DE10340777A1 - Treatment of particulate (especially organic) pigments, for use e.g. in ink-jet inks for textiles or for currying leather, involves two sequential polymerization processes on the pigments - Google Patents

Abstract

Treatment of particulate pigments comprises: (a) mixing the particulate pigments with a nonionic surfactant; (b) dispersing the mixture in an aqueous medium; (c) (co)polymerizing a first monomer (mixture) in presence of the dispersion to give a water-insoluble (co)polymer on the pigment surface; and (d) (co)polymerizing a second monomer (mixture).

Description

• a) Vermischen von Pigment in partikulärer Form mit mindestens einem nichtionischen oberflächenaktiven Stoff,
• b) Dispergieren der so erhältlichen Mischung von Pigment in partikulärer Form und nicht-ionischem oberflächenaktiven Stoff in wässrigem Medium,
• c) Polymerisieren mindestens eines ersten Monomers oder Copolymerisation einer ersten Mischung von Comonomeren in Gegenwart einer Dispersion nach b), wobei wasserunlösliches Polymer oder Copolymer an der Oberfläche der Pigmente in partikulärer Form gebildet wird,
• d) Hinzufügen mindestens eines zweiten Monomers oder einer zweiten Mischung von Comonomeren und Polymerisation oder Copolymerisation.

The present invention relates to a process for the treatment of pigments in particulate form, comprising the following steps:

• a) mixing pigment in particulate form with at least one nonionic surfactant,
• b) dispersing the resulting mixture of pigment in particulate form and nonionic surfactant in aqueous medium,
• c) polymerizing at least one first monomer or copolymerizing a first mixture of comonomers in the presence of a dispersion according to b), wherein water-insoluble polymer or copolymer is formed on the surface of the pigments in particulate form,
• d) Addition of at least one second monomer or mixture of comonomers and polymerization or copolymerization.

Farther The present invention relates to the use of the invention treated Pigments in particulate Mold for the preparation of colorant preparations, in particular for preparations for the coloring of leather. Furthermore, the present invention relates a process for coloring leather and colored leather using the pigments according to the invention treated in particulate form. After all The present invention relates to shoes made of colored leather according to the invention.

at The finishing is usually leather coated in several layers. Particularly common is a three-layer coating, wherein the first coating is a so-called primer, the For example, pigments, binders and auxiliaries to achieve the liability of the entire dressing contains. As a second coating one uses a so-called cover layer, which usually sets a little harder is considered the first layer. The third layer is a finish on, that's the final one Appearance and the grip decisively influenced. As order methods for all Layers serve more common Coating techniques such as spraying, brushing, casting, printing and laminating.

Finish, Topcoat or topcoat is the last name in the leather industry Shift order and thus the last operation in the actual Leather production.

At Colorant preparations used in modern colorization processes of substrates such as leather, demanding requirements are made. Colored substrates should have a high brilliance of the colors, the coloring should be permanent be, i. have high fastness properties, such as rubbing fastness and sweat-fastness. In some cases let yourself However, the brilliance of colorings still to be desired. This applies, for example in the application of binder-containing colorant preparations, if you want to produce trichromes. One often observes one Migration of pigments after application, and this can lead to color irregularities. Also Occasionally one observes unwanted fatty rashes, the favored by the migration of pigments. Continue observed that mixed colors do not or only poorly produce leave and colored with pigment mixtures substrates due to the different migration behavior of different pigments the time a uneven appearance to get. Furthermore leaves in some cases Improve the feel of printed substrates.

Farther have to the resulting colored leathers have good fastnesses, e.g. rub fastness, Light fastness, perspiration fastness, Water fastness and wet rub fastness, wash fastness and chemical cleaning resistance exhibit. These requirements also apply when coloring with Pigment-containing preparations.

There are attempts to treat pigments by coating them with a polymer. US 3,133,893 discloses the coating of pigments treated with a surfactant with polyacrylonitrile prepared in a polymerization step which is synthesized in the presence of the pigment. The pigments thus coated can be incorporated into fibers. For use in the coloration of substrates, the haptic properties such as the handle, however, are often unsatisfactory for modern requirements.

US 4,608,401 discloses a process for encapsulating pigments for latex paints, in which pigment particles are dispersed with water-insoluble monomers and a detergent under non-shear conditions in water and then subjected to emulsion polymerization conditions. For use in the coloring of substrates are the haptic egg However, for example, the handle is often unsatisfactory for modern requirements.

US 4,680,200 discloses a process for the encapsulation of non-pretreated pigments in which pigment particles with styrene and the oligomer Polywet KX-3 from Uniroyal are dispersed in water and then subjected to the conditions of an emulsion polymerization.

US 3,544,500 discloses a process for preparing pigments coated with specific polymers which are prepared by physically adsorbing water-soluble polymers to the polymer and then introducing an unsolvated anchor component. However, the use of water-soluble polymers for coating pigments for inks for the ink-jet process is not advantageous because the coating is peeled off again upon prolonged storage of the ink. In addition, especially printed textiles are not sufficiently wet and perspiration fast, and the wash fastness is also insufficient in many cases.

US 4,608,401 describes a process for the preparation of coated pigments, which is limited to those pigments which have no ionic charges. The pigments mentioned are enveloped by a suspension polymerization of a water-insoluble monomer. For use in the coloration of substrates, the haptic properties such as the handle, however, are often unsatisfactory for modern requirements.

Out EP-A 1 245 653 discloses a process for the preparation of inks for the ink-jet process, according to the pigment particles with water-soluble Monomers such as acrylic acid and optionally further Comonomers mixed and then an emulsion polymerization be subjected. The waterfastness and especially the washfastness of substrates printed with the disclosed inks is in many make unsatisfactory.

It So there was the task, a method for the treatment of pigments in particulate To provide a mold which is known from the prior art Disadvantages avoids. Furthermore, there was the task of treated pigments in particulate To provide form. After all The task consisted of applications for treated pigments in particulate form to provide.

Accordingly, became Found the initially defined method.

The inventive method is based on pigments in particulate form. Among pigments are in the Practically insoluble, within the scope of the present invention, dispersed finely divided, organic or inorganic colorants according to the definition in DIN 55944. The process according to the invention preferably proceeds from organic pigments.

Exemplary selected organic pigments are - monoazo pigments: CI Pigment Brown 25; CI Pigment Orange 5, 13, 36 and 67; CI Pigment Red 1, 2, 3, 5, 8, 9, 12, 17, 22, 23, 31, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 52: 1 , 52: 2, 53, 53: 1, 53: 3, 57: 1, 63, 112, 146, 170, 184, 210, 245 and 251; CI Pigment Yellow 1, 3, 73, 74, 65, 97, 151 and 183; - Disazo pigments: CI Pigment Orange 16, 34 and 44; CI Pigment Red 144, 166, 214 and 242; CI Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176 and 188; - Anthanthrone pigments: CI Pigment Red 168 (CI Vat Orange 3); - anthraquinone pigments: CI Pigment Yellow 147 and 177; CI Pigment Violet 31; - anthraquinone pigments: CI Pigment Yellow 147 and 177; CI Pigment Violet 31; - Anthrapyrimidine pigments: CI Pigment Yellow 108 (CI Vat Yellow 20); - Quinacridone pigments: CI Pigment Red 122, 202 and 206; CI Pigment Violet 19; - Quinophthalone pigments: CI Pigment Yellow 138; - Dioxazine pigments: CI Pigment Violet 23 and 37; - flavanthrone pigments: CI Pigment Yellow 24 (CI Vat Yellow 1); - Indanthrone pigments: CI Pigment Blue 60 (CI Vat Blue 4) and 64 (CI Vat Blue 6); - isoindoline pigments: CI Pigment Orange 69; CI Pigment Red 260; CI Pigment Yellow 139 and 185; - Isoindolinone pigments: CI Pigment Orange 61; CI Pigment Red 257 and 260; CI Pigment Yellow 109, 110, 173 and 185; - isoviolanthrone pigments: CI Pigment Violet 31 (CI Vat Violet 1); - metal complex pigments: CI Pigment Yellow 117, 150 and 153; CI Pigment Green 8; - Perinone pigments: CI Pigment Orange 43 (CI Vat Orange 7); CI Pigment Red 194 (CI Vat Red 15); - Perylene pigments: CI Pigment Black 31 and 32; CI Pigment Red 123, 149, 178, 179 (CI Vat Red 23), 190 (CI Vat Red 29) and 224; CI Pigment Violet 29; Phthalocyanine pigments: CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and 16; CI Pigment Green 7 and 36; - Pyranthrone pigments: CI Pigment Orange 51; CI Pigment Red 216 (CI Vat Orange 4); - Thioindigo pigments: CI Pigment Red 88 and 181 (CI Vat Red 1); CI Pigment Violet 38 (CI Vat Violet 3); Triaryl carbonium pigments: CI Pigment Blue 1, 61 and 62; CI Pigment Green 1; CI Pigment Red 81, 81: 1 and 169; CI Pigment Violet 1, 2, 3 and 27; CI Pigment Black 1 (aniline black); CI Pigment Yellow 101 (aldazine yellow); CI Pigment Brown 22.

Examples for special Details of preferred pigments are: C.I. Pigment Yellow 138, C.I. Pigment Red 122, C.I. Pigment Violet 19, C.I. Pigment Blue 15: 3 and 15: 4, C.I. Pigment Black 7, C.I. Pigment Orange 5, 38 and 43 and C.I. Pigment Green 7.

you can according to the invention of Starting mixtures of two or more different pigments. Preferably, mixtures of two or more different Pigments at least one organic pigment and at least one another pigment, chosen made of soot, Iron oxide pigment and titanium dioxide pigment.

you is based on pigments which are in particulate form, i. in Form of particles. Usually you go out so-called crude pigments, these are untreated pigments, as they occur after the pigment synthesis. The particles can be regular or irregular Have shape, for example, can the particles in spherical or near spherical Form or in needle form.

In an embodiment In the present invention, the particles are more spherical or near spherical Form before, i. The relationship longest Diameter to smallest diameter is in the range of 1.0 to 2.0, preferably to 1.5.

The or the pigments in particulate Form are in a step a) with at least one non-ionic surfactants Mixed fabric.

Examples of suitable nonionic surface-active substances are, for example, ethoxylated mono-, di- and tri-alkylphenols (degree of ethoxylation: from 3 to 50, alkyl radical: C ₃ -C ₁₂ ) and also ethoxylated fatty alcohols (EO degree: from 3 to 80; ₈ -C ₃₆ ). Examples are the Lutensol ^® grades from BASF AG or the Triton ^® grades from Union Carbide. Particular preference is given to ethoxylated linear fatty alcohols of the general formula III nC _× H _{2x + 1} -O (CH ₂ CH ₂ O) _y -H III where x are integers in the range of 10 to 24, preferably in the range of 12 to 20. The variable y preferably stands for integers in the range of 5 to 50, more preferably 8 to 40.

ethoxylated linear fatty alcohols of general formula III are usually as a mixture of different ethoxylated fatty alcohols with different Degree of ethoxylation. The variable y is within the scope of the present Invention for the mean (number average).

The Mixing pigment in particulate form and at least one nonionic surfactant Fabric is made in equipment suitable for mixing, preferably in mills such as for example, ball mills or agitator ball mills. Especially suitable is the ball mill Drais Superflow DCP SF 12.

When suitable time for the mixing has proven to be for example ½ hour to 48 hours, although a longer one Duration is conceivable. Preferred is a time for mixing from 5 to 24 hours.

Print- and temperature conditions during mixing are generally not critical, For example, normal pressure has proven suitable. When Temperatures, for example, have temperatures in the range of 10 ° C to 100 ° C as proved suitable.

The ratio from pigment to particulate Form to non-ionic surface active Fabric can be chosen in a wide range and can, for example range from 10: 1 to 2: 1.

During the execution from step a) you can add water. Also one can usual non-ionic Add grinding aid.

Of the mean diameter of pigment in particulate form lies after step a) usually in the range of 20 nm to 1.5 μm, preferably in the range of 50 to 200 nm, more preferably in the range from 80 to 150 nm.

In Step b) dispersing the one obtainable after step a) Mixture of pigment in particulate Form and non-ionic surfactant Cloth in watery Medium. For dispersion one can use any devices, for example, stirred Kettle or stirred Piston.

Under aqueous For the purposes of the present invention, media become such liquid media understood that contain water as an important component, for example at least 40% by weight, preferably at least 55% by weight.

In Step b) may be the weight ratio the mixture of pigment in particulate form and non-ionic surfactants Substance to watery Medium in the range of 1: 1.5 to 1:15, preferably 1: 2.5 to 1: 9 are.

print and temperature conditions for Step b) are generally not critical, for example Temperatures in the range of 5 to 100 ° C suitable, preferably 20 to 85 ° C and pressures in the range of normal pressure up to 10 bar.

By the dispersion after step b) gives a dispersion.

In Step c) polymerizing at least one first monomer or copolymerizes a first mixture of comonomer in the presence of a Dispersion, available to b), wherein water-insoluble Polymer or copolymer formed on the surface of the pigment particles becomes.

to execution from step c), at least one monomer or at least one is added Mixture of comonomers to a dispersion obtainable according to b). The addition For example, in one portion, in several portions or also be continuous. If you have at least different monomers would like to copolymerize with each other, you can do it first Add a comonomer and then the second and possibly further Comonomers. In another embodiment, all comonomers are added in one serving too.

monomer or comonomers can be added in bulk or in aqueous dispersion.

As monomers or comonomers in step c) are selected such monomers or comonomers which are sparingly soluble in water. By poorly water-soluble Mo monomers or comonomers are understood to mean those monomers or comonomers whose solubility in water at 50 ° C 1 × 10 ^-1 mol / I or less.

preferred examples for Monomers or comonomers in step c) are vinylaromatic compounds and poorly water-soluble α, β-unsaturated carboxylic acid derivatives.

in der R⁷ und R⁸ unabhängig voneinander jeweils für Wasserstoff, Methyl oder Ethyl stehen, R⁹ Methyl oder Ethyl bedeutet und k eine ganze Zahl von 0 bis 2 bedeutet; ganz besonders bevorzugt sind R⁷ und R⁸ jeweils Wasserstoff, und ganz besonders bevorzugt gilt k = 0.Preferably, at least one compound of general formula IV is chosen as the vinylaromatic compound,

in which R ⁷ and R ⁸ are each independently hydrogen, methyl or ethyl, R ^{9 is} methyl or ethyl and k is an integer from 0 to 2; Most preferably, R ⁷ and R ^{8 are} each hydrogen, and most preferably k = 0.

in der die Variablen wie folgt definiert sind:
R¹ gewählt aus
– unverzweigtem oder verzweigtem C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;
– oder Wasserstoff,
ganz besonders bevorzugt sind Wasserstoff und Methyl;
R² gewählt aus
– unverzweigtem oder verzweigtem C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n- Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;
– oder ganz besonders bevorzugt Wasserstoff.
R³ gewählt aus
– unverzweigtem oder verzweigtem C₄-C₁₀-Alkyl, wie n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; ganz besonders n-Butyl und 2-Ethylhexyl.Preferably, a poorly water-soluble α, β-unsaturated carboxylic acid derivative is a compound of general formula I,

where the variables are defined as follows:
R ¹ selected from
Unbranched or branched C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl , sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
- or hydrogen,
very particular preference is given to hydrogen and methyl;
R ² selected from
Unbranched or branched C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl , sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
- or very particularly preferably hydrogen.
R ³ selected from
Unbranched or branched C ₄ -C ₁₀ -alkyl, such as n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; especially n-butyl and 2-ethylhexyl.

In one embodiment of the present invention, the ratio of pigment to amount is present Monomer or comonomers in step c) in the range of 3: 1 to 1: 2, preferably in the range 2: 1 to 1: 1.5.

you may in step c) use mixtures of the aforementioned monomers. For example, mixtures of styrene and n-butyl acrylate very suitable, the mixing ratio is arbitrary.

Preferably is polymerized under the conditions of an emulsion polymerization. Very particularly preferred are so-called "starved conditions " i.e. one uses little or preferably no wetting agent. So receives no measurable levels of stabilized droplets of first monomer or first mixture of comonomers, and the proportion of wetting agent is used for meshing the pigment surface and for the transport of the first monomer or first mixture of comonomers through the continuous aqueous Phase. Wetting agents are, for example, organic sulfur compounds suitable, for example, alkyl sulfates, alkyl sulfonates, alkylarylsulfonates, Alkyl ether sulfates, alkylaryl ether sulfates, sulfosuccinates such as sulfosuccinic monoesters and sulfosuccinic acid diester; Furthermore, organic phosphorus compounds such as Alkyl ether suitable.

Usually is polymerized using at least one initiator. At least one initiator may be a peroxide. Examples of suitable Peroxides are alkali metal peroxodisulfates, e.g. sodium, Ammonium peroxodisulfate, hydrogen peroxide, organic peroxides such as diacetyl peroxide, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, Didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis (o-toloyl) peroxide, Succinyl peroxide, tert-butyl peracetate, tert-butyl permalate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl perneodecanoate, tert-butyl perbenzoate, tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxy-2-ethylhexanoate and diisopropyl peroxydicarbamate. Also suitable are azo compounds such as, for example, azobisisobutyronitrile, Azobis (2-amidopropane) dihydrochloride and 2,2'-azobis (2-methylbutyronitrile).

Redox initiators are also suitable, for example, peroxides and oxidizable sulfur compound. Very particular preference is given to systems composed of acetone bisulfite and organic peroxide such as tert-C ₄ H ₉ -OOH, Na ₂ S ₂ O ₅ (sodium disulfite) and organic peroxide such as tert-C ₄ H ₉ -OON or combinations of alkali metal salts of HO- CH ₂ SO ₂ H and organic peroxide such as tert-C ₄ H ₉ -OOH. Also, systems such as ascorbic acid / H ₂ O _{2 are} particularly preferred.

When Polymerization temperature can be temperatures in the range of 20 up to 100 ° C, preferably 50 to 85 ° C choose. The chosen one Temperature is dependent from the decay characteristic of the initiator used.

The Printing conditions are generally not critical, suitable for example pressures in the range of normal pressure up to 10 bar.

When Duration for Step c) have, for example, 1 to 30 minutes as suitable proven, preferably 2 to 10 minutes and more preferably 3 to 5 minutes.

Of course you can you add the reaction mixture other additives, the customary in emulsion polymerization are, for example, glycols, polyethylene glycols, protective colloids and buffer / pH regulators.

you receives after step c) polymer or copolymer-coated pigment in particulate form, which is obtained in the form of isolated particles. One does not observe measurable ones or only very small ones Shares of agglomerates, for example, less than 2 wt .-%, preferably less than 0.2% by weight.

The in step c) on the surface of the pigment in particulate Form formed polymer or copolymer is water insoluble.

you can in a further step, the c) available with dispersed Coated polymer or copolymer Pigment particles by cleaning operations, for example filtration, Decant, isolate washing and for the exercise of step d) of the method according to the invention redisperse. Preferably, however, one processes according to c) available dispersed with polymer or copolymer coated pigment particles in situ further.

In step d) of the process according to the invention, at least one second monomer or a monomer is added second mixture of comonomers to the dispersion of step c) or the worked up and redispersed coated pigments and polymerised or copolymerized.

there one speaks in connection with the present invention also then from a second mixture of comonomers in step d), if one has used a monomer in step c) and in step d) a Added mixture of two comonomers. Likewise one speaks in the Also related to the present invention of a second monomer in step d), if in step c) a mixture of comonomers used and in step d) adds a monomer.

Do you wish To add a second mixture of comonomers, one adds at least one comonomer to, different from the monomer or comonomers from step c) is.

In an embodiment The present invention uses in step c) a vinyl aromatic Compound as a monomer and in step d) at least one monomer or comonomer which swells polymer or copolymer from step c) can. By "source" is meant that under normal conditions at least 5 wt or comonomer embedded in the polymer or copolymer from step c) physically can be.

wobei die Variablen wie folgt definiert sind:
R⁴ gewählt aus
– unverzweigtem oder verzweigtem C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;
– oder Wasserstoff;
ganz besonders bevorzugt sind Wasserstoff und Methyl;
R⁵ gewählt aus
– unverzweigtem oder verzweigtem C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;
– oder ganz besonders bevorzugt Wasserstoff.
R⁶ wird gewählt aus unverzweigtem oder verzweigtem C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl.Very particular preference is given to adding at least one monomer or comonomer of the general formula II

where the variables are defined as follows:
R ⁴ selected from
Unbranched or branched C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl , sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
- or hydrogen;
very particular preference is given to hydrogen and methyl;
R ^{5 is} selected
Unbranched or branched C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl , sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
- or very particularly preferably hydrogen.
R ⁶ is selected from straight-chain or branched C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n Nonyl, n-decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

Do you wish in step d) add a mixture of comonomers, so it is sufficient if at least one comonomer of the monomer or comonomer from step c) is different. That's the way it is, for example possible, in step c) use styrene and in step d) a mixture from methyl acrylate and styrene.

The Glass transition temperature of the polymer or copolymer formed in step d) For example, you can determine that you are in a separate Experiment under conditions of emulsion polymerization the corresponding Produces pigment-free polymer or copolymer, which does not polymer or copolymer after step c), and then the Glass transition temperature according to DSC (differential thermal analysis, differential Scanning calorimetry).

In a particularly preferred embodiment In the present invention, one or more are used in step d) Monomers or comonomers selected from: n-butyl acrylate, 2-ethylhexyl acrylate, methyl acrylate, Ethyl acrylate.

In a particularly preferred embodiment of the present invention if in step d) at least% by weight of n-butyl acrylate is used.

In an embodiment the present invention is the weight ratio of second monomer or second mixture of comonomers from step d) to pigment from step a) in the range of 0.7: 1 to 10: 1, preferably 1.5: 1 to 5: 1, more preferably 2: 1 to 4: 1.

All in all you choose the amount of monomers or comonomers from step c) and d) of the inventive method so that the ratio Polymer or copolymer to pigment in the range of 1: 1 to 5: 1, preferably in the range of 2: 1 to 3: 1.

In Step d) is polymerized or copolymerized preferably under the conditions of an emulsion polymerization. It is usually used at least one initiator, wherein the initiator or initiators are selected can from the above.

you can use at least one emulsifier anionic, cationic or non-ionic.

Common nonionic emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (degree of ethoxylation: from 3 to 50, alkyl radical: C ₄ -C ₁₂ ) and ethoxylated fatty alcohols (degree of ethoxylation: from 3 to 80, alkyl radical: C ₈ -C ₃₆ ). Examples are the Lutensol ^® brands from BASF Aktiengesellschaft and the Triton ^® grades from Union Carbide.

Typical anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C ₈ to C ₁₂ ), of sulfuric monoesters of ethoxylated alkanols (degree of ethoxylation: from 4 to 30, alkyl radical: C ₁₂ -C ₁₈ ) and ethoxylated alkylphenols (degree of ethoxylation: from 3 to 50, Alkyl radical: C ₄ -C ₁₂ ), of alkylsulfonic acids (alkyl radical: C ₁₂ -C ₁₈ ), of alkylarylsulfonic acids (alkyl radical: C ₉ -C ₁₈ ), and of sulfosuccinates, such as, for example, succinic acid mono- and diesters.

Suitable cationic emulsifiers are generally C ₆ -C ₁₈ -alkyl-, aralkyl- or heterocyclic radical-containing primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts, thiazolinium salts and salts of amine oxides, quinolinium salts , Isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts. Examples include dodecylammonium acetate or the corresponding hydrochloride, the chlorides or acetates of the various 2- (N, N, N-trimethylammonium) ethylparaffinsäureester, N-cetylpyridinium chloride, N-Laurylpyridiniumsulfat and N-cetyl-N, N, N-trimethylammonium bromide, N- Dodecyl-N, N, N-trimethylammonium bromide, N, N-distearyl-N, N-dimethylammonium chloride and the gemini surfactant N, N- (lauryldimethyl) ethylenediamine dibromide. Numerous other examples can be found in H. Stache, Tensid-Taschenbuch, Carl-Hanser-Verlag, Munich, Vienna, 1981, and in McCutcheon's, Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989.

In an embodiment In the present invention, the amount of the emulsifier is selected so that the mass ratio between the second monomer or second mixture of comonomers on the one hand and Emulsifier on the other hand greater than Is 1, preferably greater than 10 and more preferably greater than 20th

The Order of addition of the reactants from step d) is on not critical.

In an embodiment in the present invention, the initiator is added when passing through for example, stirring has produced a milky-looking emulsion.

When Polymerization temperature can be temperatures in the range of 20 up to 100 ° C, preferably 50 to 85 ° C choose. The chosen one Temperature is dependent from the decay characteristic of the initiator used.

The Printing conditions are generally not critical, suitable for example pressures in the range of normal pressure up to 10 bar.

When Duration for the polymerization or copolymerization in step d) can be choose a time in the range of 30 minutes to 12 hours, preferably are 2 to 3 hours.

zusetzen, in denen die Variablen wie folgt definiert sind:
R¹⁰ gewählt aus
– unverzweigtem oder verzweigtem C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;
oder Wasserstoff;
– ganz besonders bevorzugt sind Wasserstoff und Methyl;
R¹¹ gewählt aus
– unverzweigtem oder verzweigtem C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;
– oder ganz besonders bevorzugt Wasserstoff.
R¹² wird gewählt aus unverzweigtem oder verzweigtem C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl,
– oder ganz besonders bevorzugt Wasserstoff.
X gewählt aus
– Wasserstoff,
– Glycidyl

– Gruppen mit tertiären Aminogruppen wie beispielsweise -O-(CH₂)_b-N(CH₃)₂ oder -NH-(CH₂)_b-N(CH₃)₂, wobei b eine ganze Zahl im Bereich von 2 bis 6 ist,
– Gruppen mit Hydroxygruppen wie beispielsweise -O-(CH₂)_b-OH,
– enolisierbaren Gruppen mit 1 bis 20 C-Atomen, beispielsweise Acetoacetyl

wobei
R¹³ wird gewählt aus unverzweigtem oder verzweigtem C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl.In one embodiment of the present invention, in step d) as comonomer up to 5 wt .-%, preferably 1 to 4 wt .-%, based on monomers or comonomers from step d), of at least one compound of general formula V a to Vb

in which the variables are defined as follows:
R ¹⁰ selected from
Unbranched or branched C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl , sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
or hydrogen;
- very particularly preferred are hydrogen and methyl;
R ¹¹ selected out
Unbranched or branched C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl , sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
- or very particularly preferably hydrogen.
R ¹² is selected from straight or branched C ₁ -C ₁₀ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n Nonyl, n-decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl,
- or very particularly preferably hydrogen.
X selected
- hydrogen,
- glycidyl

Tertiary amino groups such as -O- (CH ₂ ) _b -N (CH ₃ ) ₂ or -NH- (CH ₂ ) _b -N (CH ₃ ) ₂ , wherein b is an integer in the range of 2 to 6 is
Groups with hydroxy groups such as -O- (CH ₂ ) _b -OH,
- Enolisierbaren groups with 1 to 20 C-atoms, for example acetoacetyl

in which
R ¹³ is selected from straight or branched C ₁ -C ₁₀ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n Nonyl, n-decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

Most preferably, in formula Va or Vb, R ^{10 is} selected from hydrogen and methyl, and R ¹¹ and R ¹² are each hydrogen.

In a further embodiment of the present invention used in step d) as comonomers 1 to 14 wt .-% of (meth) acrylonitrile are based on the total amount of comonomers.

In a further embodiment of the present invention in step d) up to 16 wt .-%, preferably 0.5 to 2.5 wt .-%, based on the total amount of comonomers, cationic or slightly protonatable Comonomers are used, for example amino-containing Comonomers such as e.g. N, N-dimethylaminoethyl (meth) acrylamide and 3- (N, N-dimethylamino) propyl (meth) acrylamide.

In a further embodiment of the present invention in step d) are used as comonomers: in each case 1 to 5% by weight (Meth) acrylamide, ureido (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (Meth) acrylamide propanesulfonic acid, branched or unbranched, or the sodium salt of vinylsulfonic acid, respectively based on the total amount of comonomers.

enthält, wobei in Formel VI die Variablen wie oben stehend definiert sind.In one embodiment of the present invention, the second mixture of comonomers is selected to range from 0.1 to 3% by weight, based on the amount of pigment in particulate form, of one or more unsaturated carboxylic acids of formula VI

In Formula VI, the variables are defined as above.

In a further embodiment of the present invention in step d) combinations of easily protonatable and light deprotonatable comonomers such as combinations of Amino group-containing comonomers and ethylenically unsaturated Carboxylic acids. Preference is given to combinations of (meth) acrylic acid and 3- (N, N-dimethylamino) propyl (meth) acrylamide and combinations of (meth) acrylic acid and dimethylaminoethyl (meth) acrylamide, more preferably in a weight ratio of 1: 3, for example 1.5% by weight of acrylic acid and 4.5% by weight of 3- (N, N-dimethylamino) propyl (meth) acrylamide, respectively based on the total amount of comonomers. Another preferred Combination is 0.3% by weight of acrylamidopropanesulfonic acid Isomer mixture with 0.5 to 3 wt .-% of (meth) acrylamide. Other preferred Combinations are 0.5 to 1.5 wt .-% acrylic acid or 1 to 3 wt .-% methacrylic acid with 0.5 to 3% by weight of (meth) acrylamide.

One Another object of the present invention are pigments in particulate Form, treated by the method according to the invention. They usually fall in the form of aqueous Dispersions, which are also the subject of the present invention are, and can by measures known to those skilled in the art be easily separated.

Aqueous dispersions according to the invention treated according to the invention Pigments in particulate Can shape a solids content of 10 to 50 wt .-%, preferably 30 to 40 Wt .-% have.

Treated according to the invention Pigments are enveloped with at least one layer of polymers or copolymers which of monomers or comonomers from step c) and monomers or derive comonomers from step d). The majority of the invention treated Pigments are enveloped with two layers of polymers or copolymers, wherein the layers can be interpenetrating and do not have to be strictly divorced. The so characterized Particles are hereinafter also referred to as pigment-containing polymer particles designated.

The treated according to the invention Pigments in particulate Can shape in admixture with polymer or copolymer, which differs from Monomers or mixtures of comonomers derived from step d).

In a preferred embodiment According to the present invention, pigments treated according to the invention are in a mixture with polymer or copolymer, which is derived from monomers or Derives mixtures of comonomers from step d). That of monomers or mixtures of comonomers derived from step d) polymer or copolymer falls preferably in the form of spherical Particles on. The particles thus characterized are described below also called pigment-free polymer particles.

In a preferred embodiment is the weight ratio Pigment-containing polymer particles to pigment-free polymer particles in the range of 10 to 0.1 to 10 to 3, preferably from 10 to 0.5 to 10 to 2.

kann beispielsweise im Bereich von 1,2 bis 10 liegen, bevorzugt im Bereich von 2 bis 5.In a preferred embodiment, the mean radii r (pigment-free polymer particles) are smaller than the average radii r (pigment-containing polymer particles), in each case based on the number average. The radii ratio

may for example be in the range of from 1.2 to 10, preferably in the range of from 2 to 5.

One Another object of the present invention is the use treated according to the invention Pigments in particulate Form as or for the preparation of colorant preparations. Another The present invention is a process for the preparation of colorant formulations using inventively treated Pigments in particulate Shape. Another object of the present invention are colorant preparations, prepared using pigments treated in accordance with the invention in particulate form. For the preparation of colorant preparations according to the invention can the conditions according to the invention wäßri Use dispersions as such and also from the dispersions of the invention separated treated according to the invention Pigments.

One Another object of the present invention is the use the treated according to the invention Pigments in particulate Form for coloring leather. Another object of the present invention is a process for coloring leather using the treated pigments according to the invention in particulate Shape, and another object of the present invention colored leather, available by a method according to the invention for the coloring of leather.

Under Leather is pretanned, tanned in the context of the present invention and optionally retanned leather or processed accordingly synthetic replacement material to understand what is going on during at least a tanning step already treated with at least one dye may have been. Leather in the context of the present invention can already hydrophobicized or greased.

Treated according to the invention Pigment in particulate Mold tolerates yourself with the commercial aids for the Finishing of leather, which is used to regulate the grip, color, Course and viscosity can be inserted. These are generally solutions (eg leveling agents, Products based on glycol ethers, ethers, such as. B. butylglycol, methoxypropanol, Tributoxyethyl phosphate) or emulsions / dispersions with casein, Grow silicones in the usual Application quantities or application concentrations (see F. Stather, Gerbereichemie u. Tannery Technology, Akademie Verlag Berlin, 1967, S.507-632).

In a special embodiment The present invention is the process of the invention for coloring a method for pot dyeing of leather in the barrel Purpose of covering errors that in a previous staining of Leather in the barrel have emerged. After normal staining with customary in tanning Dyes in the drum dyeing is used to cover errors with pigment treated according to the invention in particulate form worked, which is a much higher Has light fastness as dyes, determined, for example, after DIN EN ISO 5 B02.

In another special embodiment The present invention is the process of the invention for the coloring of leather by a process for the aniline-like spray-dyeing of leather, hereinafter also called spray-dye according to the invention. In erfindungemäßer spray dyeing remains The natural surface and structure of leather preferably unchanged.

to execution a spray dye according to the invention according to the invention treated pigment in particulate Form with water and surfactant and injects the resulting mixture by means of devices known per se on undyed leather.

When Surfactants are well known ionic and nonionic surfactants suitable, preferably non-ionic surfactants. Especially preferred Nonionic surfactants are, for example, alkoxylated saturated or unsaturated fatty alcohols or alkoxylated saturated or unsaturated Fatty amines, i. Alcohols or amines with more than 14 carbon atoms.

• – 1 bis 30, bevorzugt 5 bis 25 Gew.-% erfindungsgemäß behandeltes Pigment in partikulärer Form,
• – 0,1 bis 10, bevorzugt 1 bis 5 Gew.-% Tensid,

und der Rest ist Wasser, wobei Angaben in Gew.-% jeweils auf die Mischung bezogen sind. Eine oder mehrere bereitete Mischungen spritzt man auf ungefärbtes Leder.In one embodiment of the present invention, mixtures are prepared

• From 1 to 30, preferably from 5 to 25,% by weight of pigment treated according to the invention in particulate form,
• From 0.1 to 10, preferably from 1 to 5,% by weight of surfactant,

and the remainder is water, where in wt .-% in each case based on the mixture. One or more prepared mixtures are sprayed onto undyed leather.

In another embodiment The present invention is the process of the invention for the coloring of leather to a process for dressing leather. Aim of finishing leather, also called coating of leather, is it the leather you want Appearance, special haptic properties and use fastness to give such as Knick elasticity Amine resistance, Wet and dry rub fastness and waterfastness.

In an embodiment goes the process of the invention for coloration of pre-tanned, tanned and optionally retanned leather, which is already known per se hydrophobed and dyed can be.

First, at least one Grundierdispersion or - if a two-layer primer is desired, first a so-called primer, then the Grundierdispersion - which may contain one or more inventively treated pigments, in an amount on the leather to be colored, that per m ² Leather surface about 10 to 100 g of solids are applied, preferably 20 to 50 g / m ² . The application can be carried out by methods known per se, for example rollcoats, brushing, spraying, airless spraying, printing, laminating, plushing, brushing, casting or spraying Temperature in the range of 30 to 80 ° C., preferably 60 to 80 ° C. The application of at least one Grundierdispersion can be carried out in one or more steps, which can be carried out the same or different and each interrupted by an intermediate drying at the above temperatures could be.

• α1) mindestens ein erfindungsgemäß behandeltes Pigment in partikulärer Form, beispielsweise 1 bis 10 Gew.-%, bevorzugt 1,5 bis 5 Gew.-%
• β1) mindestens ein Wachs, wie beispielsweise oxidiertes Polyethylenwachs, Carnaubawachs oder Montanwachs, beispielsweise bevorzugt 1 bis 15 Gew.-%,
• γ1) mindestens ein Biozid, beispielsweise 1,2-Benzisothiazolin-3-on („BIT") (kommerziell erhältlich als Proxel^®-Marken der Fa. Avecia Lim.) und dessen Alkalimetallsalze; andere geeignete Biozide sind 2-Methyl-2H-isothiazol-3 („MIT") und 5-Chlor-2-methyl-2H-isothiazol-3-on („CIT"). Im Allgemeinen sind 10 bis 150 ppm Biozid ausreichend.
• δ1) optional mindestens ein Bindemittel, beispielsweise Acrylat-Methacrylat-Copolymerbinder. Dabei kann es vorteilhaft sein, wenn die Comonomerzusammensetzung des zusätzlichen Binders annähernd mit dem Copolymer gemäß d) übereinstimmt. Für Automobilleder kann eine Abmischung mit einem Urethanbinder von weiterem Vorteil sein.

Primer dispersions used according to the invention, which are also referred to below as the inventive base emulsions, are usually aqueous. They may contain other nonaqueous solvents such as ethylene glycol, N-methylpyrrolidone, 3-methoxypropanol and propylene carbonate. In a preferred embodiment, base dispersions according to the invention comprise the following constituents:

• α1) at least one pigment treated according to the invention in particulate form, for example 1 to 10% by weight, preferably 1.5 to 5% by weight
• β1) at least one wax, such as, for example, oxidized polyethylene wax, carnauba wax or montan wax, for example preferably 1 to 15% by weight,
• γ1) at least one biocide, for example 1,2-benzisothiazolin-3-one ( "BIT") (commercially available as Proxel ^® brands from) from Avecia Lim and its alkali metal salts;.. other suitable biocides are 2-methyl-2H- isothiazole-3 ("MIT") and 5-chloro-2-methyl-2H-isothiazol-3-one ("CIT") Generally, 10 to 150 ppm biocide is sufficient.
• δ1) optionally at least one binder, for example acrylate-methacrylate copolymer binder. It may be advantageous if the comonomer composition of the additional binder approximately coincides with the copolymer according to d). For automobile leather, blending with a urethane binder may be further beneficial.

bottoming can at least one filling and anti-sticking agents. Suitable examples are aqueous formulations, containing fatty acid esters, Protein or Proteins and inorganic filler, the chosen one can be made of silicates and clay minerals.

Inventive primer dispersions can have a solids content of 10 to 80 wt .-%, are preferred From 20 to 50% by weight.

Then you can To apply a topcoat according to known methods. The topcoat can be made from the usual Consist of components.

• α2) mindestens ein Pigment in partikulärer Form, beispielsweise im Bereich von 0,05 bis 5 Gew.-%,
• δ2) optional mindestens ein weiteres Bindemittel, bevorzugt 20 bis 70 Gew.-%,
• ε2) optional mindestens ein Verdickungsmittel.

In one embodiment of the present invention, the cover layer contains, in each case based on the total mass of cover layer:

• α2) at least one pigment in particulate form, for example in the range from 0.05 to 5% by weight,
• δ2) optionally at least one further binder, preferably from 20 to 70% by weight,
• ε2) optionally at least one thickener.

In a preferred embodiment of the present invention the topcoat at least one binder whose hardness is higher as the hardness the primer layer.

Subsequently, it is possible to apply a finish, also known as seasoning dispersion, whereby about 5 to 30 g / m ^{2 of} leather surface are applied as a finish. The finish or topcoat serves to protect the leather and, in addition to high flexibility, also ensures good scratch resistance, oil and water resistance. Depending on the desired article it should have gloss or dullness, ie you can also add matting agents. Desserts may include, for example: formulations of at least one acrylate- or polyurethane-based binder, a crosslinking agent, egg white, nitrocellulose emulsion, organic or inorganic matting agent-based fillers, silicone wax, fatty acid esters, fatty acids.

Inventive seasoning dispersions can besides treated according to the invention Pigment in particulate Form further, known per se binders, for example Polyurethane dispersion prepared according to EP-A2 0 392 352.

facings and seasoning dispersions can contain one or more thickening agents. Exemplary crosslinkable copolymers based on acrylic acid and acrylamide and thickeners based on polyurethane or polyvinylpyrrolidone or acrylate (co) polymers called.

To Application of the finish can be dried under normal conditions, for example, at temperatures in the range of 60 to 80 ° C, and then iron, for example at temperatures in the range of 90 to 160 ° C. You can also do it hydraulically hot press, for example, at reduced pressure and temperatures in the range from 70 to 100 ° C. Conventional ironing equipment or continuous ironing machines are contemplated.

at the method according to the invention For the finishing of leather one uses in at least one step - primer, Applying the topcoat and finish - at least one formulation of the invention.

Subsequently, it is possible to apply a finish in the form of a dispersion, also called finish dispersion in the context of the present invention, whereby about 10 to 30 g / m ^{2 of} leather surface finish dispersion are applied.

• α3) mindestens ein erfindungsgemäß behandeltes Pigment in partikulärer Form, beispielsweise im Bereich von 0,05 bis 5 Gew.-%,
• β3) optional mindestens ein Wachs, wie beispielsweise oxidiertes Polyethylenwachs oder Montanwachs, geeignete Mengen sind beispielsweise 20 bis 70 Gew.-%,
• γ3) optional mindestens ein Biozid, beispielsweise 1,2-Benzisothiazolin-3-on („BIT") (kommerziell erhältlich als Proxel®-Marken der Fa. Avecia Lim.) und dessen Alkalimetallsalze; andere geeignete Biozide sind 2-Methyl-2H-isothiazol-3 („MIT") und 5-Chlor-2-methyl-2H-isothiazol-3-on („CIT"). Im Allgemeinen sind 10 bis 150 ppm Biozid ausreichend.
• δ3) optional mindestens ein weiteres Bindemittel, beispielsweise Urethangruppenhaltige Bindemittel.

In one embodiment of the present invention, the seasoning dispersion contains

• α3) at least one pigment treated according to the invention in particulate form, for example in the range from 0.05 to 5% by weight,
• β3) optionally at least one wax, such as, for example, oxidized polyethylene wax or montan wax, suitable amounts are, for example, 20 to 70% by weight,
• γ3) optionally at least one biocide, for example 1,2-benzisothiazolin-3-one ("BIT") (commercially available as Proxel® brands from Avecia Lim.) and its alkali metal salts, other suitable biocides being 2-methyl-2H -isothiazol-3 ("MIT") and 5-chloro-2-methyl-2H-isothiazol-3-one ("CIT") Generally, 10 to 150 ppm of biocide is sufficient.
• δ3) optionally at least one further binder, for example urethane group-containing binders.

Of course, seasoning dispersions more usual Contain ingredients such as shellac or one or more other pigments or nitrocellulose.

mit Molekulargewichten M_w im Bereich von 100.000 bis 200.000 g/mol, in denen die Reste R¹⁰ und R¹¹ gleich oder verschieden sein können und wie oben stehend definiert sind.Finishing dispersions may contain one or more thickeners. By way of example, crosslinkable copolymers based on acrylic acid and acrylamide may be mentioned. Preferred examples are copolymers having from 85 to 95% by weight of acrylic acid, from 4 to 14% by weight of acrylamide and about 1% by weight of the (meth) acrylamide derivative of formula VII

with molecular weights M _w in the range of 100,000 to 200,000 g / mol, in which the radicals R ¹⁰ and R ^{11 are the} same or may be different and as defined above.

To Application of the finish can be dried under normal conditions, for example, at temperatures in the range of 60 to 80 ° C, and then iron, for example at temperatures in the range of 90 to 160 ° C. You can also do it hydraulically hot press, for example, at reduced pressure and temperatures in the range from 70 to 100 ° C. Conventional ironing equipment or continuous ironing machines are contemplated.

in the The scope of the present invention includes at least one layer, selected from primer layer, topcoat and finish, at least one treated according to the invention Pigment in particulate form. Preferably, however, contain at least two, more preferably at least three layers at least one treated according to the invention Pigment in particulate Shape.

you observed that treated according to the invention Pigments in particulate Form colored according to the invention Leather to a measurable extent neither agglomerate nor a tendency to migrate.

One Another aspect of the present invention is colored leather, prepared using at least one invention treated Pigments in particulate Shape. Draw leather according to the invention by pleasant haptic properties with particularly uniform coloration and low migration tendency of the pigment in particulate form made and are therefore particularly suitable for the production of shoes. Leathers according to the invention are also suitable especially as furniture leather and in the car interior area.

The Invention will be explained by working examples.

General remarks:

The Glass transition temperature was measured using a DSC DSC822 (TA8200 series) DSC Company Mettler-Toledo determined with an autosampler TSO 801RO. The DSC instrument was with a temperature sensor FSR5 equipped.

It was worked according to DIN 53765.

It in each case the second heating curve of the evaluation was used. cooling down each at -110 ° C, heating rate: 20 ° C / min, Heating up to 150 ° C, Hold for 5 minutes at 150 ° C, subsequently cooling down to -110 ° C, heating rate: 20 ° C / min, Heating up to 150 ° C.

I. Preparation of treated according to the invention pigment

example 1

I.1 a) Mixing of a Pigments with a non-ionic surfactant

In a stirred ball mill of the type Drais Superflow DCP SF 12 were ground together: 1800 g Pigment Blue 15: 3 450 g nC ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₂₅ H 24 g glutaraldehyde 30 g tetramethylolacetylenediurea 3696 g distilled water

The Milling was continued until the pigment particles became medium Diameter of 100 nm.

you obtained mixture I.1 a) from pigment in particulate form and non-ionic surfactant.

NC ₁₈ H ₃₇ - (OCH ₂ CH ₂ ) ₂₅ -OH is ethylene oxide ethoxylated n-octadecanol, prepared according to the following procedure:
242 g of n-octadecanol and 0.1 mol KOH flakes were dewatered in a autoclave at a temperature of 100 ° C and a pressure of 1 mbar in a period of 2 hours, then expanded with nitrogen and purged 3 times with nitrogen and then to 130 ° C in an autoclave. After reaching the temperature 1100 g of ethylene oxide were metered in continuously within 3 h 20 min at a pressure of up to 6.1 bar. After complete addition, it was allowed to react until pressure constancy was reached. It was then cooled to 100 ° C and degassed in an autoclave at 1 mbar for 60 min and the reaction product was filled at 70 ° C. The yield was 1337 g.

I.2 a) Mixing of a Pigments with a non-ionic surfactant

In a stirred ball mill of the type Drais Superflow DCP SF 12 were ground together: 1800 g Pigment Green 7 450 g nC ₁₈ H ₃₇ O (OCH ₂ CH ₂ O) ₂₅ -H 24 g glutaraldehyde 30 g tetramethylolacetylenediurea 3696 g distilled water

The Milling was continued until the pigment particles became medium Diameter of 100 nm.

you obtained mixture I.2 a) from pigment in particulate form and non-ionic surfactant.

I.1 b) dispersing the Mixture of I.1 a) in water

mit a = 3 als wässrige Lösung und 60 g Styrol zu, und stellte mit Ameisensäure einen pH-Wert von 4,5 ein.In a 1 liter vessel with stirrer, nitrogen inlet and two metering devices, 267 g of the mixture of I.1 a) were dispersed with 270 g of distilled water with stirring. 10 g of 28% by weight of 30% by weight aqueous solution of

with a = 3 as an aqueous solution and 60 g of styrene, and adjusted with formic acid to a pH of 4.5.

you obtained dispersion I.1 b) of pigment in particulate form in watery Medium.

I.2 b)

attempt 1.1 b) was repeated, but with mixture I.2 a) instead of I.1 a). Dispersion 1.2 b) of pigment in particulate form was obtained in watery Medium.

I.1 c) Polymerization

Nitrogen was passed through dispersion I.1 b) over a period of 10 minutes. Subsequently, the mixture was heated to 85 ° C. Thereafter, 0.29 t-butyl hydroperoxide (70 wt% in water) and 0.2 g of HO-CH ₂ -SO ₂ Na were added.

you observed the formation of a water-insoluble polymer on the pigment particles.

I.2 c) polymerization

attempt I.1 c) was repeated, but with dispersion I.2 b) instead of I.1 b).

you observed the formation of a water-insoluble polymer on the pigment particles.

I.1 d) Add one Mixture of comonomers and further copolymerization

mit a = 3, 8,3 g 45 Gew.-% wässrige Lösung von Natrium-(di-2-ethylhexylsuccinat)-sulfonat (Natriumsalz von Sulfobernsteinsäuredi-2-ethylhexylester), 150 g n-Butylacrylat 88,7 g Styrol 3,8 g Acrylsäure 7,5 g Verbindung V a.1 als 15 Gew.-% Lösung in Wasser

5 minutes after the addition of tert-butyl hydroperoxide and HO-CH ₂ -SO ₂ H from step I.1 c), a mixture was added over a period of 90 minutes, which was composed as follows: 130 g completely desalinated water 12.5 g 30 Wt .-% aqueous solution of

with a = 3, 8.3 g 45% by weight aqueous solution of sodium (di-2-ethylhexylsuccinate) sulfonate (sodium salt of sulfosuccinic di-2-ethylhexyl ester), 150 g n-butyl acrylate 88.7 g styrene 3.8 g acrylic acid 7.5 g Compound V a.1 as a 15% by weight solution in water

At the same time, the addition of a solution of 1.25 g of Na ₂ S ₂ O ₈ in 100 g of water was begun and the addition was carried out over a period of 105 minutes. During the addition, the temperature was maintained at 85 ° C.

After completion of the addition was stirred for 30 minutes at 85 ° C and then for deodorization simultaneously a solution of 1.1 g of tert-butyl hydroperoxide (70 wt .-% in water) in 25 g of distilled water and a solution of 0.7 g of NaO-CH ₂ -O-SO ₂ H in 25 g of distilled water over a period of 90 minutes added.

After that was cooled to room temperature and with 25% by weight aqueous Ammonia adjusted to a pH of 7.

Subsequently was the so available Dispersion over a 120 μm mesh and then over a 15 μm mesh filtered.

you got a watery Dispersion I1.1 d) containing pigment treated according to the invention in particulate form. The solids content was 34.6 wt .-%, the dynamic viscosity was 35 mPa · s. The particle size distribution of the type obtainable as described above treated according to the invention Pigments in particulate Form gave a maximum at 135 nm. The determination of the particle size takes place with the help of photon correlation spectroscopy (PCS), also as quasi-elastic light scattering (QELS) known.

The Measurement Method is described in the ISO13321 standard. This is a dilute aqueous polymer dispersion (c ~ 0.005 wt%).

I.2 d) Add one Mixture of comonomers and further copolymerization

Example I.1d) was repeated but the following monomers were added: 20 g styrene 118.7 g methyl methacrylate 100 g n-butyl acrylate 3.8 g acrylic acid 7.5 g Methacrylamide.

you received dispersion I.2 d), containing the invention treated Pigment in particulate Shape.

I.3 d) Adding one Mixture of comonomers and further copolymerization

example I.1 d) was repeated, but starting from I.2 c) instead of I.1 c). This gave dispersion I.3 d) containing the invention treated Pigment in particulate Shape.

II. Application examples

II.1. Production of Shoe upper leather

commercial Shoe upper crust, made of wet blue, was dyed with leather colored (5 wt .-%, based on Crust dry weight, diluted 1:10, residence time 60 minutes in a barrel at 35 ° C).

Thereafter, a pot dyeing was carried out with the dispersion I.1 d) according to the invention:
500 parts by weight of water per 1 part by weight of shoe upper crust, 2.5% by weight (based on crust dry weight) of pigment I.1 d) treated according to the invention, diluted 1:10, no further additives, residence time in the drum at 50 ° C. for 30 minutes ,

After that the fleet was drained, the leather with 200 parts by weight of water washed up, fleet drained, the leather jacked up for 12 hours, stretched, hangsried, Stolled, 3 hours milled and tense.

result was a perfectly colored Leather with optically flawless surface.

II.2. Spray-dyeing of undyed Chrome-tanned cattle crust leather (aniline-like color)

It was prepared a mixture: 200 g pigment I.3d) treated in accordance with the invention in particulate form, 15 g Surfactant of the formula cis-CH ₃ - (CH ₂ ) ₇ -CH = CH- (CH ₂ ) ₈ -NH- (CH ₂ CH ₂ O) ₁₂ -OH and 785 g demineralized water.

On an undyed chromium-tanned bovine crust leather, a uniform surface application was carried out by spray-coating with the air-spray gun with the above-described mixture, thereby applying about 30 g / m ^{2 of} bovine crust leather. Thereafter, the leather was dried at 80 ° C. and then stored for one day under standard conditions.

The following performance characteristics were found: extrusion properties: very well Lightfastness (DIN EN ISO 5-B02) 4 Water drop authenticity IUF 420 5 Migration fastness according to DIN EN ISO 15701 4 to 5 Rubbing fast dry VESLIC 1000

Claims (18)

Process for the treatment of pigments in particulate form, comprising the following steps: a) mixing of pigment in particulate Mold with at least one nonionic surfactant, b) Dispersing the so available Mixture of pigment in particulate Form and non-ionic surfactant Cloth in watery Medium, c) polymerizing at least one first monomer or copolymerizing a first mixture of comonomers in the presence a dispersion according to b), wherein water-insoluble polymer or copolymer on the surface the pigments in particulate Shape is formed, d) Add at least one second Monomers or a second mixture of comonomers and polymerization or copolymerization. A method according to claim 1, characterized in that in step d), a polymer or copolymer having a glass transition temperature T _g of less than 20 ° C is produced. Method according to claim 1 or 2, characterized that the pigments in particulate form are organic pigments is. Method according to one of claims 1 to 3, characterized in that it is the first monomer is a vinyl aromatic compound or a compound of general formula I.

where in formula I the variables are defined as follows: R ¹ selected from hydrogen, unbranched or branched C ₁ -C ₁₀ -alkyl, R ² selected from hydrogen, unbranched or branched C ₁ -C ₁₀ -alkyl, R ³ selected from unbranched or branched C ₄ -C ₁₀ -alkyl. Method according to one of claims 1 to 4, characterized that the first mixture of comonomers is a mixture from at least one vinyl aromatic compound and at least a compound of general formula I. Method according to one of claims 1 to 5, characterized in that in a compound of general formula IR ¹ and R ² are selected to be hydrogen. Method according to one of claims 1 to 6, characterized in that the second monomer is added to a monomer of general formula II,

wherein the variables in formula II are defined as follows: R ⁴ selected from hydrogen, unbranched or branched C ₁ -C ₁₀ -alkyl, R ⁵ selected from hydrogen, unbranched or branched C ₁ -C ₁₀ -alkyl, R ⁶ selected from unbranched or branched C ₁ -C ₁₀ alkyl. Method according to one of claims 1 to 7, characterized that the second mixture of comonomers is at least one monomer of general formula II. Method according to one of claims 1 to 8, characterized in that in a compound of general formula II R ⁴ is hydrogen or methyl and R ⁵ is selected to be hydrogen. Method according to one of claims 8 to 9, characterized that in the second mixture of comonomers at least one comonomer, selected vinylaromatic compound and a compound of the general Formula I, is included. Method according to one of claims 1 to 10, characterized in that in step d) up to 5 wt .-%, based on the second mixture of comonomers, of at least one compound of formula Va or Vb

wherein the variables are defined as follows: R ¹⁰ to R ^{12 are the} same or different and selected from hydrogen and unbranched or branched C ₁ -C ₁₀ -alkyl, X selected from hydrogen, glycidyl, groups having tertiary amino groups and enolisable groups having 1 to 20 C-atoms. Treated pigments in particulate form, obtainable according to a method according to claims 1 to 11th Use of treated pigments in particulate form according to claim 12 for the coloring of leather. Use according to claim 13, characterized that it is a dressing of leather. Process for the coloring of leather, characterized that one pre-dyed Leather with at least one treated pigment in particulate form treated according to claim 12. aqueous Primer dispersions containing at least one treated pigment in particulate Mold according to claim 12, as well as at least one of the following components: at least one wax, at least one biocide or at least one Binder. Colored leather, obtainable by a process according to claim 15. Shoes made of colored leather according to claim 17th