DE4020272A1 - PIGMENTS BASED ON DOUBLE-LAYER HYDROXIDES, PROCESS FOR THEIR PREPARATION AND THEIR USE - Google Patents

Abstract

The invention concerns water-insoluble pigments based on double-layer hydroxides and water-soluble dyes, the pigments being obtained by reacting double-layer hydroxides formed in situ and water-soluble anionic dyes. The invention also concerns suitable processes for the production of pigments of this kind for use as the colour medium in washing and cleaning agents, soaps, cosmetics, lacquers, paints, foddstuffs, plastics and other polymers.

Description

The present invention relates to water-insoluble pigments the basis of bilayer hydroxides and water-soluble color materials, a process for their preparation and their use.

Bilayer hydroxides are known in the literature, for example R. Allmann, "Chimia" 24 (1970), p. 99 ff. Chemically they mixed basic hydroxo salts of divalent and trivalent metal cations.

Natural and synthetic double-layer hydroxides give the Er heat or calcine continuously from water. The crystalwas This is completely removed at 200 ° C, higher temperatures ren for the removal of water from the hydroxide skeleton and of Carbon dioxide from the carbonate contained as usual anion. The Structures of bilayer hydroxides become involved in this process degraded, the X-ray diffraction diagrams show only broad and little characteristic lines for periclase (MgO). Due to the un different composition, also with regard to the water content, are line broadening and displacements in X-ray diffraction to explain diagram.

From about 200 ° C is more or less continuously, if anwe send, CO ₂ and water from the decomposing hydroxide abge abge split, with around 400 ° C in a DTA diagram again a significant Lich endothermic peak occurs (WT Reichle, "Chemtech "(January 1986), page 58). In this calcination, the bulk density is reduced, the pore volume increases and the specific surface area increases.

If the calcination temperature does not significantly exceed 600 ° C, so the processes are reversible: the mixed oxide forms under water and anions up the layered compound back. At higher tem In the end, the poorly organized mixed oxide finally goes into good crystalline and less reactive products and ultimately spinel and MgO over.

In EP-A-02 06 798 water-insoluble pigments consisting from a complex of a water-insoluble inorganic substrate with anion-exchanging properties, especially magnesium or aluminum-containing bilayer hydroxides, a water soluble dye and an anionic amphiphilic material, be wrote. The amphiphilic material is convenient to organic fatty acids or their salts, as well as to sulfonated organic compounds. As a suitable double-layer hydroxide is here, for example, called synthetic hydrotalcite, as water soluble dyes, for example, anionic organic dyes substances. According to the method described here are such water-insoluble pigments prepared by the already before formed bilayer hydroxide, the dye and the amphiphilic Material in a liquid medium, such as water mitein other contact.

In a publication by S. Miyata in "Clays and Clay Minerals ", 28, No. 1, pp. 50-56, 1980, are physico-chemical eggs properties of synthetic hydrotalcites, which is a typical class se of said double-layer hydroxides, described. Thus, the chemisorption of naphthol yellow S - depending on the Molar ratio of aluminum to magnesium and aluminum -  certainly. For this purpose, the previously synthesized hydrotalcite in a introduced aqueous solution of the dye, the solids abfil triert and determines the residual amount of the dye in the filtrate.

In contrast, the object of the present invention is new water-insoluble pigments based on bilayer Hydroxides and water-soluble dyes are available len, which - compared with those of the prior art due to greater stability against chemical and physical agents as well as a higher occupancy rate Distinguish such dyes.

The present invention accordingly relates to novel water-insoluble Pigments based on double-layer hydroxides and water-soluble union dyes, which are characterized in that they can be obtained by reacting in situ forming double layer hydroxides and water-soluble anionic dyes in aqueous or aqueous media, the in situ bil double-layer hydroxides have the general formula (I)

in which
M ^II for at least one divalent metal cation,
M ^III for at least one trivalent metal cation,
A is the equivalent of an anion of a mono- or more basic acid,
1/6 x 1/2 and
0 m 1 stands.

The pigments according to the invention which form with in situ Double layer hydroxides are recovered, have opposite to the  the prior art known pigments which are obtained by adsorption of the Dyes to already preformed bilayer hydroxides Herge obviously major structural differences on. Surprisingly, it was found that the Sta bilität of the pigments according to the invention in the light fastness test and compared to oxidizing agents is significantly greater than the ver comparable colored bilayer hydroxide pigments of the prior art of the technique. In addition, the nature of the production of the invention requires proper pigments, that this is a much larger amount of anio niche dyes in the forming bilayer structure incorporate than the known pigments of the prior art. These Property is hereinafter also referred to as "higher occupancy density" characterized (see the examples). The above Differences are all the more surprising than to actually accept would have been that an already preformed double-layer hydroxide should impart the same properties to the pigments as one in situ, bilayer hydroxide forming.

A preferred embodiment of the present invention is that in the pigments, the divalent metal cation (M ^II ) is selected from among magnesium, calcium, manganese, iron, cobalt, nickel, copper, zinc and cadmium, while the trivalent metal cation (M ^III ) preferably made of aluminum or chromium manganese, iron, cobalt and nickel. If the above - in connection with the refining of the general formula (I) - of at least one divalent or trivalent metal cation is mentioned, it means that in such double-layer hydroxides, if necessary, in each case several divalent or trivalent metal cations next to each other can.

In principle, the anion (A) may also consist of a case of on or off polybasic acids are selected. According to the invention preferred  Anions include hydroxide, chloride, bromide, iodide, nitrate, chlorate, Perchlorate, carbonate, sulphate, thiosulphate, tungstate, chromate and Hexacyanoferrat and in principle also a large number of organic Anions, for example, picrates.

All mentioned variations of divalent metal cat ions, the trivalent metal cations and the anions are prin basically known from R. Allmann (loc cit.).

Particularly preferred are pigments based on in situ themselves forming bilayer hydroxides selected from hydro talcite, zinc / aluminum phase, magaldrate and / or pyroaurite.

Hydrotalcite is known to be a natural mineral with the ideal formula

[Mg₆Al₂ (OH) ₁₆] CO₃ · 4H₂O,

whose structure is derived from that of brucite (Mg (OH) ₂ ). The synthesis of hydrotalcite is described, for example, in DE-C-33 06 822, DE-A-33 46 943 and DE-A-15 92 126.

The choice of water-soluble, anionic dyes is not critical, because in principle all commercially available or syn ethylenically preparable water-soluble anionic dyes for Production of pigments are suitable. An essential advance however, the anionic character of the dyes is since neutrally charged or positively charged dyes only very ge rings affinity for said double-layer hydroxides aufwei sen.  

However, preferred are water-soluble, organic, anionic color substances selected from the group of anthraquinone or naph tholfarbstoffe. Exemplary for this purpose are the following dyes Alizarin Red S, Nitroso R, Acid Green 41 and Naphthol Yellow S.

Such water-soluble, organic, anionic dyes within the meaning of the invention also count so-called "optical brighteners", as commonly used in detergent formulations the, for example, the disodium salt of 4,4'-bis (1,3,5-tri azinyl- (6) -amino) -stilbene-2,2'-disulphonic acid (= Blankophor® BBH, Bayer AG) or 4,4'-distyrylbiphenyl derivatives (= Tinopal® CBS-X, Ciba-Geigy AG).

Another object of the present invention is a Verfah ren for the preparation of the above, water-insoluble pigments based on double-layer hydroxides and water-soluble Dyes. This method is characterized in that in-situ forming bilayer hydroxides and water-soluble anionic dyes in aqueous or aqueous media with with each other, with the bilayer forming in situ forming Hydroxides the general formula (1)

in which M ^II , M ^III , A, x and m are as defined above.

For the purposes of the invention, to enforce the method - in view of the bilayer hydroxides forming in situ - in principle, two possibilities: According to a first embodiment Form of the method according to the invention is in this case of the corresponding, previously calcined bilayer hydroxides,  whose crystal structure is a disordered mixed oxide of said represents divalent and trivalent metal cations. In the implementation with the anionic dyes in the said aqueous media The structure of the mixed oxide structure is formed in situ in situ Bilayer hydroxides back. For the purposes of the invention are here preferably such calcined bilayer hydroxides are incorporated previously calcined at temperatures up to about 600 ° C.

This first embodiment of the method according to the invention is Consequently, characterized in that the in situ formation of the Bilayer hydroxides of the general formula (I) previously calci nierte double-layer hydroxides of the general formula (I). These previously calcined bilayer hydroxides are powdered or in the form of an aqueous slurry, optionally may also contain polar organic solvents, preferably while stirring with a solution of anionic, organic color substances in contact. Subsequently, the solids content separated from the supernatant solution. Here it is without Be indicates whether a suspension of the calcined bilayer Hydroxides gives a solution of dyes, or to a solution of dyes, a suspension of the calcined bilayer Hydroxides are. Measures for separating the solids content, d. H. the resulting wet pigment from the supernatant solution, are known in principle to the person skilled in the art. Examples are le simply called decantation or filtration.

The second process variant of the present invention is that the preparation of the pigments is performed by in situ precipitation (also sometimes referred to as flash or conti precipitation) of the bilayer hydroxides in the presence of the anionic dyes. In this case, the water-soluble salts of double-layer hydroxides Me tallcationen in the desired stoichiometric ratio to be added to an aqueous or aqueous solution of an anionic dye and formed by increasing the pH of the double-layer hydroxides in the presence of water-soluble anionic dyes. The reaction of the in situ forming bilayer hydroxides with the anionic dyes is thus carried out in this process variant during the flash precipitation in the alkaline Be rich, ie at pH values of <7, preferably in the pH range of 9 to 13. The setting the aqueous or aqueous medium to the desired pH is carried out, for example, by adding the hydroxides of said metal cations (M ^II ) and (M ^III ) or by addition of alkali metal hydroxides, such as sodium hydroxide. During the reaction, the resulting suspension is stirred and the resulting solids content - as described above - separated from the supernatant solution. The so-called flash precipitation of double-layer hydroxides is generally described in EP-A-02 07 811.

The second embodiment of the method according to the invention is therefore characterized in that the preferably water-soluble salts of the metal cations (M ^II ) and (M ^III ) is used for in situ formation of the bilayer hydroxides of the general formula (I), wherein the pH of the aqueous or aqueous medium to alkaline values, preferably to pH values in the range of 9 to 13. As the water-soluble salts of the metal cations (M ^II ) and (M ^III ), in particular the salts of said Me cation with the above-defined anions (A) in Be costume, but also the oxides or hydroxides of these metal cations can be used according to the invention.

Preferably, water is the solvent, i. H. as an aqueous Me dium, for the inventive method suitable.  

However, since in particular by the presence of polar organic Solvent the solubility of water-soluble, anionic In some cases, it is possible to improve dyes in some cases the presence of these solvents is preferred, so that the formation the pigments in solvent mixtures of water and polar or ganic solvents is carried out, the latter esp especially short-chain alcohols, preferably methanol, ethanol and / or propanol, as well as ketones and especially here Acetone. The mixing ratios of water to organic Lö usually range from 5: 1 to 1: 5, preferably in the range of 1: 3 to 3: 1 and in particular at 1: 1.

The temperature of the reaction of the double forming in situ Layered hydroxides and dyes are not critical. Preferably the reaction is carried out at room temperature, although each Temperature between the melting point and the boiling point of Lö is suitable. By applying pressure, the Tempe If appropriate, the solvent may also be above normal Boiling point can also be increased, if this is for the sake of Lös sensitivity of the dye in special cases is desired.

Following the preparation of the pigments of the invention kön NEN this in a particular embodiment known per se th methods are rendered hydrophobic. This happens in particular by adding sodium salts of fatty acids, as in principle EP-A-02 06 798 for the water-insoluble described therein Pigments is known.

The use of the pigments of the invention are virtually none Set limits. However, the pigments are preferred as color carriers in detergents, dishwashing detergents and cleaners, soaps, cosmetics,  Paints, coatings, foodstuffs, plastics and polymers used.

As well as classical dyes with absorptions in the range of visible light also ultraviolet radiation absorbing color substances, for example optical brighteners, can be used NEN, it is possible to provide the invention provided Pigments also as a carrier for optical brighteners in detergents use.

In particular, after a later made hydrophobing of he retaining pigments is a further improved stability To detect light and oxidants.

From the examples described below it is clear that the According to the invention produced pigments significantly better physi have kalische stabilities than comparable pigments, the the literature are known.

To investigate the lightfastness of the pigments with Alumi triturated and with water to a spreadable paste thickened. After a longer irradiation time with a xenon Lamp color differences occur to the non-irradiated sites. The pigments of the invention show a significantly lower Brightening compared to pigments of the prior art.

In the treatment of pigments with oxidizing agents, such as Hypo Chlorite solution, you will also find a significantly increased color stability of the pigments of the invention in comparison to the pure dye solutions, resulting in the use of such Pigmen te in bleach-containing suspensions, for example in liquid detergent formulations, is of particular advantage.

Examples

In the examples below, the following abbreviations are used:
HT = hydrotalcite
cal. HT = calcined hydrotalcite,
flash HT = "flash" precipitated hydrotalcite.

Whenever "calcined hydrotalcite" is mentioned below, so this is generally understood to mean a product which by Er heat from commercially available hydrotalcite to 500 ° C over 2 Hours (mass loss about 40 wt .-%) was produced.

The term "flash-precipitated hydrotalcite" becomes a product which is obtained by in situ synthesis of the hydrotalcite from the corresponding metal salts was prepared.

Examples 1 to 6 relate to the preparation of fiction corresponding pigments based on in situ forming hydro Talcit from previously calcined hydrotalcite and also their Bele Density with different anionic dyes. The Ver Examples 1 and 2 show corresponding values for not Inventive pigments according to the prior art.

Examples 7 and 8 relate to the preparation of erfindungsge According pigments on the basis of flash-precipitated hydrotalcite and their occupation density. In Examples 9 to 11, the Her position of pigments according to the invention on the basis of others, in situ forming bilayer hydroxides shown.

Examples 12 to 14 and Comparative Example 3 relate to Light fastness and oxidation stability of the invention  Pigments, again in comparison to prior art pigments technology. In Example 15, the occupation density of inventive Pigments when using different solvents and in Example 16 the preparation of hydrophobicized, inventive Pigments shown.

example 1

50 ml of an aqueous dye solution containing 1 g / l alizarin red S Hydrate were used with different amounts of calcined hydrotal cits and stirred for 30 min at 20 ° C. After this time the suspension was filtered or centrifuged and the residual Dye concentration determined photometrically.

Table 1 below gives the residual concentrations obtained to dye in the supernatant solution again.

Table 1 cal. HT (g / l) Restkonz. (Mg / l) 1.04 782 1.52 578 2.02 377 3.0 7 4.0 <1 5.0 <1

Example 2

50 ml of an aqueous dyestuff solution with 2 g / l Alizarin Red S hydrate were ver with different amounts of calcined hydrotalcite ver set and stirred for 30 min at 20 ° C. After that time, the The suspension is filtered or centrifuged and the residual Farbstoffkon Center determined photometrically.

Table 2 below shows the data obtained.

Table 2 cal. HT (g / l) Restkonz. (Mg / l) 2.0 1155 4.0 637 5.0 627 5.6 184 6.0 131 6.5 71 7.0 13 10.0 <1

Example 3

50 ml of an aqueous dye solution containing 1 g / l of nitroso-R Salt was mixed with varying amounts of calcined hydrotalcite added and stirred for 30 min at 20 ° C. After that time was the suspension is filtered or centrifuged and the residual color substance concentration determined photometrically.  

Table 3 below shows the data obtained.

Table 3 cal. HT (g / l) Restkonz. (Mg / l) 1 674 2 549 3 493 4 354 7 173 10 75 12 49 14 26 16 7 18 3 20 <2

Comparative Example 1

50 ml of an aqueous dye solution containing 1 g / l alizarin red S Hydrate were not calcined with different amounts Hydrotalcits and stirred for 30 min at 20 ° C. After this Time the suspension was filtered or centrifuged and the Residual dye concentration determined photometrically.

Table 4 below shows the data obtained.  

Table 4 non-cal. HT (g / l) Restkonz. (Mg / l) 2 803 5 532 6.5 410 8th 317 10 7 12 7 14 5 16 <1

Comparative Example 2

50 ml of an aqueous dye solution containing 1 g / l of nitroso-R Salt was mixed with varying amounts of uncalcined hydro talcits and stirred for 30 min at 20 ° C. After this time the suspension was filtered or centrifuged and the residual Dye concentration determined photometrically.

Table 5 below shows the data obtained.  

Table 5 non-cal. HT (g / l) Restkonz. (Mg / l) 20 549 40 270 60 131 70 105 80 84 90 68 100 46

Example 4

300 mg of calcined hydrotalcite were added to a solution of 50 ml of alizarin red S (c ₀ = 2 g / l) and 150 ml of dist. Added water and stirred at 20 ° C for 30 min. After this time, the residual dye content of 130 mg / l was determined photometrically after filtration. The occupation density is calculated to be 0.86 mmol / g.

X-ray diffraction diagram of the dried product (Cu K _α ):

The deep-colored sample was calcined at 500 ° C for 2 h. It There remained a greyish powder that calculated mass loss 60.6%. The prepared X-ray diffractogram showed the Lines for calcined hydrotalcite.  

X-ray diffraction diagram of the calcined product (Cu K _α ):

Determination of the coverage with nitroso-R salt: 150 mg of calcined hydrotalcite were added to a solution of 50 ml of nitroso-R salt solution (c ₀ = 1 g / l) and 100 ml of distilled water and the procedure described above , The residual content of dye gave 490 mg / l, the coverage thus 0.45 mmol / g.

X-ray diffraction diagram of the dried product (Cu K _α ):

When heated to 500 ° C disappeared in this pigment, the Colour. There was a white product left.

Example 5

50 ml of an aqueous dye solution containing 1 g / l Acid Green 41 were ver with different amounts of calcined hydrotalcite ver and stirred for 30 min at 20 ° C. After that time, the The suspension is filtered or centrifuged and the residual Farbstoffkon Center determined photometrically.

Table 6 below shows the data obtained.  

Dye: Acid Green 41 cal. HT (g / l) Restkonz. (Mg / l) 0.40 670 0.60 458 1.40 54 2.00 <1 2.60 <1

Example 6

50 ml of an aqueous dye solution containing 1 g / l naphthol yellow S were mixed with different amounts of calcined hydrotalcite added and stirred for 30 min at 20 ° C. After that time was the suspension is filtered or centrifuged and the residual dye concentration determined photometrically.

Table 7 below shows the data obtained.  

Dye: naphthol yellow S cal. HT (g / l) Restkonz. (Mg / l) 0.60 752 1.40 572 2.00 415 2.60 274 3.40 152 4.00 85

Example 7

It describes the preparation of a pigment of the invention based on 10 mmol flash-precipitated hydrotalcite, starting from a solution of 15.4 g Mg (NO ₃ ) ₂ × 6 H ₂ O (60 mmol) and 7.5 g Al (NO ₃ ) ₃ × 9 H ₂ O in 500 ml of water. The above solution was added with vigorous stirring to an alkaline solution containing 7.2 g of alizarin sulfonate (= alizarin red S hydrate). This was an intensely colored precipitate. After the end of the addition of the metal salt solution was stirred for a further 2 h. In the filtered mother liquor, a concentration of alizarin sulfonate of only 13.6 mg / l was found. The coverage then calculated to be 1.18 g per g of hydrotalcite or 3.29 mmol / g.

Example 8

Analogously to Example 7 was added to the metal salt solution mentioned therein additionally containing alizarin sulfonate (total volume 3 l),  a solution of 30 g of 50% sodium hydroxide in 50 ml of water given to vigorous stirring. This was also an intense colored precipitate. Photometric became a residual color concentrate determined concentration of 135 mg / l. After that there was an occupancy density of 1.11 g per g of hydrotalcite, or 3.09 mmol / g.

Example 9

50 ml of an aqueous dye solution containing 1.0 g / l alizarin sulfonate and 300.8 mg of a calcined Zn / Al phase (general formula I = x = 0.18, A = CD ₃ ^2- ) were prepared analogously to Example 1 He heated a Zn / Al phase to 500 ° C over 2 hours, loss of mass about 40 wt .-% - given and stirred for 30 min at 20 ° C. After this time, the suspension was filtered or centrifuged zen and the residual dye concentration of 737 mg / l be true. The coverage density was thus D, 12 mmol / g.

Example 10

Analogously to Example 1, 50 ml of an aqueous dye solution containing 1.0 g / l alizarin sulfonate with 299.6 mg of calcined magaldrate (magaldrate = (Mg ₁₀ Al ₅ (OH) ₃₁ ) (SO ₄ ) ₂ × nH ₂ O) - prepared analogously Example 9 - added and stirred for 30 min at 20 ° C. After this time, the suspension was filtered or centrifuged and the residual dye concentration was determined photometrically to be 784 mg / l. The occupation density is calculated as D, 10 mmol / g.

Example 11

As in Example 1, to a solution of 519.8 mg Alizarinsul fonate in 300 ml of water, 5.01 g of calcined pyroaurite (pyroaurite = (Mg ₆ Fe ₂ (OH) ₁₆ ) CO ₃ × 4.5 H ₂ O) - prepared analogously Example 9 - added and stirred for 30 min at 20 ° C. After this time the suspension was filtered and the residual dye concentration was determined photometrically to 429.6 mg. The occupation density is 0.05 mmol / g.

Example 12

The pigments of the invention and comparative samples based on uncalcined hydrotalcite and alizarin sulfonate were in 20% concentration with alumina mortar and with distil Stirred water to a spreadable paste. thereupon they were applied to an alumina foil and at room temperature to dry. In parallel, as a reference Aqueous dye solutions to the alumina support painted and also dried. The samples were taken with a "Sunlight improviser" in the day / night rhythm irradiated. When "Sunlight Improvisator" served a "Xenotest 150" device, system Cassella, original Hanau, equipped with a Xenon burner Xe 1500 with the prescribed according to DIN 54 004 color temperature zwi between 5500 and 6500 ° K.

The pure dye solutions were first colored after 4 h to recognize differences. After 6 hours, a brightening was observed the pigments based on uncalcined hydrotalcite, while the pigments of the invention no changes showed.

The nitroso R salt pigments of all samples were prinzi However, according to the Alizarinsulfonat examples, but occurred here already at shorter exposure times color differences. In the reference sample (aqueous solution of the dyes) were after 1 h not yet, but after 3 h clear color differences too  recognize. For pigments based on uncalcined Hydrotalcite was already slight after 1 h and clear after 3 h noticeable color differences noticeable.

The pigments according to the invention were free after 1 h and after 3 h only very small color differences visible.

Example 13

The pigments of the invention and comparative samples based on non-calcined hydrotalcite - ie cal.HT and HT + Acid Green 41 and flash HT and HT + Alizarinsulfonat - were 20% strength with Al ₂ O ₃ and some water triturated and in a thickness of about 1 mm applied to an Al ₂ O ₃ film and dried in air ge. Thereafter, the samples were exposed to xenon light (see Example 12). Using a colorimeter, the reflected light intensity was measured as a percentage against a white standard (TiO ₂ , 100%).

The pigments according to the invention showed from the reactions of calcined hydrotalcite or the flash precipitation clearly ge lower reflection values than the comparable samples of the Umset tongues with uncalcined hydrotalcite. A clear trend is therefore foreseeable: The from the reactions with non-calcined Hydrotalcite obtained pigments are less color stable, as from the Curves (reflection intensity versus time) basically larger slopes result. This is a measure of the lightening and thus to see for the lower light stability.

Table 8 below gives the obtained reflection data again.  

Table 8

Example 14

There were suspensions of 75 mg of the mentioned in Example 4 Pig prepared in 25 ml of distilled water and 2% Added sodium hypochlorite solution. A whitening of the pigments showed up only after 1 h; After 1.5 hours, there was still a small one Pink color back.

Comparative Example 3

Analogously to Example 14, corresponding suspensions of the pigments prepared from uncalcined hydrotalcite and proceed as above.

After 1 h, the pigments were already colorless.

Example 15

Each 50 ml of an aqueous Alizarinsulfonat solution with the con concentration of 1 g / l were mixed with 50 ml of methanol, 50 ml of isopropanol and 150 ml of methanol. After addition of 100 mg each calcine Hydrotalcite was the dye concentration in the filtered Samples determined as described above.

Table 9 below gives the data obtained for the Bele density again.

Table 9 Water / methanol laydown 1: 1 0.35 mmol / g 1: 3 0.26 mmol / g Water / isopropanol laydown 1: 1 0.74 mmol / g

Example 16

There were suspensions of 100 mg of those described in Example 4 Pigments made in 50 ml of distilled water and with a Solution of 50 mg of sodium oleate in 50 ml of water. After 30 min Stirring at 20 ° C, the solids were filtered off and washed. The solids were resuspended in water and treated with about 1/10 the amount of liquid is mixed with oil. After mixing the Samples and separation were the total solids in the suspended organic phase.

Claims (14)

1. Water-insoluble pigments based on double-layer hydroxides and water-soluble dyes, characterized in that they are obtained by reacting in situ forming double-layer hydroxides and water-soluble anionic Dyfen fen in aqueous or aqueous media, wherein the in-situ forming double layer Hydroxides the general formula (I) in which
M ^II for at least one divalent metal cation,
M ^III for at least one trivalent metal cation,
A is the equivalent of an anion of a monobasic or polybasic acid,
1/6 x 1/2 and
0 m 1 stands. 2. Pigments according to claim 1, characterized in that M ^II is selected from among Mg, Ca, Mn, Fe, Co, Ni, Cu, Zn and Cd. 3. Pigments according to claim 1, characterized in that M ^{III is} selected from Al, Cr, Mn, Fe, Co and Ni. 4. Pigments according to claim 1, characterized in that A is selected from Cl ^- , Br ^- , J ^- , NO₃ ^- , ClO₃ ^- , ClO₄ ^- , OH ^- , CO₃ ^2- , SO₄ ^2- , S₂O₃ ^2- , WO₄ ^2- , CrO₄ ^2- and [Fe (CN) ₆] ^3- . 5. Pigments according to Claims 1 to 4, characterized in that the in-situ forming bilayer hydroxides are selected hydrotalcite, Zn / Al phase, magaldrate and / or pyroaurite. 6. Pigments according to Claims 1 to 4, characterized in that the water-soluble, anionic dyes are selected from the Group of anthraquinone and naphthol dyes and the optical brightener. 7. Process for the preparation of water-insoluble pigments according to Claims 1 to 6, characterized in that in situ forming bilayer hydroxides and water-soluble anionic Dyes in aqueous or aqueous media with each other sets, wherein the forming in situ bilayer hydroxides the have general formula (I). 8. A process for the preparation of the pigments according to claim 7, characterized characterized in that the in situ formation of the bilayer Hydroxides previously calcined bilayer hydroxides of the general Formula (I) uses. 9. A process for the preparation of the pigments according to claim 7, characterized in that one uses for in situ formation of Doppelschich- hydroxides, preferably water-soluble salts of the metal cations (M ^II ) and (M ^III ), wherein the pH of the aqueous or aqueous medium to alkaline values, preferably to pH values in the range 9 to 13, sets. 10. A process for the preparation of the pigments according to claims 7 to 9 characterized in that one is aqueous or hydrous Medium water or mixtures of water and polar organic Lö ses, preferably short-chain alcohols used.   11. A process for the preparation of the pigments according to claims 7 to 10, characterized in that the reaction at room temperature performed. 12. A process for the preparation of the pigments according to claims 7 to 11, characterized in that these are known per se Ver be rendered hydrophobic, in particular by adding sodium salting of fatty acids. 13. Use of the pigments according to claims 1 to 6 as a color carrier in washing, rinsing and cleaning agents, soaps, cosmetics, varnishes, Paints, foodstuffs, plastics and polymers. 14. Use of the pigments according to claims 1 to 6 as a carrier of optical brighteners in detergents.