An aqueous polyurethane-urea dispersion having enhanced hydrogen bonding and ionic interactions, and methods of making and using the same

Abstract

This invention discloses an aqueous polyurethane-urea dispersion with enhanced hydrogen bonding and ionic interactions, generated through the reaction of components A1) an isocyanate reactive component, A2) an aminocarboxylic acid / sulfonic acid compound containing a tertiary amino group, B) a small molecule polyol / amine, C) a macromolecule polyol, and D) a polyisocyanate. The chain structure of this aqueous polyurethane-urea contains more hydrogen bond donors (imino groups) and acceptors (carbonyl groups), and these hydrogen bond donors / acceptors are close together in the molecular chain, enabling the formation of multiple and adjacent hydrogen bonds, resulting in enhanced intra- and inter-chain hydrogen bonding interactions. Simultaneously, the side chain structure of the polyurethane-urea contains tertiary amino and carboxylic acid / sulfonic acid groups, which can form ion pairs in an aqueous system, further enhancing ionic interactions. Applications of this aqueous polyurethane-urea dispersion in textile and synthetic leather coatings demonstrate excellent properties such as scratch resistance, ethanol rubbing resistance, and water washing resistance.

Description

Technical Field

[0001] This invention relates to an aqueous polyurethane-urea dispersion, which can be applied to substrates such as leather, fabric and paper, and is used in fields such as leather finishing, paper printing, printing and dyeing inks, printing coatings, packaging coatings, and matte nail polish. Background Technology

[0002] Polyurethane is a class of polymeric compounds with repeating urethane bonds (-NH-COO-) in the main chain. It is mainly produced by stepwise polymerization of polyisocyanates and polyols. Sometimes other compounds with two or more active hydrogens are added. For example, in the synthesis of waterborne polyurethane, it is usually obtained by reacting polyisocyanates, polyols and a small amount of polyamines to form water-dispersible polyurethane-urea polymers, collectively referred to as polyurethane.

[0003] Polyurethanes can be viewed as block copolymers formed by alternating flexible soft segments and rigid hard segments. The strength of the intermolecular forces in polyurethane molecules is characterized by cohesive energy or cohesive energy density. The cohesive energy of common functional groups in waterborne polyurethanes is approximately: urea group > urethane group > ester group > ether group > methylene group. This is because the imino, hydroxyl, and amino groups on urea and urethane groups are proton donors required for hydrogen bonding, while the urea carbonyl group on urea groups, the urethane carbonyl group on urethane groups, the ester carbonyl group on soft-segment polyester polyols, and the ether oxygen group on polyether polyols are proton acceptors required for hydrogen bonding. This allows different degrees of hydrogen bonding to form between hard segments and between hard and soft segments within or between molecular chains.

[0004] However, the number or density of hydrogen bonds that can be formed by hydrogen bond donors / acceptors in the chain structure of polyurethane in the prior art is limited. More importantly, the distance between two adjacent hydrogen bonds is relatively large, the degree of ordering that can be achieved is low, and the role of physical cross-linking points is relatively weak. Summary of the Invention

[0005] One objective of this invention is to provide an aqueous polyurethane-urea dispersion with a chain structure containing more hydrogen bond donors (imino groups) and acceptors (carbonyl groups). These hydrogen bond donors / acceptors are located close together within the molecular chain, enabling the formation of multiple and adjacent hydrogen bonds, resulting in enhanced intra- and inter-chain hydrogen bond interactions. Furthermore, the side chain structure of the polyurethane-urea contains tertiary amino groups and carboxylic acid / sulfonic acid groups, which can form ion pairs in an aqueous system, further enhancing ionic interactions.

[0006] The aqueous polyurethane-urea dispersion provided by this invention has polyurethane-urea molecular chains with reinforced and adjacent intermolecular / intramolecular hydrogen bond interactions. Two examples of hydrogen bond interactions formed after the reaction by the isocyanate reactive component represented by Formula I are as follows:

[0007]

[0008] Another objective of this invention is to provide application examples of waterborne polyurethane-urea dispersions in textile synthetic leather, exhibiting excellent properties such as scratch resistance, ethanol rub resistance, and water wash resistance. It can be applied to substrates such as leather, fabric, and paper, and is used in leather finishing, paper printing, printing inks, printing coatings, packaging coatings, and matte nail polish. Coatings made from it have improved mechanical properties, scratch resistance, ethanol rub resistance, and water wash resistance.

[0009] To achieve the above objectives, the present invention adopts the following specific technical solution:

[0010] In one aspect, an aqueous polyurethane-urea dispersion is provided, prepared by reacting components comprising the following amounts:

[0011]

[0012] Based on the total mass of the above-mentioned reaction components being 100%.

[0013] In some examples, the isocyanate-reactive component A1 has a reactive group that can react with isocyanates, preferably from a hydroxyl or amino group, and has the following general structural formula:

[0014]

[0015] Wherein, X1 is selected from hydroxyalkyl or aminoalkyl groups having 1-6 carbon atoms. A simplified structural formula of a hydroxyalkyl or aminoalkyl group can be illustrated as -(CH2). m OH or -(CH2) m NH2, where m is a natural number from 1 to 6; X2 is selected from methylene, imino, or oxygen; X3 is selected from imino or carbonyl; X4 is selected from hydrogen, aminoalkyl or hydroxyalkyl or aminoketone or hydroxyketone / ester group with 1 to 6 carbon atoms. An example structural formula of aminoketone or hydroxyketone / ester group is -CO(CH2). y NH2 or -CO(O)(CH2) y OH, y takes the value of a natural number from 1 to 5.

[0016] The component A1) isocyanate reactive component has an amide (-CONH-) or urethane (-NHCOO-) structure after reacting with the isocyanate group. Preferably, the number of imino and carbonyl (ester) groups in the molecular structure is not less than 2, especially having two adjacent imino or carbonyl (ester) groups, for example, the following three residue structures:

[0017]

[0018] Component A2) is an aminocarboxylic acid / sulfonic acid compound containing a tertiary amino group, having at least one amino group that can react with an isocyanate group, and having the following general structural formula II:

[0019]

[0020] Wherein, R1 and R2 may be the same or different, and are selected from hydrogen, alkyl, alkylamino or piperazine-containing residues with 1-5 carbon atoms; X5 is selected from carboxyl or sulfonic acid group; X6 is selected from hydrogen or amino; n is 0-5;

[0021] For example, component A2) can be, for example, N-(2-aminoethyl)-N-methylglycine, N-(2-aminoethyl)-N-methyl-β-alanine, N,N'-bis(2-aminoethyl)glycine, 4-[(2-aminoethyl)propylamino]-1-butyric acid, 3-[bis(2-aminoethyl)amino]-1-propanesulfonic acid, 3-[(6-aminohexyl)methylamino]-1-propanesulfonic acid, 2-{ethyl[3-(ethylamino)propyl]amino}-ethanesulfonic acid, 2-amino-4-(dimethylamino)butyric acid, 3-{methyl[2-(piperazin-1-yl)ethyl]amino}propionic acid, etc.

[0022] Component B) has a functionality of not less than 2 and a molecular weight of 60-300 g / mol; wherein:

[0023] The small molecule polyol is selected from one or more of ethylene glycol, diethylene glycol, 1,2-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, neopentyl glycol, trimethylolpropane, and pentaerythritol.

[0024] The small molecule polyol may also be a dihydroxycarboxylic acid with a potentially ionic water-dispersible group, selected from dimethylolpropionic acid or dimethylolbutyric acid; optionally, the carboxylic acid is provided with anionic water-dispersible groups by neutralizing it with a base, wherein the base used for neutralization is preferably a tertiary amine or an inorganic base, such as triethylamine, N,N'-dimethylethanolamine or triethanolamine, and such inorganic base is preferably lithium hydroxide, sodium hydroxide, potassium hydroxide or sodium bicarbonate, preferably triethylamine or N,N'-dimethylethanolamine;

[0025] The small molecule polyamine can be selected from one or more of aromatic, aliphatic, and alicyclic polyamines, such as 4,4'-diaminodiphenylmethane, ethylenediamine, N-hydroxyethyl ethylenediamine, isophorone diamine, 1,6-hexanediamine, 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, or hydrazine.

[0026] The small molecule polyamine may also include a carboxylic acid (sodium) or sulfonic acid (sodium) having a potentially ionic or ionic water-dispersible group, preferably at least one of sodium 2-[(2-aminoethyl)amino]acetate, sodium 2-[(2-aminoethyl)amino]propionate, sodium 2-[(2-aminoethyl)amino]ethanesulfonate or sodium 2-[(2-aminoethyl)amino]propanesulfonate.

[0027] The number average molecular weight of the macromolecular polyol in component C) is preferably 500-8000 g / mol, more preferably 1000-3000 g / mol;

[0028] The macromolecular polyol of component C) is one or more selected from polycarbonate polyols, polyester polyols, polyether polyols, polysulfide polyols, polyacetal polyols, polyvinyl polyols, or polysiloxane polyols. Preferred macromolecular polyols are polyether polyols, such as homopolymers, random copolymers, and block copolymers of polyethylene glycol, polypropylene glycol, polyglycerol, and polytetramethylene ether glycol; more preferably, those from Wanhua Chemical. F3056D, 2020D and / or BASF's pTHF2000.

[0029] The component D) polyisocyanate is selected from one or more of aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates, preferably from one or more of 1,4-phenyl diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and 1,4-cyclohexyl diisocyanate; more preferably from one or two of hexamethylene diisocyanate and / or isophorone diisocyanate.

[0030] In another aspect, the present invention provides a method for preparing the aforementioned waterborne polyurethane-urea dispersion, comprising the following steps:

[0031] 1) React component C) macromolecular polyol and D) polyisocyanate to generate prepolymer O;

[0032] 2) The prepolymer O is further reacted with the small molecule polyol of component B) to generate polyurethane-urea P;

[0033] 3) Under high-speed shear conditions, dispersing water is added to form a polyurethane-urea dispersion, and then aqueous polyurethane-urea dispersion is obtained after solvent removal;

[0034] The addition of component A1) isocyanate reactive component can be carried out in any of steps 1), 2), or 3), and the addition of component A2) aminocarboxylic acid / sulfonic acid compound containing tertiary amino group and small molecule polyamine can be carried out in step 2) or 3).

[0035] In some examples of the preparation method of the above-mentioned waterborne polyurethane-urea dispersion provided by the present invention, the reaction in step 1) is carried out at a temperature of 65-80°C, preferably 70-75°C, and for a reaction time of 1-3 hours, preferably 1-2 hours.

[0036] In some preferred examples, the reaction in step 1) is preferably carried out in the presence of an organic solvent selected from one or more of acetone, 2-butanone, N-methylpyrrolidone, and N-ethylpyrrolidone, preferably at least one of acetone or butanone.

[0037] In some preferred embodiments, the reaction in step 1) further includes the addition of a catalyst selected from one or more tertiary amine catalysts, organotin catalysts, and organobismuth catalysts, preferably from one or more of triethylamine, 1,4-diazabicyclo-[2,2,2]-octane, dibutyltin oxide, dibutyltin dilaurate, bismuth neodecanoate, and bismuth 2-ethylhexanoate, more preferably from bismuth neodecanoate and / or bismuth 2-ethylhexanoate. The amount of catalyst used is 100-1000 ppm, based on 100% of the total weight of components B)-D).

[0038] In some preferred examples, step 1) of the preparation method specifically involves heating component C) to 45-55°C and stirring until homogeneous, then adding component D) and mixing, then adding the catalyst, and heating to 65-80°C for 1-3 hours.

[0039] In some examples, the reaction described in step 2) involves the small molecule polyol reacting with the prepolymer at a temperature of 70-80°C for 2-3 hours.

[0040] Step 2) or 3) The reaction temperature of the small molecule polyamine, the aminocarboxylic acid / sulfonic acid compound containing tertiary amino group and the prepolymer is 25-40℃, and the reaction time is 15-30 minutes.

[0041] In some preferred embodiments, the reaction described in step 2) is preferably carried out in an environment containing an organic solvent selected from one or more of acetone, 2-butanone, N-methylpyrrolidone, and N-ethylpyrrolidone, preferably from acetone and / or N-ethylpyrrolidone. The organic solvents described in steps 1) and 2) may be the same or different.

[0042] In some preferred examples, after adding dispersing water under high-speed shear conditions in step 3) to form a dispersion, the organic solvent is removed by vacuum distillation to obtain an aqueous polyurethane-urea dispersion.

[0043] According to the preparation method of the above-mentioned aqueous polyurethane-urea dispersion provided by the present invention, the solid content (polyurethane resin content) is 35.0-50.0% and the particle size is 50-300nm.

[0044] In another aspect, the waterborne polyurethane-urea dispersion provided by the present invention can be applied to substrates such as leather, fabric and paper, and can be used in fields such as leather finishing, paper printing, printing and dyeing inks, printing coatings, packaging coatings, and matte nail polish.

[0045] One application example is in the synthetic leather layer of textiles. During application, a post-crosslinking agent, wetting agent, thickener, and defoamer need to be added. This mixture is prepared from components comprising the following parts by weight:

[0046] Waterborne polyurethane-urea dispersion, 40.00-50.00 parts;

[0047] The crosslinking agent is 0.50-1.50 parts, preferably 0.50-1.00 parts;

[0048] Thickener: 0.50-2.00 parts, preferably 0.50-1.00 parts;

[0049] The wetting agent is 0.50-2.00 parts, preferably 1.00-2.00 parts;

[0050] The defoamer is used in an amount of 0.10-0.30 parts, preferably 0.10-0.20 parts.

[0051] The beneficial effects of this invention are as follows:

[0052] This waterborne polyurethane-urea chain structure has more hydrogen bond donors (imino) and acceptors (carbonyl), and these hydrogen bond donors / acceptors are close together in the molecular chain, enabling the formation of multiple and adjacent hydrogen bonds, resulting in enhanced intra- and inter-chain hydrogen bond interactions. Simultaneously, the side chain structure of the polyurethane-urea contains tertiary amino and carboxylic acid / sulfonic acid groups, which can form ion pairs in aqueous systems, exhibiting enhanced ionic interactions. When applied as a surface treatment agent for leather products, it demonstrates excellent scratch resistance and ethanol rubbing resistance; when applied as a printing coating for textiles, it exhibits excellent scratch resistance and wash resistance. Detailed Implementation

[0053] To further illustrate the present invention, preferred embodiments are described below in conjunction with specific examples. However, it should be noted and understood that these specific examples are only for further illustrating the features and methods of the present invention, and are not intended to limit the present invention.

[0054] I. All percentages in this invention are by weight, unless otherwise stated. The raw materials used in the examples are as follows:

[0055] HDI (hexamethylene diisocyanate, Wanhua Chemical Group Co., Ltd.);

[0056] IPDI (Isophorone diisocyanate, Wanhua Chemical Group Co., Ltd.);

[0057] pTHF2000 (polybutadiene glycol, hydroxyl value 56.00 mgKOH / g, number average molecular weight 2000, functionality 2, BASF, Germany);

[0058] DL-2000D (polypropylene glycol, hydroxyl value 56.00mgKOH / g, number average molecular weight 2000, functionality 2, Shandong Lanxing Dongda Co., Ltd.);

[0059] BDO (1,4-Butanediol, Wanhua Chemical Group Co., Ltd.);

[0060] DMPA (dimethylolpropionic acid, Persto, Sweden);

[0061] TEA (triethylamine, Xilong Scientific Co., Ltd.);

[0062] EDA (ethylenediamine, BASF, Germany);

[0063] BHEOA (N,N'-bis(2-hydroxyethyl)oxalamide, Beijing Bailingwei Technology Co., Ltd.);

[0064] BAEOA (N,N'-bis(2-aminoethyl)oxalamide, ABC Labtory);

[0065] HEC (2-hydroxyethylhydrazine carbamate, Sigma-Aldrich);

[0066] ADABA (2-amino-4-(dimethylamino)butyric acid, Aikon Biopharmaceutical Co., Ltd.);

[0067] MPEAPA (3-{methyl[2-(piperazin-1-yl)ethyl]amino}propionic acid, Haohong Biopharmaceutical Co., Ltd.);

[0068] CX-100 (aziridine crosslinking agent, DSM);

[0069] A801 (Thickener, Wanhua Chemical Group Co., Ltd.);

[0070] SL-3248 (wetting agent, Chongyao Technology Development Co., Ltd.);

[0071] BYK-024 (Defoamer, BYK GmbH, Germany).

[0072] Preparation of waterborne polyurethane-urea dispersion

[0073] Example 1

[0074] Heat 200.00g of DL-2000D to 50℃ and stir until well mixed, then add 86.00g of... IPDI and 0.15 grams After reacting at 80°C for 2 hours, 9.00 g of DMPA, 9.00 g of BHEOA and 5.00 g of BDO were added, and finally 30.90 g of acetone was added. The temperature was raised to 80°C and the reaction continued for 3 hours.

[0075] The temperature was lowered to below 50°C, 216.40 g of acetone was added, and after thorough mixing, 6.78 g of TEA was added at below 40°C for 5 minutes to neutralize. Then, 583.43 g of deionized water was added under shear dispersion conditions of 1200-1500 rpm, followed by metered addition of 5.00 g of EDA and 0.95 g of ADABA. The reaction was continued at 30°C for 25 minutes. Finally, acetone was removed by vacuum distillation to obtain an aqueous polyurethane-urea dispersion.

[0076] Example 2

[0077] Heat 200.00g of DL-2000D to 50℃ and stir until well mixed, then add 86.00g of... IPDI and 0.15 grams After reacting at 80°C for 2 hours, 9.00 g of DMPA, 2.00 g of HEC and 8.00 g of BDO were added, and finally 30.90 g of acetone was added. The temperature was raised to 80°C and the reaction continued for 3 hours.

[0078] The temperature was lowered to below 50°C, 216.40 g of acetone was added, and after thorough mixing, 6.78 g of TEA was added at below 40°C for 5 minutes to neutralize. Then, 583.43 g of deionized water was added under shear dispersion conditions of 1200-1500 rpm, followed by metered addition of 5.00 g of EDA and 2.20 g of MPEAPA. The reaction was continued at 30°C for 25 minutes. Finally, acetone was removed by vacuum distillation to obtain an aqueous polyurethane-urea dispersion.

[0079] Example 3

[0080] Heat 220.00g of pTHF2000 to 50°C and stir until well mixed, then add 10.00g of... HDI, 60.00 grams IPDI, 9.00g BHEOA and 0.06g After reacting at 65°C for 1 hour, 9.00 g of DMPA and 30.70 g of acetone were added, and the temperature was raised to 75°C to continue the reaction for 2 hours.

[0081] The temperature was lowered to below 50°C, 276.40 g of acetone was added, and after thorough mixing, 6.03 g of TEA was added at below 40°C for 5 minutes to neutralize. Then, 579.54 g of deionized water was added under shear dispersion conditions of 1200-1500 rpm, followed by metered addition of 5.00 g of EDA and 1.20 g of ADABA. The reaction was continued at 25°C for 15 minutes. Finally, acetone was removed by vacuum distillation to obtain an aqueous polyurethane-urea dispersion.

[0082] Example 4

[0083] Heat 220.00 g of pTHF2000 to 50°C and stir until well mixed, then add 75.00 g of pTHF2000. IPDI and 0.03 grams After reacting at 70°C for 1 hour, 6.00 g of DMPA, 8.00 g of BDO and 30.90 g of acetone were added, and the temperature was raised to 75°C to continue the reaction for 3 hours.

[0084] The temperature was lowered to below 50°C, 216.32 g of acetone was added, and after thorough mixing, 4.52 g of TEA was added at below 40°C for 5 minutes to neutralize. Then, 585.00 g of deionized water was added under shear dispersion conditions of 1200-1500 rpm. Next, 3.00 g of EDA, 3.00 g of BAEOA, and 1.60 g of MPEAPA were metered in, and the reaction was continued at 35°C for 30 minutes. Finally, acetone was removed by vacuum distillation to obtain an aqueous polyurethane-urea dispersion.

[0085] Example 5

[0086] Heat 220.00 g of pTHF2000 to 50°C and stir until well mixed, then add 75.00 g of pTHF2000. IPDI and 0.03 grams After reacting at 70°C for 1 hour, 6.00 g DMPA, 2.00 g HEC, 6.00 g BDO and 30.60 g acetone were added, and the temperature was raised to 75°C to continue the reaction for 3 hours.

[0087] The temperature was lowered to below 50°C, 216.32 g of acetone was added, and after thorough mixing, 4.52 g of TEA was added at below 40°C for 5 minutes to neutralize. Then, 587.65 g of deionized water was added under shear dispersion conditions of 1200-1500 rpm, followed by metered addition of 4.40 g of EDA and 1.00 g of ADABA. The reaction was continued at 25°C for 25 minutes. Finally, acetone was removed by vacuum distillation to obtain an aqueous polyurethane-urea dispersion.

[0088] Comparative Example 1:

[0089] The difference from Example 1 is that BHEOA and ADABA are not added, the amount of BDO added is increased to 9.70 grams, and everything else remains the same.

[0090] Comparative Example 2:

[0091] The difference from Example 1 is that BHEOA is not added, the amount of BDO added is increased to 9.70 grams, 1.00 grams of ADABA is added after dispersion, and everything else remains the same.

[0092] Comparative Example 3:

[0093] The difference from Example 2 is that MPEAPA is not added, but everything else remains the same.

[0094] Comparative Example 4:

[0095] The difference from Example 3 is that after adding the dispersing water, 5.00 grams of EDA are added by metering, but ADABA is not added, and everything else remains the same.

[0096] Comparative Example 5:

[0097] The difference from Example 4 is that BAEOA is not added. After adding the dispersion water, 4.00 g of EDA and 1.60 g of MPEAPA are added by metering. Everything else remains the same.

[0098] Comparative Example 6:

[0099] The difference from Example 5 is that the amount of BDO added is increased to 7.50 grams, and the amount of EDA added is 4.40 grams; HEC and ADABA are not added, and everything else remains the same.

[0100] Table 1 Mechanical properties of waterborne polyurethane-urea

[0101]

[0102] Preparation of waterborne polyurethane-urea coating

[0103] The waterborne polyurethane-urea dispersion provided by this invention, in one application case of textile synthetic leather, requires the addition of a post-crosslinking agent, wetting agent, thickener, and defoamer. The amounts of each component are as follows:

[0104] Waterborne polyurethane-urea dispersion, 45.00 parts;

[0105] Crosslinking agent 1.0 part;

[0106] Thickener 0.7 parts;

[0107] 2.0 parts wetting agent;

[0108] 0.2 parts of defoamer;

[0109] Under stirring conditions, add post-crosslinking agent CX-100 and wetting agent SL-3248 to the waterborne polyurethane-urea dispersion. After 5 minutes, add thickener A801 ​​and adjust the pH value to 8.0-9.0. Finally, add defoamer BYK-024 and stir for half an hour before use.

[0110] Preparation of synthetic leather coating: The slurry was applied to PVC leather using a 20µm wire rod, baked at 80℃ for 5 minutes, removed from the oven and allowed to return to room temperature before subsequent testing.

[0111] Preparation of textile coating: Using a 120-mesh sieve, after printing 3 times and 9 cuts on a high-elastic fabric, the sample was placed at room temperature for 48 hours and then the water washing performance was directly tested.

[0112] Scratch resistance test method: scratch with fingernail, observe the degree of scratch on the coating surface and whether powder comes off, and record the number of finger scratches before the destructive scratch and powder come off.

[0113] Ethanol rubbing resistance test method: Take 95% industrial ethanol, test the color fastness to dry and wet rubbing a number of times, and observe whether there are any adverse phenomena such as peeling or brightening of the paper surface.

[0114] Water resistance test method: Place the test sample directly in the washing machine and wash it at 60℃ and 1200rpm for 1.5 hours / cycle, for a total of five washes. Observe the surface condition after each wash. If there is no damage after 5 washes, wash until damage occurs and record the number of washes before damage occurs.

[0115] The waterborne polyurethane-urea prepared above, which can be used for synthetic leather, forms a coating on PVC that exhibits excellent scratch resistance and ethanol rubbing resistance. Specific results are shown in Table 2.

[0116] Table 2 Performance of waterborne polyurethane-urea coatings

[0117]

[0118]

[0119] The waterborne polyurethane-urea prepared above, which can be used in textiles, forms a coating on the fabric after curing. This coating exhibits excellent scratch resistance and washability, as shown in Table 3.

[0120] Table 3 Performance of waterborne polyurethane-urea coatings

[0121] Implementation Cases Scratch resistance Water-resistant Example 3 >20 times >5 times, maximum 22 times Example 4 >20 times >5 times, maximum 17 times Example 5 >20 times >5 times, maximum 23 times Comparative Example 4 10-20 times >5 times, maximum 10 times Comparative Example 5 10-20 times <3 times Comparative Example 6 <10 times <3 times Commercially available competing products 10-20 times >5 times, maximum 13 times

[0122] This invention cannot list all the embodiments involved in the invention's description; only a few specific implementation examples are given. However, those skilled in the art will readily recognize that the foregoing embodiments are merely specific forms in which the invention can be implemented. The invention is not limited to the aforementioned specific details and can be implemented in other specific forms without departing from its main characteristics. Therefore, the specific embodiments should be considered exemplary rather than restrictive in any way. The scope of the invention has been indicated by the claims rather than the detailed description; any changes made based on this, as long as they fall within the meaning and scope of the equivalents of the claims, should be considered part of the invention.

Claims

1. A waterborne polyurethane-urea dispersion, characterized in that, It is prepared by reacting components including the following amounts: A1) Isocyanate reactive component, 0.5-3%; A2) Aminocarboxylic acid / sulfonic acid compounds containing tertiary amino groups, 0.2-0.8%; B) Small molecule polyols / amines, 4-8%; C) Macromolecular polyols, 63-72%; D) Polyisocyanates, 22-28%; Based on the total mass of the above-mentioned reactants being 100%; in: The component A1) has the following general structural formula: Wherein, X1 is selected from hydroxyalkyl or aminoalkyl groups having 1-6 carbon atoms; X2 is selected from methylene, imino or oxy; X3 is selected from imino or carbonyl; X4 is selected from hydrogen, aminoalkyl or hydroxyalkyl or aminoketone or hydroxyketone or hydroxy ester groups having 1-6 carbon atoms; The component A2) has the following general structural formula: Wherein, R1 and R2 may be the same or different, and are selected from hydrogen, alkyl, alkylamino or piperazine residues with 1-5 carbon atoms; X5 is selected from carboxyl or sulfonic acid group; X6 is selected from hydrogen or amino; n is 0-5.

2. The aqueous polyurethane-urea dispersion according to claim 1, characterized in that, Component A2) is selected from N-(2-aminoethyl)-N-methylglycine, N-(2-aminoethyl)-N-methyl-β-alanine, N,N'-bis(2-aminoethyl)glycine, 4-[(2-aminoethyl)propylamino]-1-butyric acid, 3-[bis(2-aminoethyl)amino]-1-propanesulfonic acid, 3-[(6-aminohexyl)methylamino]-1-propanesulfonic acid, 2-{ethyl[3-(ethylamino)propyl]amino}-ethanesulfonic acid, 2-amino-4-(dimethylamino)butyric acid, and 3-{methyl[2-(piperazin-1-yl)ethyl]amino}propionic acid.

3. The aqueous polyurethane-urea dispersion according to claim 1, characterized in that, The functionality of component B) is not less than 2, and the molecular weight is 60-300 g / mol.

4. The aqueous polyurethane-urea dispersion according to claim 1 or 3, characterized in that, The small molecule polyol is selected from one or more of ethylene glycol, diethylene glycol, 1,2-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, neopentyl glycol, trimethylolpropane, pentaerythritol, and dihydroxycarboxylic acids having a potentially ionic water-dispersible group. The small molecule polyamine is selected from one or more of aromatic, aliphatic, and alicyclic polyamines.

5. The aqueous polyurethane-urea dispersion according to claim 4, characterized in that, The small molecule polyamine may optionally include at least one of sodium 2-[(2-aminoethyl)amino]acetate, sodium 2-[(2-aminoethyl)amino]propionate, sodium 2-[(2-aminoethyl)amino]ethanesulfonate, or sodium 2-[(2-aminoethyl)amino]propanesulfonate.

6. The aqueous polyurethane-urea dispersion according to claim 4, characterized in that, The dihydroxycarboxylic acid having a potentially ionic water-dispersible group is selected from one or more of dimethylolpropionic acid and dimethylolbutyric acid. The small molecule polyamine is selected from one or more of 4,4'-diaminodiphenylmethane, ethylenediamine, N-hydroxyethylethylenediamine, isophorone diamine, 1,6-hexanediamine, 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, or hydrazine.

7. The aqueous polyurethane-urea dispersion according to claim 1, characterized in that, The number average molecular weight of the macromolecular polyol in component C) is 500-8000 g / mol.

8. The aqueous polyurethane-urea dispersion according to claim 1, characterized in that, The number average molecular weight of component C) macromolecular polyol is 1000-3000 g / mol.

9. The aqueous polyurethane-urea dispersion according to claim 1 or 7, characterized in that, Component C) is one or more of polycarbonate polyol, polyester polyol, polyether polyol, polysulfide polyol, polyacetal polyol, polyvinyl polyol or polysiloxane polyol.

10. The aqueous polyurethane-urea dispersion according to claim 9, characterized in that, Component C) is selected from homopolymers, random copolymers, and block copolymers of polyethylene glycol, polypropylene glycol, polyglycerol, and polytetramethylene ether glycol.

11. The aqueous polyurethane-urea dispersion according to claim 1, characterized in that, Component D) is selected from one or more of aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.

12. The aqueous polyurethane-urea dispersion according to claim 11, characterized in that, Component D) is selected from one or more of 1,4-phenyl diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and 1,4-cyclohexyl diisocyanate.

Images