Polyurethane-polyurea aqueous dispersion, method for preparing the same, and use thereof

Abstract

This invention discloses a polyurethane-polyurea aqueous dispersion, a method for preparing the same, and its use, wherein the aqueous dispersion contains polyurethane-polyurea of ​​a specific theoretical molecular weight, which contains terminal carboxyl groups, sulfonate groups, and carboxylate groups dispersed therein, with a carboxylate group content of 1.49 to 11.9 mmol / 100g, a sulfonate group content of 0.26 to 7.9 mmol / 100g, a terminal carboxyl group content of 0.5 to 3.7 mmol / 100g, and a molecular weight of 60,000 to 390,000. The specific theoretical molecular weight is a theoretically designed molecular weight, obtained by the terminal group calculation method. This polyurethane-polyurea aqueous dispersion avoids cracking and pinhole problems during glove production and improves production stability.

Description

Technical Field

[0001] The present invention belongs to the field of polyurethane-polyurea dispersions, and specifically relates to an aqueous polyurethane-polyurea dispersion, a preparation method therefor, and use thereof.

Background Art

[0002] Currently, there are relatively few studies on aqueous polyurethane-polyurea dispersions used for disposable polyurethane gloves, and industrially produced glove products are not available on the market. Research results show that the problem lies in that the stability of the dispersion affects the pass rate of gloves, and it has been clarified that the stability of the dispersion is an important factor affecting the production of gloves.

[0003] Most existing solutions focus on studies of the basic physical properties of polyurethane gloves, and do not address problems such as the pass rate, which is the main factor limiting industrialization of the gloves.

[0004] In this field, in order to improve the pass rate in mass production, it is an urgent need to solve the problem of pass rate and eliminate defects such as cracks and pinholes in gloves during glove production.

Summary of the Invention

[0005] One object of the present invention is to provide an aqueous polyurethane-polyurea dispersion. The present inventors have conducted studies on the types, contents, molecular weight design, etc. of ionic groups that affect aggregation, and by providing a dispersion with few defects that can be stably industrially produced, the present invention ensures that no cracks or pinholes occur in products during the production process, and greatly improves the pass rate.

Means for Solving the Problems

[0006] In order to achieve the above object of the invention, the present invention adopts the following technical solutions.

[0007] A polyurethane-polyurea aqueous dispersion, wherein the dispersion contains a polyurethane-polyurea of ​​a specific theoretical molecular weight containing terminal carboxyl groups, sulfonate groups, and carboxylate groups, wherein the carboxylate group content is 1.49 to 11.9 mmol / 100g, the sulfonate group content is 0.26 to 7.9 mmol / 100g, the terminal carboxyl group content is 0.5 to 3.7 mmol / 100g, and the molecular weight is 60,000 to 390,000, and the specific theoretical molecular weight is a theoretically designed molecular weight obtained by the terminal group calculation method.

[0008] In one embodiment of the present invention, the dispersion is prepared by reacting raw materials containing the following components. Component a: High molecular weight polyol Component b: Polyisocyanate A hydrophilic compound comprising: component c1, which contains 2-3 hydroxyl groups that are reactive with NCO and whose hydrophilic group is a carboxyl group; and component c2, which contains 2-3 amino groups that are reactive with NCO and whose hydrophilic group is a salt-forming group. Optional component d: Low molecular weight alcohol chain extender Component e: A compound that ionizes the latent group in component c. Component f: Polyamine with a number-average molecular weight of 500 g / mol or less Component g: A monofunctional compound containing a carboxyl group and an amino group that can react with isocyanate.

[0009] In one embodiment of the present invention, the proportions of each component of the dispersion are as follows: Component a: 65-90 parts, preferably 74-88 parts Component b: 8-25 parts, preferably 10-20 parts Component c: 1 to 6 parts, preferably 1.5 to 4.8 parts Component d: 0-4 parts, preferably 0-3 parts Component e: 0.1 to 5 parts, preferably 0.1 to 3 parts Component f: 0-6 parts, preferably 0-3 parts Ingredients: 0.05 to 1 part, preferably 0.085 to 0.6 parts The proportions of each component mentioned above are based on mass.

[0010] In this invention, a polyurethane segment containing a carboxyl group at its terminal is designed by reacting a monofunctional compound g containing a carboxyl group with an isocyanate. By introducing the monofunctional compound, the molecular weight of the product can be controlled within an appropriate range, thus avoiding production defects in glove products caused by an inappropriate molecular weight. Furthermore, since terminal carboxyl groups are more reactive than carboxyl groups in the chain, when this dispersion is applied to the manufacture of products such as gloves, the terminal carboxyl groups of the dispersion react more efficiently with the etherified amino resin of the glove matrix resin, significantly improving the degree of crosslinking. As a result, the mechanical properties of the gloves are not reduced by terminal encapsulation.

[0011] In the polyurethane-polyurea dispersion according to the present invention, by using a combination of hydrophilic groups, an appropriate amount of carboxylate ions provides sensitivity to electrolytes, while an appropriate amount of sulfonate ions has lower electrolyte sensitivity than carboxylate ions. This helps to maintain a balance in the electrolyte sensitivity of the emulsion, reducing sludge formation and leathering during glove manufacturing. Furthermore, by controlling the molecular weight of the polyurethane within an appropriate range, the wet film formed by the instantaneous demulsification of the emulsion does not experience volume shrinkage and cracking due to its large molecular weight and high cohesive energy, nor does it suffer from insufficient strength and slipperiness due to its small molecular weight. This avoids problems such as cracking and slipperiness.

[0012] In one embodiment of the present invention, component a is one or more diols, triols, and tetraols having a number average molecular weight of 500 to 6000 g / mol, preferably one or more polyester polyols, polyether polyols, polycarbonate polyols, and polycaprolactone polyols having 2 to 3 functional groups and a number average molecular weight of 500 to 5000 g / mol.

[0013] In one embodiment of the present invention, component b is one or more aromatic, aliphatic, and alicyclic polyisocyanates, preferably one or more aromatic, aliphatic, and alicyclic polyisocyanates having at least two isocyanate groups.

[0014] Component b preferably has the molecular formula Y(NCO)2, where Y represents a divalent aliphatic hydrocarbon group having 4 to 12 carbon atoms, a divalent alicyclic hydrocarbon group having 6 to 15 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms, or a divalent aromatic aliphatic hydrocarbon group having 7 to 15 carbon atoms. Suitable diisocyanates may include tetramethylene diisocyanate, methylpentamethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 4,4'-dicyclohexylpropane diisocyanate, 1,4-benzene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'- and 2,4'-diphenylmethane diisocyanate, tetramethylxylyl diisocyanate, p-xylylene diisocyanate, p-isopropylidene diisocyanate, and mixtures of these compounds.

[0015] Component b may contain a small amount of a more functional polyisocyanate known in polyurethane chemistry, or a modified polyisocyanate containing, for example, a carbodiimide group, an allophanate group, an isocyanurate group, a carbamate group, and / or a biuret group. Preferably, it is hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate, or toluene diisocyanate.

[0016] In one embodiment of the present invention, in component c, c1 is methylolpropionic acid and / or methylolbutyric acid, and c2 is sodium 2-[(2-aminoethyl)amino]ethanesulfonate and / or sodium ethylenediaminopropionate.

[0017] In one embodiment of the present invention, component d is one or more selected from ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-dihydroxycyclohexane, 1,4-dihydroxymethylcyclohexane, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and 2-ethyl-1,3-hexanediol, preferably one or more selected from 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, and 1,4-cyclohexanedimethanol.

[0018] In one embodiment of the present invention, component e is an organic base, preferably one or more of triethylamine, dimethylethanolamine, and aqueous ammonia, and more preferably triethylamine.

[0019] In one embodiment of the present invention, component f is a polyamine having a number average molecular weight of 60 to 500 g / mol, preferably one or more of ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-hexanediamine, 2-methyl-1,5-diamine, isophoronediamine, 4,4-diaminodicyclohexylmethane, piperazine, and diethylenetriamine, more preferably ethylenediamine and / or isophoronediamine.

[0020] In one embodiment of the present invention, the carboxyl group of said component g is capable of reacting with an etherified amino resin, and the compound is basic; preferably, component g is a basic amino acid such as histidine or phenylalanine, more preferably phenylalanine.

[0021] Another object of the present invention is to provide a preparation method for preparing a polyurethane-polyurea aqueous dispersion.

[0022] A preparation method for preparing a polyurethane-polyurea aqueous dispersion, wherein the preparation method comprises: step S1 of charging component a, component b, component c1, optional component d, and a solvent into a reaction vessel and allowing them to react until the NCO content approaches or reaches a theoretical value, to obtain a prepolymer having terminal isocyanate groups; step S2 of lowering the temperature and adding a solvent for dilution; step S3 of adding component f and component c2 to react, adding component e for neutralization, adding component g to react, adding water for dispersion to obtain a dispersion, and removing the solvent to obtain a solvent-free polyurethane-polyurea aqueous dispersion.

[0023] In one embodiment of the present invention, the components in the preparation method are as follows. Component a: high molecular weight polyol Component b: polyisocyanate Component c: a hydrophilic compound, comprising component c1 containing 2 to 3 hydroxyl groups reactive to NCO and having a carboxyl hydrophilic group, and component c2 containing 2 to 3 amino groups reactive to NCO and having a salt-forming hydrophilic group Optional component d: low molecular weight alcohol chain extender Component e: a compound that ionizes the latent groups of component c Component f: polyamine having a number average molecular weight of 500 g / mol or less Component g: a monofunctional compound containing a carboxyl group and an amino group capable of reacting with isocyanate

[0024] In one embodiment of the present invention, the proportions of each component in the preparation method are as follows: Component a: 65-90 parts, preferably 74-88 parts Component b: 8-25 parts, preferably 10-20 parts Component c: 1 to 6 parts, preferably 1.5 to 4.8 parts Component d: 0-4 parts, preferably 0-3 parts Component e: 0.1 to 5 parts, preferably 0.1 to 3 parts Component f: 0-6 parts, preferably 0-3 parts Ingredients: 0.05 to 1 part, preferably 0.085 to 0.6 parts

[0025] In one embodiment of the present invention, the reaction temperature in S1 is 60-80°C.

[0026] In one embodiment of the present invention, the solvent in S1 is acetone.

[0027] In one embodiment of the present invention, the temperature of the heating reaction in S2 is 40-45°C.

[0028] In one embodiment of the present invention, the solvent in S2 is acetone.

[0029] In one embodiment of the present invention, component g in S3 is added after component c1 of the polyurethane is neutralized with component e and after the reaction of component c2 is completed.

[0030] In one embodiment of the present invention, in S3, the temperature of the heating reaction is 40-45°C.

[0031] In one embodiment of the present invention, the solvent in S3 is acetone.

[0032] In one embodiment of the present invention, the solid content of the dispersion obtained in S3 is 35 wt% or more.

[0033] Compared to conventional technologies, in S3, the addition of component g after the neutralizing agent component e is consumed aims to control the molecular weight via the monoamino group, rather than increasing the hydrophilicity of the chain segments through neutralization. Furthermore, the presence of carboxyl groups allows for crosslinking with etherified amino resins in subsequent glove manufacturing, and the acidity of the carboxyl groups can catalyze the crosslinking reaction.

[0034] Another object of the present invention is to provide the use of polyurethane-polyurea aqueous dispersions.

[0035] The use of a polyurethane-polyurea aqueous dispersion, wherein the dispersion is the above-described dispersion or a dispersion prepared by the above-described preparation method, and the use includes the manufacture of gloves and / or condoms.

[0036] A further object of the present invention is to provide a flexible and elastic product.

[0037] A flexible elastic product, the flexible elastic product being manufactured using the above-mentioned dispersion or using a dispersion prepared by the above-mentioned preparation method, the flexible elastic product including gloves and / or condoms. [Effects of the Invention]

[0038] Compared to conventional technology, the technical solution according to the present invention has the following beneficial effects.

[0039] In the polyurethane-polyurea dispersion according to the present invention, by using a combination of hydrophilic groups, the carboxylate ions provide sensitivity to electrolytes, while the sulfonate ions have lower electrolyte sensitivity than the carboxylate ions. This helps to maintain a balance in the electrolyte sensitivity of the emulsion, reducing sludge formation and leathering during glove manufacturing. Furthermore, by controlling the molecular weight of the polyurethane within an appropriate range, the wet film formed by the instantaneous demulsification of the emulsion does not experience volume shrinkage and cracking due to its large molecular weight and high cohesive energy, nor does it suffer from insufficient strength and slipperiness due to its small molecular weight. This avoids problems such as cracking and slipperiness. [Modes for carrying out the invention]

[0040] To facilitate understanding of the present invention, the present invention will be described in more detail below with reference to examples. It should be understood that the following examples are provided solely for the purpose of better understanding the present invention and do not imply that the present invention is limited to these examples.

[0041] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art. The term "and / or" as it may be used herein includes any and all combinations of one or more related enumerations.

[0042] If specific experimental steps or conditions are not specified in the examples, they should be carried out according to the corresponding conventional experimental steps or conditions in the art. Unless otherwise specified, all reagents and equipment used are conventional products that are commercially available.

[0043] Hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI): Manufactured by Manka Chemical Co., Ltd. Polyester polyol 1: Polyadipic acid-neopentyl glycol polyester, Mn=2000, manufactured by Manka Chemical Co., Ltd. Polyester polyol 2: Polyadipic acid-isophthalic acid-1,4-butanediol polyester, Mn=2000, manufactured by Manka Chemical Co., Ltd. Polyester polyol 3: Polyadipic acid-2-methyl-1,3-propylene glycol polyester, Mn=2000, manufactured by Manka Chemical Co., Ltd. Polyester polyol 4: Polycarbonate polyol (initiators: 1,6-hexanediol and 1,5-pentanediol) Mn=2000, manufactured by Asahi Kasei Corporation, Japan. Polyester polyol 5: Polyadipic acid-neopentyl glycol-hexanediol polyester, Mn=1500, manufactured by Manka Chemical Co., Ltd. Polyether polyol 1: polyoxypropylene diol, Mn=2000, number of functional groups 2, manufactured by Manka Chemical Co., Ltd. Polyether polyol 2: polytetrahydrofranzol, Mn=2000, number of functional groups 2, manufactured by Mitsubishi Corporation of Japan. Dimethylolpropionic acid (DMPA): Manufactured by Perstorp 2-[(2-aminoethyl)amino]ethanesulfonate sodium (50 wt%), neopentyl glycol (NPG), isophorone diamine (IPDA): Manufactured by Manka Chemical Co., Ltd. Triethylamine (TEA), phenylalanine, histidine, ethanolamine: Manufactured by Guon Yao Chemical Research Institute.

[0044] pH value: Measured using a Metrohm6173 model pH meter.

[0045] Average particle size: The polyurethane dispersion is diluted with water to a concentration of 0.5 wt% and measured using a Malvern Nano-ZS90.

[0046] -NCO measurement: The -NCO content in polyurethane synthesis is measured according to the Chinese Chemical Industry Standard "HG / T2409-92 Measurement of isocyanate group content in polyurethane prepolymers". An NCO analyzer manufactured by Metrohm GmbH of Switzerland is used.

[0047] The specific theoretical molecular weight is the theoretical design molecular weight, obtained by the NCO end group calculation method. The formula is: Theoretical design molecular weight = 8400 / end-encapsulated NCO%.

[0048] Example 1 400 g of polyester polyol 1, 78 g of IPDI, 7.0 g of DMPA, and 152 g of acetone were placed in a 1 L four-necked round-bottom flask equipped with a nitrogen inlet and a nitrogen outlet, and the mixture was stirred at 80°C until the NCO content reached 1.2 wt% (theoretical value 1.2 wt%). The temperature was lowered to 45°C, 600 g of acetone was added for dilution, and the temperature was maintained at 43°C. Then, while mechanically stirring, a mixture of 5 g of 2-[(2-aminoethyl)amino]ethanesulfonate sodium (50 wt%) diluted with water and 6 g of IPDA was added and reacted for 15 minutes, 6.0 g of triethylamine was added and neutralized for 5 minutes, 2.5 g of phenylalanine diluted with 30 times 80°C water was added and the reaction was continued for 5 minutes, and while rapidly stirring at 1000 r / min, 950 g of deionized water was added and dispersed for 15 minutes. Acetone was separated by vacuum distillation at 55°C and a vacuum of 0.09 MPa to obtain a solvent-free dispersion with a solid content of 35 wt%, an average particle size of 103 nm, and a pH of 8.1. The theoretically designed molecular weight is 65,000, with a terminal carboxyl group content of 2.9 mmol / 100g, a carboxylate group content of 11.8 mmol / 100g, and a sulfonate group content of 2.6 mmol / 100g.

[0049] Example 2 450 g of polyester polyol 2, 78 g of IPDI, 4.0 g of DMPA, and 152 g of acetone were placed in a 1 L four-necked round-bottom flask equipped with a nitrogen inlet and a nitrogen outlet, and the mixture was stirred at 78°C until the NCO content reached 1.18 wt% (theoretical value 1.18 wt%). The temperature was lowered to 44°C, and 730 g of acetone was added for dilution, and the temperature was maintained at 44°C. Then, while mechanically stirring, a mixture of 8 g of 2-[(2-aminoethyl)amino]ethanesulfonate sodium (50 wt% content) diluted with water and 5 g of IPDA was added and reacted for 15 minutes, 3.0 g of triethylamine was added and neutralized for 5 minutes, 0.8 g of phenylalanine diluted with 30 times 80°C water was added and the reaction was continued for 5 minutes, and 1098 g of deionized water was added and dispersed for 15 minutes while rapidly stirring at 1000 r / min. Subsequently, acetone was separated by vacuum distillation at 55°C and a vacuum of 0.09 MPa, yielding a solvent-free dispersion with a solid content of 35 wt%, an average particle size of 173 nm, and a pH of 8.5. The theoretically designed molecular weight is 223,000, the content of terminal carboxyl groups is 0.87 mmol / 100g, the content of carboxylate groups is 5.4 mmol / 100g, and the content of sulfonate groups is 3.8 mmol / 100g.

[0050] Example 3 450 g of polyester polyol 3, 45 g of HDI, 42 g of IPDI, 2.0 g of DMPA, 8 g of NPG, and 170 g of acetone were placed in a 1 L four-necked round-bottom flask equipped with a nitrogen inlet and a nitrogen outlet. The mixture was stirred at 75°C until the NCO content reached 1.64 wt% (theoretical value 1.64%). The temperature was then lowered to 43°C, 700 g of acetone was added to dilute the mixture, and the temperature was maintained at 45°C. Subsequently, while mechanically stirring, a mixture of 15 g of 2-[(2-aminoethyl)amino]ethanesulfonate sodium (50 wt%) diluted with water and 5 g of IPDA was added and reacted for 15 minutes. Then, 1.2 g of triethylamine was added and neutralized for 5 minutes, and 1.5 g of phenylalanine diluted with 30 times 80°C water was added and the reaction was continued for 5 minutes. While stirring at high speed at 1000 r / min, then 1130 g of deionized water was added and dispersed for 15 minutes while stirring at high speed. Subsequently, acetone was separated by vacuum distillation at 55°C and a vacuum of 0.09 MPa to obtain a solvent-free dispersion with a solid content of 37 wt%, an average particle size of 115 nm, and a pH of 8.3. The theoretically designed molecular weight is 123,000, the content of terminal carboxyl groups is 1.59 mmol / 100g, the content of carboxylate groups is 2.62 mmol / 100g, and the content of sulfonate groups is 3.69 mmol / 100g.

[0051] Example 4 560 g of polyester polyol 4, 45 g of HDI, 48 g of IPDI, 15 g of DMPA, and 185 g of acetone were placed in a 1 L four-necked round-bottom flask equipped with a nitrogen inlet and a nitrogen outlet, and the mixture was stirred at 80°C until the NCO content reached 0.9 wt% (theoretical value 0.9%). The temperature was lowered to 45°C, and 700 g of acetone was added for dilution, and the temperature was maintained at 43°C. Then, while mechanically stirring, 5 g of 2-[(2-aminoethyl)amino]ethanesulfonate sodium (50 wt%) diluted with water was added and reacted for 15 min, then 5.66 g of triethylamine was added and neutralized for 5 min, and 1.0 g of histidine diluted with 30 times 80°C water was added and the reaction was continued for 5 min, and then 1330 g of deionized water was added and dispersed for 15 min while rapidly stirring at 1000 r / min. Subsequently, acetone was separated by vacuum distillation at 55°C and a vacuum of 0.09 MPa, yielding a solvent-free dispersion with a solid content of 35 wt%, an average particle size of 90 nm, and a pH of 8.3. The theoretically designed molecular weight is 221,000, the content of terminal carboxyl groups is 0.9 mmol / 100g, the content of carboxylate groups is 8.2 mmol / 100, and the content of sulfonate groups is 1.9 mmol / 100g.

[0052] Example 5 300g of polyether polyol 1, 300g of polyether polyol 2, 25g of TDI, 90g of IPDI, 19g of DMPA, and 185g of acetone were placed in a 1L four-necked round-bottom flask equipped with a nitrogen inlet and a nitrogen outlet. The mixture was stirred at 80°C until the NCO content reached 0.97 wt% (theoretical value 0.97%). The temperature was lowered to 45°C, 700g of acetone was added to dilute the mixture, and the temperature was maintained at 43°C. Subsequently, while mechanically stirring, a mixture of 9 g of 2-[(2-aminoethyl)amino]ethanesulfonate sodium (50 wt%) diluted with water and 3 g of IPDA was added and reacted for 15 minutes. Then, 7.17 g of triethylamine was added and neutralized for 5 minutes. 0.70 g of phenylalanine diluted 30 times with 80°C water was added and the reaction was continued for 5 minutes. Then, while rapidly stirring at 1000 r / min, 1530 g of deionized water was added and dispersed for 15 minutes. Subsequently, acetone was separated by vacuum distillation at 55°C and a vacuum of 0.09 MPa, yielding a solvent-free dispersion with a solid content of 35 wt%, an average particle size of 110 nm, and a pH of 8.7. The theoretical design molecular weight is 350,000, the content of terminal carboxyl groups is 0.56 mmol / 100 g, the content of carboxylate groups is 9.4 mmol / 100, and the content of sulfonate groups is 3.1 mmol / 100 g.

[0053] Example 6 450 g of polyester polyol 5, 25 g of TDI, 90 g of IPDI, 19 g of DMPA, and 185 g of acetone were placed in a 1 L four-necked round-bottom flask equipped with a nitrogen inlet and a nitrogen outlet, and the mixture was stirred at 80°C until the NCO content reached 1.14 wt% (theoretical value 1.14%). The temperature was lowered to 45°C, and 700 g of acetone was added for dilution, and the temperature was maintained at 43°C. Then, while mechanically stirring, a mixture of 9 g of 2-[(2-aminoethyl)amino]ethanesulfonate sodium (50 wt% content) diluted with water and 3 g of IPDA was added and reacted for 15 minutes, then 7.17 g of triethylamine was added and neutralized for 5 minutes, and 0.70 g of phenylalanine diluted with 30 times 80°C water was added and the reaction was continued for 5 minutes, and then 1230 g of deionized water was added and dispersed for 15 minutes while rapidly stirring at 1000 r / min. Subsequently, acetone was separated by vacuum distillation at 55°C and a vacuum of 0.09 MPa, yielding a solvent-free dispersion with a solid content of 38 wt%, an average particle size of 100 nm, and a pH of 8.7. The theoretically designed molecular weight is 280,000, the content of terminal carboxyl groups is 0.69 mmol / 100g, the content of carboxylate groups is 11.75 mmol / 100, and the content of sulfonate groups is 3.93 mmol / 100g.

[0054] Comparative Example 1 The difference compared to Example 2 is that 0.8 g of phenylalanine was replaced with 0.3 g of equimolar ethanolamine that does not contain a carboxyl group. The dispersion has a solid content of 35 wt%, an average particle size of 178 nm, and a pH of 8.5. The theoretical design molecular weight is 223,000, the terminal carboxyl group content is 0 mmol / 100g, the carboxylate group content is 5.4 mmol / 100g, and the sulfonate group content is 3.8 mmol / 100g.

[0055] Comparative Example 2 Compared to Example 1, the difference is that component g is added before neutralization. 400 g of polyester polyol 1, 78 g of IPDI, 7.0 g of DMPA, and 152 g of acetone were placed in a 1 L four-necked round-bottom flask equipped with a nitrogen inlet and a nitrogen outlet, and the mixture was stirred at 80°C until the NCO content reached 1.2 wt% (theoretical value 1.2 wt%). The temperature was lowered to 45°C, 600 g of acetone was added for dilution, and the temperature was maintained at 43°C. Then, while mechanically stirring, a mixture of 5 g of 2-[(2-aminoethyl)amino]ethanesulfonate sodium (50 wt%) diluted with water and 6 g of IPDA was added and reacted for 15 minutes, 2.5 g of phenylalanine diluted with 30 times 80°C water was added and the reaction was continued for 5 minutes, 7.3 g of triethylamine was added and neutralized for 5 minutes, and 950 g of deionized water was added and dispersed for 15 minutes while rapidly stirring at 1000 r / min. Acetone was separated by vacuum distillation at 55°C and a vacuum of 0.09 MPa to obtain a solvent-free dispersion with a solid content of 35 wt%, an average particle size of 109 nm, and a pH of 8.2. The theoretically designed molecular weight is 65,000, the content of terminal carboxyl groups is 0.42 mmol / 100g, the content of carboxylate groups is 14.28 mmol / 100g, and the content of sulfonate groups is 2.6 mmol / 100g.

[0056] Preparation of glove matrix resin (liquid material): The dispersion prepared above was diluted with deionized water to a solid content of 15 wt%. Based on the mass of the diluted dispersion, 0.5 wt% colored paste, 5 wt% titanium dioxide, and 1.5% methyl etherified amino resin were added. The mixture was stirred at low speed (250 r / min) for 30 minutes to prepare it for use.

[0057] Preparation of the coagulation solution: Using deionized water, an aqueous solution containing 10 wt% CaCl2 and 5 wt% release agent (calcium stearate) was prepared, stirred continuously for 1 hour, and prepared for use.

[0058] Glove manufacturing: 1) The washed glove molds were placed in a 100°C oven to dry. 2) Remove the glove-shaped mold, let it cool to 55°C, immerse it in the coagulation solution for 8 seconds, then remove it and dry it in an oven at 130°C. 3) Remove the dried glove mold, let it cool to 60°C, immerse it in the prepared matrix resin for 8 seconds, remove it and leave it for 1 minute (to check if the wrist of the glove slips down), then immerse it in 50°C deionized water for 1 minute, remove it and dry it in a 130°C oven for 18 minutes. 4) After drying, the glove mold was removed, dipped in the glove coating agent, removed, air-dried, and demolded to obtain the finished glove.

[0059] Performance testing: Cracking: After demolding, when the glove was inflated and observed, straight and cross-shaped cracks were found. Tensile strength test: The palm portion of the glove was cut into a dumbbell shape measuring 6 mm in width and 115 mm in length, and its tensile strength was tested using a tensile testing machine. A tensile testing machine manufactured by Kotetsu Co., Ltd. was used, and the test was performed at a tensile speed of 200 mm / min. Alcohol resistance: After inflating the gloves, 55% alcohol was sprayed onto the surface, and the presence of cracks due to dissolution in the finger seams was observed.

[0060] The results of the performance tests are shown in Table 1.

[0061] [Table 1]

[0062] As can be seen from the table, gloves manufactured based on the polyurethane-polyurea aqueous dispersion of the present invention are free from cracking and have the characteristics of a high pass rate and good alcohol resistance.

[0063] It will be readily apparent that the above embodiments are merely illustrative examples to clearly illustrate the present invention and do not imply that the invention is limited thereto. Those skilled in the art will understand that other variations and modifications are possible based on the above description. It is not necessary, but impossible, to list all embodiments here. Obvious variations and modifications derived therefrom are also within the scope of protection of the present invention.

Claims

1. A polyurethane-polyurea aqueous dispersion, wherein the dispersion comprises a polyurethane-polyurea of ​​a specific theoretical molecular weight containing terminal carboxyl groups, sulfonate groups, and carboxylate groups, wherein the carboxylate group content is 1.49 to 11.9 mmol / 100g, the sulfonate group content is 0.26 to 7.9 mmol / 100g, the terminal carboxyl group content is 0.5 to 3.7 mmol / 100g, and the molecular weight is 60,000 to 390,000, and the specific theoretical molecular weight is a theoretically designed molecular weight obtained by a terminal group calculation method.

2. The dispersion according to claim 1, characterized in that it is prepared by reacting raw materials containing the following components. Component a: High molecular weight polyol Component b: Polyisocyanate Component c: A hydrophilic compound comprising component c1, which contains 2 to 3 hydroxyl groups that are reactive with NCO and whose hydrophilic group is a carboxyl group, and component c2, which contains 2 to 3 amino groups that are reactive with NCO and whose hydrophilic group is a salt-forming group. Optional component d: Low molecular weight alcohol chain extender Component e: A compound that ionizes the latent group in component c. Component f: Polyamine with a number-average molecular weight of 500 g / mol or less Component g: A monofunctional compound containing a carboxyl group and an amino group that can react with isocyanate.

3. The dispersion according to claim 1 or 2, characterized in that the proportions of each component of the dispersion are as follows. Component a: 65 to 90 parts, preferably 74 to 88 parts Component b: 8 to 25 parts, preferably 10 to 20 parts Component c: 1 to 6 parts, preferably 1.5 to 4.8 parts Component d: 0 to 4 parts, preferably 0 to 3 parts Component e: 0.1 to 5 parts, preferably 0.1 to 3 parts Component f: 0 to 6 parts, preferably 0 to 3 parts Component g: 0.05 to 1 part, preferably 0.085 to 0.6 parts

4. The dispersion according to any one of claims 1 to 3, characterized in that component a is one or more diols, triols, and tetraols having a number average molecular weight of 500 to 6000 g / mol, preferably one or more polyester polyols, polyether polyols, polycarbonate polyols, and polycaprolactone polyols having 2 to 3 functional groups and a number average molecular weight of 500 to 5000 g / mol.

5. The dispersion according to any one of claims 1 to 4, characterized in that component b is one or more aromatic, aliphatic, and alicyclic polyisocyanates, preferably one or more aromatic, aliphatic, and alicyclic polyisocyanates having at least two isocyanate groups.

6. The dispersion according to any one of claims 1 to 5, characterized in that, in the component c, c1 is methylolpropionic acid and / or methylolbutyric acid, and c2 is sodium 2-[(2-aminoethyl)amino]ethanesulfonate and / or sodium ethylenediaminopropionate.

7. The dispersion according to any one of claims 1 to 6, characterized in that component d is one or more selected from ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-dihydroxycyclohexane, 1,4-dihydroxymethylcyclohexane, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and 2-ethyl-1,3-hexanediol, preferably one or more selected from 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, and 1,4-cyclohexanedimethanol.

8. The dispersion according to any one of claims 1 to 7, characterized in that component e is an organic base, preferably one or more of triethylamine, dimethylethanolamine, and aqueous ammonia, and more preferably triethylamine.

9. The dispersion according to any one of claims 1 to 8, wherein the component f is a polyamine having a number average molecular weight of 60 to 500 g / mol, preferably one or more of ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-hexanediamine, 2-methyl-1,5-diamine, isophoronediamine, 4,4-diaminodicyclohexylmethane, piperazine, and diethylenetriamine, more preferably ethylenediamine and / or isophoronediamine.

10. The dispersion according to any one of claims 1 to 9, characterized in that the carboxyl group of component g can react with the etherified amino resin, and the compound is basic, preferably component g is a basic amino acid, such as histidine or phenylalanine, more preferably phenylalanine.

11. A method for preparing a polyurethane-polyurea aqueous dispersion according to any one of claims 1 to 10, wherein the preparation method is: Step S1 involves adding component a, component b, component c1, an arbitrary component d, and a solvent to a reaction vessel and reacting them until the NCO content approaches or reaches the theoretical value to obtain a prepolymer having isocyanates at the ends. Step S2 involves lowering the temperature and adding a solvent to dilute the solution. A preparation method characterized by comprising step S3, which involves adding component f and component c2 and reacting them, adding component e and neutralizing it, adding component g and reacting it, adding water and dispersing it to obtain a dispersion, removing the solvent to obtain a solvent-free polyurethane-polyurea aqueous dispersion.

12. The preparation method according to claim 11, characterized in that the components in the preparation method are as follows. Component a: High molecular weight polyol Component b: Polyisocyanate Component c: A hydrophilic compound comprising component c1, which contains 2 to 3 hydroxyl groups that are reactive with NCO and whose hydrophilic group is a carboxyl group, and component c2, which contains 2 to 3 amino groups that are reactive with NCO and whose hydrophilic group is a salt-forming group. Optional component d: Low molecular weight alcohol chain extender Component e: A compound that ionizes the latent group of component c. Component f: Polyamine with a number-average molecular weight of 500 g / mol or less Component g: A monofunctional compound containing a carboxyl group and an amino group that can react with isocyanate.

13. The preparation method according to claim 11 or 12, characterized in that the proportion of each component in the preparation method is as follows. Component a: 65 to 90 parts, preferably 74 to 88 parts Component b: 8 to 25 parts, preferably 10 to 20 parts Component c: 1 to 6 parts, preferably 1.5 to 4.8 parts Component d: 0 to 4 parts, preferably 0 to 3 parts Component e: 0.1 to 5 parts, preferably 0.1 to 3 parts Component f: 0 to 6 parts, preferably 0 to 3 parts Component g: 0.05 to 1 part, preferably 0.085 to 0.6 parts

14. The reaction temperature in S1 is 60-80°C. The preparation method according to claim 11, characterized in that the solvent in S1 is acetone.

15. The temperature of the heating reaction in S2 is 40-45°C. The preparation method according to claim 11, characterized in that the solvent in S2 is acetone.

16. In S3, component g is added after component c1 of the polyurethane is neutralized with component e and after the reaction of component c2 is complete. And / or, in S3, the temperature of the heating reaction is 40-45°C. and / or, the solvent in S3 is acetone, The preparation method according to claim 11, characterized in that the solid content of the dispersion obtained in S3 is 35 wt% or more.

17. Use of a polyurethane-polyurea aqueous dispersion which is a dispersion according to any one of claims 1 to 10, or a dispersion prepared by a preparation method according to any one of claims 11 to 16, wherein the use includes the manufacture of gloves and / or condoms.

18. A flexible elastic product manufactured using a dispersion according to any one of claims 1 to 10, or a dispersion prepared by a preparation method according to any one of claims 11 to 16, wherein the flexible elastic product includes gloves and / or condoms.

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