WO2007003264A2

WO2007003264A2 - Polyaspartic acid derivatives in covering agents containing polysiloxane

Info

Publication number: WO2007003264A2
Application number: PCT/EP2006/005830
Authority: WO
Inventors: Josephus Slaats; Jürgen REINERS; Michael Franken
Original assignee: Lanxess Deutschland Gmbh
Priority date: 2005-07-02
Filing date: 2006-06-17
Publication date: 2007-01-11
Also published as: KR20080026150A; CN101213266A; WO2007003264A3; EP1904556A2; BRPI0613117A2; DE102005031043A1

Abstract

The invention relates to a mixture containing A) at least one polyaspartic acid derivative and B) at least one polysiloxane.

Description

Polyaspartic acid derivatives in polysiloxane-containing coating compositions

The invention relates to mixtures comprising polyaspartic acid derivatives and polysiloxanes, their preparation and use for reducing the tack in PUR and / or acrylate coatings, corresponding coating dispersions and the substrates coated therewith.

It is known to use polysiloxanes in the coating sector above all as defoamers, deaerators, leveling agents or as a tribological additive (that is to say as lubricants, grip agents or for setting up a specific so-called stick-slip effect).

Such applications are described for example in EP-A 994 136 and WO-A-2003/091349.

However, polysiloxanes also have disadvantages in the finish, for example in the top coat of the leather finish: it may happen that the stickiness of the leather directly after the drying channel of a spraying machine is still too high, so that the leathers can not be stacked immediately without the finishing layers stick together and the leather can not later be separated without damaging the finish.

This requires large storage capacities until the stickiness disappears.

Another problem is that the dressing layer after the short heating time in the drying channel due to the not yet completed crosslinking reaction in the polyurethane and / or Polyacrylatfϊlm does not have the excellent fastness properties, which has the leather after complete reaction, so that some stickiness of the Surface even after drying can not be excluded.

Despite the technical advances in leather finishing with purely aqueous formulations, there is still a need to improve the stackability of the freshly dressed leather, which in turn improves the efficiency of leather finishing (shorter drying times, improvement of in-house operations).

The object of the invention was to provide polysiloxane-containing mixtures which, especially in polyurethane and / or polyacrylate coating dispersions, can markedly reduce the tackiness of the coatings obtained therewith. Surprisingly, it has now been found that mixtures containing

A) at least one polyaspartic acid derivative and

B) at least one polysiloxane

significantly reduce the stickiness, in particular of PUR- and / or polyacrylate-coated substrates, while at the same time at least maintaining or even improving the other intended performance properties, such as mechanical properties and optical and haptic properties, in particular in flexible substrates such as leather or textile. In particular, in the case of corresponding topcoats based on PU and / or polyacrylates, e.g. on leather obtained a coating with a very dry and pleasant feel.

The mixture preferably contains as polyaspartic acid derivatives of component A) optionally hydrophobically modified polyaspartic acid, its salts, esters and / or amides, in particular polyaspartic acid salts with counterions from the group lithium, sodium, potassium, ammonium, alkylammonium, dialkylammonium, trialkylammonium, tetralkylammonium , wherein preferably partial esters or partial amides of polyaspartic acid, particularly preferably hydrophobically modified polyaspartic acid derivatives, in particular hydrophobically modified esters or amides of polyaspartic acid are used.

Preferred polyaspartic acid derivatives A) are, for example, polyaspartic acid and polyaspartic acid salts with counterions from the group lithium, sodium, potassium, ammonium, alkylammonium, dialkylammonium, trialkylammonium, tetralkylammonium, where the reaction with the counterion-yielding base may be partial or complete. Such products are known per se and are obtainable, for example, by dissolving polysuccinimide in water in the presence of the corresponding base.

Likewise preferred polyaspartic acid derivatives A) are partial esters or partial amides of polyaspartic acid.

The term hydrophobically modified polyaspartic acid derivatives are preferably understood as meaning those derivatives of polyaspartic acid which have hydrocarbon radicals having 1 to 60 carbon atoms, preferably alkyl radicals having 1 to 60 carbon atoms, in particular alkyl radicals having 8 to 30 carbon atoms as substituents. Preference is given to polyaspartic acid derivatives which are not completely dissolved in water but form a disperse phase in a continuous phase of water.

Suitable hydrophobically modified polyaspartic esters are, for example, also those known from EP 0 959 091 A1 and EP-A-959 090, of hydrophobically modified polyaspartic acid Esteramiden derived copolymers containing aspartic acid aspartic acid ester, aspartic acid amide units, other proteinogenic or non-proteinogenic amino acid units and iminodisuccinate units as structural units.

Still other possible polyaspartic acid derivatives A) are described in EP-A 1 518 881.

Very particularly preferred polyaspartic acid derivatives A) are (co) polymers which

a) structural units of the general formula I

contain, where

W is a trivalent radical from the group

stands in the

indicates the orientation for the incorporation of the radical W in the formula I, and Z represents the radicals -OH, -O ^" M ⁺ or -NR ¹ R ² , where R ¹ and R ² independently of one another

Hydrogen, optionally substituted alkyl radicals, alkenyl radicals, aralkyl radicals or

Cycloalkyl radicals which are represented by O atoms, N atoms, Si atoms or amide, carbonate,

Urethane, urea, allophanate, biuret, isocyanurate groups or mixtures thereof may be interrupted and

M ^{+ represents} H ⁺ or an alkali ion, an NH ₄ -In or a primary, secondary, tertiary or quaternary aliphatic ammonium radical which preferably bears a C ₁ -C ₂₂ -alkyl or -hydroxyalkyl group,

b) at least 5 mol%, preferably at least 10 mol%, based on the units of the formula I, structural units of the general formula Ia

contains, where

R ^ represents a hydrocarbon radical with Ci-Cgo atoms, preferably a saturated C _j -Cö _Q alkyl, especially for a Cg-C3 alkyl, and _Q regardless of

R ^ is hydrogen or has the same meaning as R ^, and

c) optionally contain polyether units having an average molecular weight of 200- 6000 g / mol.

The radicals W are derived, for example, from the hydrocarbon skeletons of the polycarboxylic acids from the following group or their anhydrides:

Dicarboxylic acids or dicarboxylic acid anhydrides such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, tricarboxylic acids or their anhydrides such as 1,2,3-propanetricarboxylic acid, citric acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,3-cyclohexanetricarboxylic acid, 2,3,5-Norbornantricarbonsäure, trimellitic acid, trimellitic anhydride, ^• and tetracarboxylic acids or their anhydrides or bisanhydrides such as 1,2,3,4-butane tetracarboxylic acid, 1, 2,4,5-cyclohexanetetracarboxylic acid, 2,3,5,6- Norbornanetetracarboxylic acid, 2,3,5,6- Norbomantetracarbonsäureanhydid, pyromellitic acid, Pyromellithsäurebisanhydrid etc. derive. Preference is given to maleic acid, fumaric acid, maleic anhydride or mixtures thereof with trimellitic anhydride or pyromellitic bisanhydride.

Suitable radicals M ⁺ are, for example, hydrogen (H +), hydroxyethylammonium, bis (2-hydroxyethyl) ammonium, tris (2-hydroxyethyl) ammonium, triethylammonium, tetraethylammonium, ammonium, butylammonium, N-methyl-N-bis (2-hydroxyethyl ) -ammonium, N-dimethyl-N- (2-hydroxyethyl) -ammonium, N-diethyl-N- (2-hydroxyethyl) -ammonium, benzyltrimethylammonium, morpholinium, hexadecylammonium, oleylammonium, octadecylammonium, as well as alkali ions such as sodium, potassium, lithium , Preference is given to sodium, potassium, hydrogen, ammonium, 2-hydroxyethylammonium, bis (2-hydroxyethyl) ammonium, tris (2-hydroxyethyl) ammonium, triethylammonium, tetraethylammonium.

Suitable nitrogen substituents R ¹ and R ² are independently, for example, optionally substituted Ci-C ₂ oo-alkyl or C ₂ -C ₂ o-alkenyl groups such as methyl, ethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, butyl, hexyl , Octyl, 2-ethyl-hexyl, octenyl, decyl, undecyl, undecenyl, dodecyl, tetradecyl, hexadecyl, oleyl, octadecyl, 12-hydroxy-9-octadecenyl, eicosanyl, 3-heptamethyl-trisiloxanyl-propyl, N-2- (e.g. 3-dimethylethoxysilyl-1-propyl) amino-1-ethyl, N-2- (3-methyl-diethoxysilyl-1-propyl) amino-1-ethyl, N, N-dimethyl-2-aminoethyl, N , N-diethyl-2-aminoethyl, N, N-dimethyl-3-amino-1-propyl, N, N-dimethyl-2-amino-1-propyl, N, N-diethyl-3-amino-1-propyl , N, N-diethyl-2-amino-1-propyl, morpholinoethyl, morpholinopropyl, piperazinoethyl, ethoxy-ethyl, ethoxy-ethoxy-ethyl, butoxy-ethoxy-ethoxy-ethyl, 2-methoxy-ethyl, tetrahydrofurfuryl, 5-hydroxy -l-pentyl, benzyl, N, N-dimethyl-aminocyclohexyl, 2-sulfoethyl, sodium or potassium salt, methoxycarbonyl-methyl, or C ₅ -Cio-cycloalkyl radicals such as cyclohexyl, by oxygen atoms or ester, amide, urethane, urea, allophanate, biuret and carbonate groups interrupted C ₂ -C ₂ oo radicals such as stearoyloxyethyl, Stearyloxyethoxyethyl, Stearylcarbamoyloxyethyl and Radicals derived from polyethers, preferably based on ethylene oxide and / or propylene oxide, such as, for example, methyloxy- (polyoxyethylene) -2-oxypropyl-1-methyloxy- (polyoxyethylene-co-oxypropylene) -2-oxypropyl-1, ethyloxy- (polyoxyethylene) -2-oxyethyl-1, ethyloxy- (polyoxypropylene) -2-oxypropyl-1, ethyloxy- (polyoxyethylene) -2-oxypropyl-1, and radicals of the formulas

wherein

R ^7, R ⁸ is C _r C ₃ -alkyl, C ₂ -C ₃ -alkenyl or C ₅ -C are ₀ cycloalkenyl,

n, m is a number from 1 to 100, preferably from 1 to 50, and

M ^{+ has} the meaning given above.

Further suitable radicals -NR ¹ R ^{2 are} derived by abstraction of an H atom of monofunctional polyethers with primary amino groups based on oxirane, methyl oxirane, tetrahydrofuran or mixtures thereof, the polyether segments random or blockwise can be arranged. Particular preference is given to radicals derived from monofunctional aminopolyethers which have polyoxypropene and / or polyoxyethene units in any desired order. Such products are known per se and, for example, under the name Jeffamine ^® M-600, Jeffamine ^® M-1000, Jeffamine ^® M-2070, Jeffamine® available M-2005 (products of Huntsman).

Also suitable are radicals -NR ¹ R ² , which are derived by abstraction of an H atom of monofunctional polyethers with primary amino groups, resulting from the reaction of polyisocyanates with monofunctional hydroxyl-terminated polyethers and subsequent hydrolysis. Instead of the hydrolysis, it is also possible to react the remaining isocyanate groups, for example with excess primary diamines, so that a free amino group remains.

Suitable polyisocyanates for preparing the monofunctional polyether having primary amino groups are: isophorone diisocyanate, bis (isocyanatocyclohexyl) methane, xylylene diisocyanate, 1,4-bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, toluylene diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane -2,4'-diisocyanate, the isocyanurate, biuret, allophanate, urea, uretdione group-containing oligomers of the aforementioned diisocyanates.

As monofunctional hydroxyl-functional polyethers, the alkoxylation products known per se from polyurethane chemistry on the basis of monofunctional starter alcohols obtained by polymerization of ethene oxide or propene oxide onto e.g. Methanol, ethanol or butanol, etc., are known.

Suitable diamines are: 1,2-ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1, 4-butylenediamine, 1, 2-dimethyl-1, 2-ethylenediamine 1, 6-hexamethylenediamine, isophoronediamine, bis (aminocyclohexyl) methane, xylylenediamine.

Preferably, the structural unit of the formula I corresponds to the formula II

embedded image in which

has the meaning given above. Preferred structural units of the formula Ia correspond to the formula Ib

embedded image in which

R ³ and R ^{4 have} the abovementioned meaning.

In a preferred embodiment, the polyaspartic acid derivative of component A) contains ester-group-containing units of the formula

embedded image in which

W has the above meaning and R is any organic radical in an amount of less than 5 wt .-%, in particular less than 2 wt .-%, preferably less than 1 wt .-%, based on the copolymer.

Preferred units of the formula Ia, in particular units of the formula Ib, contain as the radical of the formula -NR ^ R ^ one which is derived from compounds of the formula HNR- ^ R ^, as such the following compounds are preferred: secondary, preferably primary amines, such as 2-ethylhexylamine, 1-octylamine, 1-decylamine, 1-undecylamine, 1-dodecylamine, tetradecylamine, perfluorohexyl-1H, 1H, 2H, 2H-ethylamine, perfluorooctyl-1H, 1H, 2H, 2H-ethylamine, perfluorodecyl-1H, 1H, 2H, 2H-ethylamine, N-aminoethyl-N-methyl-perfluorooctylsulfonamide, hexadecylamine, octadecylamine, octadecenylamine, tallow fatty amine, hydrogenated tallow fatty amine, oleylamine, 12-hydroxy-octadec -9-enylamine, Eicosanylamin, dehydroabietylamine, Stearoyloxypropylamin, 2-butyl-octylamine, 4-octyl-hexadecylamine, Docosanylamin (C _22), tetra-cosanylamin (C _24), Triacontanylamin (C ₃ 0) and mixtures thereof. Very particularly preferred radicals of the formula -NR ^ R ^, which are derived from compounds of the formula HNR ³ R ⁴ , in particular of Cs to C ₃ o-mono-alkylamines.

The optionally present polyether units can be incorporated in the main chain of the copolymer or in the side chain or in the main chain and side chain.

Suitable polyether units (structural units from c)) are derived for the side chain of monofunctional amino-polyethers or for the backbone of diamino-polyethers.

Examples of monofunctional amino polyethers which may be mentioned are:

α-methyl-ω- (3-aminopropyl) -polyoxyethene, α-methyl-ω- (2-aminopropyl) -polyoxyethene, α-methyl-ω- (3-aminopropyl) -polyoxypropene, α-methyl-ω- (2 aminopropyl) -polyoxypropen or the corresponding mixed polyethers which are derived from ethene oxide and propene oxide, the ethoxylation and propoxylation products of C ₂ -C ₄ fatty alcohols. Such polyether amines are generally commercially available raw materials and, for example, as under the name Jeffamine ^® M-600, Jeffamine ^® M-1000, Jeffamine ^® M-2005, or Jeffamine ^® M-2070 (M = monofunctional amine; number = average molecular weight) Surfonamine ML-300 (products of Huntsman) available. Further suitable monofunctional amino-polyethers are accessible, for example, by reacting a monofunctional OH-functional polyether with a diisocyanate in a molar ratio of 1: 1 or an excess of diisocyanate, the resulting reaction product optionally freed from excess diisocyanate and the isocyanate groups then to the amine hydrolyzed. Examples are reaction products of propene oxide polyethers or Polyethenoxidpolyethem or Mischpolyethern based on ethene oxide and propene oxide, which were started on monofunctional alcohols such as methanol, ethanol, methoxyethanol, methoxy-diethylene glycol, butanol, butyldiglycol, etc., with diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, bis ( isocyanato-cyclohexyl) -methane, xylylene diisocyanate, tolylene diisocyanate, etc. (preferably in the molar ratio NCO: OH of 2: 1) and hydrolysis of the resulting NCO prepolymer to give the monoamine or by reaction of the resulting NCO prepolymer with diamines to form a monoamine. Preference is given to monofunctional polyetheramines which have a number average molecular weight of 200 to 6000 g / mol.

Examples of diamino polyethers which may be mentioned are:

α, ω-bis (3-aminopropyl) -polyoxypropene, α, ω-bis (2-amino-1-propyl) -polyoxypropene, α, ω-bis (2-amino-1-propyl) -poly (oxyethene-co -oxypropene), α, ω-bis (2-amino-1-ethyl) -polyoxyethene, α, ω-bis (2-amino-1-ethyl) -poly (oxyethene-co-oxypropene), α, ω-bis (2-amino-1-ethyl) -polyoxypropene, α, ω-bis (2-amino-1-propyl) -poly (oxyethene-co-oxybutene), α, ω-bis (2-amino-1-ethyl) -poly (oxyethylene-co-oxy-butene), α, ω-bis (4-amino-1-butyl) -polyoxybutene, α, ω-bis (4-amino-1-butyl) -poly (oxybutene-co-) oxypropene), α, ω-bis (4-amino-1-butyl) -poly (oxybutene-co-oxy-ethene), α, ω-bis (6-amino-1-hexylcarbamoyl) -polyoxybutene, α, ω-bis (6-amino-1-hexyl-carbamoyl) -polyoxyethene, α, ω-bis (6-amino-1-hexyl-carbamoyl) -polyoxypropene or mixtures thereof. Preference is given to diaminopolyethers based on propene oxide and / or ethene oxide having an average molar mass of 200-4000 g / mol. Such diamino polyethers are usually commercially available and for example under the name Jeffamine® D-230, Jeffamine® D-400, Jeffamine® D-2000 and Jeffamine® ED-600, Jeffamine® ED-2003, Jeffamine® XTJ 511 (products of the company Huntsman; D series = difunctional PO-based diamino polyethers; ED series = difunctional diamino polyethers based on EO / PO, number = average molecular weight). Preference is furthermore given to diaminopolyethers which are obtained by reacting diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, bis-isocyanatocyclohexylmethane with hydroxyl-functional polyethers based on ethene oxide, propene oxide or tetrahydrofuran or their copolyethers or mixtures thereof in a molar ratio of NCO: OH greater than 1: 1 and subsequent hydrolysis of terminal isocyanate group are available. Instead of the hydrolysis, a reaction of the terminal isocyanate group with diamines is possible in order to obtain suitable diamino-polyethers. In this case, the diamine should be used in excess.

In addition to the hydroxyl-functional polyethers mentioned in the preceding paragraph are also common in polyurethane chemistry hydroxy-terminated building blocks such as polycarbonate, polyester, Polyestercarbonatdiole and Polyethercarbonatdiole, for example, by reaction of the aforementioned hydroxyl-functional polyethers and other conventional building blocks such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hexanediol , Caprolactone by polycondensation with diphenyl carbonate or dimethyl carbonate (with elimination of phenol or methanol) and / or by polycondensation with adipic acid, glutaric acid, terephthalic acid, isophthalic acid (with elimination of water) or mixtures derived therefrom as raw materials for the preparation of diamino polyether the synthetic route described above, provided that at least one of the blocks contains incorporated in the polymer chain polyether units. Suitable diisocyanates and diamines for the reaction of these building blocks are the already mentioned diisocyanates and diamines. Particularly preferred reactants for this synthesis are polyethers based on oxirane and methyloxirane having two hydroxyl end groups, diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate and diamines such as ethylenediamine, hexamethylenediamine and isophoronediamine.

Another possibility for the preparation of suitable diaminofunctional polyethers is the base-catalyzed addition of acrylonitrile to hydroxyl-terminated polyethers and subsequent hydrogenation of the nitrile groups to amino groups.

Another possibility is the catalytic amination of the polyethers with ammonia. Of course, all linear amino-terminated polyurethanes, polyureas or polyurethane ureas, in the synthesis of which polyethers are incorporated in the main chain, are suitable as raw materials for the preparation of the polyether-modified copolymers according to the invention. In addition to the polyethers based on ethene oxide and / or propene oxide and / or tetrahydrofuran or mixed polyethers or any mixtures thereof, these polyurethanes, polyureas or polyurethane ureas may also be any other polymer diols customary in polyurethane chemistry (C4 polyethers, polyesters, polycarbonates, polyestercarbonates ), low molecular weight diols (butanediol, hexanediol, the adducts of ethylene oxide or propylene oxide with tallow fatty amine hydrogenated tallow fatty amine), hydrophilizing agents (dimethylol propionic acid, the adduct of sodium bisulfite to a 1,4-butenediol-initiated propylene oxide polyether having a molecular weight between 300 and 1000 g / mol), diamines (hydrazine hydrate, ethylenediamine, hexamethylenediamine, isophoronediamine, bis (aminocyclohexyl) methane, N- (2-aminoethyl) -2-aminoethane-sulfonic acid sodium salt, N- (2-aminoethyl) -2- aminopropionic acid sodium salt), bis-aminopropyl-terminated polysiloxanes having mops of between 200 and 3000 g / mol, etc., as raw materials.

Particularly preferred are polyethene oxide and / or polypropene oxide units containing diamines having an average molecular weight of 200 to 6000 g / mol.

The prefix "poly" in the abovementioned commodity designations preferably has a value such that the corresponding monoamines or diamines have a preferred number average molecular weight of from 200 to 4000 g / mol, preferably from 400 to 2500 g / mol.

In a preferred embodiment, the proportion of units of the formula (I) with

together (ie both possible meanings of W) more than 50 mol%, based on the sum of all units of the formula (I), in particular more than 80 mol%, very particularly preferably more than 90 mol%.

Preferred copolymers according to the invention contain structural units of the formulas (IIa) and (Ub)

In addition, the copolymers according to the invention may contain further divalent bridge members V in the main chain which are different from the units a), b) and c).

Preferred copolymers contain 0 to 10 mol% of such divalent bridge members V in the main chain, based on the sum of all units of formula I, wherein V is a bivalent radical derived from polycarboxylic acids, polyamines, lactams or aminocarboxylic acids. The bridge members V are preferably derived from polyamines, in particular diamines, or polycarboxylic acids, in particular dicarboxylic acids, and from aminocarboxylic acids or their lactams.

These units may be contained in the main chain and then preferably serve to link the units of the formula I, Ia, Ib, II, IIa, IIb with one another in any order. They can also serve to link different polyether units that are incorporated in the main chain. It is also possible for a plurality of divalent radicals from the abovementioned group of polycarboxylic acids, polyamines, lactams and aminocarboxylic acids to be condensed and thus incorporated into longer bridge members.

Preferred bridge members V are derived from the following polyamines (VI): ethylenediamine, 1,2- and 1,3-propylenediamine, 1,6-hexamethylenediamine, isophoronediamine, bisaminocyclohexylmethane, diethylenetriamine, triethylenetetramine, bishexamethylenetriamine, diaminocyclohexane, xylylenediamine, Bis-3-aminopropyl ether, bis-aminomethyltricyclo [5.2.1.0 ² ' ⁶ ] decane. Preference is given to diamines, in particular ethylenediamine and propylenediamine, isophoronediamine, hexamethylenediamine.

Preferred bridge members V are derived from the following polycarboxylic acids (V-2): oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, tartaric acid, cyclohexane-1,2-dicarboxylic acid, cyclohexane-l, 3-dicarboxylic acid, cyclohexane-l, 4 dicarboxylic acid, 1-cyclohexene-1,2-dicarboxylic acid anhydride, 4-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic anhydride, 3-cyclohexene-1,2-dicarboxylic anhydride, norbornane-2,3-dicarboxylic acid , Norbornane-2,3-dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-1,2-dicarboxylic acid. Preference is given to dicarboxylic acids, in particular succinic acids, glutaric acid, adipic acid. Preferred bridge members V are derived from the following aminocarboxylic acids (V-3): glycine, alanine, aspartic acid, glutamic acid, other naturally occurring amino acids, aminopropionic acid, aminobutyric acid, aminohexanecarboxylic acid. Glycine, aspartic acid, glutamic acid are preferred.

Preferred bridge members V are derived from the following lactams (V-4): butyrolactam, caprolactam, laurolactam. Preference is given to caprolactam.

Suitable longer bridge members V can also be obtained by condensation or cocondensation reaction of the aforementioned building blocks V-I to V-4. Due to the terminal amino groups and / or carboxyl groups, these bridge members are incorporated in the main chain during the preparation of the preferred 10 (co) polymers of the component.

As end groups, the preferred (co) polymers of component A) preferably have the following radicals, which can be defined via the starting materials and preferably from the optionally used polycarboxylic acids, dicarboxylic acids, polyamines, diamines, lactams, ammonia, amines, polyethers and for the preparation the monofunctional and difunctional polyether

Derive 15 monomer units used. In particular, the end groups may be based on the following radicals: alkyl radicals, alkoxy radicals, alkylamino radicals, cycloalkylamino radicals or aliphatic amino-substituted aralkyl radicals, polyetheramino radicals, N-substituted maleimide radicals, OH, COOH, CONH ₂ and NH ₂ groups, and radicals, which are derived from aspartic acid and its derivatives. Preferred end groups are, for example, hydroxyl, amino, carboxyl and its salts,

20 Carboxylic acid amide, N-substituted maleimide, N-substituted aspartic acid amide, methyl, ethyl, butyl, methyloxy, ethoxy, butoxy, butylamino, hexylamino, decylamino, dodecylamino, tetradecylamino, hexadecylamino, octadecylamino, eicosanylamino, N-methyl-N-octadecylamino, bis (octadecyl) amino, benzylamino and 2-hydroxyethylamino.

Particular preference is given to polyether-modified copolymers having a number average molecular weight of from 500 to 50,000, preferably from 1,500 to 30,000, g / mol, in particular those which are

5 to 35 mol% of structural units of the formula IIa and

Contain from 15 to 90 mol% of structural units of the formula IIb,

in each case based on the sum of the structural units of the formula I.

30. Preference is given to those copolymers of component A) which contain from 10 to 90% by weight, in particular from 30 to 80% by weight, of structural units of the formula I, in each case based on the copolymer. Preferably, the copolymer of component A) consists of more than 95 wt .-%, in particular more than 98 wt .-% of the structural units of the formula I, Ia, optionally the polyether units and optionally divalent bridge members.

In a particular embodiment - hereinafter referred to as Al - consists of the copolymer of component A) to more than 95 wt .-%, in particular more than 98 wt .-% of structural units of the formula I and optionally polyether units, wherein

i) 50 to 100 mol%, in particular 70 to 100 mol%, based on the sum of these two

Units attributable to structural units of the formula I, of which at least 5 mol%, in particular 5 to 35 mol%, based on the units of the formula I, those of the formula Ia, in particular of the formula Ib correspond, and

ii) 0 to 50 mol%, preferably 0 to 30 mol%, based on the sum of these two units, of polyether units having an average molecular weight of 200 to 6000 g / mol.

In a very particularly preferred embodiment Al, the radical -NR ³ R ⁴ in formula Ia, in particular Ib, represents radicals which are derived from the following amines HNR ³ R ⁴ : dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, hexadecenylamine, octadecenylamine, tallow fatty amine, hydrogenated Tallow fatty amine, N-methyl-octadecylamine, perfluorohexyl-1H, 1H, 2H, 2H-ethylamine, perfluorooctyl-1H, 1H, 2H, 2H-ethylamine, perfluoro-decyl-1H, 1H, 2H, 2H-ethylamine, N-aminoethyl- N-methyl-perfluorooctylsulfonamide, branched aliphatic amines derived from the corresponding Guerbet alcohols, such as 2-butyl-1-octylamine, 2-hexyl-1-octylamine, 2-butyl-1-decylamine, 2-hexylamine 1-decylamine, 2-octyl-1-decylamine, 2-hexyldodecylamine, 2-octyldodecylamine, 2-decyl-1-tetradecylamine, dodecylhexadecylamine, tetradecyl-octadecylamine, hexadecyl-octadecylamine, hexadecyl-eicosanylamine, and amino compounds, by reacting Guerbet alcohols such as 2-butyl-l-octanol, 2-hexyl-l-octanol, 2-butyl-l-decanol, 2-H Exyl-l-decanol, 2-octyl-l-decanol, 2-hexyl-dodecanol, 2-octyl-dodecanol, 2-decyl-1-tetadecanol, dodecyl-hexadecanol, tetradecyl-octadecanol, hexadecyl-octadecanol, hexadecyl eicosanol with Hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, cyclohexylene diisocyanate, bis (isocyanatocyclohexyl) methane in a molar ratio of 1: 1 to 1.5: 1 and subsequent hydrolysis of the NCO groups or by reaction of the NCO groups are obtained with excess diamine, or mixtures of the aforementioned amines HNR ³ R ⁴ .

In a particular embodiment A1, the copolymer of component A) comprises polyether units of component ii) derived from diamines of the formula

Jeffamine XTJ 511: molecular weight approx. 220 g / mol m = 2.0 n + p = 2.0

600 g / mol m = 9.0 n + p = 3.6 Jeffamine ED-2003: molar mass approx. 2000 g / mol m = 38.7 n + p = 6.0

Jeffamine D-230: molar mass approx. 230 g / mol x = 2 - 3

Jeffamine D-400: Molar mass approx. 400 g / mol x = 5 - 6

Jeffamine D-2000: molar mass approx. 2000 g / mol x = approx. 33

Jeffamine D-4000: molecular weight about 4000 g / mol x = about 68

derived.

In a likewise particular embodiment - hereinafter referred to as A2 - consists of the copolymer of component A) to more than 95 wt .-%, in particular more than 98 wt .-% of structural units of the formula I, of which

i) at least 5 mol%, in particular 5 to 50 mol%, based on the structural units of the formula I, of the formula Ia, in particular Ib correspond and

ii) at least 1 mol%, in particular 1 to 50 mol%, based on the units of the formula I, the formula Ic, in particular the formula Id correspond

wherein W has the meaning given above,

R ^ is a radical containing more than two ether groups, which are derived from Cz-Cβ-alkylene oxide units, which is optionally substituted by urethane, carbonate, urea, biuret, allophanate, isocyanate, alkylene, cycloalkylene or aralkylene groups is interrupted and

R6 is hydrogen or has the meaning of R ^.

In a preferred embodiment A2, the radical -NR ³ R ⁴ in formula Ia, in particular Ib has the same meaning as stated for the embodiment Al above.

In a preferred embodiment A2, the radical -NR ⁵ R ^{6 is derived} from amines of the formulas HNR ⁵ R ⁶ which correspond to the abovementioned monofunctional amino-polyethers, in particular primary amino-polyethers.

Particular preference is given to polyether units of components ii) which are derived from the following monoamines:

wherein

R is H or C 1 -C 4 -alkyl, in particular H or CH 3,

R ^{1 is} H or CH 3 and

a number from 5 to 50 means, in particular

600 g / mol molar ratio PO / EO = 9/1 Jeffamine XTJ-506 (M-1000): molar mass approx. 1000 g / mol molar ratio PO / EO = 3/19 2000 g / mol molar ratio PO / EO = 39/6 Jeffamine M-2070: molar mass approx. 2000 g / mol molar ratio PO / EO = 10/3.

and monofunctional polyether units obtained by reacting hexamethylene diisocyanate, isophorone diisocyanate, bis (4-isocyanatohexyl) methane, tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, xylylene diisocyanate, isocyanurate, uretdione, Allophanate, urea groups containing oligomers of the above diisocyanates with monofunctional hydroxyl-terminated polyethers, the latter being obtained by alkoxylation of monofunctional starter alcohols such as methanol, ethanol, butanol with ethene oxide, propene oxide or mixtures thereof, and subsequent hydrolysis of the remaining isocyanate group or reaction of the remaining isocyanate group an excess of diamines such as ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,6-hexamethylenediamine, isophoronediamine, bis (aminocyclohexyl) methane to give the monofunctional polyetheramine, such as

embedded image in which

R, R 'and n have the abovementioned meaning

and

R 'is H or CH3.

Very particular preference is given to those polyaspartic acid derivatives, in particular polyaspartic acid amides of component A), which contain no polyether groups.

Very particularly preferred components A) are, for example, polyaspartic acid and its salts with sodium, potassium, ammonium and amines and alkanolamines as counterion.

Very particularly preferred components A) are hydrophobically modified polyaspartic acid derivatives, in particular the amide derivatives which are obtainable by incorporation of alkyl radicals having 1 to 60 C atoms, in particular alkyl radicals having 8 to 30 C atoms and optionally polyether units, into the polyaspartic acid polymer, as described above in the embodiments Al and A2. Such products are known, for example, from EP-A 842 300 and EP-A 1 518 881. Particularly preferred are hydrophobically modified polyaspartic acid derivatives, in particular hydrophobically modified esters or amides of polyaspartic acid, as described for example in DE-A 195 28 782.

The polyaspartic acid derivatives of component A) can also be prepared in the manner described in EP-A 1 518 881 or in an analogous manner.

Preferred polyether-modified polyaspartic acid derivatives of component A) according to embodiment A1 have weight average molecular weights of from 500 to 30,000, preferably from 1,000 to 20,000, in particular from 1,000 to 10,000, g / mol by gel permeation chromatography (calibrated with polystyrene). The structural units are preferably arranged alternately, block-wise or randomly distributed.

The polyaspartic acid derivatives of component A) may also contain branching points which, for example, in the case of maleic anhydride by incorporation of iminodisuccinate or by incorporation of Nitrilo trisuccinate or in concomitant use of tri- or tetracarboxylic acids or by Michael addition of polyamines to the double bond of maleimide End groups and further reaction of the resulting secondary amine can arise. However, particularly preferred are products which are soluble in water or homogeneously dispersible. However, crosslinked products are less preferred for use according to the invention as leather auxiliaries. In the case of branched structures, preference is given to copolymers which have a proportion of <5 mol% (based on structural units I) of branched structures in order to ensure sufficient solubility or miscibility with water. However, it may be possible to reduce the molar masses by using monofunctional compounds in the condensation reaction in such a way that a higher proportion of branching becomes accessible. Suitable monofunctional compounds for controlling the molecular weights are monocarboxylic acids such as formic acid, acetic acid, propionic acid, benzoic acid, cyclohexanecarboxylic acid, stearic acid, or monoamines such as butylamine, dibutylamine, aminoethanol, hexylamine, dodecylamine, hexadecylamine, octadecylamine, octadecenylamine, and the above monofunctional polyetheramines.

The optionally polyether-modified polyaspartic acid derivatives of component A), in particular polyaspartic acid amides, are preferably self-dispersing. However, it is also possible to use external dispersants; As such, in principle cationic, anionic and nonionic dispersants come into question, as they are e.g. in "Methods of Organic Chemistry" (Houben-Weyl), 4th Edition, Volume XTV / 1, Georg Thieme Verlag, Stuttgart 1961, p 190 f. are described.

Preferred dispersants include, for example Cg-Cig-n-alkyl sulfates, Cg-Cig-n-alkyl benzene sulphonates, Cs-C i g n-alkyl-trimethyl-ammonium salts, _N-di-Cs-C1 8-alkyl-dirnethyl-ammonium- salts, Cg-Qg-n-alkyl-carboxylates, Cg-Qg-n-alkyl-dmethylamine oxides, Cg-Cig-n-alkyl-dimethyl- phosphine oxides and - preferably - oligoethylene glycol mono-Q-cis-alkyl ethers having an average of 2 to 30 ethoxy groups per molecule. The n-alkyl radicals may also be replaced by partially unsaturated linear aliphatic radicals. Particularly preferred dispersants are oligoethylene glycol mono-Ci-Ci ₄ alkyl ethers having an average of 4 to 12 ethoxy groups per molecule, in particular oligoethylene glycol mono-Cu-alkyl ethers having an average of 8 ethoxy groups per molecule.

Preferred dispersants further include oleic acid, oleic acid sarcosides, ricinoleic acid, stearic acid, fatty acid partial esters of polyols such as glycerol, trimethylolpropane or pentaerythritol and their acylation, ethoxylation and propoxylation products, e.g. Glycerol monostearate and monooleate, sorbitan monostearate and monooleate, sorbitan tristearate and trioleate and their reaction products with dicarboxylic acid anhydrides such as succinic anhydride, maleic anhydride, phthalic anhydride or tetrahydrophthalic anhydride, reaction products of bis (hydroxymethyl) tricyclodecane and maleic anhydride or succinic anhydride and derivatives thereof, preferably in the form of their alkali or ammonium salts.

Particularly preferred dispersants are salts of long-chain fatty acids, preferably of oleic acid and an aminoalcohol, preferably hydroxyethylamine, bishydroxyethylamine or trishydroxyethylamine.

For the preparation of an aqueous dispersion, it is generally recommended to meter the dispersant into the reaction mixture before, during or after the dispersion at from 7O ⁰ C to 140 ⁰ C with stirring. It is also possible to disperse the reaction mixture in an aqueous dispersant solution.

The dispersant content is generally not more than 30, preferably 3 to 15 wt .-%, based on the aqueous dispersion of component A).

The solids content of the dispersions of component A) is preferably from 5 to 60% by weight, particularly preferably from 10 to 40% by weight. The average particle size of the dispersed polyaspartic acid amides is generally 50 to 1000, preferably 50 to 700 and in particular 80 to 400 nm. The pH during the dispersion is preferably set between 5 and 11, particularly preferably 6 to 10.

For application in the coating, it may be advantageous to reduce the particle size of the disperse phase. For this purpose, an already obtained pre-emulsion under high shear rate can be aftertreated in known dispersing machines such as jet dispersers with suitable nozzles, high-pressure emulsifying machines or mixers with rotor-stator principle. It is also possible to generate the dispersion in situ in the chambers or nozzles of the mentioned devices. The Dispersion time can be between a few minutes up to 4 hours. The dispersion is preferably carried out in a temperature range between 20 and 75 ⁰ C.

Furthermore, it is advantageous in the context of the invention to subject the resulting dispersions (component A) to bleaching. The bleaching can be carried out oxidatively or reductively. Preference is given to oxidative bleaching. Suitable oxidizing agents are hydrogen peroxide or alkali metal or ammonium persulfate in aqueous solution. The bleach may be in the temperature range between 20 and 9O ⁰ C, preferably between 30 and 60 ⁰ C are performed. Unused bleach is then destroyed with a reducing agent. As a reducing agent, for example, sodium bisulfite solution, or peroxide-decomposing enzyme formulations based on oxidoreductases are as besipielsweise BAYREDUKT ^® EPK (product of LANXESS Germany GmbH). The decomposition of radicals of the oxidizing agent is advantageously carried out at temperatures between 20 and 45 ⁰ C in the pH range between 5 and 8.

Suitable polysiloxanes of component B) are known per se and commercially available.

For the inventive mixtures especially or branched polysiloxanes predominantly substituted if necessary by fluorine atoms and / or unterbrochenenen by heteroatoms linear Ci-C _Σ o-alkyl, aryl and aralkyl radicals substituted Si atoms are suitable as components B) contain.

The basic skeleton of the siloxanes may contain predominantly D units and optionally M units, but may also have branches through T and Q units, it being possible for the structural elements to be combined as desired. Examples of products with T units are e.g. Polysilsesquioxanes accessible by hydrolysis of trialkoxysilanes.

In the case of polysiloxanes, D units are repeat units which lead to a linear polysiloxane chain, for example of the general formula - [Si (CH ₃ ) ₂ -O] -, in which the 2 valences of the silicon remaining after abstraction of the 2 adjacent O atoms Atoms are saturated by hydrocarbon radicals.

In the case of polysiloxanes, M units are repeating units which form the end groups of a linear or branched polysiloxane chain, for example of the general formula Si (CH ₃ VO-), in which the 3 valencies of the Si atoms remaining after abstraction of the adjacent O atom are saturated by hydrocarbon radicals are.

T units in the case of polysiloxanes are repeat units which lead to a branched polysiloxane chain, for example of the general formula - [O-Si (CH ₃ ) O] -, in which the valence of the Si atoms remaining after abstraction of the 3 adjacent O atoms are saturated by hydrocarbon radicals. Q units in the case of polysiloxanes are repeating units which lead to a branching in a polysiloxane chain, the Si atom being coordinated by 4 oxygen atoms.

The polysiloxanes may be, for example, simple polydialkylsiloxanes with or without reactive groups on the silicon units (alkoxysilane groups, silanol groups). Also suitable are polysiloxanes with organofunctional substituents, or those which are substituted by polyether units. The organofunctional substituents may be charge neutral or ionic in nature. There may also be several substituents in the polysiloxane chain side by side. It is also possible to use mixtures of the polysiloxanes.

Suitable organofunctional substituents bonded to Si atoms are e.g. 3-aminopropyl, N (2-aminoethyl) -aminopropyl, hydroxymethyl, hydroxyethyl, hydropropyl, hydroxybutyl,

Hydroxyundecyl etc. and the corresponding Alkylenoxidaddukte this amino and

Hydroxy-functional polysiloxanes, carboxyl group-containing substituents which can be replaced by any desired

Spacer groups to which Si atoms may be bonded, epoxyalkyl, epoxyalkoxyalkyl,

Epoxycycloalkyl-alkyl, Epoxycylcloalkoxyalkyl, vinyl, allyl, several OH-containing alkyl radicals such as glucosylaminoalkyl, etc. Spacer groups can, for example, alkylene radicals, or by ester, urethane, urea, carbonate, imino or amide interrupted

Be alkylene radicals.

Preferred polysiloxanes are used as aqueous dispersions of the aforementioned Polysüoxan types.

Particularly preferred are polysiloxanes having a molecular weight of 500 to 200,000 g / mol and / or a degree of polymerization of 7 to 2750 (SiO units) (and / or having a viscosity, measured at 25 ° C, from 25 to 500,000 cP at 25 ⁰ C, in particular 100 to 250,000 cP, preferably 1000 to 250,000).

Polysiloxanes are suitable in which the valences remaining on the Si atom after abstraction of the O atoms are saturated by hydrocarbon radicals. In particular, the hydrocarbon radicals have 1-60 carbon atoms and may be interrupted by heteroatoms such as O, N, S and P or by functional groups such as hydroxy, amino, epoxy, isocyanato, carbamoyl, ureido, alkoxycarbonyl, trimethylsilyloxy, carboxyl, carboxylate, sulfonic acid , Sulphonate, phosphoric acid, phosphate, mercapto. The following hydrocarbon radicals may be mentioned as examples: methyl, ethyl, propyl, isopropyl, butyl, cyclohexyl, cyclohexylalkyl, phenyl, aralkyl, 3-hydroxypropyl, 3-aminopropyl, 3-glycidoxypropyl (= 3- (l, 2-epoxypropoxy) propyl) , Epoxycyclohexyl-ethyl; N- (2-aminoethyl) 3-aminoprop-1-yl, 11-carboxy-undec-1-yl, 2-carboxyethyl, 2-carboxy-propyl, hydroxy-poly (oxyethylene) -oxy-alkyl, alkoxy-poly ( oxyethylene) -oxy-alkyl, hydroxy-poly (oxypropylene) -oxy-alkyl, alkoxy poly (oxypropylene) -oxy-alkyl, etc. It is also possible that the polysiloxanes carry a plurality of substituents independently of one another on the same hydrocarbon radical or independently carry the substituents on various hydrocarbon radicals along the polysiloxanes.

Particularly preferred polysiloxanes are polydimethylsiloxanes which are predominantly composed of M, D, T and Q units and optionally also have reactive chain ends of the silanol group and alkoxysilyl group type or optionally hydroxy, carboxy, amino-functionalized alkyl radicals.

Such polysiloxanes, which may for example also be present as silicone emulsions, are known to the person skilled in the art and are commercially available.

Particular preference is also given to the carboxyl-functional polysiloxanes of EP-A 1 108 765. Preference is given to the carboxyl-containing polysiloxanes described in the examples, which are obtained by reacting aminopolysiloxane derivatives with polycarboxylic anhydrides and the cyanurea-containing polysiloxanes from EP-A 1 263 992, which are advantageously used because of the reactive groups in the dressing.

Further suitable polysiloxanes are e.g. in EP-A 0 757 108 (page 2, lines 36 to 41).

Very particular preference is given to high molecular weight polysiloxane resins, which may also be present in the form of polysiloxane resin emulsions, in particular those polysiloxanes having a viscosity of 100 to 200,000 cSt at 25 ° C., which are commercially available. Examples include: Dow Corning Fluid 200 (viscosity 60000 cP), DC 200 with a viscosity of 100, 200 or 500 cP, Dow Corning 3289 Bladder Lubricant (viscosity 200000 cP), Dow Corning Q2-3238 Dispersible Silicone Additives.

Preferred mixtures according to the invention contain

0.5 to 70% by weight of component A),

0.5-70% by weight of component B)

and water, the contents being based on the dry residue of components A) and B).

The pH of the mixture according to the invention, in particular as a dispersion, is preferably 4.5 to 12, preferably in the pH range from 4.5 to 10, in particular from 5 to 8. Particular preference is given to mixtures according to the invention comprising

From 5 to 70% by weight, in particular from 5 to 35% by weight, of component A)

From 5 to 70% by weight, in particular from 30 to 60% by weight, of component B)

From 5 to 70% by weight of water, in particular from 5 to 65% by weight,

wherein the contents of the components A) and B) refer to the dry residue, and the total dry residue of the mixture 10 to 70 wt .-%, in particular 20 to 70 wt .-%, and the mixture has a viscosity of 50 to 5000 mPas, in particular 100 to 4000 mPas, at 20 ⁰ C and 100 s' ¹ has.

The dry residue is the concentration that can be detected gravimetrically as the residue after evaporation of the volatiles such as water and solvent.

The mixture generally has an average particle size (measured by laser correlation spectroscopy or ultracentrifuge) of from 30 to 1000, preferably from 30 to 700, and particularly preferably from 50 to 400 nm.

The mixture according to the invention may also contain conventional additives, such as the already mentioned dispersants, emulsifiers, pH-regulating additives (acids, bases for adjusting a pH of the mixture between 5 and 8), and optionally conventional material protection agents, these additives in one the components A) or B) may be contained or may be added separately.

The invention further relates to a process for the preparation of the mixture according to the invention, characterized in that component A) and component B) are mixed, preferably dispersed under shear in component B) and preferably the total dry residue with water to 10 to 70 wt .-% sets. The mixing, in particular the dispersion is generally carried out at 10 ⁰ C to 15O ⁰ C, optionally under pressure, preferably under pressure at 15 ⁰ C to 100 ⁰ C, more preferably at 15 ° C to 70 ⁰ C with the addition of shear energy.

It is also possible to disperse component B) in component A). The addition of water to adjust the total dry residue of the mixture can be made at the beginning, during or at the end of the dispersion.

Preference is given to the process for preparing the mixture according to the invention by adding A) to component B) with shearing and addition of water. Suitable shear units are stirrers of generally conventional geometry, but also high-speed stirrers or devices with a rotor-stator principle, such as dissolvers, Ultra-Turrax, and nozzle technologies and high-pressure emulsification techniques such as homogenizers, microfluidizers or jet dispersers with nozzle technology. It is also possible to obtain stable dispersions by treatment with ultrasound.

The mixture according to the invention can be formulated with other customary additives known to those skilled in the art and auxiliaries for the ready-to-use coating composition.

The invention further relates to the use of the mixture according to the invention for reducing the tackiness of coatings of substrates based on aqueous polyurethane and / or polyacrylate dispersions.

The invention further relates to a process for the preparation of coating dispersions which are suitable for coating substrates, in particular for leather finishing, characterized in that mixtures according to the invention with at least one polyurethane and / or polyacrylate polymer and optionally pigment pastes and conventional finishing auxiliaries, which are described in preferred form below, mixes. In this mixture, a homogeneous mixture is preferably obtained. Thereafter, the viscosity is preferably adjusted to the proper for the type of application spray viscosity of 15 to 35 seconds (flow time in Ford cup, nozzle 4mm) and stirred the crosslinker.

The invention further relates to coating dispersions containing a mixture according to the invention and

C) at least one polyurethane and / or polyacrylate polymer.

Preferred components C) are polyurethane dispersions.

Particularly preferred are polyurethane dispersions which are obtainable from the following building blocks:

1) one or more polyisocyanates

2) one or more polyols based on polyethers, polyesters, polycarbonates, polyester carbonates, polyether carbonates having a molecular weight of 500 to 12000 g / mol and having a functionality of 2

3) one or more, different from 2) polyols having a functionality greater or smaller than 2

4) short-chain polyols having a functionality of 1 to 4 5) short chain polyols having ionic groups

6) one or more amino-functional compounds which may also carry ionic groups,

7) optionally a blocking agent for the capping of still free isocyanate groups

8) neutralizing agents and

9) water.

Suitable polyisocyanates 1) are preferably diisocyanates such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate, bis (isocyanatocyclohexyl) methane, and the di- and trimers of the aforementioned diisocyanates having an NCO functionality greater than 2.

Suitable polyols 2) are polyethers, such as poly (oxypropylene) diols, poly (oxyethylene) diols having a molecular weight of 500 to 12,000 g / mol, preferably a molecular weight of 500 to 4000 g / mol, particularly preferably having a molecular weight of 500 to 2500 g / mol, poly (tetrahydrofuran) diols having a molecular weight of 200 to 4000 g / mol, mixed polyethers of EO and PO and random or block copolyethers of the type of polytetrahydrofuran-ethylene oxide copolyether, polytetrahydrofuran-propylene oxide copolyether , Polytetrahydrofuran-Ethylöenoxid.Propyklenoxid, wherein the blocks of the monomer units may be arranged differently among each other, that is, an AB structure, ABA structure, BAB structure, A-random (B + C) -A may have etc. Such raw materials are known per se to the person skilled in the art and are commercially available.

Suitable polyols 3) are, for example, polyethers which are obtainable by reacting polyhydric alcohols having a functionality greater than 2, such as trimethylolpropane, pentaerythritol, glycerol, sorbitol, etc., with alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide and mixtures thereof.

Suitable polyols 4) are linear or branched monoalcohols such as ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, 2-ethylhexanol, octanol, up to the C30 alcohol.

Suitable polyols 4) are furthermore diols, such as ethanediol, propanediol, butanediol, hexanediol, bis (2-hydroxyethoxy) benzene, bis-2,2- [4- (2-hydroxyethoxy) -phenyl] -propane, bis-hydroxymethyltricyclo [5.2.1.0 ² ' ⁶ ] decane.

Suitable polyols 4) are trifunctional alcohols such as trimethylolpropane, glycerol, 1,1,1-tris (2-hydroxyethoxy-methyl) -propane, etc. Suitable polyols 4) having an OH functionality of 4 and higher are, for example, pentaerythritol, sorbitol, Gluconolactone, polyglycerol etc. Suitable ionic group-containing polyols 5) are dimethylolpropionic acid, dihydroxybutyric acid, dimethylolbutyric acid, tartaric acid, sulfo-containing diols, such as adducts of sodium disulfite with propoxylated 1,4-butanediol.

Suitable amino-functional compounds 6) are ethylenediamine, isophoronediamine, bis (aminocyclohexyl) methane, N- (2-aminoethyl) 2-aminoethane-1-sulfonic acid and its alkali metal salts, N- (2-aminoethyl) 2-aminoethane-1 carboxylic acid, Michael adducts of acrylic acid with isophoronediamine, cyanamide, diethylenetriamine, aminoethanol, diethanolamine.

Suitable blocking agents may be butanone oxime, dimethylpyrazole, pyrazole, caprolactam, sodium bisulfite, acetylacetone, diethyl malonate.

Suitable neutralizing agents 8) are, for example, triethylamine, N, N-dimethyl-aminoethanol, tripropylamine, N-methyl-bis (2-hydroxyethyl) amine, diethyl-aminoethanol, tris (2-hydroxyethyl) amine.

The processes for the preparation of polyurethane dispersions are known per se.

They are accessible, for example, by melt dispersing methods, acetone methods, etc. An overview of the preparation processes is described, for example, in Houben-Weyl, Methods of Organic Chemistry, Volume E 20, Macromolecular Chemistry, G. Thieme Verlag, Stuttgart, 1987 (pages 1659 to 1681).

Particularly suitable film-forming components for use in topcoating formulations are polyurethane dispersions whose films have a Shore A hardness of more than 50, in particular 50-100. The adjustment of the hardness Shore A by changing the reactants and the adjustment of the stoichiometric ratios of the reactants and the reaction parameters for the reaction are known in the art.

Also suitable are mixtures of different polyurethane dispersions to the desired Shore hardness A (measured on films) greater than 50, in particular 50-100, and certain properties such as tensile strength, modulus, etc., from leather articles to leather articles and depending on Application target may vary. Therefore, a large number of aqueous polyurethane dispersions for leather finishing are commercially available.

Very particular preference is given to those polyurethane dispersions which contain no solvents, such as NMP or other co-solvents, which are sometimes used to improve film formation, for example propylene glycol diacetate, methoxypropyl acetate, methoxypropanol, ethoxyethyl acetate, ethoxyethanol, etc.

Suitable components B) are also polyacrylate dispersions. The preparation of polyacrylate dispersions is generally carried out by solution or emulsion copolymerization.

This is known for example from: US Pat. No. 5,221,284, US Pat. No. 5,376,459.

Preferred polyacrylates have a molecular weight of 10,000 to 1,000,000 g / mol.

Particularly preferred are polyacrylate dispersions which are selected from at least one of the following monomers obtainable by free-radical copolymerization:

1) acrylic acid and methacrylic acid and their derivatives of the formula CH ₂ = CR '-CO-OR ² , wherein R ^{1 is} hydrogen or methyl and R ^{2 is} a hydrocarbon radical having 1 to 40 carbon atoms, which is also fluorine, hydroxy , may be substituted Ci- ₄ -Alkylammo, Ci _-4 -alkoxy, carbonyl groups, and polyether groups,

2) acrylic acid amide, methacrylamide and their derivatives,

3) styrene and substituted styrenes,

4) acrylonitrile,

5) vinyl esters such as vinyl acetate, vinyl propionate and / or

6) Unsaturated dicarboxylic acids such as crotonic acid, itaconic acid or maleic anhydride.

Suitable components C) are also mixtures of polyacrylate and polyurethane dispersions or dispersions obtained by grafting acrylate comonomers onto polyurethane dispersions (PUR-P AC hybrids), provided that they have a hardness sufficient to produce topcoats Shore A and are crosslinkable or crosslinkable with conventional crosslinkers.

Contain preferred coating dispersions

A) at least one polyaspartic acid amide containing 50-90 mol% of the structural units of the formula

IIa) and IIb), in particular 0-35 mol% of the structural units of the formula IIa) and 15-90 mol

% of the structural units of Fomel IIb), and 5-50 mol% of the structural units of the formula Ib) (particularly preferably with -NR ₃ R ₄ with R ₃ = H and R ₄ = hydrogenated tallow fatty amine), in each case based on the sum of the structural elements of the formula I),

^■ wherein M ⁺ is hydrogen, sodium or potassium and / or the radical of an alkanolamine, particularly ethanolamine, diethanolamine, diethylaminoethanol, dimethylaminoethanol, ethyldiethanolamine, methyldiethanolamine or triethanolamine is, B) at least one polysiloxane having a viscosity of 10,000 to 500,000 mPas at 25 ° C and

C) at least one aqueous polyurethane, wherein the film formed from its aqueous dispersion having an average particle size of 10 to 300 nm has a Shore A hardness of 20 to 100 and / or at least one aqueous polyacrylate.

Particularly preferred are coating dispersions containing

From 0.5 to 50, preferably from 5 to 40, particularly preferably from 10 to 30,% by weight of component A),

0.5 to 70, preferably 5.0 to 60, particularly preferably 10 to 50 wt .-% of component B) and

From 0.5 to 40, preferably from 0.5 to 30, particularly preferably from 1.0 to 20,% by weight of component C),

wherein the amounts A), B) and C) in each case relate to dry residues,

and water.

Crosslinking agents and conventional additives, in particular the abovementioned additives, may be contained as further components.

When using the coating dispersions for producing a topcoate, the coating dispersions according to the invention, as described above, preferably contain further customary additives:

For example, crosslinking agents, rheological additives (thickeners), flow control agents, defoamers, deaerators, matting agents, grip agents, antioxidants and / or pigments for shading.

Crosslinkers are, for example, polyisocyanates, polyepoxides, polyaziridines, polycarbodiimides, melamine-formaldehyde condensates, organometallic compounds (eg siccatives) for accelerating oxidatively drying binder systems and mineral crosslinkers (such as ZnO), or in the case of UV-crosslinkable systems, the corresponding polymerization initiators when energy is supplied in the form of visible light or higher energy radiation in the UV range, initiate the polymerization and cause crosslinking of binder systems containing the polymerizable group. Particularly preferred are polyisocyanates which are hydrophilic modified are preferably those which can be easily distributed homogeneously by stirring in the finishing liquor at room temperature.

The crosslinking agent-activated coating dispersions generally have a pot life of 1 to 24 hours, preferably between 1 and 12 hours at room temperature, and should be applied to the substrate as soon as possible after activation of the mixture. After one too long waiting time, the mixture can not be used without restrictions regarding the achievable final properties of the coating.

It is also possible to use so-called dual-cure systems for crosslinking. This crosslinking is based on the combination of different curing mechanisms, e.g. rapid UV curing combined with slower cure via an addition mechanism (epoxide, carbodiimide, aziridine, or isocyanate crosslinking).

Rheological additives include, for example, thickeners to adjust the viscosity of the formulation to the correct peak viscosity. Outlet times of 10-50 seconds in the Ford cup with nozzle 4 mm are preferred. Particularly suitable are polyacrylate thickeners or nonionic, associative polyurethane thickeners.

Antioxidants are additives that can be added to the coating dispersion to prevent any heat yellowing or discoloration of the coating due to excessive exposure and weathering during use. Suitable auxiliaries of this type are for example sterically hindered phenols or hindered amine light stabilizers, so-called. HALS amines (such as Tinuvin ^® 765, Ciba Specialties Company).

Pigment masterbatches are preferably concentrates which are used after dilution in the formulation in order to be able to nuance the color of the coated substrate.

Flow control agents, for example, special polyethermodifϊzierte polydimethylsiloxanes as Aquaderm ^® Fluid H (LANXESS Germany GmbH). Suitable polyether siloxanes are mentioned, for example, in EP-A-0318751 (page 3, line 28 to page 4, line 11). Further polyether siloxanes are known per se to the person skilled in the art and are commercially available.

Antifoaming agents can be, for example, various silicone-containing antifoams or component-free antifoams based on component B) or solid defoamers.

Matting agents are different from component B), for example silicate-containing or silicate-free formulations based on organic nanoparticles for adjusting the gloss or the degree of matting.

Suitable matting agents are, for example, amorphous fumed silicas, spherical particles based on silicates or polysilsesquioxanes. The silica particles may be present as such or modified by a surface treatment with, for example, organosilanes. Also, organic particles such as crosslinked or uncrosslinked commercially available polyacrylate-based microbeads which are monodisperse-accessible, or microbeads based on polyurethane precipitation dispersions, which as a rule have a somewhat broader particle size distribution than the polyacrylates have, are suitable for matting advantageous. Particular preference is given to aqueous products or matting agents which can be incorporated directly without agglomeration in the coating formulation or can be dispersed in as an aqueous concentrate. Therefore, the matting agents are often already aqueous formulations which are added as a concentrate as needed to the finish formulation (coating dispersion). The matting agents contained therein have, for example, an average particle size of 5 to 50 μm, preferably 5 to 25 μm.

Gripping means are additives for setting a non-blocking, pleasant silky surface touch or special effects of the finished coated / dressed leather articles. These are wax emulsions, special silicone formulations developed for this purpose or fluorine-containing aqueous dispersions.

Particularly preferred coating dispersions, preferably for the production of automotive leather finishes, consist of the following components:

A) 5-200 parts by weight of polyaspartic acid amide A) (use as aqueous dispersion),

B) 10-100 parts by weight of silicone component B),

C) 50-500 parts by weight of polyurethane dispersion and / or polyacrylate dispersion C),

D) 10-200 parts by weight of crosslinker (use 100% or optionally diluted up to 50% in solvents not NCO-reactive solvents such as propylene glycol diacetate, butyl acetate, ethoxyethyl acetate, methoxypropyl acetate, propylene carbonate, etc.),

E) 1-120 parts by weight of thickener solution (use after predilution with water in the ratio 1: 1),

F) 0-100 parts by weight of pigment paste (use as aqueous / organic formulation),

G) 0.5-30 parts by weight of flow additive (flow control agent) (use as aqueous formulation),

H) 0-500 parts by weight of matting agent (use as an aqueous formulation),

I) 0-100 parts by weight of gripping agent (use 100% or aqueous / organic formulation),

J) 0-500 parts by weight of brightener (use as formulation)

K) 0 to 300 parts by weight of other additives, eg fillers (use as aqueous formulation) L) and water,

wherein the specified parts by weight relate to ready-to-use aqueous raw material formulation and the sum of all components A) to K) and water are so dimensioned that 1000 parts by weight of a ready-to-spray topcoat are formed.

Preferred of these coating dispersions preferably contain more than 85%, in particular more than 90%, preferably more than 95%, particularly preferably more than 98% of the components A), B), C), D), E), F), G), H), I), J), optionally K) and water.

It is also possible to use the component A) according to the invention in combination with other hydrophobically modified polyacrylate dispersions.

It is also possible to use water repellents based on polyacrylate or silicone active substances or fluorine-containing copolymers or other polyurethane-based fluorocarbon resins based on commercially available building blocks such as OH-containing perfluoroalkyl telomeres.

However, it is also possible to combine other commercially available silicone emulsions with the agents according to the invention.

It is possible to use the coating dispersions according to the invention as base coats (primer) or for top coats. Particularly preferred is the use in topcoats. The use is preferably carried out in topcoats which have the composition described above.

The wet application rate of the coating dispersions according to the invention as basecoats, preferably adjusted to an injection viscosity of 15 to 30 seconds (measured in the Ford cup, nozzle 4 mm), is preferably 1 to 10 grams per square foot (sqft).

The wet application rate of the coating dispersions according to the invention as a topcoat, preferably adjusted to an injection viscosity of 15 to 30 seconds (measured in the Ford cup, nozzle 4 mm), is preferably 1 to 10 grams per square foot (sqft). The dry application amount is preferably 0.5 to 5 g / sq.

As application methods are the usual application techniques such as casting, spraying, plushing, or direct and indirect roller application methods such as roll coating, reverse roll coating etc. Particularly preferred is in the leather finishing the job by means of spray guns and sharpening machines.

^■ After application, the leather, preferably in a drying apparatus such as a dry box or on a conveyor belt in a drying tunnel at temperatures between 50 and 100 ⁰ C (set temperature at the drying device) dried for a period of between 1 minute and 5 minutes and then stacked.

The leathers which have been dressed or coated with topping formulations containing the mixtures or the coating dispersions according to the invention are tack-free and can easily be separated from one another after cooling, while the leathers produced according to the prior art and then hot were stacked, stick to the dressing layer to each other or can be very difficult to separate, which is sometimes possible only with damage of the dressing layers.

In addition, the leathers produced using the mixtures or coating dispersions according to the invention have a very high level of fastness and are therefore particularly suitable for the production of automotive leather.

The invention furthermore relates to leather comprising the agents according to the invention and substrates coated with at least one inventive mixture or a coating dispersion according to the invention.

Preferred substrates are leather, textile, non-woven and other flexible and non-flexible materials.

The resulting leathers are particularly suitable for the production of automotive leather, which must meet particularly high standards in terms of fastness properties.

The percentages of the following examples, unless otherwise indicated, are by weight; Parts are parts by weight.

Preparation Examples

Description of special raw materials

Polyether 1 α, ω-bis (2-aminopropyl) poly (oxypropylene),

as JEFF AMINE ^® D-2000, which has an average molecular weight of about 2000 g / mol and an N content = 1.41 wt .-% (Huntsman)

Polyether 2 α-methyl-ω- (2-aminopropyl) poly (oxypropylene-co-oxyethylene)

such as JEFFAMINE ^® XTJ 506 (M-1000) having an average molecular weight of about 1000 g / mol, EO / PO = 19/3 and an N content = 1.36 wt .-% having (Fa. Huntsman )

Polyether 3 α-methyl-ω- (2-aminopropyl) poly (oxypropylene-co-oxyethylene)

as JEFFAMINE ^® XTJ 505 (M-600), which has an average molar mass of about 600 g / mol, EO / PO = 1/9, and an N content = 2.31 wt .-% having (Fa. Huntsman)

Polyether 4 α-methyl-ω- (2-aminopropyl) poly (oxypropylene-co-oxyethylene) as

JEFFAMINE ^® XTJ 507 (M-2005), having an average molecular weight of about 2000 g / mol, EO / PO = 6/39, and an N content = 0.69 wt .-% having (Fa. Huntsman).

Auxiliaries used in the application examples;

Pigment: highly concentrated, finely divided emulsifier-free pigment dispersion with very low binder content; like EUDERM Colors B / C-N; 20-65% depending on the pigment, LANXESS

e.g. black pigment: EUDERM Black B-N, 23% by weight

Filler: anionic dispersion; soft antikle- and fillers for aqueous

Binder primers such as EUDERM Nappa Soft S; about 25% by weight, LANXESS

Primer aid: anionic dispersion - auxiliary for aqueous primers for drying, such as EUDERM Paste DO; 52Gew .-%; LANXESS

Polyurethane binder 1: medium hardness aliphatic anionic polyurethane dispersion such as BAYDERM Bottom 51 UD; 35% by weight; Rohm and Haas

Polyacrylate binder: (Component C) Polyacrylate dispersion for use in topcoats such as HYDRHOLAC CL-I; about 37% by weight, Rohm and Haas

Silicone 1: aqueous silicone emulsion, solids content about 59% by weight, handle

Thickener: associative polyurethane thickener such as Acrysol RM-1020, solids content 20

Wt .-%; Rohm and Haas

Matting agent: polyurethane formulation with matting components

HYDRHOLAC UD-2 ;, solids content. 24% by weight, Rohm and Haas.

Polyurethane binder 2: (component C) hard polyurethane dispersion with high light fastness for

Topcoats with good physical properties, such as BAYDERM Finish 61 UD; Solids content about 40% by weight; Rohm and Haas.

Crosslinker: water-dispersible polyisocyanate with an NCO content of 8.5

Wt .-%, as a 50% solution in propylene glycol diacetate, such as AQUADERM XL 50th

Flow control agent: silicone-based; 100% by weight: AQUADERM Fluid H, LANXESS. PREPARATIONS

Example 1 (Component A)

Molar Ratio MSA: Polyether 1: NH ₃ : hydrogenated tallow fatty amine = 1: 0.1: 1: 0.25

195.0 g of diethylene glycol are placed in a stirred reactor. At room temperature, 245.1 g of maleic anhydride (2.5 mol) are added while stirring and the mixture is heated to 65 ⁰ C until the onset of the exothermic reaction. C 500.0 g (0.25 mol) of Polyether 1 are then metered in with cooling at 6O ^0, so that the temperature in the range 50 to 70 ⁰ C remains. Thereafter, 170.0 g (2.5 mol) of ammonia water 25% within 2.5 hours with cooling between 50 and 6O ⁰ C added. It is stirred at 7O ⁰ C for 1 hour.

The reactor is then gradually evacuated to 200 mbar and further heated with simultaneous distillation of water until a bottom temperature of 130-140 ⁰ C is reached and no more reaction water passes.

At 14O ⁰ C 168.5 g (0.625 mol) of molten hydrogenated tallow fatty amine (C ₆ / C ₈ alkylamine mixture with primary amino groups) are added under nitrogen. It is stirred for 7 hours at 135- 140 ⁰ C. Then 42.0 g of oleic acid are added, stirred for 15 minutes and then added starting at 125 ° C and the highest stirring step, a solution of 2000 g of water and 18.0 g of ethanolamine within 90 minutes. After the start of the feed of the ethanolamine solution, 80 g of 50% sodium hydroxide solution are added in parallel in 10 minutes. This gives a brown dispersion. During dispersion, the internal temperature drops to 85 ° C. After cooling to 65 ° C., 0.5 g of an aqueous defoamer preparation are added. At reduced stirring speed 100.0 g of hydrogen peroxide 35% within 20 minutes at 60-70 ⁰ C are metered. It is stirred for 4 hours at 65 ⁰ C and then cooled to 30-38 ⁰ C. At 30-38 ⁰ C, 1.0 g defoamer, and then 3.0 g of a reducing agent in 2 portions added. It is stirred for 3 hours at 35 ° C, cooled below 30 ⁰ C and filled through a 100 micron filter.

Solids content: 30.7% by weight

Aspect: yellow dispersion

pH: 7.78 (diluted 1: 4 (c = 20%), potentiom.)

Viscosity (20 °): 40.3 seconds (Ford cup, nozzle 4 mm)

510 mPas at 20 ⁰ C, D = 100 sec ^'1

average particle size: d ₅₀ = 140 nm (Coulter LS 230) (??) Mw (GPC) 11200 g / mol

Example 2 (component A)

2.1. Production of the precursor

Molar ratio MSA: ammonia: fatty amine = 1: 1.2: 0.15

Analogous to the conditions of Example 1, a precursor is prepared:

Template: 390.0 g of diethylene glycol

Addition 1: 490.3 g (5 mol) of maleic anhydride, then

Addition 2: 408.0 g (6 mol) of ammonia water (25%) in 3 hours at 50-60 ⁰ C then stirred at 70 ⁰ C for 1 hour. This is followed by vacuum distillation (max 200 mbar) until

Sump temperature 140 ⁰ C is reached and no more water distilled off. Then takes place at 140 ⁰ C.

Addition 3: 202.2 g (0.75 mol) of hydrogenated tallow fatty amine (Cj ₆ / C ₈ alkylamine mixture with primary

Amino groups) previously melted at 80 ^° C. The mixture is stirred at 140 ^° C. for 3 hours. This gives 1094.5 g of a red-brown melt, which is discharged and comminuted after cooling. Equivalent weight, based on monomer unit, of maleic anhydride = 218.9 g

(1 mol of MSA = 218.9 g precursor).

2.2. Implementation of the precursor from section 2.1.

Molar Ratio MSA: NH3: Fatty amine: Polyether 2 = 1: 1.2: 0.15: 0.35

109.45 g of the 2.1. described pre-product (0.5 mol) are initially charged at 140 ⁰ C. Then 175 g (0.175 mol) of a heated to 80 ⁰ C melt of polyether 2 are added. The mixture is stirred for a further 4 hours at 140 ⁰ C and then cooled to 115 ° C. Then 14.25 g of oleic acid are added, stirred for 5 minutes, and starting at 115 ° C.und highest stirrer speed, a solution of 465 g of water and 6.1 g of ethanolamine within 60 minutes, the batch is cooled to 65 ° C. , After addition of 0.5 g of defoamer, 20.0 g of 35% hydrogen peroxide are added at 65 ^° C. within 10 minutes. It is stirred for 4 hours at 65 ° C and then cooled to 35 ° C. At 35 ^° C., 0.2 g of defoamer and 1.5 g of a reducing agent are metered in in 2 portions within 30 minutes. After completion of the addition is stirred for 3 hours at 25-35 ° C and then filled over 100 micron filter.

Solids content: 34.6% by weight Aspect: light brown solution

pH: 6.23 (diluted 1: 4 (c = 20%), potentiom.)

Viscosity (20 °): 16 seconds (Ford cup, nozzle 4mm),

59 HiPaS (IOO s- ¹ ^ O ⁰ C)

Example 3: (Component A)

Molar ratio MSA: NH3: fatty amine: polyether 3 = 1: 1.2: 0.15: 0.15

Analogous to example 2, section 2.2. be 109.45 g of the under Example 2, Section 2.1. described pre-product (0.5 mol) with 45 g (0.075 mol) of polyether 3 at 140 ⁰ C for 4 hours. After cooling to 65 ⁰ C 8.4 g of oleic acid are added and added a solution of 280 g of water and 3.6 g of ethanolamine within 60 minutes. It is stirred for 10 minutes. Then at 65 ° C 20.0 g of hydrogen peroxide 35% are added within 10 minutes. The mixture is stirred for 3 hours at 65.degree. At 35 ° C., 0.2 g defoamer are subsequently metered in 1.5 g of a reducing agent in 2 portions within 30 minutes. After completion of the addition, stirring is continued for 2 hours at 25-35 ⁰ C and the mixture is then filled through 100 micron filter.

Solids content: 28.4% by weight

Aspect: yellow-orange dispersion

pH: 5.19 (diluted 1: 4 (c = 20%), potentiom.)

Viscosity: about 80 mPas (100 s \ 2O ⁰ C)

Example 4 (component A)

4.1. Production of the precursor Molar ratio MSA: ammonia: fatty amine = 1: 1.2: 0.25

Analogous to the precursor (see Example 2, Section 2.1), a precursor is prepared, with the modification that 337.0 g (1.25 mol) of hydrogenated tallow fatty amine (Q ₆ / Cig-alkylamine mixture with primary amino groups), previously 80 ⁰ C was melted, are used. The reaction time is 3 hours at 14O ⁰ C. 1229.3 g of red-brown melt are discharged and comminuted after cooling.

Equivalent weight precursor B, based on monomer unit maleic anhydride = 245.86 g (1 mol MSA = 245.86 g precursor).

4.2. Implementation of the precursor from section 4.1.

Mole Ratio MSA: NH3: Fatty amine: Polyether 2 = 1: 1.2: 0.25: 0.15

To 122.9 g of the under Example 4, Section 4.1. precursor (0.5 mol) are metered described a temperature-controlled at 8O ⁰ C melt of polyether 2 at 140 ⁰ C 75 g (0.075 mol) and reacted for 4 hours at 140 ⁰ C. Then, at 115 ° C 8.4 g of oleic acid are added, stirred for 5 minutes and added starting at 115 ° C and the highest agitator 365 g of water and 3.63 g of ethanolamine within 60 minutes, the batch is cooled to 65 ⁰ C. After addition of 0.5 g of defoamer, 20.0 g of 35% hydrogen peroxide are added at 65 ° C. within 10 minutes. The mixture is stirred for 4 hours at 65 ⁰ C and the reaction mixture cooled to 35 ⁰ C. At 35 ° C., 0.25 g of defoamer and then 1.5 g of a reducing agent are metered in in 2 portions within 15 minutes. After completion of the addition, the mixture is stirred for 3 hours at 35 ° C and the mixture is then filled through 100 micron filter.

Solids content: 29.6% by weight

Aspect: pale yellow dispersion

pH: 5.58 (diluted 1: 4 (c = 20%), potentiom.)

Viscosity (20 °): approx. 120 mPas (10O s ^"1 , 20 ⁰ C)

Example 5: (component A).

Molar ratio MSA: NH3: fatty amine: polyether 2: primary / tert. Amine = 1: 1.2: 0.25: 0.25: 0.25

To 122.9 g of the under Example 4, Section 4.1. 125 g (0.125 mol) of polyether 2 and 12.8 g (0.125 mol) of 3-aminopropyl-dimethylamine are metered in and the mixture is stirred at 140 ^° C. for 6 hours. Then 8.4 g of oleic acid are added at 125 ° C, stirred for 5 minutes and starting at 125 ° C and the highest stirrer speed, a solution of 465 g of water and 3.63 g of ethanolamine dosed within 60 minutes and stirred for another 30 minutes, the Approach cooled to 65 ° C. At 65 ° C 20.0 g of hydrogen peroxide 35% are added within 10 minutes. It is stirred for 4 hours at 65 ° C. 0.25 g of defoamer and then in 1.5 g of a reducing agent in 2 portions are then metered in at 35 ^° C. within 15 minutes. After completion of the addition, stirring is continued for 3 hours at 35 ^° C. and the batch is then filled through a 100 μm filter.

Solids content: 30.4% by weight

Aspect: brown, thin dispersion

pH: 7.09 (diluted 1: 4 (c = 20%), potentiom.)

Viscosity (20 °): approx. 30 mPas (100

20 ° C)

Example 6: (Component A)

Molar Ratio MSA: NH3: Fatty amine: Polyether 4 = 1: 1.2: 0.25: 0.225

To 122.9 g of the under Example 4, Section 4.1. precursor (0.5 mol) described are metered in at 140 ⁰ C 225 g (0.1125 mol) of polyether 4 and reacted for 7 hours at 140 ⁰ C. Then cooled to 120 ⁰ C, added 16.8 g of oleic acid, stirred for 15 minutes and then metered at the highest stirrer speed, a solution of 620 g of water and 7.26 g of ethanolamine within 60 minutes starting at 115 ° C, the approach on 65 ° C is cooled. The mixture is then stirred for 30 minutes and 3 g of 50% sodium hydroxide added in 50 g of water. At 65 ° C 20.0 g of hydrogen peroxide 35% are added within 10 minutes. It is stirred for 3 hours at 65 ° C. Then 100 g of water are added. At 35 ° C., 0.25 g defoamer and then 1.5 g of a reducing agent are added in 15 minutes. After completion of the addition, the mixture is stirred for 3 hours at 25-35 ° C and the mixture is then filled through 100 micron filter.

Solids content: 28.8% by weight

Aspect: viscous yellow dispersion

pH: 7.24 (diluted 1: 4 (c = 20%), potentiom.) av. Particle size: 119 nm

Example 7: (Component A)

7.1. Production of the precursor

Mole ratio MSA / trimellitic anhydride: NH3: fatty amine = 0.83 / 0.17: 1.25: 0.208

The reaction vessel is charged with 234.0 g of diethylene glycol and 294.15 g of maleic anhydride (3 mol) and 115.2 g of trimellitic anhydride (0.6 mol) are introduced at room temperature with stirring. The mixture is heated to 65 ⁰ C, wherein an exothermic reaction at 50 ⁰ C starts and the temperature rises to 87 ° C. After cooling to 55 ° C, 306.0 g of ammonia water (25%, 4.5 mol) in 3 hours at 50-60 ⁰ C added. After completion of the addition for 1 hour at 7O ⁰ C is stirred. In the subsequent vacuum distillation (200 mbar) is heated until the bottom temperature has reached 14O ⁰ C and no distillate passes more.

Under nitrogen, 202.2 g (0.75 mol) of a 80 ⁰ C hot melt of hydrogenated tallow fatty amine (Ci6 / Cig-alkylamine mixture with primary amino groups) was added at 140 ⁰ C. The mixture is stirred at 14O ⁰ C for 7.5 hours. This gives 872.8 g of red-brown melt, which is discharged and comminuted after cooling.

Equivalent weight of precursor based on monomer unit maleic anhydride = 290.9 g. (1 mol MSA = 290.9 g precursor).

7.2. Reaction of the precursor from section 7.1.

MSA / trimellitic anhydride molar ratio: NH3: fatty amine: polyether 2 = 0.83 / 0.17: 1.25: 0.208: 0.1245

145.15 g of the precursor described in Example 7, Section 7.1 (0.5 mol) are melted in a reactor. Then at 140 ⁰ C 75 g (0.075 mol) of polyether 2, which was previously melted at 80 ⁰ C added. The mixture is stirred at 140 ^° C. for 4 hours. At 115 ° C 8.4 g of oleic acid are added, stirred for 5 minutes and starting at 115 ° C and the highest stirrer speed, a solution of 200 g of water and 3.65 g of ethanolamine added within 45 minutes, the approach cooled to 90 ⁰ C. becomes. After addition of 0.15 g of defoamer is stirred for 20 minutes, 7.5 g of 50% sodium hydroxide solution added. It is cooled to 65 ° C. At 65 ° C 11.8 g of hydrogen peroxide 35% are added within 10 minutes and stirred for 3 hours. After cooling to 35 ⁰ C 0.25 g of defoamer and then 1.5 g of a Reducing agent added in 15 minutes. It is stirred for 1 hour at 25-35 ° C and adjusted the solids content.

Solids content: 33.7% by weight

Aspect: pale yellow dispersion

pH: 5.62 (diluted 1: 4 (c = 20%), potentiom.)

Viscosity (20 °): 148 mPas (100 s \ 2O ⁰ C)

average particle size: 292 nm

Example 8 (Component A)

Molar Ratio MSA: Polyether 1: NH 3: Fatty amine: Polyether 2 = 1: 0.05: 1.0: 0.25: 0.5

In a stirred reactor 39.0 g of diethylene glycol are introduced. At room temperature, 49.05 g of maleic anhydride (0.5 mol) are added while stirring and the mixture is heated to 65 ° C until the start of the exothermic reaction. Subsequently, at 55 ^° C., 50.0 g (0.025 mol) of polyether 1 are added in 30 minutes with cooling. Thereafter, 34.0 g (0.5 mol) of ammonia water 25% within 45 minutes with cooling between 50 and 60 ⁰ C metered. It is stirred for 1 hour at 70 ⁰ C. The reactor is then gradually evacuated to 200 mbar and further heated with simultaneous distillation of water until a bottom temperature of 130-140 ⁰ C is reached and no more reaction water passes. There are obtained 36 g of distillate. , Which has been previously melted at 80 ⁰ C was added - at 140 ⁰ C under nitrogen, 33.7 g (0.125 mol) of hydrogenated tallow fatty amine (alkylamine mixture with primary amino groups C ₁₆ / C _8). It is stirred for 3 hours at 135-140 ⁰ C. Then 250 g (0.25 mol) of polyether 2 (80 ⁰ C hot melt) are added and stirred at 140 ⁰ C for 4 hours. After cooling to 115 ° C 8.4 g of oleic acid are added, stirred for 10 minutes and then starting at 115 ⁰ C and the highest stirring step, a solution of 600 g of water and 3.6 g of ethanolamine dosed within 60 minutes. After cooling to 65 ° C 40.0 g of hydrogen peroxide 35% within 10 minutes at 65 ⁰ C are added at reduced stirring speed. It will be 3 hours 65 ⁰ C stirred and then cooled to 35 ° C, 0.5 g of defoamer and 3.0 g of a reducing agent in 2 portions. It is stirred for 3 hours at 35 ⁰ C, cooled under 3O ⁰ C and filled through a 100 micron filter.

Solids content: 37.7% by weight

Aspect: dark brown solution

pH: 7.79 (diluted 1: 4 (c = 20%), potentiom.)

Example 9 (Component A)

Molar ratio MSA: NH3: hydrogenated tallow fatty amine = 1: 1.1: 0.25

In a stirred reactor 265.0 g of diethylene glycol are introduced. At room temperature, 332.5 g of maleic anhydride (3.39 mol) are added with stirring and the mixture is heated to 55 ⁰ C. Ammonia water are then at 55 ⁰ C with cooling 277.2 g (4.08 mol NH ₃₎ are metered (25%), so that the temperature in the range 50 to 6O ⁰ C remains. After the addition is stirred at 70 ⁰ C for 1 hour. The reactor is then gradually evacuated to 200 mbar and heated with simultaneous distilling off of water until a bottom temperature of 130-140 ⁰ C is reached and no more reaction water passes.

At 140 ⁰ C under nitrogen 228.8 g (0.85 mol) of molten hydrogenated tallow fatty amine (Ci ₆ / Ci ₈ -Alkylamin mixture with primary amino groups) was added and maintained at 140 ⁰ C for 6 hours. Then it is cooled and added at 13O ⁰ C 57.2 g of oleic acid, stirred for 15 minutes. With further cooling, starting at 120 ⁰ C and the highest stirring step, a solution of 900 g of water and 24.6 g of ethanolamine added within 45 minutes. At 6O ⁰ C 3 g of antifoam are added and then 53.5 g of 50% sodium hydroxide solution. This gives a light brown dispersion. At reduced stirring speed 80.0 g of hydrogen peroxide 35% within 60 minutes at 60-70 ⁰ C are metered. It is stirred for 3 hours at 65 ° C and then cooled to 30 ⁰ C. At 3O-38 ° C 0.4 g of defoamer and then 10.0 g of a reducing agent are added in portions. The mixture is then stirred for 1 hour at 35 ° C, cooled to room temperature and filled through a 100 micron filter.

Solids content: 34.5% by weight

Aspect: pale yellow dispersion

pH value: 6.8 (diluted 1: 4 (c = 20%), potentiometric) Viscosity (20 °): 150 mPa.s at 2O ⁰ C, D = 100 sec ^"1

average particle size: d ₅₀ = 180 nm (Coulter LS 230)

Mw (GPC) 4500-6000 g / mol

Production Example 10

Preparation of a mixture of components A) and B according to the invention

60 parts by weight of a high molecular weight silicone resin (Dow Corning 3289, silicone content: 80%) (component B) are initially charged at room temperature. 32.5 parts by weight of the product of Preparation Example 9, which is present as an aqueous dispersion (component A), are added at room temperature and dispersed with rapid stirring, wherein the temperature rises to about 40 ⁰ C. The mixture is stirred for a further 1 hour after completion of the addition, whereby a homogeneous mixture is obtained. It is then adjusted with 7.5 parts by weight of water to a solids content of 60 wt .-% and cooled to room temperature.

APPLICATION EXAMPLES for leather treatment

The examples given are intended to illustrate the invention, but by no means limit. All quantities are per 1000 parts.

Description of the general procedure for dressing:

Application of the primer (base-coat):

The starting material used was a crust (made from bovine wet blue) with a thickness of 1.0-1.2 mm.

Before applying the primer, the leather is pre-milled in the crust state in the millcass for 6 hours and then placed on a stuffer.

The primed leather, obtained with an application rate of 3 - 4 g / sqft wet injected 2 times, 2 minutes, were dried after each application at a temperature of 90 ⁰ C.

Then the leathers were put on a box for 4 hours and then milled for 6 hours in the Millfaß. Application of Topcoats:

First, the topcoat formulations were prepared according to the table below by stirring the components in the order given. The crosslinker was finally added and the spray viscosity adjusted by adding thickener and water. The mixtures thus obtained have a pot life of about 4 hours and were sprayed immediately after the preparation of the corresponding primed crust (2 crosses, dry application rate: 0.6-0.7 g / qfs (g / sqft) (airless spray gun) and a Temperature of 100 ⁰ C dried for 2 minutes.

The tack of the finish immediately after drying was determined and evaluated as follows. After drying, the leather is allowed to cool and tests for temporary stickiness by rubbing the side of the scar on the side of the scar, hearing or feeling how the leather slowly or rapidly unfolds.

The resulting leathers were conditioned, blank samples were punched out and evaluated by the following methods:

a) stickiness

Two pieces of leather (6 cm x 4 cm) are put together with scars on scars and folded in the middle. Then place the sample on a glass plate, cover sample with a glass plate and set

1 kg weight on the entire assembly. Then take the weighted sample and place it for 1 hour in a convection oven, which is maintained at a temperature of 80 ⁰ C.

After 1 hour, the sample is taken out and allowed to cool for 10 minutes without weight. Then you determine the stickiness by pulling apart the two end pieces of the samples with your fingers. It is determined whether the leather pieces are easy to separate, whether they are less easy to separate or are very difficult to separate.

b) kink resistance of the leather dry / wet (Bally Flexometer))

100000 kinks, dry leather specimens,

The damage was visually evaluated after this number of buckling.

20000 kinks, wet leather specimens. The damage was visually evaluated after this number of buckling. c) wet rub fastness (Veslic wet rub tester)

20x10 mm leather specimens were clamped in the wet rub tester and a felt was moved 500 times over the specimen at a defined feed rate 500 times and visually scored for the damage of the finish layer and the stain of the felt after the end of the test.

The following variants were evaluated:

dry leather, dry felt,

dry leather, wet felt (kept moist with water),

wet leather, wet felt (kept moist with water),

Leather dry, felt soaked with alkaline sweat solution,

Leather dry, felt soaked with petrol.

d) adhesive strength (method)

The specimens were glued to the meat side by means of contact adhesive (Loctite 454) on a rigid steel pad. Then a self-adhesive tape was glued on the dressing and 24

Hours loaded with a load of 5 kg at 20 ⁰ C. Thereafter, the tape was peeled off and the force required to tear off the tape was measured. In addition, damage to the finish is evaluated. Ideally, the entire dressing is torn down

Damage to the scar from, i. it is almost reached the tear strength of the leather in the z direction.

e) Abrasion resistance (Taber)

This test is carried out in accordance with DIN EN 14327.

f) heat yellowing

A leather sample 2cm x 2cm is punched out of a leather sample of 5cm x 5cm, so that this serves as a comparison. Place the leather sample (2cm x 2cm) at 120 ⁰ C for 24 hours in a convection oven. After the test, this sample is with. of the larger sample with the gray scale to evaluate the degree of yellowing. Application Examples 1 and 2

Example 1 (= comparative example).

Example 2 (= according to the invention)

The starting material used was an automotive nappa crust with a thickness of 1.0-1.2 mm.

The following table shows the formulations for the spray primer and for the two topcoats subsequently applied with a spray gun.

operation

Preparation: Crust for 6 hours, studs

Base coat: 2x spray 3.0-4.0 g / qfs (wet); millen for 6 hours, galleries

Top coat: 2x spray 2 x 0.7 g / qfs (dry); Stollen.

The leathers were evaluated for optical and physical properties:

It can be seen from the physical test results that no serious differences can be seen between the leathers of Application Examples 1 and 2.

The only difference is in the stickiness test. It can be seen that the top coat from Application Example 2 with the mixture according to the invention from Preparation Example 10 has a significantly lower tack than the comparison topcoat with conventional silicone according to Application Example 1.

Application Examples 3 to 5

Production of car upholstery leather - checking the yellowing test and physical properties

The starting material used was an automotive crust with a thickness of 1.0-0.2 mm.

The following table shows the formulations of the spray primer applied to the 3 Crust and for the topcoats subsequently applied by means of a spray gun.

Operation:

Preparation: Vorülen 6 hours, studs.

Base coat: 2 x spray 3.0- 4.0 gr / qfs (wet), zero for 6 hours, studs

Top coat: 2 inject 2 x 0.7 gr / qfs. dry, studs

The leathers with a topcoat without test product (Application Example 3), a topcoat with a mixture of test product and silicone, wherein the same product proportions compared to Example 5 were used (Application Example 4), and with a topcoat containing a previously prepared mixture of test product and silicone (Application Example 5) were evaluated for their properties as follows:

Overall verdict: The leathers of application examples 3 to 5 have approximately the same high level of physical fastness, with the leathers of 3 and 5 getting the best rating. Furthermore, it should be noted that the leather produced according to the invention according to Application Example 5 is significantly less sticky than the leather of Application Example 3 and the leather of Application Example 4 does not stick at all.

Claims

claims

1. mixture containing

A) at least one polyaspartic acid derivative and

B) at least one polysiloxane.

2. Mixture according to claim 1, containing in addition water.

3. Mixture according to at least one of claims 1 to 2, characterized in that as polyaspartic acid derivatives of component A) optionally hydrophobically modified polyaspartic acid, their salts, esters and / or amides, in particular polyaspartic acid and polyaspartic acid salts with counterions from the Group lithium, sodium, potassium, ammonium, alkylammonium, dialkylammonium, trialkylammonium,

Tetralkylammonium, preferably partial esters or partial amides of polyaspartic acid, particularly preferably hydrophobically modified polyaspartic acid derivatives, in particular hydrophobically modified esters or amides of polyaspartic acid are used.

4. Mixture according to at least one of claims 1 to 3, characterized in that as polyaspartic acid derivative A) (co) polymers are used, the

a) structural units of the general formula I

contain, where

W is a trivalent radical from the group

stands in the

* indicates the orientation for the incorporation of the radical W into the formula I, and

Z represents the radicals -OH, -O ^' M ⁺ or -NR ¹ R ² , where R ¹ and R ² independently of one another represent hydrogen, optionally substituted alkyl radicals, alkenyl radicals, aralkyl radicals or

M ⁺ for H ⁺ or an alkali ion, an NH ₄ -IOn or a primary, secondary, tertiary or quaternary aliphatic ammonium radical, preferably a Ci-C ₂₂ alkyl or

-Hydroxyalkyl group bears,

b) at least 5 mol%, based on the units of the formula I, of structural units of the general formula Ia

contains, where

R.3 for a hydrocarbon radical with C \ -Cgg- atoms, preferably a saturated C _j -Cgo radical, in particular C3-C3Q-alkyl radical and, independently thereof

R.4 is hydrogen or has the same meaning as R ^, and

c) optionally contain polyether units having an average molecular weight of 200-6000 g / mol.

A mixture according to claim 4, characterized in that polyaspartic acid derivatives A) are used as polyaspartic acid amides in which the structural units of the formula I correspond to the formula II

and the structural units of the formula Ia correspond to the formula Ib

wherein

Z, R ³ and R ^{4 have} the meaning given in claim 4.

6. Mixtures according to at least one of claims 4 to 5, characterized in that is used as polyaspartic acid derivatives of component A) polyaspartic acid amides in which the proportion of units of the formula (I) with

together more than 50 mol%, based on the sum of all units of the formula (I), in particular more than 80 mol%, very particularly preferably more than 90 mol%.

Mixtures according to at least one of Claims 4 to 6, characterized in that polyaspartic acid amides which contain structural units of the formula (IIa) and (IIb) are used as polyaspartic acid derivatives of component A)

embedded image in which

R and R ² and M have the meaning given in claim 4,

contain.

Mixtures according to at least one of claims 4 to 7, characterized in that is used as polyaspartic acid derivatives of components A) polyaspartic acid amides containing more than 95 wt .-%, in particular more than 98 wt .-% of structural units of the formula I and optionally Polyether units consist, wherein

i) 50 to 100 mol%, in particular 70 to 100 mol%, based on the sum of these two units, attributable to structural units of the formula I, of which at least 5 mol%, in particular 5 to 35 mol%, based on the Units of the formula I, those of the formula Ia, in particular of the formula Ib correspond, and ii) 0 to 50 mol%, preferably 0 to 30 mol%, based on the sum of these two units, of polyether units having an average molecular weight of 200 to 6000 g / mol.

9. Mixtures according to at least one of claims 4 to 7, characterized in that is used as polyaspartic acid derivatives of the components A) polyaspartic acid amides, more than 95 wt .-%, in particular more than 98 wt .-% of structural units of the formula I. exist, of which

embedded image in which

W has the meaning given in claim 4,

R ^ is a radical containing more than two ether groups derived from C ₂ -C ₆ alkylene oxide units, optionally substituted by urethane, carbonate, urea, biuret, allophanate, isocyanate, alkylene, Cycloalkylene or aralkylene groups is interrupted and

R ^ is hydrogen or has the meaning of R ^.

10. Mixtures characterized in that the polysiloxane of component B) has a molecular weight of 500 to 200,000 g / mol.

11. A process for the preparation of mixtures according to at least one of claims 1 to 10, characterized in that the components A) and B) are mixed together.

12. Use of the mixture according to at least one of claims 1 to 10 for reducing the tackiness of polyurethane and / or polyacrylate coatings of substrates.

13. containing coating dispersions,

a mixture according to at least one of claims 1 to 10 and

C) at least one polyurethane and / or polyacrylate polymer.

14. Coating dispersions according to claim 13, comprising at least one polyurethane binder, which has a Shore A hardness of 50 to 100 as a film

15. Coating dispersions according to claim 13, comprising at least one polyacrylate lat by free-radical copolymerization obtainable from at least one monomer from the following groups

1) acrylic acid and methacrylic acid and their derivatives of the formula CK ^ = CR ¹ -CO-OR ² , wherein R ^{1 is} hydrogen or methyl and R ^{2 is} a hydrocarbon radical having 1 to 40 carbon atoms, which is also fluorine, hydroxy , Ci _-4 alkylamino, Ci. ₄ alkoxy, carbonyl groups and polyether groups may be substituted,

2) acrylamide, methactylamide and their derivatives,

3) styrene and substituted styrenes,

4) acrylonitrile,

5) vinyl esters such as vinyl acetate, vinyl propionate and / or

6) Unsaturated dicarboxylic acids such as crotonic acid, itaconic acid or

Maleic anhydride.

16. Coating dispersions according to claim 13, comprising a mixture according to at least one of claims 4 to 10.

17. A process for the preparation of coating dispersions according to claim 13, characterized in that mixing a mixture according to at least one of claims 1 to 10 and at least one polymer dispersion comprising at least one polyurethane and / or polyacrylate binder together.

18. Substrates coated with at least one coating dispersions according to claim 13 to 17.