A polyurethane-urea dispersion

Abstract

The present invention relates to an aqueous polyurethane-urea dispersion comprising water and a polyurethane-urea, wherein the polyurethane-urea is obtained by at least partly deprotonating the reaction product of at least components (A)-(F): (A) from 60.0 to 80.0% by weight of one or more polyether polyols with a number average molecular weight of from 500 to 4000 g / mol and a hydroxy functionality from 1.9 to 2.1, wherein said polyether polyols comprise at least 65.0% by weight, based on the total weight of the polyether polyols (A), of one or more polytetrahydrofuran polyol, (B) from 5.0 to 12.0% by weight of one or more polyethers with a hydroxy functionality from 0.9 to 1.1 and a number average molecular weight of from 1500 to 2500 g / mol, (C) from 0.5 to 2.0% by weight of one or more isocyanate-reactive compounds containing at least one carboxylic acid group that can be converted into a salt group which is capable to render the polyurethane-urea dispersible in water, (D) from 0.4 to 2.0% by weight of one or more branching agents having a hydroxy functionality of 3.0 (D1) and / or from 1.0 to 5.0% by weight of one or more branching agents having an isocyanate functionality from 3.0 to 4.0 (D2), (E) from 10.0 to 30.0% by weight of one or more diisocyanates, (F) from 0.1 to 5.0% by weight of one or more amine functional chain extenders and / or one or more amine functional chain terminators, wherein the amounts of (A) to (F) are given based on the weight of the polyurethane-urea, and wherein said deprotonating is effected by reacting said reaction product with one or more amines and / or ammonia.

Description

[0001] A POLYURETHANE-UREA DISPERSION

[0002] The present invention is directed to an aqueous polyurethane urea dispersion for use in superfine fibers nonwoven products, in particular for use in superfine fibers nonwoven synthetic leather.

[0003] The superfine fiber, namely fiber with a fineness of less than 0.3 denier (the diameter is 5 microns or less), has the characteristics of structure simulation, high air permeability, good soft handfeel, high physical and mechanical properties, and is an ideal substitute material for genuine leather, and can be applied in the fields of decoration, automotive, bags, shoes, clothing (Faux Real: Genuine Leather and 200 Years of Inspired Fakes, Robert Kanigel, Joseph Henry Press, 2007).

[0004] Superfine fibers generally need to be impregnated with polyurethane to obtain soft and supple handfeel. Solvent-type polyurethane (polyurethane dimethylformamide solution) is widely used in the industry. However, dimethylformamide (DMF) has reproductive toxicity and is increasingly banned by producers of superfine fibers non-woven products, so attempts have been made to impregnate superfine fibers with aqueous polyurethane dispersions.

[0005] In recent years, the sea-island type bicomponent superfine fiber products using polyester (polyethylene terephthalate PET) as an island component and alkali-soluble polyester (COPET) as a sea component, nylon as an island component and alkali-soluble polyester (COPET) as a sea component, or polyester (PET) as an island component and polyvinyl alcohol (PVA) as a sea component have appeared in the market (Hiroshi Fu, et al. (2023), Current advances on sea-island microfiber nonwoven materials preparation technology and its applications: a review, The Journal of The Textile Institute, DOI: 10.1080 / 00405000.2023.2278373). Since only hot alkali or hot water is needed for fiber opening rather than a solvent such as toluene, sea-island superfine fiber nonwoven material is more environment-friendly and is more and more favored by the market.

[0006] In addition, for the environmental protection needs, more and more superfine fiber nonwoven synthetic leather is prepared by a thermo-coagulation process. It is therefore required that the aqueous polyurethane dispersion has good thermo-coagulation properties. Further, in the preparation of superfine fiber synthetic leather some extremely harsh conditions are applied, such as alkaline dissolution process, high temperature cooking process, and acid-base cycle color stripping process. It is therefore required that the aqueous polyurethane dispersion has good acid / alkaline boiling resistance.

[0007] CN113929860A describes water-based polyurethane dispersions for use in the preparation of ultrafine fiber synthetic leather by impregnation. The polyurethane is prepared by reacting a first polyol component, a second polyol component, an isocyanate, a hydrophilic carboxylic acid component, an alcohol, an amine, and a crosslinker; the first polyol component includes the combination of one or more polytetrahydrofuran diol and polyoxypropylene diol, the second polyol component is a nonionic polyoxyethylene polyol with a number average molecular weight of 800-1200, and the mass of the second polyol is 5 to 10% of the total mass of the first polyol component, the second polyol component and the isocyanate. It has been found that the thermo-coagulation properties and / or the acid / alkaline boiling resistance of the water-based polyurethane dispersions disclosed in CN113929860A may not exhibit the desired level of performance.

[0008] The object of the present invention is to provide an aqueous polyurethane dispersion with improved thermo-coagulating properties and / or acid / alkaline boiling resistance.

[0009] This object has surprisingly been achieved by an aqueous polyurethane-urea dispersion comprising water and a polyurethane-urea, wherein the polyurethane-urea is obtained by at least partly deprotonating the reaction product of at least components (A)-(F) :

[0010] (A) from 60.0 to 80.0% by weight of one or more polyether polyols with a number average molecular weight of from 500 to 4000 g / mol and a hydroxy functionality from 1.9 to 2.1 , wherein said polyether polyols comprise at least 65.0% by weight, based on the total weight of the polyether polyols (A), of one or more polytetrahydrofuran polyol,

[0011] (B) from 5.0 to 12.0% by weight of one or more hydrophilic polyethers with a hydroxy functionality from 0.9 to 1.1 and a number average molecular weight of from 1500 to 2500 g / mol,

[0012] (C) from 0.5 to 2.0% by weight of one or more isocyanate-reactive compounds containing at least one carboxylic acid group that can be converted into a salt group which is capable to render the polyurethane-urea dispersible in water, (D) from 0.4 to 2.0% by weight of one or more branching agents having hydroxy functionality of 3.0 (D1) and / or from 1.0 to 5.0% by weight of one or more branching agents having isocyanate functionality from 3.0 to 4.0 (D2),

[0013] (E) from 10.0 to 30.0% by weight of one or more diisocyanates,

[0014] (F) from 0.1 to 5.0% by weight of one or more amine functional chain extenders and / or one or more amine functional chain terminators, wherein the amounts of (A) to (F) are given based on the weight of the polyurethane-urea, and wherein said deprotonating is effected by reacting said reaction product with one or more amines and / or ammonia.

[0015] The amounts of (A), (B), (C), (D), (E) and (F) preferably add up to 100%.

[0016] It has surprisingly been found that the aqueous polyurethane dispersions of the present invention are able to improve the thermo-coagulating properties and / or the acid / alkaline boiling resistance. Preferably, both the thermo-coagulating properties and the acid / alkaline boiling resistance are improved.

[0017] For all upper and / or lower boundaries of any range given herein, the boundary value is included in the range given, unless specifically indicated otherwise. Thus, when saying from x to y, means including x and y and also all intermediate values.

[0018] The aqueous polyurethane-urea dispersion according to the present invention comprising dispersed polymer particles comprising at least one polyurethane, usually polyurethane- urea. Methods for preparing polyurethanes are known in the art and are described in for example the Polyurethane Handbook 2nd Edition, a Carl Hanser publication, 1994, by G. Oertel.

[0019] Component (A)

[0020] The aqueous polyurethane-urea dispersion of the present invention comprises from 60.0 to 80.0% by weight, based on the weight of the polyurethane-urea, of one or more polyether polyols with a number average molecular weight of from 500 to 4000 g / mol and a hydroxy functionality from 1.9 to 2.1, preferably of 2.0, wherein said polyether polyols comprise at least 65.0% by weight, based on the total weight of the polyether polyols (A), of one or more polytetrahydrofuran polyol.

[0021] The one or more polyether polyols (A) preferably have a number average molecular weight of from 1000 to 2500 g / mol.

[0022] The one or more polyether polyols (A) preferably comprise at least 70.0% by weight, based on the total weight of the polyether polyols (A), of one or more polytetrahydrofuran polyol, more preferably the one or more polyether polyols (A) comprise at least 75.0% by weight, based on the total weight of the polyether polyol (A), of one or more polytetrahydrofuran polyol.

[0023] The one or more polyether polyols (A) preferably further comprise one or more polypropylene glycol and / or one or more polytrimethylene ether glycol as this may be beneficial for the soft hand feel of an article comprising a substrate coated or impregnated with the dispersion of the current invention. The amount of the one or more polypropylene glycol polyol and / or one or more polytrimethylene ether glycol, based on the total weight of the polyether polyol (A), is preferably at least 15.0% by weight, more preferably at least 20.0% by weight. Component (A) more preferably consists essentially of, or consists of the combination of (i) one or more polytetrahydrofuran polyol and (ii) one or more polypropylene glycol polyol and / or one or more polytrimethylene ether glycol.

[0024] The concept of hydroxy functionality is familiar to the skilled person. It indicates the number of reactive OH groups (hydroxyl groups) that are present on average per molecule. The term “hydroxy functionality” refers to the average number of reactive hydroxyl groups, -OH, present per molecule of the -OH functional material that is being described. In the production of a polyurethane, the hydroxyl groups react with isocyanate groups, -NCO, that are attached to an isocyanate compound. The term "hydroxyl number" or “hydroxyl value” refers to the number of reactive hydroxyl groups available for reaction, and is expressed as the number of milligrams of potassium hydroxide equivalent to the hydroxyl content of one gram of the polyol (ASTM D4274-16). The term "equivalent weight" refers to the weight of a compound divided by its valence. For a polyol, the equivalent weight is the weight of the polyol that will combine with an isocyanate group, and may be calculated by dividing the number average molecular weight of the polyol by its functionality. The equivalent weight of a polyol may also be calculated by dividing 56,100 by the hydroxyl number of the polyol: Equivalent Weight (g / eq) = (56.1x1000) / OH number. Component (B)

[0025] The aqueous polyurethane-urea dispersion of the present invention comprises from 5.0 to 12.0% by weight, based on the weight of the polyurethane-urea, of one or more polyethers with a hydroxy functionality from 0.9 to 1.1 , preferably a hydroxy functionality of 1.0, and a number average molecular weight of from 1500 to 2500 g / mol. The one or more polyethers (B) are preferably one or more polyoxyalkylene monoalkyl ether having a terminal -O-R group, wherein R is preferably a Ci to C4 alkyl group, more preferably R is a methyl or butyl group. More preferably, the one or more polyethers (B) are selected from the group consisting of ethylene oxide polymers, copolymers of ethylene oxide and propylene oxide and any mixtures of two or more thereof. Even more preferably, the one or more polyethers (B) are one or more copolymers of ethylene oxide and propylene oxide, wherein the molar ratio of ethylene oxide to propylene oxide is preferably in the range of from 75:25 to 90:10, more preferably in the range from 80:20 to 85:15.

[0026] Component (C)

[0027] The aqueous polyurethane-urea dispersion of the present invention comprises from 0.5 to 2.0% by weight, based on the weight of the polyurethane-urea, of one or more isocyanatereactive compounds containing at least one carboxylic acid group that can be converted into a salt group which is capable to render the polyurethane-urea dispersible in water. The one or more isocyanate-reactive compounds containing at least one carboxylic acid group that can be converted into a salt group which is capable to render the polyurethane-urea dispersible in water (C) are preferably dihydroxy alkanoic acids, more preferably a,a- dimethylolpropionic acid and / or a,a-dimethylolbutanoic acid.

[0028] Component (D)

[0029] The aqueous polyurethane-urea dispersion of the present invention comprises one or more branching agents (D) selected from the group consisting of branching agents having a hydroxy functionality of 3.0 (D1), branching agents having an isocyanate functionality from 3.0 to 4.0 (D2) and any mixture of two or more thereof. The aqueous polyurethane-urea dispersion of the present invention preferably comprises from 0.4 to 2.0% by weight, based on the weight of the polyurethane-urea, of one or more branching agents having a hydroxy functionality of 3.0 (D1) and / or from 1.0 to 5.0% by weight, based on the weight of the polyurethane-urea, of one or more branching agents having an isocyanate functionality from 3.0 to 4.0 (D2). The one or more branching agents (D1) preferably have a molar mass lower than 500 g / mol, more preferably lower than 400 g / mol, more preferably lower than 200 g / mol, even more preferably lower than 150 g / mol. Preferred branching agents (D1) are glycerol and / or trimethylolpropane, most preferred component (D1) is trimethylolpropane in view of its high reactivity and hence high branching efficiency. The one or more branching agents (D2) preferably have a number average molecular weight from 150 to 1500 g / mol. Preferred branching agents (D2) are modified aliphatic polyisocyanates and / or modified cycloaliphatic polyisocyanates based on any one or more diisocyanates as mentioned for component (E). The modified aliphatic polyisocyanate and the modified cycloaliphatic polyisocyanate preferably have each independently one or more of the following structures: iminooxadiazinedione, isocyanurate, uretdione, allophanate and / or biuret.

[0030] The concept of isocyanate functionality is familiar to the skilled person. It indicates the number of reactive NCO groups (isocyanate groups) that are present on average per molecule. The term “isocyanate functionality” refers to the average number of reactive isocyanate groups, -NCO, present per molecule of the -NCO functional material that is being described. The average isocyanate functionality of a branching agent (D2) can be calculated as below:

[0031] Average isocyanate functionality = number average molecular weight of the branching agent (D2) * (NCO% of (D2) / 42). The number average molecular weight of the branching agent (D2) is determined with the method as described below, however using polystyrene standards instead of polyethyleneglycol standards. The NCO% of (D2) is determined by titration according to DIN-EN ISO 11909-2007. 42 is the molar mass of a single isocyanate group.

[0032] Component (E)

[0033] The aqueous polyurethane-urea dispersion of the present invention comprises from 10.0 to 30.0% by weight, based on the weight of the polyurethane-urea, of one or more diisocyanates (E). The one or more diisocyanates (E) preferably comprise (cyclo)aliphatic diisocyanates in an amount, based on the total weight of the diisocyanates (E), of at least 90.0% by weight, more preferably of at least 95.0% by weight. Most preferably, the one or more diisocyanates (E) are (cyclo)aliphatic diisocyanates. Preferably, the one or more diisocyanates (E) are selected from the group consisting of diisocyanates having the general formula Y(NCO)2 or any mixture of two or more thereof, where Y is a C4-C12 divalent non-cyclic aliphatic hydrocarbon group (i.e. not containing a cycloaliphatic group) or Y is a C6-C15 divalent aliphatic hydrocarbon group comprising at least one cycloaliphatic group.

[0034] In a preferred embodiment, the one or more diisocyanates (E) are selected from the group consisting of 1,5-pentamethylenediisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (I PDI), cyclohexane-1,4-diisocyanate, 1,3- and 1,4- bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate (H12MDI) and any mixture of two or more thereof. More preferably, the one or more diisocyanates (E) are selected from the group consisting of 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI ) and any mixture of two or more thereof. The dicyclohexylmethane diisocyanate is preferably 4,4’- dicyclohexylmethane diisocyanate (4,4’-Hi2MDI). Even more preferably, the one or more diisocyanates (E) are selected from the group consisting of 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and any mixture thereof.

[0035] Component (F)

[0036] The aqueous polyurethane-urea dispersion of the present invention comprises from 0.1 to 5.0% by weight, based on the weight of the polyurethane-ureasof component (F).

[0037] Component (F) is one or more amine functional chain extenders and / or one or more amine functional chain terminators.

[0038] The one or more amine functional chain terminators are preferably selected from the group consisting of diethanolamine, propylamine, butylamine, amylamine, hexylamine, 1- tetradecylamine and any mixtures of two or more thereof.

[0039] The one or more amine functional chain extenders are preferably selected from the group consisting of compounds with a NH2 and / or NH functionality of 2, preferably selected from the group consisting of hydrazine, 1,2-ethanediamine, 1,4-butanediamine, 2-methyl-1,5- pentanediamine, 1,6- hexamethylene-diamine, 1,4-hexamethylenediamine, isophorone diamine (i.e. 3- aminomethyl-3,5,5-trimethylcyclohexylamine), 1,3- bis(aminomethyl)cyclohexane, xylylenediamine, piperazine, 2,5-dimethylpiperazine, 1,3- diamino-2-propanol, N-(2-hydroxyethyl)-ethylene diamine, N,N-bis(2-hydroxyethyl)-ethylene diamine and any mixture of two or more thereof. Preferably, component (F) is one or more amine functional chain extenders, i.e. the aqueous polyurethane-urea dispersion of the present invention comprises from 0.1 to 5.0% by weight, based on the weight of the polyurethane-ureasof one or more amine functional chain extenders.

[0040] The polyurethane-urea present in the dispersion of the invention is obtained by at least partly deprotonating the reaction product of at least components (A)-(F) as described herein above, wherein said deprotonating is effected by reacting said reaction product with one or more amines and / or ammonia. “At least partly deprotonating” refers to the process of partially or completely removing protons from the carboxylic acid groups that are incorporated into the polyurethane-urea through component (C), thereby rendering the polyurethane-urea dispersible in water. The one or more amines and / or ammonia are preferably used in such an amount that the polyurethane-urea has a neutralizing degree of from 30 to 100%, wherein the neutralizing degree is calculated according to the following formula:

[0041] ((motor molar amount carboxylic acid in (C)) x 100%.

[0042] The one or more amines are preferably tertiary amines, preferably selected from the group consisting of triethylamine, N,N-diisopropylethylamine, tributylamine, N,N- dialkylalkanolamines (such as N,N-dimethylethanolamine, N,N-dimethylpropanolamine, N,N-dipropylethanolamine, and 1-dimethylamino-2-methyl-2-propanol), N-alkyl-N,N- dialkanolamines, and trialkanolamines (such as triethanolamine) and any mixture of two or more thereof.

[0043] Preferably, the polyurethane-urea is the reaction product of at least components (A)-(G), and more preferably the polyurethane-urea is the reaction product of components (A)-(G):

[0044] (A) from 60.0 to 80.0% by weight of one or more polyether polyols with a number average molecular weight of from 500 to 4000 g / mol and a hydroxy functionality from 1.9 to 2.1 , wherein said polyether polyols comprise at least 65.0% by weight, based on the total weight of the polyether polyols (A), of one or more polytetrahydrofuran polyol, (B) from 5.0 to 12.0% by weight of one or more polyethers with a hydroxy functionality from 0.9 to 1.1 and a number average molecular weight of from 1500 to 2500 g / mol,

[0045] (C) from 0.5 to 2.0% by weight of one or more isocyanate-reactive compounds containing at least one carboxylic acid group that can be converted into a salt group which is capable to render the polyurethane-urea dispersible in water,

[0046] (D) from 0.4 to 2.0% by weight of one or more branching agents having a hydroxy functionality of 3.0 (D1) and / or from 1.0 to 5.0% by weight of one or more branching agents having an isocyanate functionality from 3.0 to 4.0 (D2),

[0047] (E) from 10.0 to 30.0% by weight of one or more diisocyanates,

[0048] (F) from 0.1 to 5.0% by weight of one or more amine functional chain extenders and / or one or more amine functional chain terminators,

[0049] (G) one or more tertiary amines and / or ammonia, wherein the amounts of (A) to (F) are given based on the weight of the polyurethane-urea, the one or more tertiary amines and / or ammonia are preferably used in such an amount that the polyurethane-urea has a neutralizing degree of from 30 to 100%, and the one or more tertiary amines are preferably selected from the group consisting of triethylamine, N,N-diisopropylethylamine, tributylamine, N,N-dialkylalkanolamines (such as N,N-dimethylethanolamine, N,N-dimethylpropanolamine, N,N-dipropylethanolamine, and 1- dimethylamino-2-methyl-2-propanol), N-alkyl-N,N-dialkanolamines, and trialkanolamines (such as triethanolamine) and any mixture of two or more thereof.

[0050] The present invention also relates to an aqueous polyurethane-urea dispersion comprising water and a polyurethane-urea, wherein the polyurethane-urea is the reaction product of at least components (A)-(G), preferably the polyurethane-urea is the reaction product of components (A)-(G):

[0051] (A) from 60.0 to 80.0% by weight of one or more polyether polyols with a number average molecular weight of from 500 to 4000 g / mol and a hydroxy functionality from 1.9 to 2.1 , wherein said polyether polyols comprise at least 65.0% by weight, based on the total weight of the polyether polyols (A), of one or more polytetrahydrofuran polyol, (B) from 5.0 to 12.0% by weight of one or more polyethers with a hydroxy functionality from 0.9 to 1.1 and a number average molecular weight of from 1500 to 2500 g / mol,

[0052] (C) from 0.5 to 2.0% by weight of one or more isocyanate-reactive compounds containing at least one carboxylic acid group that can be converted into a salt group which is capable to render the polyurethane-urea dispersible in water,

[0053] (D) from 0.4 to 2.0% by weight of one or more branching agents having a hydroxy functionality of 3.0 (D1) and / or from 1.0 to 5.0% by weight of one or more branching agents having an isocyanate functionality from 3.0 to 4.0 (D2),

[0054] (E) from 10.0 to 30.0% by weight of one or more diisocyanates,

[0055] (F) from 0.1 to 5.0% by weight of one or more amine functional chain extenders and / or one or more amine functional chain terminators,

[0056] (G) one or more tertiary amines and / or ammonia, wherein the amounts of (A) to (F) are given based on the weight of the polyurethane-urea, the one or more tertiary amines and / or ammonia are used in such an amount that the polyurethane-urea has a neutralizing degree of from 30 to 100%, and the one or more tertiary amines are selected from the group consisting of triethylamine, N,N-diisopropylethylamine, tributylamine, N,N-dialkylalkanolamines (such as N,N- dimethylethanolamine, N,N-dimethylpropanolamine, N,N-dipropylethanolamine, and 1- dimethylamino-2-methyl-2-propanol), N-alkyl-N,N-dialkanolamines, and trialkanolamines (such as triethanolamine) and any mixture of two or more thereof.

[0057] The amount of polyurethane-urea in the dispersion of the present invention is preferably at least 30% by weight, more preferably at least 35% by weight, and preferably at most 60 % by weight, more preferably at most 50% by weight, based on the total weight of the dispersion. The amount of polyurethane-urea in the dispersion is preferably at least 70% by weight, based on the solid content of the dispersion.

[0058] The aqueous dispersion according to the present invention preferably further comprises one or more antioxidants in an amount of preferably from 1.0 to 3.5% by weight, based on the amount of polyurethane-urea present in the dispersion. It has surprisingly been found that the presence of anti-oxidant in the dispersion of the invention results in an improved acid / alkaline boiling resistance, in particular in an improved alkaline boiling resistance. This is beneficial since in the preparation of the superfine fiber nonwoven synthetic leather, extremely harsh conditions, such as toluene / alkaline dissolution process at high temperature and acid-base cycle color stripping process, may be applied. The one or more antioxidants are preferably selected from the group consisting of hindered phenols, benzofuranones, hydroxyamines, phosphites, sulfur compounds, preferably the one or more antioxidants are hindered phenols, preferably selected from the group consisting of ethylene bis(oxyethylene) bis(3-tert-butyl-4-hydroxy-5-(methylhydrocinnamate), tetrakis[methylene(3,5-di-tert-butl-4-hydroxy hydrocinnamate)]methane, octadecyl 3,5-di- tert-butyl-4-hydroxyhydrocinnamate, N,N’-hexamethylene-bis(3,5-di-tert-butyl-4- hydroxyhydrocinnamamide), C7-C9 branched alkyl esters of 3,5-di-tert-butyl-4- hydroxyhydrocinnamic acid, reaction product of N-phenylbenzene amine with 2,4,4- trimethylpentene, and any mixture of two or more thereof.

[0059] The dispersion of the present invention preferably further comprises a crosslinking agent for imparting crosslinkability with the polyurethane-urea when the dispersion is subsequently heated. Preferred examples are carbodiimide or blocked isocyanate crosslinker.

[0060] The aqueous dispersion according to the present invention preferably further comprises a thermosensitive agent in an amount of preferably from 2.0 to 5.0% by weight, based on the amount of polyurethane-urea dispersion. The thermosensitive agent is preferably an organopolysiloxane polyether with a number average molecular weight of at least 10000 g / mol, wherein the thermosensitive agent preferably comprises the following structural unit: wherein PO is propylene oxide, EO is ethylene oxide and nBu is n-butyl, and wherein n is from 3 to 20, the ratio of x to y is from 70:30 to 30:70 and the number average molecular weight of (PO)x(EO)y-nBu is from 1000 to 3000. The present invention further relates to the use of the dispersion as described herein above as binding agent and / or impregnating agent for superfine fibers of a nonwoven fabric.

[0061] The present invention further relates to an article comprising a substrate coated or impregnated with a dispersion as described herein above. The substrate is preferably a superfine fiber, more preferably a superfine fiber nonwoven fabric, most preferably the substrate is a sea-island type bicomponent fiber product using polyethylene terephthalate (PET) as an island component and alkali-soluble polyethylene terephthalate (COPET) as a sea component. The present invention further relates to the use of said article in the fields of automotive, decoration, clothing, shoes and consumer-electronics.

[0062] The present invention further relates to a process for producing an article, which process comprises the following steps: i) impregnating sea-island type bicomponent superfine fibers into the dispersion as described herein above; ii) removing and drying sea-island type bicomponent superfine fibers treated in step i) and then impregnating the sea-island type bicomponent superfine fibers into hot alkali or hot water to remove the sea component in fibers to obtain superfine fibers; and iii) removing and drying the superfine fibers to obtain said article.

[0063] The process preferably further comprises a step iv) of removing and drying the superfine fiber treated in the step ii), and then impregnating the superfine fiber in a dye is further concluded between said step ii) and said step iii).

[0064] The present invention further relates to a process for producing an article, which process comprises the following steps: a) impregnating sea-island type bicomponent superfine fibers into hot alkali or hot water to remove the sea component in fibers to obtain superfine fibers; b) removing and drying the superfine fibers treated in step a), and then impregnating superfine fibers into the dispersion as described herein above; and c) removing and drying the superfine fibers to obtain said article. The process preferably further comprises a step d) of removing and drying the superfine fiber treated in the step b), and then impregnating the superfine fiber in a dye is further concluded between said step b) and said step c).

[0065] The sea component and the island component of said sea-island type bicomponent superfine fiber are different.

[0066] The island component of said sea-island type bicomponent superfine fiber can be a conventional polymer in the textile application, and is preferably one or more of the following: polyethylene terephthalate, modified polyesters such as poly(trimethylene terephthalate), cationic polyesters, nylon, other types of polyamides, polyethylene, polypropylene, and other types of polyolefins. The sea component of said sea-island type bicomponent superfine fiber is preferably a polymer that can be dissolved and removed with a treatment means such as water, an aqueous alkali solution or an aqueous acid solution, and is preferably one or more of the following: nylons, other polyamides, modified polyesters, and other spinnable polymers having the basic properties such as solubility in water, in an aqueous acid solution or in an aqueous alkali solution, most preferably the sea component is one or more of the following: alkali water-soluble polyester (COPET) and hot water-soluble polyvinyl alcohol (PVA).

[0067] Said article is preferably suitable for use in surfaces and structures in the automotive interior, decorations (walls, sofas, armchairs, carpets), handbags, suitcases, coverings, boxes, musical instruments and electronic devices. The above list is merely provided as examples and is not intended to be an exhaustive list.

[0068] The present invention is now illustrated by reference to the following examples. Unless otherwise specified, all parts, percentages and ratios are on a weight basis.

[0069] Components and abbreviations used:

[0070] PTHF2000 Polytetrahydrofuran polyol with hydroxy functionality of 2, number average molecular weight of 2000 g / mol, hydroxyl value of 56 mg KOH / g, commercially available from BASF.

[0071] PTHF1000 Polytetrahydrofuran polyol with hydroxy functionality of 2, number average molecular weight of 1000 g / mol, hydroxyl value of 112 mg KOH / g, commercially available from BASF. Desmophen® 3600Z (PPG2000) Polypropylene oxide polyols with hydroxy functionality of 2, number average molecular weight of 2000 g / mol, hydroxyl value of 56 mg KOH / g, commercially available from Covestro AG.

[0072] Desmophen® BD 1110 (PPG 1000) Polypropylene oxide polyols with hydroxy functionality of 2, number average molecular weight of 1000 g / mol hydroxyl value of 112 mg KOH / g, commercially available from Covestro AG.

[0073] Desmodur® H (HDI) 1 ,6-hexamethylene diisocyanate, commercially available from Covestro AG. Desmodur® I (I PDI) Isophorone diisocyanate, commercially available from Covestro AG. Desmodur® N3300 Aliphatic polyisocyanate, trimer of 1 ,6- hexamethylene diisocyanate with an average isocyanate functionality of 3.5, commercially available from Covestro AG.

[0074] LB25 (EO / PO2250) Polyoxyalkylene monoetherols, monohydroxyfunctional nonionic hydrophilic compounds, monofunctional polyether polyols based on ethylene oxide / propylene oxide, number average molecular weight of 2250 g / mol, hydroxyl value of 25 mg KOH / g, commercially available from Covestro AG.

[0075] MPEG 1500 Polyethylene oxide with hydroxy functionality of 1 , number average molecular weight of 1500 g / mol, hydroxyl value of 37.4 mg KOH / g, commercially available from Shanghai Dongda Chemical Company.

[0076] MPEG1000 Polyethylene oxide with hydroxy functionality of 1 , number average molecular weight of 1000 g / mol, hydroxyl value of 56.1 mg KOH / g, commercially available from Shanghai Dongda Chemical Company.

[0077] PEG 1000 Polyethylene oxide with hydroxy functionality of 2, number average molecular weight of 1000 g / mol, hydroxyl value of 112 mg KOH / g, commercially available from Shanghai Dongda Chemical Company.

[0078] Ymer N90 (PEG1250) Polyethylene oxide with hydroxy functionality of 2, number average molecular weight of 1250 g / mol, hydroxyl value of 90 mg KOH / g, commercially available from Perstorp (Shanghai) Chemical Products Trading Co., Ltd.. DMPA 2, 2-Di(hydroxymethyl)propionic acid, commercially available from Aldrich Chemical Reagents. DMBA 2,2-Di(hydroxymethyl)butyric acid, commercially available from Aldrich Chemical Reagents.

[0079] EG Ethylene glycol, commercially available from Aldrich

[0080] Chemical Reagents.

[0081] BDO 1 ,4-butanediol, commercially available from Aldrich

[0082] Chemical Reagents.

[0083] TMP Trimethylolpropane, commercially available from

[0084] Aldrich Chemical Reagents.

[0085] TEA Triethylamine, available from Aldrich Chemical

[0086] Reagents.

[0087] DMEA Dimethylethanolamine, available from Aldrich

[0088] Chemical Reagents.

[0089] IPDA Isophorone diamine, available from Aldrich Chemical

[0090] Reagents.

[0091] EDA Ethylenediamine, available from Aldrich Chemical

[0092] Reagents.

[0093] DEA Diethanolamine, available from Aldrich Chemical

[0094] Reagents.

[0095] DETA Diethylene triamine, available from Aldrich Chemical

[0096] Reagents.

[0097] AAS (Vestamin® A 95) Sodium diaminosulfonate, NH2-CH2CH2-NH-CH2CH2-

[0098] SOsNa, aqueous solution of 49% concentration, available from Evonik Industries.

[0099] Irgastab® IS 4276 Antioxidant, commercially available from BASF.

[0100] Irgastab® IS 3066 Antioxidant, commercially available from BASF.

[0101] Irganox® 245 DW Antioxidant, commercially available from BASF. Coagulant WS Heat sensitive agent, commercially available from Lanxess AG.

[0102] Desmodur® 2802 Aqueous dispersion of polycarbodiimide, commercially available from Covestro AG.

[0103] Imprafix® 2794 Aqueous dispersion of blocked isocyanate crosslinker, commercially available from Covestro AG. BorchiOGel A LA Non-associative ASE thickener, commercially available from Borchers.

[0104] Preparation of polyurethane-urea dispersion PUD1-PUD17

[0105] Preparation of PUD1

[0106] 200g PTHF2000, 56.1g Desmophen® BD 1110, and 21.5g LB 25 were dehydrated at 110 °C, 100 mbar for one hour, then 3.6g TMP and 6.5g DMBA were added under stirring. Then 30.1g Desmodur® H and 39.8g Desmodur® I were added at 65 °C, and stirred at 110 °C until 2.67% NCO content was reached. Then 592g acetone was added and the mixture was stirred until the temperature decreased to 45 °C to obtain the reaction solution. 2.5g TEA was added to the reaction solution under high speed stirring for ten minutes, followed by addition of 2.9g EDA solution dissolved in 27.9g of water, while stirring at high speed for ten minutes. Then 632g of water was added to the mixture, while stirring at high speed for ten minutes, and a dispersion was obtained. Acetone was distilled out and 10.4g of antioxidant Irgastab® IS 4276 was added to the mixture to obtain aqueous polyurethane dispersion with 35% solid content.

[0107] Preparation of PUD2

[0108] 200g PTHF2000, 56g PTHF1000 and 21.5g LB 25 were dehydrated at 110 °C, 100 mbar for one hour, then 4.1g TMP and 5.6g DMBA were added under stirring. Then 30.1g Desmodur® H and 39.8g Desmodur® I were added at 65 °C, and stirred at 110 °C until 2.67% NCO content was reached. Then 592g acetone was added and the mixture was stirred until the temperature decreased to 45 °C to obtain the reaction solution. 2.5g TEA was added to the reaction solution under high speed stirring for ten minutes, followed by addition of 2.9g EDA solution dissolved in 27.9g of water, while stirring at high speed for ten minutes. Then 632g of water was added to the mixture, while stirring at high speed for ten minutes, and a dispersion was obtained. Acetone was distilled out and 7.6g of antioxidant Irgastab® IS 4276 was added to the mixture to obtain aqueous polyurethane dispersion with 35% solid content. Preparation of PUD3

[0109] 210g PTHF2000, 56g Desmophen® 3600Z and 38.5g LB 25 were dehydrated at 110 °C, 100 mbar for one hour, then 4.7g TMP and 1 ,9g DMPA were added under stirring. Then 26.3g Desmodur® H and 34.8g Desmodur® I were added at 65 °C, and stirred at 110 °C until 2.4% NCO content was reached. Then 595g acetone was added and the mixture was stirred until the temperature decreased to 45 °C to obtain the reaction solution. 1.1g TEA was added to the reaction solution under high speed stirring for ten minutes, followed by addition of 2.5g EDA solution dissolved in 24.4g of water, while stirring at high speed for ten minutes. Then 665g of water was added to the mixture, while stirring at high speed for ten minutes, and a dispersion was obtained. Acetone was distilled out and 10.5g of antioxidant Irganox® 245 DWwas added to the mixture to obtain aqueous polyurethane dispersion with 35% solid content.

[0110] Preparation of PUD4

[0111] 288g PTHF2000 and 23g LB 25 were dehydrated at 110 °C, 100 mbar for one hour, then 3.8g TMP and 7.0g DMPA were added under stirring. Then 30.1g Desmodur® H and 39.8g Desmodur® I were added at 65 °C, and stirred at 110 °C until 2.47% NCO content was reached. Then 656g acetone was added and the mixture was stirred, until the temperature decreased to 45 °C to obtain the reaction solution. 3.7g TEA was added under high speed stirring for ten minutes, followed by addition of 3.1g EDA solution dissolved in 27.9g of water, while stirring at high speed for ten minutes. Then 720g of water was added to the mixture, while stirring at high speed for ten minutes, and a dispersion was obtained. Acetone was distilled out and 10.4g of antioxidant Irgastab® IS 4276 was added to the mixture to obtain aqueous polyurethane dispersion with 35% solid content.

[0112] Preparation of PUD5

[0113] 178.5g PTHF1000, 25.5g PEG1000, 42.5g Desmophen® 3600Z and 30.5g LB 25 were dehydrated at 110 °C, 100 mbar for one hour, then 3.8g TMP and 2.8g DMPA were added under stirring. Then 18.8g Desmodur® H and 67.9g Desmodur® I were added at 65 °C, and stirred at 110 °C until 2.76% NCO content was reached. Then 501.5g acetone was added and the mixture was stirred until the temperature decreased to 45 °C to obtain the reaction solution. 0.65g TEA was added under high speed stirring for ten minutes, followed by addition of 14.5g IPDA solution dissolved in 117.1g of water, while stirring at high speed for ten minutes. Then 765g of water was added to the mixture, while stirring at high speed for ten minutes, and a dispersion was obtained. Acetone was distilled out and 12g of antioxidant Irgastab® IS 3066 was added to the mixture to obtain aqueous polyurethane dispersion with 35% solid content.

[0114] Preparation of PUD6

[0115] 210g PTHF2000, 56g Desmophen® 3600Z and 7.2g LB 25 were dehydrated at 110 °C, 100 mbar for one hour, then 2.7g TMP and 7.8g DMBA were added under stirring. Then 26.3g Desmodur® H and 34.8g Desmodur® I were added at 65 °C, and stirred at 110 °C until 2.36% NCO content was reached. Then 595g acetone was added and the mixture was stirred until the temperature decreased to 45 °C to obtain the reaction solution. 1.1g TEA was added under high speed stirring for ten minutes, followed by addition of 2.5g EDA solution dissolved in 24.4g of water, while stirring at high speed for ten minutes. Then 630g of water was added to the mixture, while stirring at high speed for ten minutes, and a dispersion was obtained. Acetone was distilled out and 10.5g of antioxidant Irganox® 245 DWwas added to the mixture to obtain aqueous polyurethane dispersion with 35% solid content.

[0116] Preparation of PUD7

[0117] 152g PTHF2000, 152g Desmophen® 3600Z and 17.9g MPEG1500 were dehydrated at 110 °C, 100 mbar for one hour, then 3.0g TMP and 8.0g DMBA were added under stirring. Then 30.1g Desmodur® H and 39.8g Desmodur® I were added at 65 °C, and stirred at 110 °C until 2.39% NCO content was reached. Then 680g acetone was added and the mixture was stirred until the temperature decreased to 45 °C to obtain the reaction solution. 2.2g DMEA was added under high speed stirring for ten minutes, followed by addition of 2.9g EDA solution dissolved in 27.9g of water, while stirring at high speed for ten minutes. Then 720g of water was added to the mixture, while stirring at high speed for ten minutes, and a dispersion was obtained. Acetone was distilled out and 12g of antioxidant Irganox® 245 DWwas added to the mixture to obtain aqueous polyurethane dispersion with 35% solid content. Preparation of PUD8

[0118] 200g PTHF2000, 56g PTHF1000 and 21.5g LB 25 were dehydrated at 110 °C, 100 mbar for one hour, then 2.9g EG and 5.6g DMBA were added under stirring. Then 30.1g Desmodur® H and 39.8g Desmodur® I were added at 65 °C, and stirred at 110 °C until 2.68% NCO content was reached. Then 592g acetone was added and the mixture was stirred until the temperature decreased to 45 °C to obtain the reaction solution. 2.8g TEA was added under high speed stirring for ten minutes, followed by addition of 2.9g EDA solution dissolved in 27.9g of water, while stirring at high speed for ten minutes. Then 632g of water was added to the mixture, while stirring at high speed for ten minutes, and a dispersion was obtained. Acetone was distilled out and 7.6g of antioxidant Irganox® 245 DWwas added to the mixture to obtain aqueous polyurethane dispersion with 35% solid content.

[0119] Preparation of PUD9

[0120] 200g PTHF2000, 56g PTHF1000 and 35.9g LB 25 were dehydrated at 110 °C, 100 mbar for one hour, then 7.9g TMP and 2.7g DMPA were added under stirrring. Then 30.1g Desmodur® H and 39.8g Desmodur® I were added at 65 °C, and stirred at 110 °C until 2.68% NCO content was reached. Then 592g acetone was added, and the mixture was stirred until the temperature decreased to 45 °C to obtain the reaction solution. 1.8g TEA was added under high speed stirring for ten minutes, followed by addition of 2.2g EDA and 2.5g DEA solution dissolved in 20.9g of water, while stirring at high speed. Mixture gelled during stirring. No aqueous polyurethane dispersion was obtained.

[0121] Preparation of PUD10

[0122] 200g PTHF2000, 56.1g Desmophen® BD 1110 and 21.5g LB 25 were dehydrated at 110 °C, 100 mbar for one hour, then 3.6g TMP and 6.5g DMBA were added under stirring. Then 30.1g Desmodur® H and 39.8g Desmodur® I were added at 65 °C, and stirred at 110 °C until 2.67% NCO content was reached. Then 592g acetone was added, and the mixture was stirred until the temperature decreased to 45 °C to obtain the reaction solution. 2.9g EDA solution dissolved in 27.9g of water was added under stirring at high speed. Then 632g water was added, the mixture became paste-like. No aqueous polyurethane dispersion was obtained. Preparation of PUD11

[0123] 200g PTHF2000, 56g PTHF1000 and 18.0g LB 25 were dehydrated at 110 °C, 100 mbar for one hour, then 4.1g TMP was added under stirring. Then 30.1g Desmodur® H and 39.8g Desmodur® I were added at 65 °C, and stirred at 110 °C until 2.67% NCO content was reached. Then 592g acetone was added, and the mixture was stirred until the temperature decreased to 45 °C to obtain the reaction solution. 2.9g EDA and 11.5g AAS solution dissolved in 27.9g of water was added while stirring at high speed for ten minutes. Then 632g of water was added to the mixture, while stirring at high speed for ten minutes, and a dispersion was obtained. Acetone was distilled out and 7.6g of antioxidant Irgastab® IS 4276 was added to the mixture to obtain aqueous polyurethane dispersion with 35% solid content.

[0124] Preparation of PUD12

[0125] PLID12 was prepared according the same recipe as in Example 1 of CN113929860A. 220g PTHF2000, 150g Desmophen® 3600Z and 30g MPEG 1000 were dehydrated at 110 °C, 100 mbar for one hour, then 5g EG and 16g DM PA were added under stirring. Then 100g Desmodur® I was added at 65 °C, and stirred at 110 °C until 1.65% NCO content was reached. Then 660g acetone was added, and the mixture was stirred until the temperature decreased to 45 °C to obtain the reaction solution. 12.3g TEA was added under high speed stirring for ten minutes, followed by addition of 620g water, while stirring at high speed for ten minutes. 1.3g EDA and 1.4g DETA solution dissolved in 20g of water was added while stirring at high speed for 30 minutes. Acetone was distilled out to obtain aqueous polyurethane dispersion with 44% solid content.

[0126] Preparation of PUD13

[0127] 200g PTHF2000, 56g PTHF1000 and 18.2g Ymer-N90 were dehydrated at 110 °C, 100 mbar for one hour, then 3.6g TMP and 5.6g DMPA were added under stirring. Then 30.1g Desmodur® H and 39.8g Desmodur® I were added at 65 °C, and stirred at 110 °C until 2.7% NCO content was reached. 624g acetone was added, and the mixture was stirred until the temperature decreased to 45 °C to obtain the reaction solution. 2.8g TEA was added under high speed stirring for ten minutes, followed by addition of 2.9g EDA solution dissolved in 27.9g of water, while stirring at high speed for ten minutes. Then 632g of water was added to the mixture, while stirring at high speed for ten minutes, and a dispersion was obtained. Acetone was distilled out and 7.6g of antioxidant Irgastab® IS 4276 was added to the mixture to obtain aqueous polyurethane dispersion with 35% solid content.

[0128] Preparation of PUD14

[0129] 175g PTHF2000, 49.1g Desmophen® BD 1110 and 19.6g MPEG 1000 were dehydrated at 110 °C, 100 mbar for one hour, then 3.1g TMP and 5.2g DMPA were added under stirring. Then 26.3g Desmodur® H and 34.8g Desmodur® I were added at 65 °C, and stirred at 110 °C until 2.52% NCO content was reached. Then 518g acetone was added, and the mixture was stirred until the temperature decreased to 45 °C to obtain the reaction solution. 3.1g TEA was added under high speed stirring for ten mintues, followed by addition of 2.5g EDA solution dissolved in 24.4g of water, while stirring at high speed for ten minutes. Then 553g of water was added to the mixture, while stirring at high speed for ten minutes, and a dispersion was obtained. Acetone was distilled out and 7.7g of antioxidant Irganox® 245DW was added to the mixture to obtain aqueous polyurethane dispersion with 35% solid content.

[0130] Preparation of PUD15

[0131] 224g PTHF2000, 56g Desmophen® 3600Z and 62.8g LB 25 were dehydrated at 110 °C, 100 mbar for one hour, then 3.4g TMP and 1 ,3g DMBA were added under stirring. Then 26.3g Desmodur® H and 34.8g Desmodur® I were added at 65 °C, and stirred at 110 °C until 2.31% NCO content was reached. Then 595g acetone was added, and the mixture was stirred until the temperature decreased to 45 °C to obtain the reaction solution. 0.84g TEA was added under high speed stirring for ten minutes, followed by addition of 2.9g EDA solution dissolved in 24.4g of water, while stirring at high speed for ten minutes. Then 665g of water was added to the mixture, while stirring at high speed for ten minutes, and a dispersion was obtained. Acetone was distilled out and 8.4g of antioxidant Irganox® 245DW was added to the mixture to obtain aqueous polyurethane dispersion with 35% solid content.

[0132] Preparation of PUD16

[0133] 192.5g PTHF2000, 54g Desmophen® BD 1110 and 20.7g LB 25 were dehydrated at 110 °C, 100 mbar for one hour, then 3.5g BDO and 5.7g DMPA were added under stirring. Then 22.5g Desmodur® H, 38.3g Desmodur® I and 15.0g Desmodur® N 3300 were added at 65 °C, and stirred at 110 °C until 2.61% NCO content was reached. Then 626g acetone was added, and the mixture was stirred until the temperature decreased to 45 °C to obtain the reaction solution. 2.74g TEA was added under high speed stirring for ten minutes, followed by addition of 2.8g EDA solution dissolved in 26.8g of water while stirring at high speed for ten minutes. Then 5g of antioxidant Irganox® 1076 and 628g of water was added to the mixture, while stirring at high speed for ten minutes, and a dispersion was obtained. Acetone was distilled out to obtain aqueous polyurethane dispersion with 35% solid content.

[0134] Testing methods

[0135] Determination of number average molecular weight Mn

[0136] The number average molecular weight Mn, weight average molecular weight Mwand molecular weight distribution was determined with Size exclusion chromatography (SEC), using four columns (TSKgel G4000+3000+2500+2000HXL) at 40°C on a Agilent 1260 system with a DRI detector. Tetrahydrofuran (THF) was used as eluent with a flow of 0.7 mL / min. The samples were dissolved in the eluent using a concentration of 8 mg polymer per mL solvent. The solubility was assessed with a laser pen after 24 hours stabilization at room temperature; if any scattering was visible the samples were filtered first and 20 pl sample solution was injected. The MMD (molecular mass distribution) results were calculated with 12 narrow polyethyleneglycol standards from 232 to 44.000 Da.

[0137] Acid / alkaline resistance test

[0138] Test sample preparation

[0139] • Examples 1 to 6, comparative examples 1-3 and comparative examples 6-10 : To 100g of aforementioned synthesized PLID1-5, PLID16, PLID6-8 and PUD11-15, respectively 3g of Desmodur® 2802 and 5g of Imprafix® 2794 were added, and mixed homogenously. Example 7 was Example 2 further added with 5g of Coagulant WS and mixed homogeneously. Then 0.5-1 g Borchi®Gel A LA was added to each composition to achieve viscosity around 5500mPas tested by Brookfield DV2TLVTJ0 viscometer with spindle S64 at 40rpm rotation speed and room temperature. • The composition was scraped on a flat and smooth surface with a film scraper to prepare a wet film with thickness of 500pm, and a dry film sample was obtained by drying the wet film at 50°C for 30 minutes and at 150°C for 3 minutes in sequence;

[0140] • A half of the dry film was taken and a piece of 5cm*2cm was cut therefrom. The thickness and the weight of said piece of the dry film were measured, wherein the thickness of the film sample was recorded as To.

[0141] Acid / alkaline resistance test

[0142] Test was done with a laboratory sample dyeing machine (Model DYE-24, Shanghai Qianli automation equipment Co., Ltd.) according to following procedure:

[0143] 1 . Dry film sample obtained as aforementioned was put into a test dyeing cup. A NaOH solution with a concentration of 1.5% was added in an amount 15 times as large as the weight of the dry film.

[0144] 2. The test dyeing cup was heated from room temperature to 98-100°C and kept at this temperature for 50-60min.

[0145] 3. The film was taken out and cleaned with warm water for 1 hour (if the film was damaged, the subsequent steps were not needed).

[0146] 4. The film was dried by absorbing water with paper.

[0147] 5. The film was put into the test dyeing cup again, and an acetic acid solution with a pH of 4 was added in an amount 15 times as large as the weight of the film.

[0148] 6. The test dyeing cup was heated from room temperature to 90°C quickly, then heated from 90°C to 130°C at a heating speed of 1°C / min, kept at 130°C for 60 minutes, then cooled from 130°C to 70°C.

[0149] 7. The film was taken out and cleaned with warm water, and the length, width and thickness of the film was measured, wherein the length of the treated film sample was recorded as Li , the width of the treated film sample was recorded as Wi, the thickness of the treated film sample was recorded as Ti, and the swelling ratio R was calculated according to the following calculation formula: R = (Li*Wi*Ti / (5*2*To))*1OO%-1 (if the film became sticky, degraded or R was larger than 50%, it failed the test and the subsequent steps were not needed).

[0150] 8. The dry film was put into a test dyeing cup again. A NaOH solution with a concentration of 0.5% (stripping agent 6-9g / L) was added in an amount 15 times as large as the weight of the dry film. 9. The test dyeing cup was heated from room temperature to 130°C and kept at this temperature for 30min.

[0151] 10. Steps 3-7 were repeated while the length of the treated film sample was recorded as L2, the width of the treated film sample was recorded as W2, the thickness of the treated film sample was recorded as T2, and the swelling ratio R was calculated according to the following calculation formula: R = (l_2*W2*T2 / (5*2*To))*1OO%-1 (if the film became sticky, degraded or R was larger than 50%, it failed the test and the subsequent steps were not needed).

[0152] 11 . Steps 8-10 were repeated while the length of the treated film sample was recorded as L3, the width of the treated film sample was recorded as W3, the thickness of the treated film sample was recorded as T3, and the swelling ratio R was calculated according to the following calculation formula: R = (L3*W3*T3 / (5*2*To))*1OO%-1 (if the film became sticky, degraded or R was larger than 50%, it failed the test).

[0153] Heat coagulation test

[0154] • 5 g of the PUD composition was put in a 20 mL glass bottle.

[0155] • The glass bottle was heated at 70°C.

[0156] • Sample was checked after 5 min heating, a wood stick was used to stir gently. If the sample showed no flowability, it was recorded as coagulated and further testing was stopped. Otherwise, sample was further heated at 70°C, and rechecked after 10 min. If the sample showed no flowability, it was recorded as coagulated and further testing stopped. Otherwise, the sample was further heated at 100°C, and rechecked after 10 min. If the sample showed no flowability, it was recorded as coagulated and further testing was stopped. Otherwise, the sample was further heated at 100°C, and rechecked after 10 min. Table 1

[0157] 2: Amount of pTHF based on the total amount of polyether polyols with a number average molecular weight of from 500 to 4000 g / mol and a hydroxy functionality from 1.9 to 2.1 Table 2

[0158]

[0159] 1: Amount based on the weight of the polyurethane-urea

[0160] 2: Amount of pTHF based on the total amount of polyether polyols with a number average molecular weight of from 500 to 4000 g / mol and a hydroxy functionality from 1.9 to 2.1.

Claims

CLAIMS1. An aqueous polyurethane-urea dispersion comprising water and a polyurethaneurea, wherein the polyurethane-urea is obtained by at least partly deprotonating the reaction product of at least components (A)-(F):(A) from 60.0 to 80.0% by weight of one or more polyether polyols with a number average molecular weight of from 500 to 4000 g / mol and a hydroxy functionality from 1.9 to 2.1, wherein said polyether polyols comprise at least 65.0% by weight, based on the total weight of the polyether polyols (A), of one or more polytetrahydrofuran polyol,(B) from 5.0 to 12.0% by weight of one or more polyethers with a hydroxy functionality from 0.9 to 1.1 and a number average molecular weight of from 1500 to 2500 g / mol,(C) from 0.5 to 2.0% by weight of one or more isocyanate-reactive compounds containing at least one carboxylic acid group that can be converted into a salt group which is capable to render the polyurethane-urea dispersible in water,(D) from 0.4 to 2.0% by weight of one or more branching agents having a hydroxy functionality of 3.0 (D1) and / or from 1.0 to 5.0% by weight of one or more branching agents having an isocyanate functionality from 3.0 to 4.0 (D2),(E) from 10.0 to 30.0% by weight of one or more diisocyanates,(F) from 0.1 to 5.0% by weight of one or more amine functional chain extenders and / or one or more amine functional chain terminators, wherein the number average molecular weight of component (A) and component(B) is determined with the method described in the description, wherein the amounts of (A) to (F) are given based on the weight of the polyurethane-urea, and wherein said deprotonating is effected by reacting said reaction product with one or more amines and / or ammonia.

2. The dispersion according to claim 1 , wherein the one or more polyether polyols (A) comprise at least 70.0% by weight, based on the total weight of the polyether polyols (A), of one or more polytetrahydrofuran polyol, more preferably the one or more polyether polyols (A) comprise at least 75.0% by weight, based on the total weight of the polyether polyol (A), of one or more polytetrahydrofuran polyol.

3. The dispersion according to any one of the preceding claims, wherein component(A) comprises, consists essentially of, or consists of the combination of (i) one or more polytetrahydrofuran polyol and (ii) one or more polypropylene glycol polyol and / or one or more polytrimethylene ether glycol.

4. The dispersion according to any one of the preceding claims, wherein component(B) is selected from the group consisting of ethylene oxide polymers, copolymers of ethylene oxide and propylene oxide and any mixtures of two or more thereof.

5. The dispersion according to any one of the preceding claims, wherein component (B) is one or more copolymers of ethylene oxide and propylene oxide, wherein the molar ratio of ethylene oxide to propylene oxide is preferably in the range of from 75:25 to 90:10, more preferably in the range from 80:20 to 85:15.

6. The dispersion according to any one of the preceding claims, wherein the one or more branching agents (D1) have a molar mass lower than 500 g / mol, more preferably lower than 400 g / mol, more preferably lower than 200 g / mol, even more preferably lower than 150 g / mol, preferably the one or more branching agents (D1) are glycerol and / or trimethylolpropane, most preferred component (D1) is trimethylolpropane.

7. The dispersion according to any one of the preceding claims, wherein the one or more diisocyanates (E) are selected from the group consisting of diisocyanates having the general formula Y(NCO)2 or any mixture of two or more thereof, where Y is a C4-C12 divalent non-cyclic aliphatic hydrocarbon group or Y is a C6-C15 divalent aliphatic hydrocarbon group comprising at least one cycloaliphatic group.

8. The dispersion according to any one of the preceding claims, wherein the one or more diisocyanates (E) are selected from the group consisting of 1 ,5- pentamethylenediisocyanate (PDI), 1 ,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (I PDI), cyclohexane-1 ,4-diisocyanate, 1 ,3- and 1 ,4- bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate (H12MDI) and any mixture of two or more thereof, preferably the one or more diisocyanates (E) are selected from the group consisting of 1 ,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (I PDI) and any mixture thereof.

9. The dispersion according to any one of the preceding claims, wherein the one or more amines and / or ammonia are used in such an amount that the polyurethane-urea has a neutralizing degree of from 30 to 100%, wherein the neutralizing degree is calculated according to the following formula:((motor amount amine + molar amount ammonia) molar amount carboxylic acid in (C)) x 100%.

10. The dispersion according to any one of the preceding claims, wherein the polyurethane-urea is the reaction product of at least components (A)-(G):(A) from 60.0 to 80.0% by weight of one or more polyether polyols with a number average molecular weight of from 500 to 4000 g / mol and a hydroxy functionality from 1.9 to 2.1, wherein said polyether polyols comprise at least 65.0% by weight, based on the total weight of the polyether polyols (A), of one or more polytetrahydrofuran polyol,(B) from 5.0 to 12.0% by weight of one or more polyethers with a hydroxy functionality from 0.9 to 1.1 and a number average molecular weight of from 1500 to 2500 g / mol,(C) from 0.5 to 2.0% by weight of one or more isocyanate-reactive compounds containing at least one carboxylic acid group that can be converted into a salt group which is capable to render the polyurethane-urea dispersible in water,(D) from 0.4 to 2.0% by weight of one or more branching agents having a hydroxy functionality of 3.0 (D1) and / or from 1.0 to 5.0% by weight of one or more branching agents having an isocyanate functionality from 3.0 to 4.0 (D2),(E) from 10.0 to 30.0% by weight of one or more diisocyanates,(F) from 0.1 to 5.0% by weight of one or more amine functional chain extenders and / or one or more amine functional chain terminators,(G) one or more tertiary amines and / or ammonia, wherein the amounts of (A) to (F) are given based on the weight of the polyurethane-urea, the one or more tertiary amines and / or ammonia are used in such an amount that the polyurethane-urea has a neutralizing degree of from 30 to 100%, and the one or more tertiary amines are selected from the group consisting of triethylamine, N,N-diisopropylethylamine, tributylamine, N,N-dialkylalkanolamines N-alkyl-N,N-dialkanolamines, and trialkanolamines and any mixture of two or more thereof.

11. The dispersion according to any one of the preceding claims, wherein the dispersion further comprises one or more antioxidants in an amount of from 1.0 to 3.5% by weight, based on the amount of polyurethane-urea present in the dispersion.

12. The dispersion according to claim 11 , wherein the one or more antioxidants are selected from the group consisting of hindered phenols, benzofuranones, hydroxyamines, phosphites, sulfur compounds, preferably the one or more antioxidants are hindered phenols, preferably selected from the group consisting of ethylene bis(oxyethylene) bis(3-tert-butyl-4-hydroxy-5-(methylhydrocinnamate), tetrakis[methylene(3,5-di-tert-butl-4-hydroxy hydrocinnamate)]methane, octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, N,N’-hexamethylene-bis(3,5-di-tert-butyl- 4-hydroxyhydrocinnamamide), 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid C7-C9 branched alkyl esters, reaction product of N-phenylbenzene amine with 2,4,4- trimethylpentene, and any mixture of two or more thereof.

13. The dispersion according to any one of the preceding claims, wherein the amount of polyurethane-urea in the dispersion is at least 70% by weight, based on the solid content of the dispersion.

14. The dispersion according to any one of the preceding claims, wherein the dispersion further comprises a thermosensitive agent in an amount from 2.0 to 5.0% by weight, based on the amount of polyurethane-urea dispersion.

15. The dispersion according to claim 14, wherein the thermosensitive agent is an organopolysiloxane polyether with a number average molecular weight of at least 10000 g / mol, wherein the thermosensitive agent preferably comprises the following structural unit:wherein PO is propylene oxide, EO is ethylene oxide and nBu is n-butyl, and wherein n is from 3 to 20, the ratio of x to y is from 70:30 to 30:70 and the number average molecular weight of (PO)x(EO)y-nBu is from 1000 to 3000.

16. An article comprising a substrate coated or impregnated with a dispersion according to any one of the preceding claims.

17. The article according to claim 16, characterized in that the substrate is a superfine fiber, preferably the substrate is a superfine fiber nonwoven fabric, most preferably the substrate is a sea-island type bicomponent superfine fiber product using polyethylene terephthalate (PET) as an island component and alkali-soluble polyethylene terephthalate (COPET) as a sea component.

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