EP3155029A1

EP3155029A1 - Polymer dispersions containine acylmorpholines

Info

Publication number: EP3155029A1
Application number: EP15725079.6A
Authority: EP
Inventors: Juergen Mohr; Ulrich Karl; Helfried Scheidl; Manfred Dargatz; Karl Haeberle; Thorsten Pauen; Juan SALGADO VALLE
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2014-06-10
Filing date: 2015-06-03
Publication date: 2017-04-19
Also published as: US20170121537A1; WO2015189084A1; JP2017523263A; CN106459361A; KR20170018892A

Abstract

The invention relates to N-acylmorpholines as a solvent for use in methods for producing polymer dispersions.

Description

Polymer dispersions containing acylmorpholines

The present invention relates to aqueous polymer dispersions containing at least one N-acylmorpholine as solvent.

The present invention furthermore relates to a process for preparing aqueous polymer dispersions, in particular polyurethane dispersions, using at least one N-acylmorpholine as solvent.

The present invention further relates to the use of N-acylmorpholines as solvents for the preparation of aqueous polymer dispersions.

Polymer dispersions are used in many fields of technology. Widely used, for example, for coating surfaces.

Polyurethane dispersions are frequently produced industrially by the so-called "prepolymer mixing process". In it polyurethanes are first prepared in an organic solvent, often N-methylpyrrolidone, and then dispersed the resulting solution of the polyurethane in water. During and / or after their dispersion in water, the molecular weight of the polyurethane can then be further increased by means of a chain extension.

Depending on the boiling point of the solvent used, the solvent also remains in the dispersion in a distillative separation to a greater or lesser extent and influences the properties of the polyurethane dispersion.

Since not all solvents are toxicologically harmless, the solvent used should be as nontoxic as possible. WO 2005/090 430 A1 teaches the use of N- (cyclo) alkylpyrrolidones with (cyclo) alkyl radicals having 2 to 6 C atoms for this purpose. WO 10/142 617 describes substituted N- (cyclo) alkylpyrrolidones as suitable solvents.

However, there is a further need for polyurethane dispersions which are toxicologically safe and have advantageous application properties.

The object of the present invention was to provide polymer dispersions, in particular polyurethane dispersions, which are toxicologically harmless and exhibit advantageous performance properties.

This object according to the invention is achieved by aqueous polymer dispersions, in particular polyurethane dispersions containing at least one N-acylmorpholine of the formula (I)

wherein R 1 is H or an alkyl group having 1 to 18 carbon atoms and R ² , R ³ , R ⁴ and R ^{5 are} each independently H or a (cyclo) alkyl group having 1 to 18 C atoms.

Preferred radicals R ¹ are H, methyl and ethyl, particularly preferably H or methyl.

Substituted N-acylmorpholines which are particularly suitable according to the invention are those having an aliphatic (open-chain), cycloaliphatic (alicyclic, ring-shaped) preferably open-chain, branched or unbranched radical R ¹ which has 0 to 5 carbon atoms, preferably 0 to 3, particularly preferably 0 to 2 , in particular 0 to 1 carbon atoms.

A "(cyclo) alkyl radical having 1 to 18 C atoms" is understood in the context of this document to mean an aliphatic, open-chain, branched or unbranched hydrocarbon radical having 1 to 18 carbon atoms or a cycloaliphatic hydrocarbon radical having 3 to 18 carbon atoms.

Examples of suitable cycloalkyl radicals are cyclopentyl, cyclohexyl, cyclooctyl or cyclododecyl.

Examples of suitable alkyl radicals are methyl, ethyl, / so-propyl, n-propyl, n-butyl, / so-butyl, sec-butyl, fer-butyl and n-hexyl.

Preferred radicals are cyclohexyl, methyl, ethyl, / so-propyl, n-propyl, n-butyl, / is-butyl, sec-butyl and fer-butyl, particularly preferred are methyl, ethyl and n-butyl, and very particularly preferred Methyl or ethyl.

Preferred radicals R ² , R ³ , R ⁴ and R ⁵ are hydrogen, methyl, ethyl, iso-propyl and cyclohexyl, particular preference is given to hydrogen, methyl, ethyl and isopropyl, with very particular preference being given to hydrogen, methyl and ethyl and in particular Hydrogen and methyl.

Preferred compounds of the formula (I) are N-formylmorpholine, N-acetylmorpholine and N-propionylmorpholine, more preferably N-formylmorpholine and N-acetylmorpholine. In a preferred embodiment, the N-acyl morpholine (I) is formyl morpholine.

In a preferred embodiment, the N-acyl morpholine (I) is N-acetylmorpholine.

If mixtures are used, these are mixtures of up to four different substituted N-acylmorpholines, preferably up to three and more preferably two.

In the latter case, the two N-acylmorpholines are generally in a weight ratio of 10: 1 to 1:10, preferably 5: 1 to 1: 5, more preferably 3: 1 to 1: 3 and most preferably 2: 1 to 1 : 2 ago.

In a preferred embodiment, polymer dispersions according to the invention, in particular polyurethane dispersions, comprise N-formylmorpholine and N-acetylmorpholine in a weight ratio of from 10: 1 to 1:10, preferably from 5: 1 to 1: 5, more preferably from 3: 1 to 1: 3 and very particularly preferably 2: 1 to 1: 2. The amount of N-acylmorpholines based on the polymer, in particular the polyurethane, is generally 0.01-100% by weight, preferably 1-100% by weight.

Of course, the N-acylmorpholines used according to the invention can be used alone, mixed with one another or else mixed with one or more other suitable solvents.

Examples of suitable solvents are, for example, open-chain or preferably cyclic carbonates, lactones, di (cyclo) alkyl dipropylene glycol ethers and N- (cyclo) alkylcaprolactams. Carbonates are described, for example, in EP 697424 A1, there in particular from page 4, lines 4 to 29, to which reference is expressly made. Preferred are 1, 2 ethylene carbonate, 1, 2-propylene carbonate and 1, 3-propylene carbonate, more preferably 1, 2 ethylene carbonate and 1, 2-propylene carbonate. Preferred lactones are beta-propiolactone, gamma-butyrolactone, epsilon-caprolactone and epsilon-methylcaprolactone.

Di (cyclo) alkyl dipropylene glycol ethers are, for example, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol di-n-propyl ether and dipropylene glycol di-n-butyl ether, preference being given to dipropylene glycol dimethyl ether.

The di (cyclo) alkyl dipropylene glycol ether and especially dipropylene glycol dimethyl ether are generally mixtures of the positional isomers and diastereoisomers. The exact composition of the isomer mixtures does not play a role according to the invention. As a rule, this is the major isomer R-OCH ₂ CH (CH 3) OCH ₂ CH (CH 3) OR, where R is the (cyclo) alkyl radical. Dipropylene glycol dimethyl ether is commercially available as such a mixture of isomers and is usually by the CAS no. 1 1 1 109-77-4. Dipropylene glycol dimethyl ether is commercially available in high purity of mostly more than 99% by weight, for example under the trade name Proglyde® DMM from The Dow Chemical Company, Midland, Michigan 48674, USA or from Clariant GmbH, 65840 Sulzbach am Taunus, Germany.

N- (Cyclo) -alkylcaprolactams are those having an aliphatic (open-chain) or cycloaliphatic (alicyclic, ring-shaped), preferably open-chain, branched or unbranched, hydrocarbon radical having 1 to 6 carbon atoms, preferably 1 to 5, particularly preferably 1 to 4, in particular 1 to 3 and especially 1 or 2 carbon atoms.

Usable N- (cyclo) -alkylcaprolactams are, for example, N-methylcaprolactam, N-ethylcaprolactam, Nn-propylcaprolactam, N-so-propylcaprolactam, Nn-butylcaprolactam, N- / so-butylcaprolactam, N-se / butylcaprolactam, N-ferric Butylcaprolactam, N-cyclopentylcaprolactam or N-cyclohexylcaprolactam, preferably N-methylcaprolactam or N-ethylcaprolactam.

The aqueous polymer dispersions according to the invention are preferably aqueous polyurethane dispersions.

Aqueous polymer dispersions according to the invention also contain at least one polymer. As a rule, aqueous polymer dispersions according to the invention contain 10 to 75% by weight of polymer, based on the dispersion. Suitable polymer dispersions are known per se to the person skilled in the art.

As a rule, aqueous polymer dispersions according to the invention contain 90 to 25% by weight of water, based on the dispersion, the proportions of polymer, N-acylmorpholine, other additives and water supplementing to 100% by weight.

Aqueous polyurethane dispersions according to the invention furthermore contain at least one polyurethane. As a rule, aqueous polyurethane dispersions according to the invention contain 10 to 75% by weight of polyurethane, based on the dispersion. Suitable polyurethane dispersions are known per se to the person skilled in the art. In a preferred embodiment, polyurethane dispersions according to the invention comprise polyurethanes which have been prepared by the prepolymer mixture process, in particular those as described below process according to the invention for the preparation of polyurethane dispersions are described.

As a rule, aqueous polyurethane dispersions according to the invention contain 90 to 25% by weight of water, based on the dispersion.

In one embodiment, the N-acylmorpholine can also be added to a finished polymer dispersion, in particular polyurethane dispersion, that is to say after the dispersion of the polymer, in particular polyurethane, for example, in order to advantageously influence its flow and drying behavior. However, preference is given to the addition of the N-acylmorpholine before the dispersion.

Another object of the present invention is a process for the preparation of polyurethane dispersions, wherein the aqueous polyurethane dispersions are prepared as follows: I. Preparation of a polyurethane by reacting a) at least one polyfunctional isocyanate having 4 to 30 carbon atoms, b) diols, from b1) from 10 to 100 mol%, based on the total amount of the diols (b), have a molecular weight of 500 to 5000, and b2) 0 to 90 mol%, based on the total amount of the diols (b), a molecular c) optionally further polyhydric compounds other than the diols (b), having reactive groups which are alcoholic hydroxyl groups or primary or secondary amino groups, and d) the monomers (a) , (b) and (c) various monomers having at least one isocyanate group or at least one isocyanate group-reactive group further having at least one hydrophilic group or carrying a potentially hydrophilic group, thereby causing the water dispersibility of the polyurethanes, to a polyurethane in the presence of an N-acylmorpholine of the formula (I) and

II. Subsequent dispersion of the polyurethane in water,

III. wherein optionally after or during step II can add polyamines. Suitable monomers in (a) are the polyisocyanates customarily used in polyurethane chemistry, for example aliphatic, aromatic and cycloaliphatic diisocyanates and polyisocyanates, where the aliphatic hydrocarbon radicals contain, for example, 4 to 12 carbon atoms and the cycloaliphatic or aromatic hydrocarbon radicals, for example 6 to 15 carbon atoms or the araliphatic hydrocarbon radicals, for example, have 7 to 15 carbon atoms, with an NCO functionality of at least 1, 8, preferably 1, 8 to 5 and particularly preferably 2 to 4 in question, and their isocyanurates, biurets, allophanates and uretdiones. The diisocyanates are preferably isocyanates having 4 to 20 C atoms. Examples of customary diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, esters of lysine diisocyanate, tetramethylxylylene diisocyanate, trimethylhexane diisocyanate or tetramethylhexane-iisocyanate, cycloaliphatic diisocyanates such as 1, 4- , 1, 3 or 1, 2-diisocyanatocyclohexane, the trans / trans, the cis / cis and the cis / trans isomers of 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane, 1 - Isocyanato-3,3,5-trimethyl-5-

(isocyanatomethyl) cyclohexane (isophorone diisocyanate), 2,2-bis (4-isocyanatocyclohexyl) propane, 1, 3- or 1, 4-bis (isocyanatomethyl) cyclohexane or 2,4- or 2,6-diisocyanato-1 methylcyclohexane and also aromatic diisocyanates such as tolylene 2,4- or 2,6-diisocyanate and isomer mixtures thereof, m- or p-xylylene diisocyanate, 2,4'- or 4,4'-diisocyanatodiphenylmethane and isomer mixtures thereof, 1, 3 or 1, 4-phenylenediisocyanate, 1-chloro-2,4-phenylenediisocyanate, 1,5-naphthylenediisocyanate, diphenyl-4,4'-diisocyanate, 4,4'-diisocyanato-3,3'-dimethyldiphenyl,

3-methyldiphenylmethane-4,4'-diisocyanate, 1,4-diisocyanatobenzene or diphenyl ether-4,4'-diisocyanate.

There may also be mixtures of said diisocyanates. Preference is given to aliphatic and cycloaliphatic diisocyanates, with particular preference being given to isophorone diisocyanate, hexamethylene diisocyanate, meta-tetramethylxylylene diisocyanate (m-TMXDI) and 1,1-methylenebis [4-isocyanato] cyclohexane (H12MDI).

Suitable polyisocyanates are polyisocyanates having isocyanurate groups, uretdione diisocyanates, polyisocyanates containing biuret groups, polyisocyanates containing urethane or allophanate groups, polyisocyanates containing oxadiazinetrione groups, uretonimine-modified polyisocyanates of straight-chain or branched one

C4-C20-alkylene diisocyanates, cycloaliphatic diisocyanates having a total of 6 to 20 carbon atoms or aromatic diisocyanates having a total of 8 to 20 carbon atoms or mixtures thereof in consideration. The usable di- and polyisocyanates preferably have a content of isocyanate groups (calculated as NCO, molecular weight = 42 g / mol) of 10 to 60 wt .-% based on the diisocyanate and polyisocyanate (mixture), preferably 15 to 60 wt. %, and more preferably 20 to 55% by weight.

Preferred are aliphatic or cycloaliphatic di- and polyisocyanates, e.g. the abovementioned aliphatic or cycloaliphatic diisocyanates, or mixtures thereof.

Further preferred

1) isocyanurate-containing polyisocyanates of aromatic, aliphatic

and / or cycloaliphatic diisocyanates. Particular preference is given here to the corresponding aliphatic and / or cycloaliphatic isocyanato-isocyanurates and in particular those based on hexamethylene diisocyanate and isophorone diisocyanate. The isocyanurates present are in particular tris-isocyanatoalkyl or tris-isocyanatocycloalkyl isocyanurates, which are cyclic trimers of the diisocyanates, or mixtures with their higher homologs containing more than one isocyanurate ring. The isocyanato-isocyanurates generally have an NCO content of 10 to 30 wt .-%, in particular 15 to 25 wt .-% and an average NCO functionality of 3 to 4.5.

2) uretdione diisocyanates having aromatic, aliphatic and / or cycloaliphatic bound isocyanate groups, preferably aliphatically and / or cycloaliphatically bonded and in particular those derived from hexamethylene diisocyanate or isophorone diisocyanate. Uretdione diisocyanates are cyclic dimerization products of diisocyanates.

The uretdione diisocyanates can be used in the preparations as the sole component or in a mixture with other polyisocyanates, in particular those mentioned under 1).

3) biuret polyisocyanates having aromatic, cycloaliphatic or aliphatic bound, preferably cycloaliphatic or aliphatic bound isocyanate groups, in particular tris (6-isocyanatohexyl) biuret or mixtures thereof with its higher homologues. These biuret polyisocyanates generally have an NCO content of 18 to 22 wt .-% and an average NCO functionality of 3 to 4.5.

4) polyisocyanates containing urethane and / or allophanate groups with aromatic,

aliphatically or cycloaliphatically bonded, preferably aliphatically or cycloaliphatically bonded isocyanate groups, as obtained, for example, by reacting excess amounts of hexamethylene diisocyanate or of isophorone diisocyanate with polyvalent alcohols, for example trimethylolpropane, neopentylglycol, pentaerythritol, 1,4-butanediol, 1,6-hexanediol, 1,3-propanediol,

Ethylene glycol, diethylene glycol, glycerol, 1, 2-dihydroxypropane or mixtures thereof can be obtained. These polyisocyanates containing urethane and / or allophanate groups generally have an NCO content of 12 to 20% by weight and an average NCO functionality of 2.5 to 3.

5) oxadiazinetrione-containing polyisocyanates, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such oxadiazinetrione-containing polyisocyanates can be prepared from diisocyanate and carbon dioxide.

6) Uretonimine-modified polyisocyanates.

The polyisocyanates 1) to 6) can be used in a mixture, if appropriate also mixed with diisocyanates.

Particularly suitable mixtures of these isocyanates are the mixtures of the respective structural isomers of diisocyanatotoluene and diisocyanato-diphenylmethane, in particular the mixture of 20 mol% 2,4 diisocyanatotoluene and 80 mol%

2,6-diisocyanatotoluene suitable. Furthermore, the mixtures of aromatic isocyanates such as 2,4-diisocyanatotoluene and / or 2,6-diisocyanatotoluene with aliphatic or cycloaliphatic isocyanates such as hexamethylene diisocyanate or IPDI are particularly advantageous, the preferred mixing ratio of aliphatic to aromatic isocyanates 4: 1 to 1: 4 is.

As compounds (a) it is also possible to use isocyanates which, in addition to the free isocyanate groups, contain further blocked isocyanate groups, e.g. Wear uretdione or urethane groups.

If appropriate, it is also possible to use those isocyanates which carry only one isocyanate group. In general, their proportion is at most 10 mol%, based on the total molar amount of the monomers. The monoisocyanates usually carry further functional groups such as olefinic groups or carbonyl groups and serve to introduce functional groups into the polyurethane, which enable the dispersion or the crosslinking or further polymer-analogous reaction of the polyurethane. Suitable for this purpose are monomers such as isopropenyl-α, α-dimethylbenzyl isocyanate (TMI).

Preferred diols (b) are relatively high molecular weight diols (b1) which have a molecular weight of about 500 to 5,000, preferably about 100 to 3,000, g / mol.

The diols (b1) are, in particular, polyesterpolyols which are known, for example, from Ullmanns Encyklopadie der technischen Chemie, 4th Edition, Volume 19, pages 62 to 65. Before- zugt be polyester polyols are used, which are obtained by reacting dihydric alcohols with dibasic carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic anhydrides or corresponding polycarboxylic esters of lower alcohols or mixtures thereof to prepare the polyesterpolyols. The polycarboxylic acids may be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and may optionally be substituted, for example by halogen atoms, and / or unsaturated. Examples which may be mentioned are: suberic acid, azelaic acid, phthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimer fatty acids. Preference is given to dicarboxylic acids of the general formula HOOC- (CH 2) _y -COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, for example succinic acid, adipic acid, dodecanedicarboxylic acid and sebacic acid. Examples of suitable polyhydric alcohols are ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,3-diol, butene-1,4-diol, butyne-1,4-diol, pentane-1 , 5-diol, neopentyl glycol, bis (hydroxymethyl) cyclohexanes such as 1, 4-bis (hydroxymethyl) cyclohexane, 2-methyl-propane-1, 3-diol, further diethyl englykol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol , Polypropylene glycol, dibutylene glycol and polybutylene glycols into consideration. Neopentyl glycol and alcohols of the general formula are preferred

HO- (CH 2) x -OH, where x is a number from 1 to 20, preferably an even number from 2 to 20. Examples of these are ethylene glycol, butane-1, 4-diol, hexane-1, 6-diol, octane-1, 8-diol and dodecane-1, 12-diol. Also included are polycarbonate diols, e.g. by reaction of phosgene with an excess of the mentioned as synthesis components for the polyester polyols low molecular weight alcohols, into consideration.

Also suitable are lactone-based polyesterdiols, which are homopolymers or mixed polymers of lactones, preferably terminal hydroxyl-containing addition products of lactones onto suitable difunctional starter molecules. Preferred lactones are those which are derived from hydroxycarboxylic acids of the general formula HO- (CH 2) z -COOH, where z is a number from 1 to 20, preferably an odd number from 3 to 19, for example ε-caprolactone, ß-propiolactone, γ-butyrolactone and / or methyl ε-caprolactone and mixtures thereof. Suitable starter components are, for example, the low molecular weight dihydric alcohols mentioned above as the synthesis component for the polyesterpolyols. The corresponding polymers of ε-caprolactone are particularly preferred. Lower polyester diols or polyether diols can also be used as starters for the preparation of the lactone polymers. Instead of the polymers of lactones, the corresponding, chemically equivalent polycondensates of the hydroxides corresponding to the lactones can also be used. roxycarboxylic acids are used.

In addition, suitable monomers (b1) are polyether diols. In particular, they are by polymerization of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with themselves, e.g. in the presence of BF3 or by addition of these compounds, optionally in admixture or sequentially, to starting components having reactive hydrogen atoms, such as alcohols or amines, e.g. Water, ethylene glycol, propane-1, 2-diol, propane-1, 3-diol, 2,2-bis (4-hydroxydiphenyl) propane or aniline available. Particularly preferred is polytetrahydrofuran having a molecular weight of 500 to 5000 g / mol, and especially 1000 to 4500 g / mol.

The polyester diols and polyether diols can also be used as mixtures in a ratio of 0.1: 1 to 1: 9. As diols (b), in addition to the diols (b1), it is also possible to use low molecular weight diols (b2) having a molecular weight of about 50 to 500, preferably from 60 to 200, g / mol.

The monomers (b2) used are, in particular, the synthesis components of the short-chain alkanediols mentioned for the preparation of polyesterpolyols, the unbranched diols having 2 to 12 C atoms and an even number of C atoms and pentanediol-1, 5 and Ne - Opentylglykol be preferred.

The proportion of the diols (b1), based on the total amount of the diols (b), is preferably 10 to 100 mol% and the proportion of the diols (b2) is 0 to 90 mol%, based on the total amount of the diols (b). , The ratio of the diols (b1) to the diols (b2) is particularly preferably from 0.2: 1 to 5: 1, particularly preferably from 0.5: 1 to 2: 1.

The monomers (c) other than the diols (b) generally serve for crosslinking or chain extension. They are generally more than divalent non-aromatic alcohols, amines having 2 or more primary and / or secondary amino groups and compounds which carry one or more primary and / or secondary amino groups in addition to one or more alcoholic hydroxyl groups.

Alcohols of higher valency than 2, which can serve to set a certain degree of branching or crosslinking, are e.g. Trimethylolbutane, trimethylolpropane, trimethylolethane, pentaerythritol, glycerol, sugar alcohols, such as e.g. Sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xylitol, dulcitol (galactitol), maltitol or isomalt, or sugar.

Also suitable are monoalcohols which, in addition to the hydroxyl group, carry a further isocyanate-reactive group, such as monoalcohols having one or more primary groups and / or secondary amino groups, for example monoethanolamine.

Polyamines having 2 or more primary and / or secondary amino groups can be used in the prepolymer mixing process above all when the chain extension or crosslinking is to take place in the presence of water (step III), since amines are generally faster than alcohols or Water react with isocyanates. This is often required when aqueous dispersions of high molecular weight crosslinked polyurethanes or polyurethanes are desired. In such cases, the procedure is to prepare prepolymers with isocyanate groups, to rapidly disperse them in water and then to chain extend or crosslink them by adding compounds containing several isocyanate-reactive amino groups.

Amines suitable for this purpose are generally polyfunctional amines of the molecular weight range from 32 to 500 g / mol, preferably from 60 to 300 g / mol, which contain at least two primary, two secondary or at least one primary and one secondary amino group.

Examples of these are diamines such as diaminoethane, diaminopropanes, diaminobutanes, diaminohexanes, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine, IPDA), 4,4 ' Diaminodicyclohexylmethane, 1,4-diaminocyclohexane, aminoethylethanolamine, hydrazine, hydrazine hydrate or triamines such as diethylenetriamine or 1,8-diamino-4-aminomethyloctane or higher amines such as triethylenetetramine, tetraethylenepentamine or polymeric amines such as polyethyleneamines, hydrogenated polyacrylonitriles or at least partially hydrolyzed poly-N-vinylformamide each having a molecular weight of up to 2000, preferably up to 1000 g / mol. The amines may also be in blocked form, e.g. in the form of the corresponding ketimines (see, for example, CA-1 129 128), ketazines (see, for example, US-A 4,269,748) or amine salts

(see US-A 4,292,226). Oxazolidines, as used for example in US Pat. No. 4,192,937, also represent blocked polyamines which can be used for the preparation of the polyurethanes for chain extension of the prepolymers. In the use of such capped polyamines they are generally mixed with the prepolymers in the absence of water and this mixture is then mixed with the dispersion water or a portion of the dispersion water, so that the corresponding polyamines are hydrolytically released. Preference is given to using mixtures of di- and triamines, more preferably mixtures of isophoronediamine and diethylenetriamine.

The proportion of polyamines can be up to 10, preferably up to 8 mol% and particularly preferably up to 5 mol%, based on the total amount of components (b) and (c). The polyurethane prepared in step I can generally have up to 10% by weight, preferably up to 5% by weight, of unreacted NCO groups.

The molar ratio of NCO groups in the polyurethane prepared in step I to the sum of primary and secondary amino groups in the polyamine is generally selected in step III to be between 3: 1 and 1: 3, preferably 2: 1 and 1: 2, more preferably 1, 5: 1 and 1: 1.5; most preferably at 1: 1.

Furthermore, chain termination in minor amounts, i. preferably in amounts of less than 10 mol%, based on the components (b) and (c), monoalcohols are used. They serve mainly to limit the molecular weight of the polyurethane. Examples are methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1,3-propanediol monomethyl ether, n-hexanol, n-heptanol,

n-octanol, n-decanol, n-dodecanol (lauryl alcohol) and 2-ethylhexanol.

In order to achieve the water-dispersibility of the polyurethanes, the polyurethanes, besides components (a), (b) and (c), are monomers (d) which are different from components (a), (b) and (c) and have at least one isocyanate group or at least one group which is reactive toward isocyanate groups and moreover at least one hydrophilic group or a group which can be converted into hydrophilic groups. In the following text, the term "hydrophilic groups or potentially hydrophilic groups" is abbreviated to "(potentially) hydrophilic groups". The (potentially) hydrophilic groups react much more slowly with isocyanates than the functional groups of the monomers which serve to build up the polymer main chain. The (potentially) hydrophilic groups may be nonionic or, preferably, ionic, i. cationic or anionic, hydrophilic groups, or potentially ionic hydrophilic groups, and more preferably anionic hydrophilic groups, or potentially anionic hydrophilic groups.

The proportion of components with (potentially) hydrophilic groups in the total amount of components (a), (b), (c) and (d) is generally such that the molar amount of (potentially) hydrophilic groups, based on the amount by weight of all monomers (a) to (b), 30 to 1000, preferably 50 to 500 and particularly preferably 80 to 300 mmol / kg.

Examples of nonionic hydrophilic groups are mixed or pure polyethylene glycol ethers of preferably from 5 to 100, preferably from 10 to 80, ethylene oxide.

Repeat units into consideration. The polyethylene glycol ethers may also contain propylene oxide units. If this is the case, the content of propylene oxide units should not exceed 50% by weight, preferably 30% by weight, based on the mixed polyethylene glycol ether. The content of polyethylene oxide units is generally 0 to 10, preferably

0 to 6 wt .-%, based on the amount by weight of all monomers (a) to (d).

Preferred monomers with nonionic hydrophilic groups are the polyethylene glycol and diisocyanates which carry a terminally etherified polyethylene glycol radical. Such diisocyanates and processes for their preparation are disclosed in US Pat. Nos. 3,905,929 and 3,920,598.

Ionic hydrophilic groups are, in particular, anionic groups such as the sulfonate, the carboxylate and the phosphate groups in the form of their alkali metal or ammonium salts, and also cationic groups such as ammonium groups, in particular protonated tertiary amino groups or quaternary ammonium groups.

Suitable monomers having potentially anionic groups are usually aliphatic, cycloaliphatic, araliphatic or aromatic mono- and dihydroxycarboxylic acids which carry at least one alcoholic hydroxyl group or one primary or secondary amino group.

Such compounds are exemplified by the general formula

RG-R ⁴ -DG, wherein RG is at least one isocyanate-reactive group

DG at least one dispersive group and

R ^{4 is} an aliphatic, cycloaliphatic or aromatic radical containing 1 to 20 carbon atoms. Examples of RG are -OH, -SH, -NH ₂ or -NHR ^5, wherein R ⁵ is methyl, ethyl, / ^'so-propyl, n-propyl, n-butyl, / so-butyl, s / butyl, feri Butyl, cyclopentyl or cyclohexyl can be.

Preferably such components are e.g. mercaptoacetic acid, mercaptopropionic acid, thiolactic acid, mercaptosuccinic acid, glycine, iminodiacetic acid, sarcosine, alanine, β-alanine, leucine, isoleucine, aminobutyric acid, hydroxyacetic acid, hydroxypivalic acid, lactic acid, hydroxysuccinic acid, hydroxydecanoic acid, dimethylolpropionic acid, dimethylolbutyric acid, ethylenediaminetriacetic acid, hydroxydodecanoic acid , Hydroxyhexadecanoic acid, 12-hydroxystearic acid, aminonaphthalenecarboxylic acid, hydroxethanesulfonic acid, hydroxypropanesulfonic acid, mercaptoethanesulfonic acid, mercaptopropanesulfonic acid, aminomethanesulfonic acid, taurine, aminopropanesulfonic acid, N-cyclohexylaminopropanesulfonic acid, N-

Cyclohexylaminoethansulfonsäure and their alkali, alkaline earth or ammonium salts and particularly preferably the abovementioned monohydroxycarboxylic and -sulfonic acids as well as monoaminocarboxylic and -sulfonic acids.

Very particular preference is given to dihydroxyalkylcarboxylic acids, in particular having 3 to 10 carbon atoms, as are also described in US Pat. No. 3,412,054. In particular, compounds of the general formula

HO-R ¹ -CR ³ (COOH) -R ² -OH in which R ¹ and R ^{2 is} a C 1 to C 4 alkanediyl unit and R ^{3 is} a C 1 to C 4 alkyl unit. Above all, dimethylol butyric acid and especially dimethylolpropionic acid (DMPA) are preferable.

Also suitable are corresponding Dihydroxysulfonsauren and Dihydroxyphosponsauren such as 2,3-dihydroxypropanephosphonic acid and the corresponding acids in which at least one hydroxy group is replaced by an amino group, for example those of the formula

H ₂ NR -CR ³ (COOH) -R ² -NH ₂ in which R ¹ , R ² and R ^{3 may have} the same meanings as stated above.

Otherwise suitable are dihydroxy compounds having a molecular weight above 500 to 10,000 g / mol with at least 2 carboxylate groups, which are known from DE-A 4,140,486. They are obtainable by reacting dihydroxyl compounds with tetracarboxylic dianhydrides such as pyromellitic dianhydride or cyclopentanetetracarboxylic dianhydride in a molar ratio of 2: 1 to 1:05 in a polyaddition reaction. Particularly suitable dihydroxy compounds are the monomers (b2) listed as chain extenders and the diols (b1).

Potentially ionic hydrophilic groups are, above all, those which can be converted into the abovementioned ionic hydrophilic groups by simple neutralization, hydrolysis or quaternization reactions, that is, e.g. Acid groups, anhydride groups or tertiary amino groups.

Ionic monomers (d) or potentially ionic monomers (d) are e.g. in Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Volume 19, pp. 311-313 and for example in DE-A 1 495 745.

Particularly preferred monomers for cationic monomers (d) are monomers having tertiary amino groups, for example: tris (hydroxyalkyl) -amines, Ν, Ν'-bis (hydroxyalkyl) -alkylamines, N-hydroxyalkyl-dialkylamines, tris ( aminoalkyl) -amines, Ν, Ν'-bis (aminoalkyl) -alkylamines, N-aminoalkyl-dialkylamines, where the alkyl radicals and alkanediyl Units of these tertiary amines independently consist of 2 to 6 carbon atoms. Furthermore, tertiary nitrogen atoms containing polyether having preferably two terminal hydroxyl groups, such as, for example, by alkoxylation of two amines bound to amine nitrogen hydrogen atoms containing amines, eg methylamine, aniline, or Ν, Ν'-dimethylhydrazine, are accessible in per se conventional manner in consideration. Such polyethers generally have a molecular weight between 500 and 6000 g / mol.

These tertiary amines are either with acids, preferably strong mineral acids such as phosphoric acid, sulfuric acid or hydrohalic acids, strong organic acids such as formic, acetic or lactic acid, or by reaction with suitable quaternizing agents such as C 1 to C 6 alkyl halides, e.g. Bromides or chlorides, or di-Cd-C6-alkyl sulfates or di-d- to C6-alkyl carbonates in the ammonium salts.

Suitable monomers (d) with isocyanate-reactive amino groups are aminocarboxylic acids such as lysine, β-alanine, the adducts of aliphatic diprimary diamines mentioned in DE-A2034479 to α, β-unsaturated carboxylic acids such as N- (2-aminoethyl) - 2-aminoethanecarboxylic acid and the corresponding N-aminoalkyl-aminoalkylcarboxylic acids, wherein the alkanediyl units consist of 2 to 6 carbon atoms, into consideration. If monomers having potentially ionic groups are used, their conversion into the ionic form may take place before, during, but preferably after the isocyanate polyaddition, since the ionic monomers are often difficult to dissolve in the reaction mixture. The anionic hydrophilic groups are particularly preferably in the form of their salts with an alkali ion or an ammonium ion as the counterion.

Among these compounds, hydroxycarboxylic acids are preferred, with particular preference being given to dihydroxyalkylcarboxylic acids, which are very particularly preferred

a, a-bis (hydroxymethyl) carboxylic acids, in particular dimethylol butyric acid and dimethylolpropionic acid and especially dimethylolpropionic acid.

In an alternative embodiment, the polyurethanes may contain both nonionic hydrophilic and ionic hydrophilic groups, preferably simultaneously nonionic hydrophilic and anionic hydrophilic groups. In the field of polyurethane chemistry, it is well known how the molecular weight of the polyurethanes can be adjusted by selecting the proportions of the monomers reactive with each other and the arithmetic mean of the number of reactive functional groups per molecule.

Normally, the components (a), (b), (c) and (d) and their respective molar amounts are chosen so that the ratio A: B with A) the molar amount of isocyanate groups and

B) the sum of the molar amount of the hydroxyl groups and the molar amount of the functional groups which can react with isocyanates in an addition reaction

0.5: 1 to 2: 1, preferably 0.8: 1 to 1, 5, more preferably 0.9: 1 to 1, 2: 1. Most preferably, the ratio A: B is as close as possible to 1: 1.

In addition to components (a), (b), (c) and (d), monomers having only one reactive group are generally added in amounts of up to 15 mol%, preferably up to 8 mol%, based on the total amount of the components (a), (b), (c) and (d) used.

The polyaddition of components (a) to (d) is generally carried out at reaction temperatures of 20 to 180 ° C, preferably 50 to 150 ° C under atmospheric pressure.

The required reaction times can range from a few minutes to a few hours. It is known in the field of polyurethane chemistry how the reaction time is affected by a variety of parameters such as temperature, concentration of monomers, reactivity of the monomers.

To accelerate the reaction of the diisocyanates, the conventional catalysts can be used. In principle, all catalysts commonly used in polyurethane chemistry come into consideration. These are, for example, organic amines, in particular tertiary aliphatic, cycloaliphatic or aromatic amines, and / or Lewis-acidic organic metal compounds. As the Lewis acidic organic metal compounds, e.g. Tin compounds, such as tin (II) salts of organic carboxylic acids, e.g. Tin (II) acetate, stannous octoate, stannous ethylhexoate and stannous laurate and the dialkyltin (IV) salts of organic carboxylic acids, eg dimethyltin diacetate, dibutyltin diacetate, Dibutyltin dibutyrate, dibutyltin bis (2-ethylhexanoate), dibutyltin dilaurate, dibutyltin maleate, dioctyltin dilaurate and dioctyltin diacetate. Metal complexes such as acetylacetonates of iron, titanium, aluminum, zirconium, manganese, nickel and cobalt are also possible. Other metal catalysts are described by Blank et al. in Progress in Organic Coatings, 1999, Vol. 35, pages 19-29.

Preferred Lewis acidic organic metal compounds are dimethyltin diacetate, dibutyltin dibutyrate, dibutyltin bis (2-ethylhexanoate), dibutyltin dilaurate, diocyttin dilaurate, zirconium acetylacetonate and zirconium 2,2,6,6-tetramethyl-3, 5-heptanedionate. Also bismuth and cobalt catalysts and cesium salts can be used as catalysts. Suitable cesium salts are those compounds in which the following Anions are used: F, C, CIO ^" , CI0 ₃ -, CI0 ₄ -, Br, J, J0 ₃ -, CN-, OCN, N0 ₂ -, N0 ₃ -, HCOs-, CO ₃ ² -, S ² -SH-HSO ³ -, SO 3 ² -, HSO ₄ -, S0 ₄ ² -, S2O ^{2 2} -, S2O4 ² -, S2O5 ² -, S ₂ 0 ₆ ² -, S2O7 ² -,

S ₂ 0 ₈ ² -, H2PO2-, H2PO4-, HPO4 ² -, PO4 ³ -, P2O7 ⁴ -, (OCnH _{2n +} l) -, (C _n H ₂ n-l0 ₂ ) -, (CnHzn-sOz) ^" Such as

(Cn + iH2n-20 ₄ ) ² -, where n is the numbers 1 to 20.

Cesium carboxylates in which the anion is the formula are preferred

(CnH 2n-iO 2) ^" as well as (Cn + iH 2n-20 ₄ ) ² - with n equal to 1 to 20. Particularly preferred cesium salts have as anions monocarboxylates of the general formula

(CnH2n-iO2) ^" , where n is the numbers 1 to 20. Mention should be made in particular of formate, acetate, propionate, hexanoate and 2-ethylhexanoate.

Rührkessel come into consideration as polymerization, especially when provided by the concomitant use of solvents for a low viscosity and good heat dissipation.

If the reaction is carried out in bulk, extruders, in particular self-cleaning multi-screw extruders, are particularly suitable because of the usually high viscosities and the usually short reaction times.

In the so-called "prepolymer mixing process", first a prepolymer is prepared which carries isocyanate groups. The components (a) to (d) are in this case chosen so that the ratio A: B is greater than 1, 0 to 3, preferably 1, 05 to 1, 5. The prepolymer is first dispersed in water and simultaneously and / or chain-extended by reaction of the isocyanate groups with amines carrying more than 2 isocyanate-reactive amino groups, or with amines containing 2 isocyanate-reactive amino groups, chain extended. Chain extension also occurs when no amine is added. In this case, isocyanate groups are hydrolyzed to amine groups, which react with remaining isocyanate groups of the prepolymers with chain extension.

The mean particle size (z average), measured by dynamic light scattering with the Malvern® Autosizer 2 C, the dispersions according to the invention is not essential to the invention and is generally <1000 nm, preferably <500 nm, more preferably <200 nm and most preferably between 20 and under 200 nm.

The dispersions generally have a solids content of 10 to 75, preferably from 20 to 65 wt .-% and a viscosity of 10 to 500 mPas (measured at a temperature of 20 ° C and a shear rate of 250 s ^_1 .

For some applications it may be useful to adjust the dispersions to another, preferably a lower, solids content, for example by dilution. Furthermore, the dispersions prepared according to the invention can be mixed with other components typical of the applications mentioned, for example surfactants, detergents, dyes, pigments, dye transfer inhibitors and optical brighteners. The dispersions may be subjected to physical deodorizing after preparation, if desired.

A physical deodorization may consist in that the dispersion with water vapor, an oxygen-containing gas, preferably air, nitrogen or supercritical carbon dioxide, for example, in a stirred tank, as described in DE-AS 12 48 943, or in a countercurrent column, such as in DE-A 196 21 027 described, is stripped.

The amount of N-acylmorpholine (I) according to the invention in the preparation of the polyurethane is generally chosen so that the proportion in the final aqueous polyurethane dispersion, that is, after step II and optionally step III, does not exceed 30% by weight not more than 25, more preferably not more than 20, and most preferably not more than 15% by weight.

The proportion of N-acylmorpholine (I) in the finished aqueous polymer dispersion, in particular polyurethane dispersion, is generally at least 0.01% by weight, preferably at least 0.1, particularly preferably at least 0.2, very particularly preferably at least 0.5 and in particular at least 1% by weight.

The aqueous polymer dispersions according to the invention, in particular polyurethane dispersions, are advantageously suitable for coating and bonding substrates. Suitable substrates are wood, wood veneer, paper, cardboard, textiles, leather, artificial leather, fleece, plastic surfaces, glass, ceramics, mineral building materials, clothing, vehicle interiors, vehicles, metals or coated metals. They are used, for example, in the production of films or films, for impregnating textiles or leather, as dispersants, as pigment driers, as primers, as adhesion promoters, as water repellents, as detergent additive or as additive in cosmetic preparations or for the production of moldings or hydrogels.

When used as coating compositions, the polymer dispersions, in particular polyurethane dispersions, can be used in particular as primers, fillers, pigmented topcoats and clearcoats in the field of car repair or large-vehicle painting. Particularly suitable are the coating compositions for applications in which a particularly high application safety, outdoor weather resistance, optics, solvent, chemical and water resistance are required, such as in the car repair and large vehicle painting. Aqueous polymer dispersions according to the invention, in particular polyurethane dispersions or polyurethane dispersions, which have been prepared by the process according to the invention have at least one of the following advantages over polymer dispersions or polyurethane dispersions known from the prior art:

Reduced need for solvents.

The dispersions are easier to spray or atomise because less incrustations or impurities are deposited on injection tools,

low toxicity.

The prepolymer solutions have a lower viscosity.

The rheological behavior of the polyurethane dispersions is improved.

The wetting behavior of substrates or additives is improved.

Less yellowing under light and / or heat.

Higher frost resistance of the dispersions.

Improved flexibility, in particular cold flexibility of the resulting films.

Higher gloss of the obtained films.

Improved course of the movie.

Improved movie frame properties

Improved adhesion of the coating produced from the polymer dispersion on the carrier material.

The addition of N-acylmorpholines to polymer dispersions, either before, during or after the preparation and / or dispersion of the polymer or polyurethane, improves the adhesion of the coating, which is produced from such a polymer dispersion, to the support material. This applies in particular to support materials which have a polymer surface, in particular a surface of polyurethane.

In particular, polymer dispersions according to the invention have a low viscosity. Another object of the invention is the use of N-Acylmorpholinen according to formula (I) as a solvent in the preparation of polymers, in particular polyurethanes, in particular of aqueous polyurethane dispersions, preferably by the prepolymer mixing method.

Another object of the invention are aqueous polyurethane dispersions prepared by the process according to the invention.

Another object of the present invention are coating compositions comprising at least one inventive polymer dispersion, in particular polyurethane dispersion, as well as objects coated therewith. Another object of the invention is the use of polymer dispersions of the invention, in particular polyurethane dispersions for coating or impregnation of surfaces such as leather, wood, textile, synthetic leather, metal, plastics, clothing, furniture, automotive interiors, vehicles, paper, organic polymers, in particular polyurethane ,

Another object of the invention are coating compositions containing aqueous polymer dispersions, which have been prepared from polymer dispersions of the invention, as well as objects coated therewith.

Ppm and percentages used in this specification, unless otherwise indicated, are by weight percent and ppm.

Examples

I. Preparation of Polyurethane Dispersions

Abbreviations

DETA diethylenetriamine

DMEA dimethylethanolamine

DMPA dimethylolpropionic acid

EDA ethylenediamine

IPDA isophorone diamine

IPDI isophorone diisocyanate

NEP N-ethylpyrrolidone

NMP N-methylpyrrolidone

PUD polyurethane dispersion

TDI tolylene diisocyanate (80% 2,4- and 20% 2,6-isomer)

TEA triethylamine

Example 1 (Formylmorpholine as solvent)

In a stirred flask with reflux condenser and thermometer, 400 g (0.20 mol) of a polyproplyene oxide of OH number 56, 32.2 g (0.24 mol) of DMPA and 50 g of N-formylmorpholine were initially charged and stirred at 65.degree , To this was added 76.6 g (0.44 mol) of TDI and stirred at 110 ° C for 360 minutes. It was then diluted with 400 g of acetone and the NCO content to 0.01 wt.% Determined (calculated: 0.00%). Thereafter, 10.0 g (0.10 mol) of TEA were added. After dispersing with 800 g of water, the acetone was removed by distillation under reduced pressure.

This gave a finely divided PUD with 44.8% solids, a viscosity of 23 mPas at 23 ° C and a shear rate of 250 / s.

Example 2 (acetylmorpholine as solvent)

In a stirred flask with reflux condenser and thermometer 400 g (0.20 mol) of a poly propylene oxide of OH number 56, 32.2 g (0.24 mol) of DMPA and 50 g of N-acetylmorpholine and stirred at 65 ° C. , To this was added 76.6 g (0.44 mol) of TDI and stirred at 110 ° C for 360 minutes. It was then diluted with 400 g of acetone and the NCO content to 0.03 wt.% Determined (calculated: 0.00%). Thereafter, 10.0 g (0.10 mol) of TEA were added. After dispersing with 800 g of water, the acetone was removed by distillation under reduced pressure.

This gave a finely divided PUD with 38.4% solids, a viscosity of 17 mPas at 23 ° C and a shear rate of 250 / s. Comparative Example 3

Example 1 was repeated but with 50 g of NMP instead of N-formylmorpholine. The NCO content was determined to be 0.01% by weight (calculated: 0.00%).

This gave a finely divided PUD with 44.1% solids, a viscosity of 99 mPas at 23 ° C and a shear rate of 250 / s.

Comparative Example 4

Example 1 was repeated but with 50 g of NEP instead of N-formylmorpholine. The NCO content was determined to be 0.02% by weight (calculated: 0.00%).

This gave a finely divided PUD with 40.1% solids, a viscosity of 285 mPas at 23 ° C and a shear rate of 250 / s.

"Shade of polymer dispersions according to example 1 to 4,

Comparative Example 5: NMP

In a stirred flask with reflux condenser and thermometer were 400 g (0.20 mol) of a polyester diol of OH number 56 from neopentyl glycol, hexanediol-1, 6 and adipic acid, 26.09 g (0.19 mol) of DMPA and 150 g NMP submitted and stirred at 80 ° C for 30 minutes. To this was added 175.5 g (0.79 mol) of IPDI and stirred at 95 ° C. After four hours, an NCO content of 4.44% was achieved (calculated: 4.41%). After the addition of 19.71 g (0.19 mol) of TEA, the prepolymer was dispersed in 672 g of water. To the dispersion was added a mixture of 66 g of water and 22.53 g of EDA.

Example 6: Formylmorpholine

The procedure was as in Comparative Example 8, but instead of the NMP, the same mass of formylmorpholine was used.

Example 7: Acetylmorpholine

The procedure was as in Comparative Example 8, but instead of the NMP, the same mass acetylmorpholine was used. Films were prepared by pouring the dispersions shown in FIGS. 5, 6 and 7 into a glass vat and drying for 7 days at room temperature. The amount of dispersion was chosen so that dry films were obtained with a thickness of about 1 mm.

Table 2 summarizes the properties of the dispersions and the resulting films:

The viscosities were determined using a rotation viscometer from the company Paar Physica according to DI N 53019.

To determine the LD value (transparency), the particular polymer dispersion to be examined is measured in aqueous dilution in a cuvette with a cuvette of edge length 2.5 cm with light of wavelength 600 nm and compared with the corresponding permeability of water under the same measurement conditions. The permeability of water is given as 100%. The finer the dispersion, the higher the LD value measured by the method described above. The LD values were determined in 0.1% strength aqueous solution of the dispersion to be determined using a device from Hach DR / 2010 at a wavelength of 600 nm.

The mean particle sizes were determined by dynamic light scattering in a Malvern Zetasizer APS.

Film hardnesses (Shore hardnesses) were determined according to DIN EN ISO 868.

Tensile Strength and Elongation at Break were determined according to ISO 37.

Properties of the dispersions of Examples 5 to 7 and the films obtained therefrom. It can be clearly seen that the use of acyl morpholins gives dispersions with reduced viscosity and films with identical properties.

II. Finishing of leather

Used products:

Lepton® colors N

The Lepton colors N are caseinfree Lederdeckfarben.

Lepton® Filier FCG

Lepton® Filier FCG is a sizing agent based on aqueous wax dispersions, matting agents and additives. Astacin® Finish SUSI TF

Astacin® Finish SUSI TF is a very soft primer based on an aliphatic polyester urethane dispersion.

Astacin® Finish PS

Astacin® Finish PS is a soft primer based on an aliphatic polyetherurethane dispersion.

Astacin® Finish PTM

Astacin® Finish PTM is a hard and matt primer based on an aliphatic polyetherurethane dispersion and matting agent.

Corial® binder DN

Corial® Binder DN is a soft and very cold flexible primer binder based on an acrylate polymer dispersion.

Astacin® Novomatt GG

Astacin® Novomatt GG is a medium hard, matt and flexible top coat binder based on an aliphatic polyester urethane dispersion and matting agent.

Astacin® matting HS

Astacin® Matting HS is a hard, matte and flexible top coat binder based on a polycarboant dispersion and matting agent.

Astacin® Novomatt GG Astacin® Novomatt GG is a medium-hard, very matt and flexible Top Coat binder based on an aliphatic polyetherurethane dispersion, matting agents and additives. Lepton® Protector SR

Lepton® Protector SR is an anti-soiling additive based on a modified acrylate polymer dispersion and additives.

Lepton® matting AL

Lepton® Matting AL is a silicate-free polymeric matting agent. Lepton® Wax WN

Lepton® Wax WN is a silicone emulsion based on high molecular weight poly-siloxanes.

Lepton® Wax DS

Lepton® Wax DS is a low film-forming silicone emulsion based on high molecular weight poly-siloxanes. Amollan® SW

Amollan® SW is a flow control agent based on a low-viscosity silicone-polyether fluid.

Astacin® Hardener CA.

Astacin® Hardener CA is a crosslinking agent for leather finishing based on polycarbonate and emulsifiers.

Astacin® hardener CN

Astacin® Hardener CN is a leather conditioning crosslinker based on an aliphatic polyisocyanate and organic solvent.

Comparative example

1 . First primer:

A leather suitable for automotive interior applications was primed with a liquor containing a roll coater

150 parts Lepton® colors N

100 T. Lepton® Filier FCG

100 T. Astacin® Finish SUSI TF

150 T. Astacin® Finish PS 100 T. Astacin® Finish PTM

100 T. Corial® binder DN

65 T. Astacin® Novomatt GG

5 T. Amollan® SW

40 T. Astacin® Hardener CA.

The liquor is adjusted by the addition of 30 parts of water to an outlet viscosity of 40 sec in a 4 mm cup according to DIN EN ISO 2431: 201 1.

The wet coat weight was 8.0 ± 0.5 g / ft ² . The leathers were dried at 80 ° C. for 1.5 minutes in a forced-air drying tunnel.

2. Second primer:

The so easily primed leather was primed by spray application for the second time with a

Fleet containing

150 parts Lepton® colors N

100 T. Lepton® Filier FCG

100 T. Astacin® Finish SUSI TF

150 T. Astacin® Finish PS

100 T. Astacin® Finish PTM

100 T. Corial® binder DN

65 T. Astacin® Novomatt GG

5 T. Amollan® SW

40 T. Astacin® Hardener CA.

The liquor is adjusted by the addition of 130 parts of water to an outlet viscosity of 24 sec in a 4 mm cup according to DIN EN ISO 2431: 201 1.

The wet coat weight was 2.4 + - 0.2 g / ft ² . The leathers were dried at 80 ° C. for 1.5 minutes in a forced-air drying tunnel.

The primed leather was stored overnight, embossed at a temperature of 140 ° C / a pressure of 210 bar / and a residence time of 3 seconds, stored for 3 hours and milled for 3 hours.

3. First finish:

The double-primed leather was spray-applied for the first time with a

Fleet containing

150 parts Lepton® colors N

60 T. Lepton® Filier FCG

100 T. Astacin® Finish SUSI TF

150 T. Astacin® Finish PS

75 T. Astacin® Finish PTM

200 T. Astacin® matting HS

65 T. Astacin® Novomatt GG 3 T. Amollan® SW

60 T. Astacin® Hardener CN.

The liquor is adjusted by addition of 220 parts of water to an outlet viscosity of 20 sec in the mm cup according to DIN EN ISO 2431: 201 1.

The wet job weight was 2.0 + - 0.2 g / ft ² . The leathers were dried at 80 ° C. for 1.5 minutes in a forced-air drying tunnel.

4. Second finish:

The simply finished leather was spray finished for the second time with a

Fleet containing

20 parts Lepton® colors N

350 T. Astacin® matting HS

150 T. Astacin® Novomatt GG

75 T. Lepton® Protector SR

40 T. Lepton® matting AL

40 T. Lepton® wax WN

40 parts Lepton® Wax DS

3 T. Amollan® SW

120 T. Astacin® Hardener CN.

The liquor is adjusted by adding 330 parts of water to an outlet viscosity of 28 seconds in a 4 mm cup according to DIN EN ISO 2431: 201 1.

The coating weight was wet 2.0 + - 0.2 g / ft ² . The leathers were dried at 80 ° C. for 1.5 minutes in a forced-air drying tunnel.

The primed and finished leather was stored overnight. example

Steps 1 and 2 of the comparative example were repeated.

At step 3. and 4. 50 T. N-formylmorpholine were added to the liquor

exam

After each coating step, the wet adhesion of the finish was tested in accordance with DIN EN ISO 1 1644.

Wet grip of the 1. Primer 2. Primer 1. Finishing 2nd finish finishing after

DIN EN ISO

1 1644 / N / cm)

Comparative Example 5.7 4.0 2.0 3.5

Example 5.2 4.7 4.7 8.9

Claims

claims

Aqueous polymer dispersion containing at least one N-acylmorpholine of the formula

wherein R ^{1 is} H or an alkyl group having 1 to 18 C atoms and R ² , R ³ , R ⁴ and R ^{5 are} each independently a hydrogen atom or a (cyclo) alkyl group having 1 to 18 C atoms.

Polymer dispersion according to Claim 1, characterized in that the aqueous polymer dispersion contains 0.01% by weight to 30% by weight of at least one N-acylmorpholine of the formula (I).

Polymer dispersion according to claim 1 to 2, characterized in that R ^{1 is} selected from the group consisting of H, methyl or ethyl.

Polymer dispersion according to claim 1 to 3, characterized in that R ² , R ³ , R ⁴ and R ^{5 are} selected from the group consisting of hydrogen, methyl, ethyl, iso-propyl and cyclohexyl.

Polymer dispersion according to claim 1 to 4, characterized in that the substituted N-acylmorpholine is selected from at least one morpholine selected from the group consisting of N-formylmorpholine, N-acetylmorpholine and N-propionylmorpholine.

Polymer dispersion according to Claims 1 to 5, characterized in that it is a polyurethane dispersion.

Process for the preparation of aqueous polyurethane dispersions according to Claim 6, comprising the following steps:

I. Preparation of a polyurethane in the presence of an N-acylmorpholine according to

Formula (I)

wherein R ^{1 is} H or an alkyl group having 1 to 18 C atoms and R ² , R ³ , R ⁴ and R ^{5 are} each a hydrogen atom or a (cyclo) alkyl group having 1 to 18 C atoms; II. Subsequent dispersion of the polyurethane in water.

Method according to claim 7, comprising the steps

I. Preparation of a polyurethane in the presence of at least one N-acylmorpholine of the formula (I) by reacting a) at least one polyfunctional isocyanate having 4 to 30 carbon atoms, b) diols, of which b1) is from 10 to 100 mol% to the total amount of the diols (b), have a molecular weight of 500 to 5000, and b2) 0 to 90 mol%, based on the total amount of the diols (b), have a molecular weight of 60 to 500 g / mol, c) optionally further, other than the diols (b), polyvalent compounds having reactive groups which are alcoholic hydroxyl groups or primary or secondary amino groups; and d) monomers other than monomers (a), (b) and (c) at least one isocyanate group or at least one isocyanate group-reactive group further having at least one hydrophilic group or a potentially hydrophilic group, thereby causing water-dispersibility of the polyurethanes a polyurethane and II. Subsequent dispersion of the polyurethane in water,

III. optional addition of polyamines after or during step II.

A method according to claim 7 to 8, characterized in that R ^{1 is} selected from the group consisting of H, methyl, ethyl

10. The method according to claim 7 to 9, characterized in that R ² , R ³ , R ⁴ and R ^{5 are} selected from the group consisting of hydrogen, methyl, ethyl, iso-propyl and cyclohexyl.

1 1. A method according to claim 7 to 10, characterized in that the substituted N-acylmorpholine is selected from at least one morpholine selected from the group consisting of N-formylmorpholine, N-acetylmorpholine and N-propionylmorpholine.

12. Use of polymer dispersions according to any one of claims 1 to 6 or of polyurethane dispersions, prepared according to claims 7 to 1 1 for coating and bonding of wood, wood veneer, paper, cardboard, cardboard, textile, leather, synthetic leather, fleece, plastic surfaces, glass, Ceramics, mineral building materials, metals or coated metals.

13. Use of substituted N-acylmorpholines according to formula (I)

wherein R ^{1 is} H or an alkyl group having 1 to 18 C atoms and R ² , R ³ , R ⁴ and R ^{5 are} each independently a hydrogen atom or a (cyclo) alkyl group having 1 to 18 C atoms, in the preparation of polyurethanes.

14 Use of polymer dispersions according to claims 1 to 6 for the coating of surfaces such as leather, wood, textile, synthetic leather, metal, plastics, clothing, furniture, automotive interiors, vehicles, paper.

15 coating composition comprising aqueous polymer dispersions according to claim 1 to 6.