Polyurethane dispersions having a low content of acetone azine and / or butanone azine

Abstract

The invention relates to the use of at least one organic dialkyl dicarbonate for reducing the content of acetone azine and / or butanone azine in an aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and acetone azine and / or butanone azine; furthermore to a process for producing an aqueous polyurethane-polyurea dispersion having a reduced content of acetone azine and / or butanone azine; to an aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and at least one alkyl carbazate; and to an article, cosmetic, coating, adhesive layer, coating formulation, adhesive formulation and / or cosmetic formulation obtainable therefrom.

Description

[0001] Polyurethane dispersions having a low content of acetone azine and / or butanone azine

[0002] The invention relates to the use of at least one organic dialkyl dicarbonate for reducing the content of acetone azine and / or butanone azine in an aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and acetone azine and / or butanone azine; furthermore to a process for producing an aqueous polyurethane-polyurea dispersion having a reduced content of acetone azine and / or butanone azine; to an aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and at least one alkyl carbazate; and to an article, cosmetic, coating, adhesive layer, coating formulation, adhesive formulation and / or cosmetic formulation obtainable therefrom.

[0003] Aqueous polyurethane dispersions and polyurethane-polyurea dispersions may be produced utilizing acetone as a process solvent (acetone process). Acetone offers various advantages as a solvent, for example it is relatively inert towards isocyanate groups, is easily miscible with water and may be removed by distillation. In addition, the low boiling point and the absence of an azeotrope with water makes acetone an often employed process solvent for the production of polyurethane dispersions and polyurethane-polyurea dispersions having low residual solvent contents.

[0004] Hydrazine is often utilized as a chain extender in the production of polyurethane-polyurea dispersions, since the resulting polymers have advantageous properties. However, when hydrazine is used as a chain extender amine for production of polyurethane-polyurea dispersion the presence of acetone results in formation of acetone azine. Acetone azine is a hazardous substance and it is therefore desirable to keep the acetone azine content in aqueous polyurethane-polyurea dispersions low. Acetone azine has a boiling point of 133°C (at 1 atm) and is therefore not directly removable from aqueous systems by distillation without special process steps.

[0005] US3763058A, US3475377A and US3461102A describe the utilization of organic dicarbonates for modifying the end groups of polyurethane-polyurea polymers.

[0006] US3305533A describes the reaction of hydrazine monocarboxylic acid esters with organic dicarbonates in polyurethane solutions in organic solvents.

[0007] US 11193039B2 describes the utilization of organic dicarbonates in aqueous urethane-acrylate dispersions as an additive, in a function as an antioxidant or as an inhibitor against free-radical polymerization.

[0008] EP162364B1 describes the encapsulation of solid polyisocyanate particles in suspensions, wherein reactive groups of the capsule shell can be deactivated using organic dicarbonates. The use of organic dicarbonates for reducing the content of acetone azine and / or butanone azine in aqueous polyurethane-polyurea dispersions is not described in the prior art.

[0009] It is an object of the present invention to provide an aqueous polyurethane-polyurea dispersion having a low content of acetone azine and / or butanone azine which firstly exhibits consistently high quality and consistently good performance up to the time of its use, in particular by the customer, and is also suitable for use especially in the production of articles, cosmetics, coatings, adhesives or adhesive layers. It is also desirable for the aqueous polyurethane-polyurea dispersion to be producible by the very widely used acetone process using hydrazine or hydrazine hydrate while at the same time comprising very low contents of acetone azine or be producible by the butanone process using hydrazine or hydrazine hydrate while at the same time comprising very low contents of butanone azine. The butanone process is to a large extent technologically similar to the acetone process, wherein the solvent employed is 2-butanone instead of acetone. To ensure long-term stabilization of aqueous polyurethane-polyurea dispersion it shall be possible to reduce the content of acetone azine and / or butanone azine in the presence of established biocides such as isothiazolinones such as 5- chloro-2-methylisothiazolinone and 2-methylisothiazolinone.

[0010] It is a further object to provide a process for producing an aqueous polyurethane-polyurea dispersion comprising a reduced amount of acetone azine and / or butanone azine.

[0011] These objects are achieved by the use according to the invention of at least one organic dialkyl dicarbonate for reducing the content of acetone azine and / or butanone azine in an aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and acetone azine and / or butanone azine.

[0012] These objects are achieved by the process according to the invention for producing an aqueous polyurethane-polyurea dispersion having a reduced content of acetone azine and / or butanone azine comprising at least the steps of:

[0013] (A) providing an aqueous polyurethane-polyurea dispersion containing at least one polyurethane- polyurea and acetone azine and / or butanone azine;

[0014] (B) treating the aqueous polyurethane-polyurea dispersion from step (A) with at least one organic dialkyl dicarbonate; to obtain an aqueous polyurethane-polyurea dispersion having a reduced content of acetone azine and / or butanone azine.

[0015] These objects are further achieved by the aqueous polyurethane-polyurea dispersion according to the invention containing at least one polyurethane-polyurea and at least one alkyl carbazate, wherein the alkyl carbazate is preferably methyl carbazate and / or ethyl carbazate, particularly preferably methyl carbazate.

[0016] It has surprisingly been found that the use according to the invention and the process according to the invention make it possible to reduce the content of acetone azine and / or butanone azine in aqueous polyurethane-polyurea dispersions through the use of at least one organic dialkyl dicarbonate without reducing the quality and performance of the dispersion, thus making it possible to obtain aqueous polyurethane-polyurea dispersions exhibiting high quality and performance and a low content of acetone azine, even when the aqueous polyurethane-polyurea dispersions were produced by the acetone process using hydrazine or hydrazine hydrate. It is likewise possible to obtain aqueous polyurethane-polyurea dispersions of high quality and performance as well as low content of butanone azine, even if the aqueous polyurethane-polyurea dispersion was produced in a solvent containing butanone using hydrazine or hydrazine hydrate. It is further possible to reduce the content of acetone azine and / or butanone azine in the presence of established biocides such as isothiazolinones, thus making it possible to reduce operating steps and optimize production operations. It is possible for example to reduce the duration of production of aqueous polyurethane- polyurea dispersions. In the production of aqueous polyurethane-polyurea dispersions it may further be advantageous in the chain-extending of isocyanate-functional prepolymers to add a molar excess of hydrazine relative to the isocyanate groups present to influence the end group functionality of the polymers. However, addition of hydrazine in the presence of acetone also forms acetone azine or in the presence of 2-butanone forms butanone azine which can in each case entail the aforementioned disadvantages. A method of reducing the content of free acetone azine and / or butanone azine therefore makes it possible to provide products which have not been viably producible hitherto, having regard to the duration of the production process or chemicals legislation labelling of the product.

[0017] The present invention is described in detail below.

[0018] In the context of the invention “reducing the content of acetone azine and / or butanone azine” or “reduced content of acetone azine and / or butanone azine” is to be understood as meaning that the content of acetone azine and / or butanone azine in the aqueous polyurethane-polyurea dispersion 24 hours after the addition or use of the at least one organic dialkyl dicarbonate is lower based on or relative to the content of acetone azine and / or butanone azine in the aqueous polyurethane-polyurea dispersion before the addition or use of the at least one organic dialkyl dicarbonate. In the context of the invention “reducing the content of acetone azine” or “reduced content of acetone azine” is to be understood as meaning that the content of acetone azine in the aqueous polyurethane-polyurea dispersion 24 hours after the addition or use of the at least one organic dialkyl dicarbonate is lower based on or relative to the content of acetone azine in the aqueous polyurethane-polyurea dispersion before the addition or use of the at least one organic dialkyl dicarbonate. In the context of the invention “reducing the content of butanone azine” or “ reduced content of butanone azine” is to be understood as meaning that the content of butanone azine in the aqueous polyurethane-polyurea dispersion 24 hours after the addition or use of the at least one organic dialkyl dicarbonate is lower based on or relative to the content of butanone azine in the aqueous polyurethane-polyurea dispersion before the addition or use of the at least one organic dialkyl dicarbonate. It is preferable when 24 hours after the addition or use of the at least one organic dialkyl dicarbonate the content of acetone azine and / or butanone azine in the aqueous polyurethane-polyurea dispersion is reduced by more than 80% by weight, preferably more than 90% by weight, particularly preferably more than 95% by weight, yet more preferably more than 98% by weight, based on the content of acetone azine and / or butanone azine in the aqueous polyurethane-polyurea dispersion before the addition or use of the at least one organic dialkyl dicarbonate. It is preferable when the content of acetone azine and / or butanone azine in the aqueous polyurethane-polyurea dispersion 24 hours after the addition or use of the at least one organic dialkyl dicarbonate is in the range from 0% by weight to 1.0% by weight, particularly preferably from 0% by weight to 0.1% by weight, based on the total weight of the aqueous dispersion of 100% by weight. The content of acetone azine or butanone azine in the aqueous polyurethane-polyurea dispersion is determined / measured by weighing 2.0 g of sample into a 10 ml measuring flask and filled up with (analytical grade quality) toluene. The mixture is then extracted for 180 seconds and after 15 minutes holding time the upper toluenic phase is filled into a GC vial and sealed. 2 pl of the toluenic phase are injected into a GC apparatus (Agilent 8890 with fused silica-type column; Agilent Technologies, Inc., Santa Clara, CA, USA).

[0019] The retention time and the peak area of the acetone azine and / or butanone azine content are determined and compared with a reference sample (with known content of acetone azine or butanone azine) to determine the content of acetone azine or butanone azine in the sample.

[0020] The reaction product of hydrazine and acetone is called acetone azine. Butanone azine is the reaction product of hydrazine and 2-butanone. Examples relating to the production of acetone azine and butanone azine are reported in Houben-Weyl Methods of Organic Chemistry Vol. E 14b, 4th Edition Supplement Carbonyl Derivatives II: C=N Double-Bond Systems, 2014, Georg Thieme Verlag, Stuttgart, Germany.

[0021] In the context of the present invention the word “a” in connection with countable parameters is to be understood as meaning the number “one” only when this is stated explicitly (for instance by the expression "precisely one"). When reference is made hereinbelow for example to “a polyisocyanate” the word “a” is to be understood as meaning merely the indefinite article and not the number one, this therefore also encompasses an embodiment in which two or more, for example structurally dissimilar, polyisocyanates are present. “Aqueous dispersion” in the context of the invention means an aqueous dispersion, aqueous emulsion, aqueous suspension, or an intermediate state / intermediate form thereof, preferably an aqueous dispersion, aqueous emulsion and / or aqueous suspension.

[0022] More preferably, the term “dispersion” means an aqueous emulsion and / or an aqueous suspension.

[0023] According to the invention the terms “comprising” or “containing” preferably mean “consisting essentially of’ and more preferably mean “consisting of’. It should be noted that the features adduced individually in the claims can be combined with one another in any technically useful way (even across category boundaries, for example between method and device) and demonstrate further configurations of the invention. The description additionally characterizes and specifies the invention.

[0024] It should also be noted that a conjunction “and / or” used herein, between two features and linking them to one another is always to be interpreted in such a way that in a first configuration of the subject matter of the invention only the first feature can be present, in a second configuration only the second feature can be present and in a third configuration both the first and the second feature can be present.

[0025] The aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and acetone azine and / or butanone azine preferably contains no alkyl carbonate before the use or treatment with the at least one organic alkyl dicarbonate. The use or treatment of the aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and acetone azine and / or butanone azine with the at least one organic dialkyl dicarbonate reduces the content of acetone azine and / or butanone azine and forms alkyl carbazate.

[0026] The present invention relates to the use of at least one organic dialkyl dicarbonate for reducing the content of acetone azine and / or butanone azine in an aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and acetone azine and / or butanone azine. In a preferred embodiment the present invention relates to the use of at least one organic dialkyl dicarbonate for reducing the content of acetone azine in an aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and acetone azine. In a further preferred embodiment the present invention relates to the use of at least one organic dialkyl dicarbonate for reducing the content of butanone azine in an aqueous polyurethane-polyurea dispersion containing at least one polyurethane- polyurea and butanone azine.

[0027] According to the invention it is generally possible to use any polyurethane-polyurea known to those skilled in the art in aqueous dispersion. In a preferred embodiment the at least one polyurethane-polyurea was obtained or is obtainable by reacting the following synthesis components:

[0028] (a) at least one diol and / or polyol component,

[0029] (b) at least one di- and / or polyisocyanate component;

[0030] (c) at least one component comprising at least one hydrophilizing group;

[0031] (d) acetone azine and / or butanone azine, hydrazine and in each case the hydrates and salts thereof and / or a mixture of at least 2 thereof;

[0032] (e) optionally mono-, di- and / or tri-amino-functional and / or -hydroxyamino-functional compounds; and

[0033] (f) optionally other isocyanate-reactive compounds; wherein the components (a), (b), (c), (d), (e) and (f) are different. In a preferred embodiment the reaction of the synthesis components is or was carried out in acetone and / or 2-butanone or in a solvent mixture comprising acetone and / or 2-butanone. If the reaction is or was carried out in acetone or a solvent mixture comprising acetone acetone azine is formed and if the reaction is or was carried out in 2-butanone or a solvent mixture comprising 2-butanone butanone azine is formed.

[0034] In a preferred embodiment the at least one polyurethane-polyurea was obtained or is obtainable by reacting the following synthesis components:

[0035] (a) at least one diol and / or polyol component,

[0036] (b) at least one di- and / or polyisocyanate component;

[0037] (c) at least one component comprising at least one hydrophilizing group;

[0038] (d) acetone azine, hydrazine and in each case the hydrates and salts thereof and / or a mixture of at least 2 thereof;

[0039] (e) optionally mono-, di- and / or tri-amino-functional and / or -hydroxyamino-functional compounds; and

[0040] (f) optionally other isocyanate-reactive compounds; wherein the components (a), (b), (c), (d), (e) and (f) are different. In a preferred embodiment the reaction of the synthesis components is or was carried out in acetone or in a solvent mixture comprising acetone.

[0041] In a further preferred embodiment the at least one polyurethane-polyurea was obtained or is obtainable by reacting the following synthesis components:

[0042] (a) at least one diol and / or polyol component,

[0043] (b) at least one di- and / or polyisocyanate component;

[0044] (c) at least one component comprising at least one hydrophilizing group;

[0045] (d) butanone azine, hydrazine and in each case the hydrates and salts thereof and / or a mixture of at least 2 thereof; (e) optionally mono-, di- and / or tri-amino-functional and / or -hydroxyamino-functional compounds; and

[0046] (f) optionally other isocyanate-reactive compounds; wherein the components (a), (b), (c), (d), (e) and (f) are different. In a preferred embodiment the reaction of the synthesis components is or was carried out in 2-butanone or in a solvent mixture comprising 2-butanone.

[0047] Suitable diol and / or polyol components (a) are compounds having at least two isocyanate-reactive hydrogen atoms and a number-average molecular weight (determined by GPC in THF as eluent at 23°C, calibrated using polystyrene standards) of preferably 62 to 18000 g / mol, particularly preferably 62 to 4000 g / mol.

[0048] Examples of suitable structural components (a) are polyether polyols, polyester polyols, polycarbonate polyols, polylactones and polyamides. Preferred polyols (a) preferably have 2 to 4, particularly preferably 2 to 3 hydroxyl groups, especially preferably 2 hydroxyl groups. Mixtures of various such compounds are also possible.

[0049] While the teaching of the present invention may in principle be realized with any dispersed polyurethane-polyurea polymer the at least one polyurethane-polyurea present in the aqueous polyurethane-polyurea dispersion preferably contains as component (a) one or more polyester polyols and / or one or more polyether polyols and / or one or more polycarbonate polyols. In a preferred embodiment the least one polyurethane-polyurea is based on polyether polyols and / or polyester polyols and / or polycarbonate polyols. In a further preferred embodiment the at least one polyurethane-polyurea is based on at least one polyester polyol, preferably polyester diol, and / or at least one polyether polyol, preferably polyether diol, and / or at least one polycarbonate polyol, preferably polycarbonate diol.

[0050] Suitable polyester polyols are in particular linear polyester diols or also sparsely branched polyester polyols, as can be produced in a known manner from aliphatic, cycloaliphatic or aromatic di- or polycarboxylic acids such as succinic acid, methylsuccinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, terephthalic acid, isophthalic acid, o-phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, maleic acid, fumaric acid, malonic acid or trimellitic acid, and acid anhydrides such as o-phthalic, trimellitic or succinic anhydride or mixtures thereof with polyhydric alcohols, such as ethanediol, di-, tri-, tetraethylene glycol, propane- 1,2-diol, di-, tri-, tetrapropylene glycol, propane-1, 3-diol, butane- 1,4-diol, butane- 1,3 -diol, butane-2,3-diol, pentane-l,5-diol, hexane- 1,6-diol, 2, 2-dimethylpropane-l, 3-diol, 1,4-dihydroxycyclohexane, 1,4- dimethylolcyclohexane, octane-1, 8-diol, decane- 1,10-diol, dodecane- 1, 12-diol or mixtures thereof, optionally with the additional use of higher-functional polyols such as trimethylolpropane, glycerol or pentaerythritol. Cycloaliphatic and / or aromatic di- and polyhydroxyl compounds are of course also suitable as polyhydric alcohols for producing the polyester polyols. In place of the free polycarboxylic acid, it is also possible to use for the production of the polyesters the corresponding polycarboxylic anhydrides or corresponding polycarboxylic esters of lower alcohols or mixtures thereof.

[0051] The polyester polyols may also be homopolymers or copolymers of lactones preferably obtained by addition reaction of lactones or lactone mixtures, such as butyrolactone, s-caprolactonc and / or methyl-8-caprolactone, onto suitable di- and / or higher-functional starter molecules, for example the low-molecular-weight polyhydric alcohols mentioned above as synthesis components for polyester polyols. Preference is given to the corresponding polymers of 8-caprolactone.

[0052] Polycarbonates having hydroxyl groups are also suitable as polyhydroxyl components (a), for example those that can be produced by reacting diols such as butane- 1 ,4-diol and / or hexane- 1 ,6-diol with diaryl carbonates, for example diphenyl carbonate, dialkyl carbonates, for example dimethyl carbonate, or phosgene. The at least partial use of polycarbonates having hydroxyl groups can improve the resistance to hydrolysis of polyurethane-urea dispersion adhesives in the event that the aqueous polyurethane-polyurea dispersions are used for producing adhesives.

[0053] Examples of suitable polyether polyols are the polyaddition products of styrene oxides, of ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin, and mixed addition and grafting products thereof, and also the polyether polyols obtained by condensation of polyhydric alcohols or mixtures of the same and obtained by alkoxylation of polyhydric alcohols, amines and amino alcohols. Polyether polyols particularly suitable as structural components (a) are homopolymers, copolymers and graft polymers of propylene oxide, of ethylene oxide and of tetrahydrofiiran, which are accessible by addition of the epoxides mentioned or of tetrahydrofiiran onto low-molecular-weight diols or triols, such as those mentioned above as structural components for polyester polyols, or onto higher-functional low-molecular-weight polyols such as pentaerythritol or sugar, or onto water.

[0054] Suitable components (a) are also low-molecular-weight diols, triols and / or tetraols such as ethanediol, di-, tri-, tetraethylene glycol, propane- 1,2-diol, di-, tri-, tetrapropylene glycol, propane- 1,3-diol, butane- 1,4-diol, butane-l,3-diol, butane-2,3-diol, pentane-l,5-diol, hexane- 1,6-diol, 2,2- dimethylpropane-l,3-diol, 1,4-dihydroxycyclohexane, 1,4-dimethylolcyclohexane, octane-1, 8-diol, decane- 1,10-diol, dodecane- 1,12-diol, neopentyl glycol, cyclohexane- 1,4-diol, cyclohexane- 1,4- dimethanol, 1,4-, 1,3-, 1,2-dihydroxybenzene or 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), TCD diol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol or mixtures thereof, optionally with the additional use of other diols or triols not mentioned. Polyols used may also be reaction products of the polyols mentioned, in particular of the low molecular weight polyols, with ethylene oxide and / or propylene oxide.

[0055] The low-molecular-weight components (a) preferably have a molecular weight of 62 to 400 g / mol and are further preferably used in combination with the polyester polyols, polylactones, polyether polyols and / or polycarbonate polyols described above.

[0056] The polyol component (a) is preferably present in the at least one polyurethane-polyurea employed according to the invention in an amount of 20% to 94% by weight, particularly preferably in an amount of 30% to 90% by weight and very particularly preferably in an amount of 65% to 90% by weight, wherein the components (a), (b), (c), (d), optionally (e) and optionally (f) in each case sum to 100% by weight.

[0057] Suitable as components (b) are any organic compounds having at least two free isocyanate groups per molecule. Preference is given to using diisocyanates of general formula Y(NCO)2, wherein Y is a divalent aliphatic hydrocarbon radical having 4 to 12 carbon atoms, a divalent cycloaliphatic hydrocarbon radical having 6 to 15 carbon atoms, a divalent aromatic hydrocarbon radical having 6 to 15 carbon atoms or a divalent araliphatic hydrocarbon radical having 7 to 15 carbon atoms.

[0058] Examples of such diisocyanates to be used with preference are tetramethylene diisocyanate, methylpentamethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, l-isocyanato-3,3,5-trimethyl-5- isocyanatomethylcyclohexane (isophorone diisocyanate; IPDI), 4,4'- diisocyanatodicyclohexylmethane, 4,4'-diisocyanato-2,2-dicyclohexylpropane, 1,4- diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'- diisocyanatodiphenylmethane, 2,2'- and 2,4'-diisocyanatodiphenylmethane, tetramethylxylylene diisocyanate, p-xylylene diisocyanate, p-isopropylidene diisocyanate, and mixtures consisting of these compounds.

[0059] In addition to these simple diisocyanates, polyisocyanates containing heteroatoms in the radical linking the isocyanate groups and / or having a functionality of more than 2 isocyanate groups per molecule are also suitable. The former are polyisocyanates having a uretdione, isocyanurate, urethane, allophanate, biuret, carbodiimide, iminooxadiazinedione and / or oxadiazinetrione structure that are prepared for example by modification of simple aliphatic, cycloaliphatic, araliphatic and / or aromatic diisocyanates and composed of at least two diisocyanates. An example of an unmodified polyisocyanate having more than 2 isocyanate groups per molecule is, for example, 4- isocyanatomethyloctane 1,8 -diisocyanate (nonane triisocyanate). Preferred diisocyanates (b) are pentamethylene diisocyanate, methylpentamethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1- isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 4,4'-diisocyanatodicyclohexylmethane,

[0060] 1.3- and l,4-bis(isocyanatomethyl)benzene, 1,3- and l,4-bis(l-isocyanato-l-methylethyl)benzene, bis(4-( 1 -isocyanato- 1 -methylethyl)phenyl) carbonate, 4,4'-diisocyanato-2,2-dicyclohexylpropane,

[0061] 1.4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'- diisocyanatodiphenylmethane, 2,2'- and 2,4'-diisocyanatodiphenylmethane, tetramethylxylylene diisocyanate, p-xylylene diisocyanate, p-isopropylidene diisocyanate, and mixtures consisting of these compounds.

[0062] Particularly preferred components (b) are 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, hexamethylene diisocyanate, 4,4'-diisocyanatodicyclohexylmethane, l-isocyanato-3,3,5-trimethyl- 5-isocyanatomethylcyclohexane, and also mixtures consisting of these compounds.

[0063] Component (b) is present in the at least one polyurethane-polyurea employed according to the invention in an amount of generally 5 to 60% by weight, preferably 6 to 45% by weight and particularly preferably 7 to 25% by weight, wherein the components (a), (b), (c), (d), optionally (e) and optionally (f) in each case sum to 100% by weight.

[0064] Suitable components (c) are, for example, components comprising sulfonate or carboxylate groups, for example diamino compounds or dihydroxy compounds additionally bearing sulfonate and / or carboxylate groups, for example the sodium, lithium, potassium, tert-amine salts of N-(2- aminoethyl)-2-aminoethanesulfonic acid, N-(3-aminopropyl)-2-aminoethanesulfonic acid, N-(3- aminopropyl)-3-aminopropanesulfonic acid, N-(2-aminoethyl)-3-aminopropanesulfonic acid, the analogous carboxylic acids, dimethylolpropionic acid, dimethylolbutyric acid, the reaction products in the sense of a Michael addition of 1 mol of diamine, for example ethane- 1,2-diamine or isophoronediamine, with 2 mol of acrylic acid or maleic acid.

[0065] The acids are preferably used directly in the form of their sulfonate or carboxylate salts. However, it is also possible to add some or all of the neutralizing agents necessary for salt formation only during or after production of the polyurethane-polyureas.

[0066] Tertiary amines particularly suitable and preferred for salt formation include for example triethylamine, dimethylcyclohexylamine and / or ethyldiisopropylamine. Other amines may also be used for salt formation, for example ammonia, diethanolamine, triethanolamine, dimethylethanolamine, methyldiethanolamine, aminomethylpropanol and also mixtures of the amines cited and also other amines. These amines are advantageously added only after formation of the prepolymer composed of the components (a) and (b). It is also possible to use for neutralization purposes other neutralizing agents, for example sodium, potassium, lithium and calcium hydroxides.

[0067] Further suitable components (c) are non-ionically hydrophilizing, mono- or difunctional polyethers based on alcohol- or amine-started ethylene oxide polymers or ethylene oxide / propylene oxide copolymers, for example polyether LB 25 (Covestro Deutschland AG, Leverkusen, Germany), diols having a polyether side-chain containing ethylene oxide units (for example Ymer N120, Perstorp Holding AB, Malmo, Sweden) or MPEG 750, i.e. methoxypolyethylene glycol having a molecular weight of 750 g / mol, obtainable for example under the trade name Pluriol® 750 from BASF SE, Ludwigshafen, Germany.

[0068] Preferred components (c) are N-(2-aminoethyl)-2-aminoethanesulfonate, N-(2-aminoethyl)-2- aminoethanecarboxylate, and the salts of dimethylolpropionic acid and dimethylolbutyric acid.

[0069] Component (c) is present in the at least one polyurethane-polyurea employed according to the invention preferably in an amount of 0.1% to 15% by weight, particularly preferably 0.5% to 10% by weight, very particularly preferably 0.8% to 5% by weight and yet more preferably 0.9% to 3.0% by weight, wherein the components (a), (b), (c), (d), optionally (e) and optionally (f) in each case sum to 100% by weight.

[0070] Suitable components (d) include for example acetone azine and / or butanone azine and hydrazine or hydrazine hydrate. When using acetone azine and / or butanone azine these are in each case partially or completely hydrolyzed by previously or simultaneously added water before the reaction with isocyanate groups.

[0071] The component (d) employed is particularly preferably hydrazine or hydrazine hydrate. It is also possible to employ the salts or hydrates of hydrazine or acetone azine and / or butanone azine. In a very preferred embodiment hydrazine or hydrazine hydrate is added simultaneously with or after addition of acetone and / or 2-butanone, wherein it is particularly preferable to first add acetone and / or 2 -butanone and then in a later step add hydrazine or hydrazine hydrate. The addition of a mixture containing acetone and / or 2-butanone and hydrazine or hydrazine hydrate is also a preferred variant.

[0072] Components (d) are used as difimctional chain extenders preferably to build up higher molecular weights and / or optionally also to incorporate further reactive groups, for example free amino groups.

[0073] Component (d) is preferably present in the at least one polyurethane-polyurea employed according to the invention in an amount of 0.1% to 10% by weight, particularly preferably 0.2% to 5% by weight and very particularly preferably 0.5% to 3% by weight, wherein the components (a), (b), (c), (d), optionally (e) and optionally (f) in each case sum to 100% by weight.

[0074] Suitable components (e) according to the invention are mono-, di- and trifunctional amines and / or mono-, di- and trifunctional hydroxyamines, for example aliphatic and / or alicyclic primary and / or secondary monoamines, for example ethylamine, diethylamine, the isomeric propyl- and butylamines, higher linear aliphatic monoamines and cycloaliphatic monoamines, for example cyclohexylamine. Further examples are amino alcohols, i.e. compounds comprising amino and hydroxyl groups in the same molecule, for example ethanolamine, N-methylethanolamine, diethanolamine, diisopropanolamine, 1, 3 -diamino-2 -propanol, N-(2-hydroxyethyl)ethylenediamine, N,N-bis(2-hydroxyethyl)ethylenediamine and 2-propanolamine.

[0075] The components (d) and (e) are different, i.e. components (d) do not fall within the definition of component (e).

[0076] Further examples are diamines and triamines, for example ethane- 1,2-diamine, hexamethylene- 1,6- diamine, l-amino-3,3,5-trimethyl-5-aminomethylcyclohexane (isophoronediamine), piperazine, 1,4- diaminocyclohexane, bis(4-aminocyclohexyl)methane, and diethylenetriamine. It will be appreciated that it is also possible to use mixtures of two or more of the compounds (e) mentioned, optionally also together with compounds (e) that are not mentioned.

[0077] Preferred components (e) are ethane- 1,2-diamine, l-amino-3,3,5-trimethyl-5- aminomethylcyclohexane, diethylenetriamine, diethanolamine, ethanolamine, N-(2- hydroxyethyl)ethylenediamine and N,N-bis(2-hydroxyethyl)ethylenediamine.

[0078] Components (e) are used as di- or trifunctional chain extenders, preferably in order to build up higher molecular weights, or in the form of monofunctional compounds to limit molecular weights, and / or optionally as a means of additionally incorporating further reactive groups such as free hydroxyl groups.

[0079] Component (e) is preferably present in the at least one polyurethane-polyurea employed according to the invention in an amount of 0% to 10% by weight, particularly preferably 0% to 5% by weight and very particularly preferably 0.2% to 3% by weight, wherein the components (a), (b), (c), (d), optionally (e) and optionally (f) in each case sum to 100% by weight.

[0080] The component (f) for optional co-use according to the invention may be for example aliphatic, cycloaliphatic or aromatic monoalcohols having 2 to 22 C atoms, for example ethanol, butanol, hexanol, cyclohexanol, isobutanol, benzyl alcohol, stearyl alcohol, 2-ethylethanol. Components (f) may be present in the at least one polyurethane-polyurea according to the invention preferably in an amount of 0% to 20% by weight, particularly preferably 0% to 10% by weight, wherein the components (a), (b), (c), (d), optionally (e) and optionally (f) in each case sum to 100% by weight.

[0081] The lateral and / or terminal carboxyl groups may in principle be incorporated into the polymer structure via any of the synthesis components (a) to (f). They are preferably incorporated via components (c), (e) and / or (f).

[0082] Incorporation via component (c) can be accomplished for example by using dimethylolpropionic acid or dimethylolbutyric acid in the absence of neutralizing agent or with neutralizing agent added in a substoichiometric amount.

[0083] Compounds suitable for incorporation of carboxyl groups as components (e) include for example those that contain in each case only one isocyanate-reactive amino group and thus in the production of the polyurethane-polyureas according to the invention result in terminal carboxyl groups by reaction with the isocyanate component. Linear aliphatic, branched aliphatic, aliphatic-aromatic and aromatic aminocarboxylic acids are suitable. Examples include aminocarboxylic acids having a primary or secondary amino group, such as alanine, 6-aminohexanoic acid, aminoundecanoic acid, 8-aminooctanoic acid, 5 -aminopentanoic acid, 4-aminobutyric acid, aminobenzoic acid, 4- aminomethylcyclohexanecarboxylic acid, 2-aminohexanoic acid, 4-aminocyclohexanecarboxylic acid, 12-aminododecanoic acid and / or 9-aminononacarboxylic acid.

[0084] Further suitable for incorporation of carboxyl groups as component (e) are for example diaminocarboxylic acids which each have 2 isocyanate-reactive amino groups and thus in the production of the at least one polyurethane-polyurea result in lateral carboxyl groups by reaction with the isocyanate component. Examples of these are lysine, arginine and / or histidine.

[0085] Suitable for incorporation of carboxyl groups as components (f) are for example hydroxycarboxylic acids each containing only one hydroxyl group, for example hydroxypivalinic acid, hydroxyacetic acid and / or 2-hydroxpropanic acid.

[0086] Production of the aqueous polyurethane-polyurea dispersions may employ any processes known from the prior art such as the emulsifier shear force, acetone, prepolymer mixing, melt emulsifying, ketimine and solid spontaneous dispersing processes or derivatives thereof. A summary of these methods can be found in Methoden der organischen Chemie (Houben-Weyl, Erweiterungs- und Folgebande zur 4. Auflage, volume E20, H. Bartl and J. Falbe, Stuttgart, New York, Thieme 1987, pages 1671 to 1682). In accordance with the invention, preference is given to the melt emulsification, prepolymer mixing, and acetone methods. Particular preference is given to the acetone method. The use and implementation of the acetone method is prior art and is known to the person skilled in the art, from EP -A 0 232 778 for example.

[0087] In a preferred embodiment the at least one polyurethane-polyurea is present in an amount of 5% to 64% by weight, preferably 30% to 60% by weight, particularly preferably 40% to 50% by weight, in each case based on the total aqueous polyurethane-polyurea dispersion.

[0088] The at least one organic dialkyl dicarbonate has the formula R-O-C(=O)-O-C(=O)-O-R', wherein R and R' are alkyl groups and R and R’ are preferably identical. Examples include dimethyl dicarbonate, diethyl dicarbonate and di-tert-butyl dicarbonate, preferably dimethyl dicarbonate and diethyl dicarbonate, very particularly preferably dimethyl dicarbonate.

[0089] In a preferred embodiment, the at least one organic dialkyl dicarbonate is selected from the group consisting of dimethyl dicarbonate, diethyl dicarbonate, dipropyl dicarbonate, diisopropyl dicarbonate, methyl ethyl dicarbonate, di-tert-butyl dicarbonate, diisobutyl dicarbonate and / or mixtures of at least two thereof, is preferably dimethyl dicarbonate, diethyl dicarbonate and / or a mixture thereof and is particularly preferably dimethyl dicarbonate.

[0090] In a preferred embodiment the at least one organic dialkyl dicarbonate is present in an amount of 0.001 g / kg to 100 g / kg, preferably of 0.1 g / kg to 50 g / kg, particularly preferably of 0.1 g / kg to 20 g / kg, based on the total aqueous polyurethane-polyurea dispersion.

[0091] In a preferred embodiment the content of acetone azine and / or butanone azine in the aqueous polyurethane-polyurea dispersion before the addition or use of the at least one organic dialkyl dicarbonate is in the range from 0.0001% by weight to 5% by weight, preferably from 0.01% by weight to 1% by weight, based on the total weight of the aqueous polyurethane-polyurea dispersion as 100% by weight. In a preferred embodiment the content of acetone azine in the aqueous polyurethane-polyurea dispersion before the addition or use of the at least one organic dialkyl dicarbonate is in the range from 0.0001% by weight to 5% by weight, preferably from 0.01% by weight to 1% by weight, based on the total weight of the aqueous polyurethane-polyurea dispersion as 100% by weight. In a preferred embodiment the content of butanone azine in the aqueous polyurethane-polyurea dispersion before the addition or use of the at least one organic dialkyl dicarbonate is in the range from 00001% by weight to 5% by weight, preferably from 0.01% by weight to 1% by weight, based on the total weight of the aqueous polyurethane-polyurea dispersion as 100% by weight.

[0092] In a preferred embodiment the content of acetone azine and / or butanone azine in the aqueous polyurethane-polyurea dispersion 24 hours after the addition or use of the at least one organic dialkyl dicarbonate is in the range from 0% by weight to 1.0% by weight, particularly preferably from 0% by weight to 0.1% by weight, based on the total weight of the aqueous dispersion of 100% by weight. In a preferred embodiment, the content of acetone azine in the aqueous polyurethane-polyurea dispersion 24 hours after the addition or use of the at least one organic dialkyl dicarbonate is in the range from 0% by weight to 1.0% by weight, particularly preferably from 0% by weight to 0. 1% by weight, based on the total weight of the aqueous dispersion as 100% by weight. In a preferred embodiment the content of butanone azine in the aqueous polyurethane-polyurea 24 hours after the addition or use of the at least one organic dialkyl dicarbonate is in the range from 0% by weight to 1.0% by weight, particularly preferably from 0% by weight to 0.1% by weight, based on the total weight of the aqueous dispersion as 100% by weight.

[0093] In a preferred embodiment the content of acetone azine and / or butanone azine in the aqueous polyurethane-polyurea dispersion 24 hours after the addition or use of the at least one organic dialkyl dicarbonate is reduced by more than 80% by weight, preferably more than 90% by weight, particularly preferably more than 95% by weight, yet more preferably more than 98% by weight, based on the content of acetone azine and / or butanone azine in the aqueous polyurethane-polyurea dispersion before the addition or use of the at least one organic dialkyl dicarbonate. In a preferred embodiment the content of acetone azine in the aqueous polyurethane-polyurea dispersion 24 hours after the addition or use of the at least one organic dialkyl dicarbonate is reduced by more than 80% by weight, preferably more than 90% by weight, particularly preferably more than 95% by weight, yet more preferably more than 98% by weight, based on the content of acetone azine in the aqueous polyurethane-polyurea dispersion before the addition or use of the at least one organic dialkyl dicarbonate. In a preferred embodiment the content of butanone azine in the aqueous polyurethane- polyurea dispersion 24 hours after the addition or use of the at least one organic dialkyl dicarbonate is reduced by more than 80% by weight, preferably more than 90% by weight, particularly preferably more than 95% by weight, yet more preferably more than 98% by weight, based on the content of butanone azine in the aqueous polyurethane-polyurea dispersion before the addition or use of the at least one organic dialkyl dicarbonate.

[0094] The content of acetone azine or butanone azine in the aqueous polyurethane-polyurea dispersion is determined / measured by weighing 2.0 g of sample into a 10 ml measuring flask and filled up with (analytical grade quality) toluene. The mixture is then extracted for 180 seconds and after 15 minutes holding time the upper toluenic phase is filled into a GC vial and sealed. 2 pl of the toluenic phase are injected into a GC apparatus (Agilent 8890 with fused silica-type column; Agilent Technologies, Inc., Santa Clara, CA, USA).

[0095] The retention time and the peak area of the acetone azine or butanone azine content are determined / related with a reference sample (with known content of acetone azine or butanone azine) to determine the content of acetone azine or butanone azine in the sample. In a preferred embodiment the aqueous polyurethane-polyurea dispersion contains no alkyl carbonate before the addition or use of the at least one organic dialkyl dicarbonate.

[0096] In a preferred embodiment the aqueous polyurethane-polyurea dispersion contains at least one compound having a biocidal effect which is distinct from the organic dialkyl dicarbonate, wherein the at least one compound having a biocidal effect is preferably a bactericide, fungicide and / or algicide, particularly preferably at least one isothiazolinone, is yet more preferably selected from the group consisting of chloromethylisothiazolinone, methylisothiazolinone, benzisothiazolinone, octylisothiazolinone, butylbenzisothiazolinone, dichlorooctylisothiazolinone and / or mixtures of at least two of these, is yet more preferably selected from the group consisting of 5-chloro-2- methylisothiazolinone / 2 -methylisothiazolinone and / or mixtures thereof, wherein the at least one compound having a biocidal effect is preferably present in an amount of 1 to 1000 mg / kg based on the total aqueous polyurethane-polyurea dispersion.

[0097] In the context of the present invention, “having a biocidal effect” means that the corresponding compound can control microorganisms, in particular bacteria and / or fungi, and prevent them from multiplying or kill them.

[0098] Suitable compounds having a biocidal effect include all biocides known to those skilled in the art, for example algicides, bactericides, fungicides against fungi, insecticides, antifungal agents against yeasts and virucides.

[0099] Compounds having a biocidal effect preferably include one or more bactericides, fungicides against fungi, antifungal agents against yeasts and / or a mixture of at least two of these. As a compound with biocidal effect it is preferable to employ at least one biocide for in-can preservation.

[0100] In addition to the aforementioned components the aqueous dispersion may also contain any component appearing suitable to a person skilled in the art. Examples of components additionally present include binders known in coatings and adhesives technology, biocides, in-can preservatives, assistant and additive substances, in particular emulsifiers and light stabilizers, especially UV absorbers, also fillers and auxiliaries, in particular anti-settling agents, defoaming and / or wetting agents, levelling agents, reactive diluents, plasticizers, neutralizing agents, catalysts, auxiliary solvents, thickeners, additives, especially pigments, dyes or matting agents, tackifiers, or mixtures thereof.

[0101] In a preferred embodiment the aqueous polyurethane-polyurea dispersion additionally contains components selected from binders, assistant and additive substances, fillers, auxiliaries, levelling agents, reactive diluents, plasticizers, neutralizing agents, catalysts, auxiliary solvents, thickeners, additives, tackifiers and mixtures thereof.

[0102] In a preferred embodiment of the use according to the invention the at least one organic dialkyl dicarbonate is used in the process according to the invention for reducing the content of acetone azine and / or butanone azine in an aqueous polyurethane-polyurea dispersion. In a preferred embodiment of the use according to the invention the at least one organic dialkyl dicarbonate is used in the process according to the invention for reducing the content of acetone azine in an aqueous polyurethane- polyurea dispersion. In a preferred embodiment of the use according to the invention the at least one organic dialkyl dicarbonate is used in the process according to the invention for reducing the content of butanone azine in an aqueous polyurethane-polyurea dispersion.

[0103] The present invention further relates to a process for producing an aqueous polyurethane-polyurea dispersion having a reduced content of acetone azine and / or butanone azine comprising at least the steps of:

[0104] (A) providing an aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and acetone azine and / or butanone azine;

[0105] (B) treating the aqueous polyurethane-polyurea dispersion from step (A) with at least one organic dialkyl dicarbonate; to obtain an aqueous polyurethane-polyurea dispersion having a reduced content of acetone azine and / or butanone azine.

[0106] In a preferred embodiment the present invention relates to a process for producing an aqueous polyurethane-polyurea dispersion having a reduced content of acetone azine comprising at least the steps of:

[0107] (A) providing an aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and acetone azine;

[0108] (B) treating the aqueous polyurethane-polyurea dispersion from step (A) with at least one organic dialkyl dicarbonate; to obtain an aqueous polyurethane-polyurea dispersion having a reduced content of acetone azine.

[0109] In a preferred embodiment the present invention relates to a process for producing an aqueous polyurethane-polyurea dispersion having a reduced content of butanone azine comprising at least the steps of:

[0110] (A) providing an aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and butanone azine; (B) treating the aqueous polyurethane-polyurea dispersion from step (A) with at least one organic dialkyl dicarbonate; to obtain an aqueous polyurethane-polyurea dispersion having a reduced content of butanone azine.

[0111] Details and preferred embodiments of the organic dialkyl dicarbonate and of the at least one compound having biocidal activity are already described above and apply correspondingly to the use according to the invention. Details and preferred embodiments of the aqueous polyurethane-polyurea dispersion provided in step (A) of the process according to the invention are already described above and apply correspondingly to the process according to the invention. The aqueous polyurethane- polyurea dispersion provided in step (A) contains at least one polyurethane as well as acetone azine and / or butanone azine. The aqueous polyurethane dispersion provided in step (A) differs from the aqueous polyurethane dispersion obtained by step (B) in that the content of acetone azine and / or butanone azine in the aqueous polyurethane dispersion after step (B) is reduced compared to the provided aqueous polyurethane dispersion in step (A).

[0112] In the context of the present invention "providing” is to be understood as meaning that the aqueous polyurethane-polyurethane dispersion may be present in any form which appears suitable to those skilled in the art and in which it may be subjected to the treatment according to step (B) of the process according to the invention. The aqueous polyurethane-polyurea dispersion is preferably provided in a container or reactor, for example a stirred reactor. The addition of the at least one organic dialkyl dicarbonate may further also be carried out after transferring the aqueous polyurethane-polyurea dispersion into a mixing vessel, in particular fitted with a stirrer or recirculation pump. The addition of the at least one organic dialkyl dicarbonate and the treatment of the aqueous polyurethane-polyurea dispersion with at least one organic dialkyl dicarbonate may also be carried out directly into the delivery container of the dispersion.

[0113] According to the invention the aqueous dispersion has the concentrations of ingredients described above. However, according to the invention it is also possible for the aqueous polyurethane-polyurea dispersion to be diluted or concentrated before step (A). Suitable concentrations of the at least one polyurethane-polyurea present are 5 to 64% by weight, preferably 30 to 60% by weight, especially preferably 40 to 50% by weight, based in each case on the total aqueous polyurethane-polyurea dispersion.

[0114] In a preferred embodiment the aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and acetone azine and / or butanone azine was produced in step (A) by a process comprising acetone as solvent or containing at least one polyurethane-polyurea and butanone azine was produced in step (A) by a process comprising 2-butanone as solvent or containing at least one polyurethane-polyurea and acetone azine and butanone azine was produced in step (A) by a process comprising acetone and 2-butanone as solvent. In a preferred embodiment the aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and acetone azine was produced in step (A) by a process comprising acetone as solvent. In a preferred embodiment the aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and butanone azine was produced in step (A) by a process comprising 2-butanone as solvent. In a preferred embodiment the aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and acetone azine and butanone azine was produced in step (A) by a process comprising acetone as solvent or containing at least one polyurethane-polyurea and butanone azine was produced in step (A) by a process comprising acetone and 2-butanone as solvent.

[0115] According to the invention the aqueous polyurethane-polyurea dispersion may be mixed with at least one further aqueous polymer dispersion, for example with an aqueous dispersion of at least one further film-forming polymer, before step (B) of the process according to the invention.

[0116] Step (B) of the process according to the invention can generally be carried out at any temperature that appears suitable to those skilled in the art. In a preferred embodiment step (B) is carried out at 1°C to 100°C, preferably at 5°C to 50°C, particularly preferably at 10°C to 30°C.

[0117] Step (B) of the process according to the invention can generally be carried out at any pressure that appears suitable to those skilled in the art, preferably at atmospheric pressure.

[0118] In step (B) the aqueous polyurethane-polyurea dispersion may preferably be stirred, in particular using apparatuses known to those skilled in the art, in particular propeller stirrers, anchor stirrers, dissolver discs, helical stirrers, jet stirrers, for example Visco-Jet®. The mixing and / or dissolution in step (B) of the process according to the invention may also be carried out by pumped recirculation of the aqueous polyurethane-polyurea dispersion (A) using, for example, peristaltic pumps, diaphragm pumps, eccentric screw pumps.

[0119] In the treatment in step (B), reaction of the at least one organic dialkyl dicarbonate in water, i.e.the hydrolysis with the water of the polyurethane-polyurea dispersion, liberates at least one alcohol. Examples are the liberation of ethanol from diethyl dicarbonate or methanol from dimethyl dicarbonate. These alcohols may be removed from the product, for example by distillation, or may optionally also remain in the product mixture in whole or in part. The carbon dioxide formed in the reaction of the at least one organic dialkyl dicarbonate in the water, i.e. the hydrolysis with the water of the polyurethane-polyurea dispersion either remains physically dissolved in the dispersion, reacts with water to form carbonic acid or carbonates and / or may be removed from the dispersion. Partial or complete removal of the carbon dioxide formed is possible by heating the dispersion or by applying vacuum. The reaction time after addition of the at least one organic dialkyl dicarbonate to the polyurethanepolyurea dispersion is preferably one minute to 24 hours. The batch is preferably actively mixed, for example stirred, during this time. It is also possible to provide a post-reaction phase without active stirring and this may also be carried out in the delivery container.

[0120] Before adding the at least one organic dialkyl dicarbonate to the aqueous polyurethane-polyurea dispersion the at least one organic dialkyl dicarbonate may be dissolved in a suitable solvent. Examples include water-miscible solvents, for example water, monoalcohols, for example methanol or ethanol, glycols, for example propylene glycol, ketones, for example acetone or 2-butanone or N- alkyl pyrrolidones such as N-methyl -2 -pyrrolidone, N-ethyl -2 -pyrrolidone or N-butyl -2 -pyrrolidone. It is preferable to employ solvents which do not decompose the dialkyl dicarbonate or deactivate its effect. Further additives may also be added to the dialkyl dicarbonate before addition to the aqueous dispersion. In a preferred variant the dialkyl dicarbonate is added in pure form, i.e. without further premixing or pre-dilution.

[0121] In a preferred embodiment metered addition of the at least one organic dialkyl dicarbonate is effected via a nozzle. In a further preferred embodiment metered addition of the at least one organic dialkyl dicarbonate is effected via a mixing apparatus. In a further preferred embodiment the added amount and addition rate of the at least one organic dialkyl dicarbonate is controlled using a liquid flowmeter unit and a metered addition unit coupled thereto.

[0122] What is ultimately obtained after step (B) of the process according to the invention as a result of reactions including the hydrolysis of the at least one organic dialkyl dicarbonate is an aqueous polyurethane-polyurea dispersion which is largely free from the employed organic dialkyl dicarbonate. The aqueous polyurethane-polyurea dispersion obtained preferably no longer contains any organic dialkyl dicarbonate before application or use thereof.

[0123] According to the invention it is possible to add at least one compound having a biocidal effect which is distinct from the at least one organic dialkyl dicarbonate before, after or simultaneously with step (B).

[0124] However, it is also possible according to the invention for the aqueous polyurethane-polyurea dispersion obtained in step (B) to be supplied to further workup steps, for example the addition of thickeners, pigments, colour pastes, further processing auxiliaries, for example defoamers, wetting auxiliaries, coagulation auxiliaries and / or stabilizers, for example further antioxidants and UV stabilizers, that are suitable for the further processing. Processes for adding the components mentioned are known per se to those skilled in the art. According to the invention it is possible for the aqueous dispersion after step (B) to be used for producing articles, cosmetics, coatings, adhesive layers or adhesives.

[0125] In a preferred embodiment step (B) is followed by at least the following step (C):

[0126] (C) producing articles, cosmetics, coatings, adhesive layers or adhesives from the aqueous polyurethane-polyurea dispersion having a reduced content of acetone azine and / or butanone azine obtained in step (B).

[0127] Appropriate processes carried out in step (C) of the process according to the invention are known per se to those skilled in the art, for example

[0128] • dip coating, in particular for the manufacture of gloves, preferably for use in the medical field,

[0129] • production of aqueous adhesive dispersions that are processed with and without crosslinkers, for example isocyanate or polycarbodiimide crosslinkers,

[0130] • production of latent-reactive adhesive layers, adhesive films or adhesive powders, for example described in EP-A 0 922 720 or EP 2 099 840 Bl,

[0131] • production and / or coating of textiles, leather or synthetic leather and microfibre-based textiles or synthetic leather,

[0132] • use of polyurethane dispersion in hairspray, sunscreens, etc.,

[0133] • use in sizes in the production of carbon fibres, glass fibres or fibres of other mineral materials which are preferably used for producing fibre-reinforced composite materials,

[0134] • coatings on plastics, metallic materials, wood, composite materials, ceramic materials, mineral substrates such as stone

[0135] • as well as on previously coated substrates.

[0136] Preferred articles according to the invention are selected for example from articles produced by dip coating, for example disposable gloves or condoms, covers or so-called sleeves for medical devices, probes, endoscopes, coated textiles, bandages, films for wound dressings, medical foams or so-called wearable patches.

[0137] Cosmetics preferred according to the invention are selected for example from hairspray, sun cream, conditioner or mascara, etc., wherein the at least one polyurethane-polyurea employed here more preferably serves as a film-former.

[0138] Coatings preferred according to the invention are selected, for example, from primer, filler, base coat and top coat systems, coatings of wood, metal and plastics, textiles, leather, artificial leather, each in various industries, for example in cars, large vehicles, ACE (agricultural, construction & earth moving equipment), industrial coatings, furniture or fibreglass sizing. Adhesives preferred according to the invention are selected for example from polyurethane dispersion adhesives or polyurethane-polyurea dispersion adhesives employed as 1- or 2-component systems, non-reactive and reactive adhesive films, adhesive powders or adhesive layers, in each case applied to substrate surfaces.

[0139] The present invention also relates to an aqueous polyurethanene-polyurea dispersion containing at least one polyurethane-polyurea and at least one alkyl carbazate, wherein the alkyl carbazate is preferably methyl carbazate and / or ethyl carbazate, particularly preferably methyl carbazate. In a preferred embodiment the present invention relates to an aqueous polyurethanene-polyurea dispersion having a reduced content of acetone azine and / or butanone azine containing at least one polyurethane-polyurea and at least one alkyl carbazate, wherein the alkyl carbazate is preferably methyl carbazate and / or ethyl carbazate, particularly preferably methyl carbazate. In a preferred embodiment the present invention relates to an aqueous polyurethanene-polyurea dispersion having a reduced content of acetone azine containing at least one polyurethane-polyurea and at least one alkyl carbazate, wherein the alkyl carbazate is preferably methyl carbazate and / or ethyl carbazate, particularly preferably methyl carbazate. In a preferred embodiment the present invention relates to an aqueous polyurethanene-polyurea dispersion having a reduced content of butanone azine containing at least one polyurethane-polyurea and at least on alkyl carbazate, wherein the alkyl carbazate is preferably methyl carbazate and / or ethyl carbazate, particularly preferably methyl carbazate.

[0140] The aqueous polyurethane-polyurea dispersion according to the invention containing at least one polyurethane-polyurea and at least one alkyl carbazate is obtainable as a reaction product for example by the process according to the invention or by the use according to the invention.

[0141] Details and preferred embodiments of the at least one polyurethane-polyurea in the aqueous polyurethane-polyurea dispersion according to the invention and the at least one compound having biocidal effect are already described above and apply correspondingly to the use according to the invention.

[0142] In a preferred embodiment the at least one polyurethane-polyurea is present in an amount of 5% to 64% by weight, preferably 30% to 60% by weight, particularly preferably 40% to 50% by weight, in each case based on the total aqueous polyurethane-polyurea dispersion.

[0143] In a preferred embodiment the aqueous polyurethane-polyurea dispersion according to the invention contains at least one compound having a biocidal effect which is distinct from the organic dialkyl dicarbonate, wherein the at least one compound having a biocidal effect is preferably a bactericide, fungicide and / or algicide, particularly preferably at least one isothiazolinone, yet more preferably selected from the group consisting of chloromethylisothiazolinone, methylisothiazolinone, benzisothiazolinone, octylisothiazolinone, butylbenzisothiazolinone, dichlorooctylisothiazolinone and / or mixtures of at least two of these, yet more preferably selected from the group consisting of 5- chloro-2 -methylisothiazolinone / 2-methylisothiazolinone and / or mixtures thereof, wherein the at least one compound having a biocidal effect is preferably present in an amount of 1 to 1000 mg / kg based on the total aqueous polyurethane-polyurea dispersion.

[0144] In a preferred embodiment the aqueous polyurethane-polyurea dispersion according to the invention additionally contains components selected from binders, assistant and additive substances, fdlers, auxiliaries, levelling agents, reactive diluents, plasticizers, neutralizing agents, catalysts, auxiliary solvents, thickeners, additives, tackifiers and mixtures thereof.

[0145] The aqueous polyurethane-polyurea dispersion according to the invention is obtainable by the process according to the invention or the use according to the invention of at least one organic dialkyl dicarbonate for reducing the content of acetone azine and / or butanone azine in an aqueous polyurethane-polyurea dispersion. The alkyl carbazates present are the products of the reaction of the dialkyl dicarbonate with acetone azine and / or butanone azine. The present invention therefore also provides an aqueous polyurethane-polyurea dispersion obtainable or obtained by the process according to the invention and an aqueous polyurethane-polyurea dispersion obtainable or obtained by the use according to the invention.

[0146] In a preferred embodiment the at least one alkyl carbazate is present in an amount of 1 mg / kg to 10000 mg / kg, preferably 10 mg / kg to 1000 mg / kg, based on the total aqueous polyurethane-polyurea dispersion.

[0147] The present invention also relates to an article, cosmetic, coating, adhesive layer, coating formulation, adhesive formulation and / or cosmetic formulation containing at least the aqueous polyurethane-polyurea dispersion according to the invention and / or the aqueous polyurethane- polyurea dispersion according to the invention having a reduced content of acetone azine and / or butanone azine obtainable or obtained according to the process according to the invention.

[0148] Various aspects of the subject matter described herein are set out in the following numbered clauses: Clause 1. Use of at least one organic dialkyl dicarbonate for reducing the content of acetone azine and / or butanone azine in an aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and acetone azine and / or butanone azine.

[0149] Clause 2. The use of clause 1, characterized in that the at least one organic dialkyl dicarbonate is selected from the group consisting of dimethyl dicarbonate, diethyl dicarbonate, dipropyl dicarbonate, diisopropyl dicarbonate, methyl ethyl dicarbonate, di-tert-butyl dicarbonate, diisobutyl dicarbonate and / or mixtures of at least two thereof, is preferably dimethyl dicarbonate, diethyl dicarbonate and / or a mixture thereof and is particularly preferably dimethyl dicarbonate.

[0150] Clause 3. The use of clause 1 or 2, characterized in that the aqueous polyurethane-polyurea dispersion contains at least one compound having a biocidal effect which is distinct from the organic dialkyl dicarbonate, wherein the at least one compound having a biocidal effect is preferably a bactericide, fungicide and / or algicide, particularly preferably at least one isothiazolinone, is yet more preferably selected from the group consisting of chloromethylisothiazolinone, methylisothiazolinone, benzisothiazolinone, octylisothiazolinone, butylbenzisothiazolinone, dichlorooctylisothiazolinone and / or mixtures of at least two of these, is yet more preferably selected from the group consisting of 5 -chloro-2-methylisothiazolinone / 2 -methylisothiazolinone and / or mixtures thereof, wherein the at least one compound having a biocidal effect is preferably present in an amount of 1 to 1000 mg / kg based on the total aqueous polyurethane-polyurea dispersion.

[0151] Clause 4. The use of any of clauses 1 to 3, characterized in that the at least one polyurethane- polyurea is present in an amount of 5% to 64% by weight, preferably 30% to 60% by weight, particularly preferably 40% to 50% by weight, in each case based on the total aqueous polyurethane- polyurea dispersion.

[0152] Clause 5. The use of any of clauses 1 to 4, characterized in that the aqueous polyurethane- polyurea dispersion additionally contains components selected from binders, assistant and additive substances, fdlers, auxiliaries, levelling agents, reactive diluents, plasticizers, neutralizing agents, catalysts, auxiliary solvents, thickeners, additives, tackifiers and mixtures thereof.

[0153] Clause 6. The use of any of clauses 1 to 5, characterized in that the at least one polyurethane- polyurea has been obtained or is obtainable by reacting the following synthesis components:

[0154] (a) at least one diol and / or polyol component,

[0155] (b) at least one di- and / or polyisocyanate component;

[0156] (c) at least one component comprising at least one hydrophilizing group;

[0157] (d) acetone azine and / or butanone azine, hydrazine and in each case the hydrates and salts thereof and / or a mixture of at least 2 thereof;

[0158] (e) optionally mono-, di- and / or tri-amino-functional and / or -hydroxyamino-functional compounds; and

[0159] (f) optionally other isocyanate-reactive compounds; wherein the components (a), (b), (c), (d), (e) and (f) are different, preferably wherein the reaction of the synthesis components is or was carried out in acetone and / or 2-butanone or in a solvent mixture comprising acetone and / or 2-butanone.

[0160] Clause 7. The use of any of clauses 1 to 5, characterized in that the at least one polyurethane- polyurea has been obtained or is obtainable by reacting the following synthesis components:

[0161] (a) at least one diol and / or polyol component,

[0162] (b) at least one di- and / or polyisocyanate component;

[0163] (c) at least one component comprising at least one hydrophilizing group; (d) hydrazine or hydrazine hydrate;

[0164] (e) optionally mono-, di- and / or tri-amino-functional and / or -hydroxyamino-functional compounds; and

[0165] (f) optionally other isocyanate-reactive compounds; wherein the components (a), (b), (c), (d), (e) and (f) are different, preferably wherein the reaction of the synthesis components is or was carried out in acetone and / or 2-butanone or in a solvent mixture comprising acetone and / or 2-butanone.

[0166] Clause 8. The use of any of clauses 1 to 7, characterized in that the content of acetone azine and / or butanone azine in the aqueous polyurethane-polyurea dispersion before the addition or use of the at least one organic dialkyl dicarbonate is in the range from 0.0001% by weight to 5% by weight, preferably from 0.01% by weight to 1% by weight, based on the total weight of the aqueous polyurethane-polyurea dispersion as 100% by weight.

[0167] Clause 9. The use of any of clauses 1 to 8, characterized in that the content of acetone azine and / or butanone azine in the aqueous polyurethane-polyurea dispersion 24 hours after the addition or use of the at least one organic dialkyl dicarbonate is reduced by more than 80% by weight, preferably more than 90% by weight, particularly preferably more than 95% by weight, yet more preferably more than 98% by weight, based on the content of acetone azine and / or butanone azine in the aqueous polyurethane-polyurea dispersion before the addition or use of the at least one organic dialkyl dicarbonate.

[0168] Clause 10. Process for producing an aqueous polyurethane-polyurea dispersion having a reduced content of acetone azine and / or butanone azine comprising at least the steps of:

[0169] (A) providing an aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and acetone azine and / or butanone azine;

[0170] (B) treating the aqueous polyurethane-polyurea dispersion from step (A) with at least one organic dialkyl dicarbonate; to obtain an aqueous polyurethane-polyurea dispersion having a reduced content of acetone azine and / or butanone azine.

[0171] Clause 11. The process of clause 10, characterized in that the aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and acetone azine was produced in step (A) by a process comprising acetone as solvent or containing at least one polyurethane-polyurea and butanone azine was produced in step (A) by a process comprising 2-butanone as solvent or containing at least one polyurethane-polyurea and acetone azine and butanone azine was produced in step (A) by a process comprising acetone and 2-butanone as solvent.

[0172] Clause 12. The process of clause 10 or 11, characterized in that step (B) is followed by at least the following step (C):

[0173] (C) producing articles, cosmetics, coatings, adhesive layers or adhesives from the aqueous polyurethane-polyurea dispersion having a reduced content of acetone azine and / or butanone azine obtained in step (B). Clause 13. The process of any of clauses 10 to 12, characterized in that step (B) is carried out at 1°C to 100°C, preferably at 5°C to 50°C, particularly preferably at 10°C to 30°C.

[0174] Clause 14. The process of any of clauses 10 to 13, characterized in that the at least one organic dialkyl dicarbonate is selected from the group consisting of dimethyl dicarbonate, diethyl dicarbonate, dipropyl dicarbonate, diisopropyl dicarbonate, methyl ethyl dicarbonate, di-tert-butyl dicarbonate, diisobutyl dicarbonate and / or mixtures of at least two thereof, is preferably dimethyl dicarbonate, diethyl dicarbonate and / or a mixture thereof and is particularly preferably dimethyl dicarbonate.

[0175] Clause 15. The process of any of clauses 10 to 14, characterized in that the aqueous polyurethane-polyurea dispersion contains at least one compound having a biocidal effect which is distinct from the organic dialkyl dicarbonate, wherein the at least one compound having a biocidal effect is preferably a bactericide, fungicide and / or algicide, particularly preferably at least one isothiazolinone, is yet more preferably selected from the group consisting of chloromethylisothiazolinone, methylisothiazolinone, benzisothiazolinone, octylisothiazolinone, butylbenzisothiazolinone, dichlorooctylisothiazolinone and / or mixtures of at least two of these, is yet more preferably selected from the group consisting of 5-chloro-2-methylisothiazolinone / 2- methylisothiazolinone and / or mixtures thereof, wherein the at least one compound having a biocidal effect is preferably present in an amount of 1 to 1000 mg / kg based on the total aqueous polyurethane- polyurea dispersion.

[0176] Clause 16. The process of any of clauses 10 to 15, characterized in that the at least one polyurethane-polyurea is present in an amount of 5% to 64% by weight, preferably 30% to 60% by weight, particularly preferably 40% to 50% by weight, in each case based on the total aqueous polyurethane-polyurea dispersion.

[0177] Clause 17. The process of any of clauses 10 to 16, characterized in that the aqueous polyurethane-polyurea dispersion additionally contains components selected from binders, assistant and additive substances, fdlers, auxiliaries, levelling agents, reactive diluents, plasticizers, neutralizing agents, catalysts, auxiliary solvents, thickeners, additives, tackifiers and mixtures thereof.

[0178] Clause 18. The process of any of clauses 10 to 17, characterized in that the at least one polyurethane-polyurea has been obtained or is obtainable by reacting the following synthesis components:

[0179] (a) at least one diol and / or polyol component,

[0180] (b) at least one di- and / or polyisocyanate component;

[0181] (c) at least one component comprising at least one hydrophilizing group;

[0182] (d) acetone azine and / or butanone azine, hydrazine and in each case the hydrates and salts thereof and / or a mixture of at least 2 thereof;

[0183] (e) optionally mono-, di- and / or tri-amino-functional and / or -hydroxyamino-functional compounds; and (f) optionally other isocyanate-reactive compounds; wherein the components (a), (b), (c), (d), (e) and (f) are different, preferably wherein the reaction of the synthesis components is or was carried out in acetone and / or 2-butanone or in a solvent mixture comprising acetone and / or 2-butanone.

[0184] Clause 19. The process of any of clauses 10 to 17, characterized in that the at least one polyurethane-polyurea has been obtained or is obtainable by reacting the following synthesis components:

[0185] (a) at least one diol and / or polyol component,

[0186] (b) at least one di- and / or polyisocyanate component;

[0187] (c) at least one component comprising at least one hydrophilizing group;

[0188] (d) hydrazine or hydrazine hydrate;

[0189] (e) optionally mono-, di- and / or tri-amino-functional and / or -hydroxyamino-functional compounds; and

[0190] (f) optionally other isocyanate-reactive compounds; wherein the components (a), (b), (c), (d), (e) and (f) are different, preferably wherein the reaction of the synthesis components is or was carried out in acetone and / or 2-butanone or in a solvent mixture comprising acetone and / or 2-butanone.

[0191] Clause 20. The process of any of clauses 10 to 19, characterized in that the at least one organic dialkyl dicarbonate is present in an amount of 0.001 g / kg to 100 g / kg, preferably of 0.1 g / kg to 50 g / kg, particularly preferably of 0.1 g / kg to 20 g / kg, based on the total aqueous polyurethane-polyurea dispersion.

[0192] Clause 21. The process of any of clauses 10 to 20, characterized in that the content of acetone azine and / or butanone azine in the aqueous polyurethane-polyurea dispersion before the addition or use of the at least one organic dialkyl dicarbonate is in the range from 0.0001% by weight to 5% by weight, preferably from 0.01% by weight to 1% by weight, based on the total weight of the aqueous polyurethane-polyurea dispersion as 100% by weight.

[0193] Clause 22. The process of any of clauses 10 to 21, characterized in that the content of acetone azine and / or butanone azine in the aqueous polyurethane-polyurea dispersion 24 hours after the addition or use of the at least one organic dialkyl dicarbonate is reduced by more than 80% by weight, preferably more than 90% by weight, particularly preferably more than 95% by weight, yet more preferably more than 98% by weight, based on the content of acetone azine and / or butanone azine in the aqueous polyurethane-polyurea dispersion before the addition or use of the at least one organic dialkyl dicarbonate.

[0194] Clause 23. Aqueous polyurethanene-polyurea dispersion containing at least one polyurethane- polyurea and at least one alkyl carbazate, wherein the alkyl carbazate is preferably methyl carbazate and / or ethyl carbazate, particularly preferably methyl carbazate. Clause 24. The aqueous polyurethanene-polyurea dispersion of clause 23, characterized in that the at least one alkyl carbazate is present in an amount of 1 mg / kg to 10000 mg / kg, preferably 10 mg / kg to 1000 mg / kg, based on the total aqueous polyurethane-polyurea dispersion.

[0195] Clause 25. The aqueous polyurethanene-polyurea dispersion of clause 23 or 24, characterized in that the at least one polyurethane-polyurea is present in an amount of 5% to 64% by weight, preferably 30% to 60% by weight, particularly preferably 40% to 50% by weight, in each case based on the total aqueous polyurethane-polyurea dispersion.

[0196] Clause 26. The aqueous polyurethane-polyurea dispersion of any of clauses 23 to 25, characterized in that the aqueous polyurethane-polyurea dispersion additionally contains components selected from binders, assistant and additive substances, fdlers, auxiliaries, levelling agents, reactive diluents, plasticizers, neutralizing agents, catalysts, auxiliary solvents, thickeners, additives, tackifiers and mixtures thereof.

[0197] Clause 27. The aqueous polyurethane-polyurea dispersion of any of clauses 23 to 26, characterized in that the aqueous polyurethane-polyurea dispersion has been obtained or is obtainable by a process comprising at least the following steps of:

[0198] (A) providing an aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and acetone azine and / or butanone azine;

[0199] (B) treating the aqueous polyurethane-polyurea dispersion from step (A) with at least one organic dialkyl dicarbonate; to obtain an aqueous polyurethane-polyurea dispersion containing at least one alkyl carbazate.

[0200] Clause 28. The aqueous polyurethanene-polyurea dispersion of clause 27, characterized in that the aqueous polyurethane-polyurea dispersion contains at least one compound having a biocidal effect which is distinct from the organic dialkyl dicarbonate, wherein the at least one compound having a biocidal effect is preferably a bactericide, fungicide and / or algicide, particularly preferably at least one isothiazolinone, is yet more preferably selected from the group consisting of chloromethylisothiazolinone, methylisothiazolinone, benzisothiazolinone, octylisothiazolinone, butylbenzisothiazolinone, dichlorooctylisothiazolinone and / or mixtures of at least two of these, is yet more preferably selected from the group consisting of 5-chloro-2-methylisothiazolinone / 2- methylisothiazolinone and / or mixtures thereof, wherein the at least one compound having a biocidal effect is preferably present in an amount of 1 to 1000 mg / kg based on the total aqueous polyurethane- polyurea dispersion.

[0201] Clause 29. The aqueous polyurethane-polyurea dispersion of clause 27 or 28, characterized in that the aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and acetone azine was produced in step (A) by a process comprising acetone as solvent or containing at least one polyurethane-polyurea and butanone azine was produced in step (A) by a process comprising 2-butanone as solvent or containing at least one polyurethane-polyurea and acetone azine and butanone azine was produced in step (A) by a process comprising acetone and 2-butanone as solvent. Clause 30. The aqueous polyurethane-polyurea dispersion of any of clauses 27 to 29, characterized in that step (B) is followed by at least the following step (C):

[0202] (C) producing articles, cosmetics, coatings, adhesive layers or adhesives from the aqueous polyurethane-polyurea dispersion having a reduced content of acetone azine and / or butanone azine obtained in step (B).

[0203] Clause 31. The aqueous polyurethane-polyurea dispersion of any of clauses 27 to 30, characterized in that step (B) is carried out at 1°C to 100°C, preferably at 5°C to 50°C, particularly preferably at 10°C to 30°C.

[0204] Clause 32. The aqueous polyurethane-polyurea dispersion of any of clauses 27 to 31, characterized in that the content of acetone azine and / or butanone azine in the aqueous polyurethane- polyurea dispersion before the addition or use of the at least one organic dialkyl dicarbonate is in the range from 0.0001% by weight to 5% by weight, preferably from 0.01% by weight to 1% by weight, based on the total weight of the aqueous polyurethane-polyurea dispersion as 100% by weight.

[0205] Clause 33. The aqueous polyurethane-polyurea dispersion of any of clauses 27 to 32, characterized in that the content of acetone azine and / or butanone azine in the aqueous polyurethane- polyurea dispersion 24 hours after the addition or use of the at least one organic dialkyl dicarbonate is reduced by more than 80% by weight, preferably more than 90% by weight, particularly preferably more than 95% by weight, yet more preferably more than 98% by weight, based on the content of acetone azine and / or butanone azine in the aqueous polyurethane-polyurea dispersion before the addition or use of the at least one organic dialkyl dicarbonate.

[0206] Clause 34. The aqueous polyurethane-polyurea dispersion of any of clauses 23 to 33, characterized in that the at least one polyurethane-polyurea has been obtained or is obtainable by reacting the following synthesis components:

[0207] (a) at least one diol and / or polyol component,

[0208] (b) at least one di- and / or polyisocyanate component;

[0209] (c) at least one component comprising at least one hydrophilizing group;

[0210] (d) acetone azine and / or butanone azine, hydrazine and in each case the hydrates and salts thereof and / or a mixture of at least 2 thereof;

[0211] (e) optionally mono-, di- and / or tri-amino-fimctional and / or -hydroxyamino-fimctional compounds; and

[0212] (f) optionally other isocyanate-reactive compounds; wherein the components (a), (b), (c), (d), (e) and (f) are different, preferably wherein the reaction of the synthesis components is or was carried out in acetone and / or 2-butanone or in a solvent mixture comprising acetone and / or 2-butanone. Clause 35. The aqueous polyurethane-polyurea dispersion of any of clauses 23 to 33, characterized in that the at least one polyurethane-polyurea has been obtained or is obtainable by reacting the following synthesis components:

[0213] (a) at least one diol and / or polyol component,

[0214] (b) at least one di- and / or polyisocyanate component;

[0215] (c) at least one component comprising at least one hydrophilizing group;

[0216] (d) hydrazine or hydrazine hydrate;

[0217] (e) optionally mono-, di- and / or tri-amino-functional and / or -hydroxyamino-functional compounds; and

[0218] (f) optionally other isocyanate-reactive compounds; wherein the components (a), (b), (c), (d), (e) and (f) are different, preferably wherein the reaction of the synthesis components is or was carried out in acetone and / or 2-butanone or in a solvent mixture comprising acetone and / or 2-butanone.

[0219] Clause 36. Process for producing an aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and at least one alkyl carbazate, which process comprises at least the steps of:

[0220] (A) providing an aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and acetone azine and / or butanone azine;

[0221] (B) treating the aqueous polyurethane-polyurea dispersion from step (A) with at least one organic dialkyl dicarbonate; to obtain an aqueous polyurethane-polyurea dispersion containing at least one alkyl carbazate.

[0222] Clause 37. The process of clause 36, characterized in that the aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and acetone azine was produced in step (A) by a process comprising acetone as solvent or containing at least one polyurethane-polyurea and butanone azine was produced in step (A) by a process comprising 2-butanone as solvent or containing at least one polyurethane-polyurea and acetone azine and butanone azine was produced in step (A) by a process comprising acetone and 2-butanone as solvent.

[0223] Clause 38. The process of clause 36 or 37, characterized in that step (B) is followed by at least the following step (C):

[0224] (C) producing articles, cosmetics, coatings, adhesive layers or adhesives from the aqueous polyurethane-polyurea dispersion having a reduced content of acetone azine and / or butanone azine obtained in step (B).

[0225] Clause 39. The process of any of clauses 36 to 38, characterized in that step (B) is carried out at 1°C to 100°C, preferably at 5°C to 50°C, particularly preferably at 10°C to 30°C.

[0226] Clause 40. The process of any of clauses 36 to 39, characterized in that the content of acetone azine and / or butanone azine in the aqueous polyurethane-polyurea dispersion before the addition or use of the at least one organic dialkyl dicarbonate is in the range from 0.0001% by weight to 5% by weight, preferably from 0.01% by weight to 1% by weight, based on the total weight of the aqueous polyurethane-polyurea dispersion as 100% by weight.

[0227] Clause 41. The process of any of clauses 36 to 40, characterized in that the content of acetone azine and / or butanone azine in the aqueous polyurethane-polyurea dispersion before the addition or use of the at least one organic dialkyl dicarbonate is in the range from 0.0001% by weight to 5% by weight, preferably from 0.01% by weight to 1% by weight, based on the total weight of the aqueous polyurethane-polyurea dispersion as 100% by weight.

[0228] Clause 42. The process of any of clauses 36 to 41, wherein the at least one organic dialkyl dicarbonate is dimethyl dicarbonate and / or diethyl dicarbonate and the at least one alkyl carbazate is methyl carbazate and / or ethyl carbazate, preferably the at least one organic dialkyl dicarbonate is dimethyl dicarbonate and the at least one alkyl carbazate is methyl carbazate.

[0229] Clause 43. The process of any of clauses 36 to 40, characterized in that the aqueous polyurethane-polyurea dispersion contains at least one compound having a biocidal effect which is distinct from the organic dialkyl dicarbonate, wherein the at least one compound having a biocidal effect is preferably a bactericide, fungicide and / or algicide, particularly preferably at least one isothiazolinone, is yet more preferably selected from the group consisting of chloromethylisothiazolinone, methylisothiazolinone, benzisothiazolinone, octylisothiazolinone, butylbenzisothiazolinone, dichlorooctylisothiazolinone and / or mixtures of at least two of these, is yet more preferably selected from the group consisting of 5-chloro-2-methylisothiazolinone / 2- methylisothiazolinone and / or mixtures thereof, wherein the at least one compound having a biocidal effect is preferably present in an amount of 1 to 1000 mg / kg based on the total aqueous polyurethane- polyurea dispersion.

[0230] Clause 44. The process of any of clauses 36 to 43, characterized in that the at least one polyurethane-polyurea is present in an amount of 5% to 64% by weight, preferably 30% to 60% by weight, particularly preferably 40% to 50% by weight, in each case based on the total aqueous polyurethane-polyurea dispersion.

[0231] Clause 45. The process of any of clauses 36 to 44, characterized in that the aqueous polyurethane-polyurea dispersion additionally contains components selected from binders, assistant and additive substances, fdlers, auxiliaries, levelling agents, reactive diluents, plasticizers, neutralizing agents, catalysts, auxiliary solvents, thickeners, additives, tackifiers and mixtures thereof.

[0232] Clause 46. The process of any of clauses 36 to 45, characterized in that the at least one polyurethane-polyurea has been obtained or is obtainable by reacting the following synthesis components:

[0233] (a) at least one diol and / or polyol component,

[0234] (b) at least one di- and / or polyisocyanate component;

[0235] (c) at least one component comprising at least one hydrophilizing group; (d) acetone azine and / or butanone azine, hydrazine and in each case the hydrates and salts thereof and / or a mixture of at least 2 thereof;

[0236] (e) optionally mono-, di- and / or tri-amino-functional and / or -hydroxyamino-functional compounds; and

[0237] (f) optionally other isocyanate-reactive compounds; wherein the components (a), (b), (c), (d), (e) and (f) are different, preferably wherein the reaction of the synthesis components is or was carried out in acetone and / or 2-butanone or in a solvent mixture comprising acetone and / or 2-butanone.

[0238] Clause 47. The process of any of clauses 36 to 45, characterized in that the at least one polyurethane-polyurea has been obtained or is obtainable by reacting the following synthesis components:

[0239] (a) at least one diol and / or polyol component,

[0240] (b) at least one di- and / or polyisocyanate component;

[0241] (c) at least one component comprising at least one hydrophilizing group;

[0242] (d) hydrazine or hydrazine hydrate;

[0243] (e) optionally mono-, di- and / or tri-amino-functional and / or -hydroxyamino-functional compounds; and

[0244] (f) optionally other isocyanate-reactive compounds; wherein the components (a), (b), (c), (d), (e) and (f) are different, preferably wherein the reaction of the synthesis components is or was carried out in acetone and / or 2-butanone or in a solvent mixture comprising acetone and / or 2-butanone.

[0245] Clause 48. Use of any of clauses 1 to 9, characterized in that the at least one organic dialkyl dicarbonate is used in a process according to any of clauses 36 to 47 for reducing the content of acetone azine and / or butanone azine in an aqueous polyurethane-polyurea dispersion.

[0246] Clause 49. Article, cosmetic, coating, adhesive layer, coating formulation, adhesive formulation and / or cosmetic formulation containing at least the aqueous polyurethane-polyurea dispersion of any of clauses 23 to 35.

[0247] The present invention will now be elucidated by reference to examples. Experimental part

[0248] Materials and sources

[0249] The employed polyurethane dispersions (Baybond ® PU 406, Impranil ® DLC-F) were obtained from Covestro Deutschland AG, Leverkusen, DE.

[0250] All other chemicals were obtained from Sigma-Aldrich Chemie GmbH, Taufkirchen, Germany unless otherwise stated.

[0251] DMDC: Dimethyl dicarbonate

[0252] DEDC: Diethyl dicarbonate

[0253] HyHy: Hydrazine hydrate (7803-57-8, 64% hydrazine solution in water)

[0254] Unless otherwise stated all percentages are percentages by weight (% by weight).

[0255] Unless otherwise stated all procedures and analytical measurements were performed at a temperature of 23°C (room temperature).

[0256] Methods:

[0257] Determination of acetone azine / butanone azine content in polyurethane-polyurea dispersions:

[0258] 2.0 g of sample are weighed into a 10 ml measuring cylinder and fdled up with toluene (analytical grade quality). The extraction time is 180 seconds. After 15 minutes holding time the upper toluenic phase is filled into a GC vial and sealed. 2 pl of the toluenic phase are injected into a GC apparatus (Agilent 8890 with a fused silica-type column; Agilent Technologies, Inc., Santa Clara, CA, USA) The retention time and the peak area of the acetone azine or butanone azine content are determined / related with a reference sample (with known content of acetone azine or butanone azine) to determine the content of acetone azine or butanone azine in the sample.

[0259] Examples:

[0260] Experiment 1

[0261] A sample of the polyurethane dispersion Impranil® DLC-F (anionically hydrophilized PU dispersion with polycarbonate backbone, Covestro Deutschland AG, Leverkusen, Germany) was admixed with about 400 ppm of hydrazine hydrate and about 1% by weight of acetone (in each case based on the original dispersion) with stirring at room temperature and left to stand overnight. The mixture was then divided into 3 parts of 100 g each. In a container with a magnetic stirrer bar the samples were stirred and the following was added: a) nothing b) 0.1 g of dimethyl dicarbonate c) 1.0 g of dimethyl dicarbonate

[0262] Each mixture was stirred at room temperature for 5 hours. After another day at room temperature, about 24 hours after addition of the additives, an analysis of the acetone azine content was performed.

[0263] Table 1 : Results of analysis of experiment 1

[0264] Evaluation: Addition of as little as 0. 1% by weight of DMDC (based on the mass of the dispersion) achieved a reduction in the acetone azine content. The addition of 1.0% by weight of DMDC (based on the mass of the dispersion) resulted in a reduction in the acetone azine content by about 97% compared to the untreated sample.

[0265] Experiment 2

[0266] A sample of the polyurethane dispersion Baybond® PU 406 (nonionically hydrophilized PU dispersion with polyether backbone, Covestro Deutschland AG, Leverkusen, Germany) was admixed with about 200 ppm of hydrazine hydrate and about 1% by weight of acetone (in each case based on the original dispersion) with stirring at room temperature and left to stand overnight. The mixture was then divided into 4 parts of 100 g each. In a container with a magnetic stirrer bar the samples were stirred and the following was added: a) nothing b) 0.1 g of dimethyl dicarbonate c) 0.5 g of dimethyl dicarbonate d) 1.0 g of dimethyl dicarbonate

[0267] Each mixture was stirred at room temperature for 5 hours. After another day at room temperature, about 24 hours after addition of the additives, an analysis of the acetone azine content was performed.

[0268] Table 2: Results of analysis of experiment 2

[0269] Evaluation: Addition of as little as 0. 1% by weight of DMDC (based on the mass of the dispersion) achieved a noticeable reduction in the acetone azine content. The addition of 0.5% or 1.0% by weight of DMDC (based on the mass of the dispersion) resulted in a marked reduction in the acetone azine content compared to the untreated sample.

[0270] Experiment 3

[0271] A sample of the polyurethane dispersion Baybond® PU 406 (nonionically hydrophilized PU dispersion with polyether backbone, Covestro Deutschland AG, Leverkusen, Germany) was admixed with about 200 ppm of hydrazine hydrate and about 1% by weight of acetone (in each case based on the original dispersion) with stirring at room temperature and left to stand overnight. The mixture was then divided into 4 parts of 100 g each. In a container with a magnetic stirrer bar the samples were stirred and the following was added: a) nothing b) 0.1 g of diethyl dicarbonate c) 0.5 g of diethyl dicarbonate d) 1.0 g of diethyl dicarbonate

[0272] Each mixture was stirred at room temperature for 5 hours. After another day at room temperature, about 24 hours after addition of the additives, an analysis of the acetone azine content was performed.

[0273] Table 3 : Results of analysis of experiment 3

[0274] Evaluation: Addition of as little as 0. 1% by weight of DEDC (based on the mass of the dispersion) achieved a slight reduction in the acetone azine content count. The addition of 0.5% or 1.0% by weight of DEDC (based on the mass of the dispersion) resulted in a marked reduction in the acetone azine content compared to the untreated sample and the content of acetone azine was below the limit of detection of the employed method.

[0275] There were no noticeable changes to the polyurethane dispersions during and after the additions of the additives dimethyl dicarbonate and diethyl dicarbonate. Average particle size (measured by a Zetasizer, Malvern Panalytical Ltd, Malvern, UK) and dispersion viscosity (Haake Viscotester iQ, Fisher Scientific GmbH, Schwerte, DE) do not change significantly, but rather only within the range of typical variations of the analytical methods, after addition of the additive dimethyl dicarbonate. Films of the dispersions were applied to glass plates (squeegee 210 pm slot width) and dried at 50°C for 1 hour and then at 120°C for 1 hour. There were no visually detectable differences in flow, film quality or the colour of the films after addition of the additive dimethyl dicarbonate compared to the films without addition of the additives.

Claims

Claims1. Use of at least one organic dialkyl dicarbonate for reducing the content of acetone azine and / or butanone azine in an aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and acetone azine and / or butanone azine.

2. The use of claim 1, characterized in that the at least one organic dialkyl dicarbonate is selected from the group consisting of dimethyl dicarbonate, diethyl dicarbonate, dipropyl dicarbonate, diisopropyl dicarbonate, methyl ethyl dicarbonate, di-tert-butyl dicarbonate, diisobutyl dicarbonate and / or mixtures of at least two thereof, is preferably dimethyl dicarbonate, diethyl dicarbonate and / or a mixture thereof and is particularly preferably dimethyl dicarbonate.

3. The use of claim 1 or 2, characterized in that the at least one polyurethane-polyurea is present in an amount of 5% to 64% by weight, preferably 30% to 60% by weight, particularly preferably 40% to 50% by weight, in each case based on the total aqueous polyurethane- polyurea dispersion.

4. The use of any of claims 1 to 3, characterized in that the content of acetone azine and / or butanone azine in the aqueous polyurethane-polyurea dispersion before the addition or use of the at least one organic dialkyl dicarbonate is in the range from 0.0001% by weight to 5% by weight, preferably from 0.01% by weight to 1% by weight, based on the total weight of the aqueous polyurethane-polyurea dispersion as 100% by weight.

5. Process for producing an aqueous polyurethane-polyurea dispersion having a reduced content of acetone azine and / or butanone azine comprising at least the steps of:(A) providing an aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and acetone azine and / or butanone azine;(B) treating the aqueous polyurethane-polyurea dispersion from step (A) with at least one organic dialkyl dicarbonate; to obtain an aqueous polyurethane-polyurea dispersion having a reduced content of acetone azine and / or butanone azine.

6. The process of claim 5, characterized in that the aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and acetone azine was produced in step (A) by a process comprising acetone as solvent or containing at least one polyurethane-polyurea and butanone azine was produced in step (A) by a process comprising 2-butanone as solvent or containing at least one polyurethane-polyurea and acetone azine and butanone azine was produced in step (A) by a process comprising acetone and 2-butanone as solvent.

7. The process of claim 5 or 6. characterized in that step (B) is followed by at least the following step (C):(C) producing articles, cosmetics, coatings, adhesive layers or adhesives from the aqueous polyurethane-polyurea dispersion having a reduced content of acetone azine and / or butanone azine obtained in step (B).

8. The process of any of claims 5 to 7, characterized in that step (B) is carried out at 1°C to 100°C, preferably at 5°C to 50°C, particularly preferably at 10°C to 30°C.

9. The process of any of claims 5 to 8, characterized in that the at least one organic dialkyl dicarbonate is selected from the group consisting of dimethyl dicarbonate, diethyl dicarbonate, dipropyl dicarbonate, diisopropyl dicarbonate, methyl ethyl dicarbonate, di-tert- butyl dicarbonate, diisobutyl dicarbonate and / or mixtures of at least two thereof, is preferably dimethyl dicarbonate, diethyl dicarbonate and / or a mixture thereof and is particularly preferably dimethyl dicarbonate.

10. The process of any of claims 5 to 9, characterized in that the aqueous polyurethane-polyurea dispersion contains at least one compound having a biocidal effect which is distinct from the organic dialkyl dicarbonate, wherein the at least one compound having a biocidal effect is preferably a bactericide, fungicide and / or algicide, particularly preferably at least one isothiazolinone, is yet more preferably selected from the group consisting of chloromethylisothiazolinone, methylisothiazolinone, benzisothiazolinone, octylisothiazolinone, butylbenzisothiazolinone, dichlorooctylisothiazolinone and / or mixtures of at least two of these, is yet more preferably selected from the group consisting of 5 -chloro-2-methylisothiazolinone / 2 -methylisothiazolinone and / or mixtures thereof, wherein the at least one compound having a biocidal effect is preferably present in an amount of 1 to 1000 mg / kg based on the total aqueous polyurethane-polyurea dispersion.

11. The process of any of claims 5 to 10, characterized in that the at least one polyurethane- polyurea is present in an amount of 5% to 64% by weight, preferably 30% to 60% by weight, particularly preferably 40% to 50% by weight, in each case based on the total aqueous polyurethane-polyurea dispersion.

12. The process of any of claims 5 to 11, characterized in that the at least one organic dialkyl dicarbonate is present in an amount of 0.001 g / kg to 100 g / kg, preferably of 0.1 g / kg to 50 g / kg, particularly preferably of 0.1 g / kg to 20 g / kg, based on the total aqueous polyurethane- polyurea dispersion.

13. The process of any of claims 5 to 12, characterized in that the content of acetone azine and / or butanone azine in the aqueous polyurethane-polyurea dispersion before the addition or use of the at least one organic dialkyl dicarbonate is in the range from 0.0001% by weight to 5%by weight, preferably from 0.01% by weight to 1% by weight, based on the total weight of the aqueous polyurethane-polyurea dispersion as 100% by weight.

14. The process of any of claims 5 to 13, characterized in that the content of acetone azine and / or butanone azine in the aqueous polyurethane-polyurea dispersion 24 hours after the addition or use of the at least one organic dialkyl dicarbonate is reduced by more than 80% by weight, preferably more than 90% by weight, particularly preferably more than 95% by weight, yet more preferably more than 98% by weight, based on the content of acetone azine and / or butanone azine in the aqueous polyurethane-polyurea dispersion before the addition or use of the at least one organic dialkyl dicarbonate.

15. Aqueous polyurethanene-polyurea dispersion containing at least one polyurethane-polyurea and at least one alkyl carbazate, wherein the alkyl carbazate is preferably methyl carbazate and / or ethyl carbazate, particularly preferably methyl carbazate.

16. The aqueous polyurethanene-polyurea dispersion of claim 15, characterized in that the at least one alkyl carbazate is present in an amount of 1 mg / kg to 10000 mg / kg, preferably 10 mg / kg to 1000 mg / kg, based on the total aqueous polyurethane-polyurea dispersion.

17. The aqueous polyurethanene-polyurea dispersion of claim 15 or 16, characterized in that the at least one polyurethane-polyurea is present in an amount of 5% to 64% by weight, preferably 30% to 60% by weight, particularly preferably 40% to 50% by weight, in each case based on the total aqueous polyurethane-polyurea dispersion.

18. The aqueous polyurethane-polyurea dispersion of any of claims 15 to 17, characterized in that the aqueous polyurethane-polyurea dispersion has been obtained or is obtainable by a process comprising at least the following steps of:(A) providing an aqueous polyurethane-polyurea dispersion containing at least one polyurethane-polyurea and acetone azine and / or butanone azine;(B) treating the aqueous polyurethane-polyurea dispersion from step (A) with at least one organic dialkyl dicarbonate; to obtain an aqueous polyurethane-polyurea dispersion containing at least one alkyl carbazate.

19. The aqueous polyurethanene-polyurea dispersion of any of claims 15 to 18, characterized in that the aqueous polyurethane-polyurea dispersion contains at least one compound having a biocidal effect which is distinct from the organic dialkyl dicarbonate, wherein the at least one compound having a biocidal effect is preferably a bactericide, fungicide and / or algicide, particularly preferably at least one isothiazolinone, is yet more preferably selected from the group consisting of chloromethylisothiazolinone, methylisothiazolinone,benzisothiazolinone, octylisothiazolinone, butylbenzisothiazolinone, dichlorooctylisothiazolinone and / or mixtures of at least two of these, is yet more preferably selected from the group consisting of 5-chloro-2-methylisothiazolinone / 2- methylisothiazolinone and / or mixtures thereof, wherein the at least one compound having a biocidal effect is preferably present in an amount of 1 to 1000 mg / kg based on the total aqueous polyurethane-polyurea dispersion.

20. The aqueous polyurethane-polyurea dispersion of any of claims 15 to 19, characterized in that the aqueous polyurethane-polyurea dispersion containing at least one polyurethane- polyurea and acetone azine was produced in step (A) by a process comprising acetone as solvent or containing at least one polyurethane-polyurea and butanone azine was produced in step (A) by a process comprising 2-butanone as solvent or containing at least one polyurethane-polyurea and acetone azine and butanone azine was produced in step (A) by a process comprising acetone and 2-butanone as solvent.

21. The aqueous polyurethane-polyurea dispersion of any of claims 15 to 20, characterized in that step (B) is carried out at 1°C to 100°C, preferably at 5°C to 50°C, particularly preferably at 10°C to 30°C.

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