties were retained.

Test 4: Drying of the pigment preparations in the nozzles

Recordings of the nozzles made with a video camera during the metering operations showed no significant drying of the pigment preparations on and in the nozzles even after 8 weeks (metering 1 x/week). No hanging drops were observed either.

Test 5: VOC/SVOC measurement

10 wt% of the pigment preparations of examples 1 -9a (based on the total weight of the pigment preparation and application system) were added to the application system (4). The VOC and SVOC contents were determined by chamber emission method according to DIN EN ISO 16000. Measurements were made of the VOC and SVOC values after 3 and after 28 days, with the following requirements concerning the air: VOC <10 mg/m ³ after 3 days and < 1 mg/m ³ after 28 days

SVOC < 0.1 mg/m ³ after 28 days

All of the examples met the requirements.

Test 6: Rubout test The rubout test in accordance with DE-A-2202527 was carried out for examples 1 to 9a, in each case in all 4 application systems. In no case was any change in shade observed.