Polyurethane-polyurea aqueous dispersion, preparation method therefor and use thereof, slurry, method for preparing polyurethane glove, and polyurethane glove

Abstract

A polyurethane-polyurea aqueous dispersion, a method for preparing the polyurethane-polyurea aqueous dispersion, a use of the polyurethane-polyurea aqueous dispersion, a slurry containing the polyurethane-polyurea aqueous dispersion, a polyurethane glove and a preparation method therefor. The polyurethane-polyurea aqueous dispersion comprises polyurethane-polyurea having a terminal polycarboxylic acid and / or carboxylate group dispersed in water. The present disclosure effectively reduces the destructive effect of metal ions such as calcium ions from coagulant solutions on dopes containing polyurethane-polyurea aqueous dispersions for preparing gloves, thereby prolonging the service life of the dopes; moreover, the produced gloves have excellent mechanical properties, e.g., improved elongations and excellent tensile strength.

Description

Polyurethane-polyurea aqueous dispersion, preparation method, use and slurry thereof, polyurethane glove preparation method and polyurethane glove

[0001] This application claims priority to Chinese Patent Application No. 202410166280.7 filed on February 5, 2024, and the contents of the above-mentioned Chinese patent application disclosure are hereby incorporated by reference in their entirety as a part of this application. Technical Field

[0002] Embodiments of the present disclosure relate to a polyurethane-polyurea aqueous dispersion, a preparation method and use of the polyurethane-polyurea aqueous dispersion, a slurry containing the polyurethane-polyurea aqueous dispersion, and a polyurethane glove and a preparation method thereof. Background Art

[0003] Water-based polyurethane gloves, with their non-toxic, odorless, and simple production process, are a hot topic in current disposable glove research. Because the preparation methods for water-based polyurethane differ from those for nitrile and latex, the manufacturing process for water-based polyurethane gloves is significantly different, particularly with regard to the stability of the polyurethane aqueous dispersion used in the glove manufacturing process.

[0004] The flocculation method for producing water-based polyurethane gloves typically involves dipping a glove former in a coagulant solution and then dipping it in a rubber compound containing an aqueous polyurethane dispersion. The coagulant solution used in the flocculation method contains high-valent electrolyte salts, such as calcium, magnesium, and aluminum ions. During use, the metal ions inevitably migrate into the rubber compound, causing the compound to lose stability and, in severe cases, become jelly-like and unusable. Therefore, improving the rubber compound's operating life (service life) is crucial to the scalable and continuous production of polyurethane gloves.

[0005] Therefore, there is still a need in the art to provide a method that can effectively reduce the migration of metal ions from a coagulant solution into a rubber compound containing an aqueous polyurethane dispersion used to prepare gloves, thereby extending the life of the rubber compound and enabling large-scale continuous production of gloves, while also providing the gloves with excellent mechanical properties.

[0006] Summary of the Invention

[0007] The embodiments of the present disclosure provide at least a polyurethane-polyurea aqueous dispersion, a method for preparing the polyurethane-polyurea aqueous dispersion, uses of the polyurethane-polyurea aqueous dispersion, a slurry, a method for preparing polyurethane gloves, and polyurethane gloves.

[0008] In a first aspect, embodiments of the present disclosure provide a polyurethane-polyurea aqueous dispersion comprising a polyurethane-polyurea having terminal polycarboxylic acid and / or carboxylate groups dispersed in water.

[0009] In an optional embodiment, based on the total weight of the polyurethane-polyurea, the content of the terminal polycarboxylic acid and / or carboxylate groups is 7-30 mmol / 100 g, for example, 9 to 27 mmol / 100 g.

[0010] In an optional embodiment, the polyurethane-polyurea is prepared by reacting raw materials comprising the following components:

[0011] Component a: one or more polyether or polyester polyols, wherein the number average molecular weight of the polyether or polyester polyol is greater than 500 g / mol;

[0012] Component b: one or more polyisocyanates;

[0013] Component c: one or more hydrophilic compounds, wherein the hydrophilic compound contains 2-3 groups reactive with NCO, and the hydrophilic groups of the hydrophilic compound include ionic groups and / or potential ionic groups;

[0014] Optional component d: one or more alcohol chain extenders different from component a, having a number average molecular weight of 300 g / mol or less;

[0015] Component e: one or more compounds that ionize the potentially ionic groups in component c, having the structural formula R1R2R3N, wherein R1-R3 are the same as or different from each other and are independently selected from H, or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, or C5-C6 cycloalkyl groups that are unsubstituted or substituted with OH;

[0016] Component f: one or more polyamines containing at least two amino groups selected from primary and / or secondary amino groups, having a number average molecular weight of 500 g / mol or less;

[0017] Component g: one or more compounds reactive with isocyanate containing a single amino group selected from primary or secondary amino groups or a hydroxyl group and containing multiple carboxyl groups;

[0018] The terminal polycarboxylic acid and / or carboxylate groups in the polyurethane-polyurea are introduced by component g.

[0019] In an optional embodiment, the raw materials of the polyurethane-polyurea aqueous dispersion are:

[0020] - Component a is one or more of a diol, a triol and a tetraol, preferably a diol, preferably having a number average molecular weight of 500 to 6000 g / mol, for example 500 to 5000 g / mol; and / or

[0021] - Component b is one or more of aromatic, aliphatic and alicyclic polyisocyanates having at least two, preferably two, isocyanate groups; and / or

[0022] - Component c is one or more selected from dimethylolpropionic acid, dimethylolbutanoic acid, and aminosulfonates, more preferably dimethylolpropionic acid; and / or

[0023] - the component d is selected from one or more of 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, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and 2-ethyl-1,3-hexanediol; preferably, component d is selected from one or more of 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol and 1,4-cyclohexanedimethanol; and / or

[0024] - the component e is an organic tertiary amine, such as triethylamine, dimethylethanolamine, triisopropylamine, or ammonia, preferably component e is triethylamine; and / or

[0025] - the component f is a polyamine having a number average molecular weight of 60 to 500 g / mol, preferably component f is selected from 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 component f is ethylenediamine and / or isophoronediamine; and / or

[0026] - The number of carboxyl groups in the component g is 2 or more, for example 3 or more, and preferably the component g is ethylenediaminetriacetic acid.

[0027] In an optional embodiment, based on the total weight of component ag being 100%, the weight proportion of component ag is as follows:

[0028] Component a: 72-85 wt%;

[0029] Component b: 10-23 wt%;

[0030] Component c: 1.5-4 wt%;

[0031] Component d: 0-3 wt%;

[0032] Component e: 0.1-3 wt%;

[0033] Component f: 0-3 wt%;

[0034] Component g: 0.4-2.5% by weight.

[0035] In an optional embodiment, the content of polyurethane-polyurea in the polyurethane-polyurea aqueous dispersion is 35 wt % or more, based on the total weight of the polyurethane-polyurea aqueous dispersion.

[0036] In a second aspect, the present disclosure provides a method for preparing the polyurethane-polyurea aqueous dispersion of the first aspect of the present disclosure, the preparation method comprising preparing the polyurethane-polyurea by:

[0037] A prepolymer containing terminal isocyanate groups, preferably at least two terminal isocyanate groups, is reacted with a polyamine containing at least two amine groups selected from primary and / or secondary amine groups and an isocyanate-reactive compound containing a single amine group selected from primary or secondary amine groups or a hydroxyl group and containing multiple carboxyl groups.

[0038] In an optional embodiment, the preparation method comprises the following steps:

[0039] - reacting component a, component b, component c, and optionally component d in a first inert solvent to obtain a prepolymer containing terminal isocyanate groups, preferably at least two terminal isocyanate groups;

[0040] - optionally diluting with a second inert solvent;

[0041] - Add component e to neutralize, then add water to disperse evenly to obtain a dispersion containing an inert solvent;

[0042] - Add components f and g to the dispersion containing the inert solvent and continue the reaction;

[0043] - removing the inert solvent to obtain a polyurethane-polyurea aqueous dispersion free of inert solvent;

[0044] - optionally, converting the terminal carboxyl groups in the polyurethane-polyurea into carboxylate groups,

[0045] The second inert solvent is the same as or different from the first inert solvent.

[0046] In an optional embodiment, the step of converting the terminal carboxyl groups in the polyurethane-polyurea into carboxylate groups is carried out as follows: adding a basic compound to the polyurethane-polyurea aqueous dispersion without an inert solvent, wherein the basic compound is preferably an alkali metal compound, more preferably sodium hydroxide and / or sodium carbonate.

[0047] In a third aspect, embodiments of the present disclosure provide the use of the polyurethane-polyurea aqueous dispersion of the first aspect of the present disclosure, or the polyurethane-polyurea aqueous dispersion prepared by the method of the second aspect of the present disclosure, for preparing a slurry for flocculation-processed aqueous polyurethane gloves, or polyurethane gloves.

[0048] In a fourth aspect, embodiments of the present disclosure provide a slurry comprising the polyurethane-polyurea aqueous dispersion of the first aspect of the present disclosure, or the polyurethane-polyurea aqueous dispersion prepared by the method of the second aspect of the present disclosure, a crosslinker, an optional ion chelating agent, and optionally additional water.

[0049] In an optional embodiment, the cross-linking agent comprises one or more of multifunctional aziridine, carbodiimide, amino resin, and sorbitol polyglycidyl ether;

[0050] And / or, the ion chelating agent comprises one or more of sodium gluconate, sodium tartrate, disodium ethylenediaminetetraacetate, and sodium diethylenetriaminepentaacetate;

[0051] Preferably, the weight ratio of the polyurethane-polyurea aqueous dispersion, the crosslinking agent, the ion chelating agent and the additional water is 100:0.3-1.2:0.01-0.5:100-200.

[0052] In a fifth aspect, an embodiment of the present disclosure provides a method for preparing a polyurethane glove, wherein the polyurethane glove comprises a polyurethane layer, and the method comprises the step of preparing the polyurethane layer using the slurry according to the fourth aspect of the present disclosure.

[0053] In an optional embodiment, the method comprises the following steps:

[0054] S1: dipping the optionally cleaned hand mold in a coagulant solution, and optionally drying it thereafter, to obtain a first-treated hand mold;

[0055] S2: dipping the first treated hand mold in the slurry according to any one of claims 11 to 12, and optionally drying the hand mold; optionally repeating the dipping and drying process one or more times to obtain a second treated hand mold;

[0056] S3: Optionally, cleaning the second treated hand mold with water, and optionally drying it thereafter, to obtain a third treated hand mold;

[0057] S4: Optionally, dipping the hand mold subjected to the second treatment or the hand mold subjected to the third treatment into a slippery coating liquid;

[0058] S5: curling, plasticizing, and demoulding to obtain polyurethane gloves.

[0059] In an optional embodiment, the coagulant solution comprises a soluble salt, a release agent and water;

[0060] Preferably, the soluble salt is selected from one or more of calcium nitrate, calcium chloride, magnesium nitrate, magnesium chloride, zinc nitrate and zinc chloride;

[0061] Preferably, the weight ratio of the soluble salt, the release agent and water is 15-30:8-20:150-250;

[0062] And / or, the slippery coating liquid comprises one or more of PU coating, acrylic coating, corn starch coating, and talcum powder coating;

[0063] And / or, the dipping and drying process in step S2 is performed at least twice, and the drying in step S2 is oven drying; preferably, the oven drying temperature is 80-150° C., preferably 90-140° C.;

[0064] And / or, the plasticizing in step S5 is performed by baking at a temperature of 110 to 140° C. for 20 to 40 minutes.

[0065] In a sixth aspect, an embodiment of the present disclosure provides a polyurethane glove, which comprises a polyurethane layer prepared using the slurry of the fourth aspect of the present disclosure as a raw material. Preferably, the glove is obtained by the method described in the fifth aspect of the present disclosure. DETAILED DESCRIPTION

[0066] To make the purpose, technical solutions, and advantages of the embodiments of the present disclosure more clear, the technical solutions of the embodiments of the present disclosure are clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present disclosure, not all of them. Based on the described embodiments of the present disclosure, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present disclosure.

[0067] Unless otherwise specified, the meanings of the technical terms in this specification are the same as those generally understood by those skilled in the art.

[0068] Relational terms such as “first” and “second” are used merely to distinguish one element, component or method step from another with the same name, but do not necessarily require or imply any actual relationship or order between these elements, components or method steps.

[0069] In the present disclosure, when the expressions “above” and “below” are used when describing numerical values, for example, “above (below)…”, the terms “above” and “below” are meant to include the stated numerical values ​​themselves.

[0070] In the present disclosure, the terms "polyurethane-polyurea", "polyurethane-polyurea copolymer" and "polyurethane-polyurea polymer" have the same meaning, which all refer to copolymers containing urethane structural units and urea structural units and are used interchangeably, and are sometimes also simply referred to as "polyurethane".

[0071] In the present disclosure, the term "rubber" means a rubber containing a polyurethane-polyurea aqueous dispersion used to prepare gloves.

[0072] The present disclosure relates to a polyurethane-polyurea aqueous dispersion, a preparation method and use of the polyurethane-polyurea aqueous dispersion, a slurry containing the polyurethane-polyurea aqueous dispersion, and a polyurethane glove and a preparation method thereof.

[0073] The present disclosure will be described in detail below.

[0074] Polyurethane-polyurea aqueous dispersion

[0075] In a first aspect, the present disclosure provides an aqueous polyurethane-polyurea dispersion comprising a polyurethane-polyurea having terminal polycarboxylic acid and / or carboxylate groups dispersed in water.

[0076] In a preferred embodiment, the content of the terminal polycarboxylic acid and / or carboxylate groups relative to the total weight of the polyurethane-polyurea is 7.0-30 mmol / 100 g, preferably 9 to 27 mmol / 100 g, for example 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 mmol / 100 g.

[0077] In the present disclosure, unless otherwise specified, the content of the terminal polycarboxylic acid and / or carboxylate groups stated is based on the total weight of the polyurethane-polyurea.

[0078] In a preferred embodiment, the polyurethane-polyurea can be prepared by reacting raw materials comprising the following components:

[0079] Component a: one or more polyether or polyester polyols, wherein the number average molecular weight of the polyether or polyester polyol is greater than 500 g / mol;

[0080] Component b: one or more polyisocyanates;

[0081] Component c: one or more hydrophilic compounds, wherein the hydrophilic compound contains 2-3 groups reactive with NCO, and the hydrophilic groups of the hydrophilic compound include ionic groups and / or potential ionic groups;

[0082] Optional component d: one or more alcohol chain extenders different from component a, having a number average molecular weight of 300 g / mol or less;

[0083] Component e: one or more compounds that ionize the potentially ionic groups in component c, having the structural formula R1R2R3N, wherein R1-R3 are the same as or different from each other and are independently selected from H, or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, or C5-C6 cycloalkyl groups that are unsubstituted or substituted with OH;

[0084] Component f: one or more polyamines containing at least two amino groups selected from primary and / or secondary amino groups, and having a number average molecular weight of 500 g / mol or less;

[0085] Component g: one or more compounds reactive with isocyanate containing a single amino group selected from primary or secondary amino groups or a hydroxyl group and containing multiple carboxyl groups;

[0086] The terminal polycarboxylic acid and / or carboxylate groups in the polyurethane-polyurea are introduced by component g.

[0087] Component a

[0088] In an embodiment of the present disclosure, component a is one or more polyether or polyester polyols.

[0089] The hydroxyl functionality of component a can be selected as needed. In a preferred embodiment, component a is one or more of a diol, a triol, and a tetraol. In a further preferred embodiment, component a is a diol.

[0090] The number average molecular weight of component a can be selected as needed. In a preferred embodiment, the number average molecular weight of component a can be 500 g / mol or more, for example, 500 to 6000 g / mol, for example, 500 to 5000 g / mol, for example, the number average molecular weight of component a can be 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700 , 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5000, 5100, 5200, 5300, 5400, 5500, 5600, 5700, 5800, 5900, 6000 g / mole, or a range limited by any two thereof.

[0091] The number average molecular weight can be measured by conventional means in the art, such as gel permeation chromatography (GPC) or hydroxyl value (mg KOH / g) titration. Hereinafter, unless otherwise specified, the number average molecular weight refers to the number average molecular weight measured by titration.

[0092] As non-limiting examples of polyether polyols that can be used in the present disclosure, polyether polyols formed from one or more of ethylene oxide, propylene oxide, and butylene oxide can be mentioned. When it is desired to use a polyether polyol that is a triol or a tetraol, it can be obtained by using a triol (e.g., glycerol) or a tetraol (e.g., pentaerythritol) as an initiator to initiate the ring-opening polymerization of one or more of ethylene oxide, propylene oxide, and butylene oxide.

[0093] As non-limiting examples of polyester polyols that can be used in the present disclosure, there can be mentioned polyester polyols formed by the polymerization of one or more dibasic acids and one or more diols, and polyester polyols formed by the polymerization of one or more dibasic acids and one or more diols and optionally one or more tribasic or higher acids and optionally one or more trihydric or higher alcohols.

[0094] Non-limiting examples of diols include: 1,2-ethanediol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, tetrahydrofuran, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 1,2-heptanediol, 1,3-heptanediol, 1,4-heptanediol, 1,5-heptanediol, 1,6-heptanediol, 1,7-heptanediol, octanediol, nonanediol, decanediol, cyclopentanediol, cyclohexanediol, and the like.

[0095] Non-limiting examples of trihydric or higher alcohols include, for example, glycerol, pentaerythritol, and the like.

[0096] Non-limiting examples of dibasic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, phthalic acid, isophthalic acid, cyclohexanedicarboxylic acid, and the like.

[0097] Non-limiting examples of trivalent or higher acids include, for example, trimesic acid, pyromellitic acid, and the like.

[0098] Component b

[0099] In a preferred embodiment of the present disclosure, the component b is one or more of aromatic, aliphatic and alicyclic polyisocyanates having at least two, preferably two isocyanate groups.

[0100] The functionality of the isocyanate groups of component b can be selected as desired. For example, the functionality of the isocyanate groups of component b can be 2, 3, 4 or higher.

[0101] As non-limiting examples of aromatic polyisocyanates, there may be mentioned diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), naphthalene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,3-bis(1-isocyanato-1-methylethyl)benzene, dimethyldiphenyl diisocyanate, polymethylene polyphenyl isocyanate, and the like.

[0102] As non-limiting examples of cycloaliphatic polyisocyanates, mention may be made of 4,4′-dicyclohexylmethane diisocyanate (HMDI), 1,4-cyclohexane diisocyanate, cyclohexane dimethylene diisocyanate, trimethyl-1,6-hexamethylene diisocyanate (e.g. 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, and mixtures thereof), norbornane diisocyanates (e.g. 2,5-bis(isocyanatemethyl)bicyclo[2.2.1]heptane, 2,6-bis(isocyanatemethyl)bicyclo[2.2.1]heptane, or mixtures thereof), methylcyclohexyl diisocyanate and isophorone diisocyanate (IPDI).

[0103] As non-limiting example of aliphatic polyisocyanates, mention may be made of hexamethylene diisocyanate HDI.

[0104] Component c

[0105] In an embodiment of the present disclosure, component c is a hydrophilic compound containing 2-3 groups reactive with NCO, wherein the hydrophilic group of the hydrophilic compound comprises an ionic group and / or a potential ionic group.

[0106] In the context of this disclosure, an ionic group refers to a group that carries an electric charge. A non-limiting example of an ionic group is a carboxylate group.

[0107] In the context of this disclosure, a potential ionic group refers to a group that can be converted into an ionic group by a chemical reaction. The chemical reaction can be an acid-base neutralization reaction or a protonation reaction. A non-limiting example of a potential ionic group is a carboxylic acid group.

[0108] In a preferred embodiment, component c may be one or more of dimethylolpropionic acid, dimethylolbutanoic acid, and aminosulfonate, more preferably dimethylolpropionic acid.

[0109] Component d

[0110] Component d is an alcohol chain extender different from component a, and has an Mn of 300 or less. For example, the Mn of component d may be any of the following values, or a range defined by any two of the following: 300, 290, 280, 270, 260, 250, 240, 230, 220, 210, 200, 190, 180, 170, 160, 150, 140, 130, 120, 110, 100, 90, 80, 70, or 60.

[0111] As non-limiting examples of component d, mention may be made of: one or more of 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-dimethylolcyclohexane, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and 2-ethyl-1,3-hexanediol; preferably 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol and 1,4-cyclohexanedimethanol, and any combination thereof.

[0112] Component e

[0113] In the present disclosure, component e is a compound that ionizes the potential ion group in component c, which has the structural formula R1R2R3N, wherein R1-R3 are the same as or different from each other and are each independently selected from H, or a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, or a C5-C6 cycloalkyl group that is unsubstituted or substituted with OH.

[0114] As non-limiting examples, component e may be an organic tertiary amine, such as triethylamine, dimethylethanolamine, triisopropylamine, or component e may be ammonia, more preferably component e may be volatile triethylamine.

[0115] Component f

[0116] In the present disclosure, component f is a polyamine containing at least two amine groups selected from primary and / or secondary amine groups, and has an Mn of 500 g / mol or less, for example, 60 to 500 g / mol. 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500 g / mole, or a range bounded by any two thereof.

[0117] The polyamine has at least two amine groups selected from primary and / or secondary amine groups. For example, the amine groups may all be primary, all be secondary, or at least one be primary and at least one be secondary.

[0118] As non-limiting examples of component f, there may be mentioned: ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-hexanediamine, 2-methyl-1,5-diamine, isophoronediamine, 4,4-diaminodicyclohexylmethane, piperazine and diethylenetriamine or any combination thereof. More preferably, component f may be ethylenediamine and / or isophoronediamine.

[0119] Component g

[0120] In the present disclosure, component g is one or more compounds reactive with isocyanate containing a single amine group selected from a primary or secondary amine group or a hydroxyl group and containing a plurality of carboxyl groups.

[0121] In one embodiment of the present disclosure, the number of carboxyl groups in the component g is 2 or more, for example, 3 or more.

[0122] As a non-limiting example of component g, mention may be made of ethylenediaminetriacetic acid.

[0123] In an embodiment of the present disclosure, based on the total weight of component ag being 100 weight %, the weight proportion of component ag is as follows:

[0124] The content of component a may be 72-85% by weight, for example, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85% by weight, or a range limited by any two thereof;

[0125] The content of component b may be 10-23% by weight, for example, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23% by weight, or a range limited by any two thereof;

[0126] The content of component c may be 1.5-4% by weight, for example, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0% by weight, or a range bounded by any two thereof;

[0127] The content of component d can be 0-3% by weight, for example, 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8-, 2.9, 3.0% by weight, or a range bounded by any two thereof;

[0128] The content of component e can be 0.1-3% by weight, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0% by weight, or the range limited by any two thereof;

[0129] The content of component f can be 0 to 3 weight %, for example, 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0 weight %, or a range limited by any two thereof;

[0130] The content of component g can be 0.4-2.5% by weight, for example, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5% by weight, or a range limited by any two thereof.

[0131] In one embodiment of the present disclosure, based on the total weight of the polyurethane-polyurea aqueous dispersion, the content of polyurethane-polyurea in the aqueous dispersion is 35 wt % or more, for example, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 wt %, or a range limited by any two thereof.

[0132] The particle size of the polyurethane-polyurea dispersed in the polyurethane-polyurea aqueous dispersion is not particularly limited, for example, it can be: less than 2 μm, for example, 10 nm, 20 nm, 40 nm, 60 nm, 80 nm, 100 nm, 120 nm, 140 nm, 160 nm, 180 nm, 200 nm, 220 nm, 240 nm, 260 nm, 280 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, 1200 nm, 1400 nm, 1600 nm, 1800 nm, 2000 nm,

[0133] The particle size can be measured by methods well known to those skilled in the art. For example, the particle size can be measured by a laser particle size analyzer (such as commercially available from Malvern).

[0134] In the context of the present disclosure, unless otherwise specified, the terms "particle diameter", "particle size", "particle size" and "particle size" are used interchangeably.

[0135] In the context of this disclosure, unless otherwise specified, the term particle size refers to the volume average particle size D v 50, that is, in the volume cumulative distribution curve, 50% of the volume of the particles have a particle size higher than this particle size value, and 50% of the volume of the particles have a particle size lower than this particle size value.

[0136] The applicant has discovered that when the polyurethane-polyurea polymer in the polyurethane-polyurea aqueous dispersion contains terminal polycarboxyl groups and / or carboxylate structures, the terminal polycarboxyl groups and / or carboxylate structures can effectively reduce the concentration of metal ions such as calcium ions from the coagulant solution that accumulate in the rubber compound containing the polyurethane-polyurea aqueous dispersion used to prepare gloves, thereby effectively reducing the destructive effects of calcium ions and other metal ions on the rubber compound, extending the service life of the rubber compound, and simultaneously improving the mechanical properties of the produced gloves, such as having improved elongation and excellent tensile strength.

[0137] The polyurethane-polyurea copolymer also forms an aspect of the present disclosure. All the above descriptions of the polyurethane-polyurea copolymer in the polyurethane-polyurea aqueous dispersion are applicable to the polyurethane-polyurea copolymer. No further description will be given here.

[0138] Preparation method of polyurethane-polyurea aqueous dispersion

[0139] In a second aspect, the present disclosure provides a method for preparing the polyurethane-polyurea aqueous dispersion of the first aspect of the present disclosure, the preparation method comprising preparing the polyurethane-polyurea by:

[0140] A polyurethane prepolymer containing terminal isocyanate groups, preferably at least two terminal isocyanate groups, is reacted with a polyamine containing at least two amine groups selected from primary and / or secondary amine groups and an isocyanate-reactive compound containing a single amine group selected from primary or secondary amine groups or a hydroxyl group and containing multiple carboxyl groups.

[0141] The amine groups contained in the polyamine containing at least two amine groups selected from primary and / or secondary amine groups may all be primary amine groups, or all be secondary amine groups, or at least one of them may be a primary amine group and at least one may be a secondary amine group.

[0142] In a preferred embodiment, the preparation method comprises the following steps:

[0143] - reacting component a, component b, component c, and optionally component d in a first inert solvent to obtain a prepolymer containing terminal isocyanate groups, preferably at least two terminal isocyanate groups;

[0144] - optionally diluting with a second inert solvent;

[0145] - Add component e to neutralize, then add water to disperse evenly to obtain a dispersion containing an inert solvent;

[0146] - Add components f and g to the dispersion containing the inert solvent and continue the reaction;

[0147] - removing the inert solvent to obtain a polyurethane-polyurea aqueous dispersion free of inert solvent;

[0148] - optionally, converting the terminal carboxyl groups in the polyurethane-polyurea into carboxylate groups,

[0149] The second inert solvent is the same as or different from the first inert solvent.

[0150] The above descriptions on components ag in the polyurethane-polyurea aqueous dispersion of the first aspect of the present disclosure are all applicable here.

[0151] In this disclosure, "inert solvent" refers to a solvent that does not react with the components used to prepare the polyurethane-polyurea.

[0152] The first inert solvent and the second inert solvent are not particularly limited. The first inert solvent and the second inert solvent may be the same or different. For example, the first inert solvent and the second inert solvent may each independently be an ester solvent or a ketone solvent. Non-limiting examples of the ester solvent include esters formed by C1-C20 monocarboxylic acids and C1-C20 monohydric alcohols, such as ethyl acetate, methyl propionate, ethyl propionate, etc. Non-limiting examples of the ketone solvent include acetone, butanone (methyl ethyl ketone), pentanone, cyclopentanone, hexanone, cyclohexanone, etc.

[0153] The method of removing the solvent may be any method known to those skilled in the art. As a non-limiting example, the solvent may be removed by distillation under normal or reduced pressure.

[0154] In the present disclosure, the terminal carboxyl groups in the polyurethane-polyurea can be converted into carboxylate groups by using a basic compound. Preferably, the basic compound is an alkali metal compound.

[0155] As non-limiting examples of alkali metal compounds that can be used in the present disclosure, there can be mentioned alkali metal hydroxides, alkali metal carbonates, alkali metal carboxylates, alkali metal nitrates, alkali metal sulfates, alkali metal halides, alkali metal pseudohalides, etc. In a preferred embodiment of the present disclosure, the alkali metal compound is an alkali metal hydroxide and / or an alkali metal carbonate. In a more preferred embodiment, the alkali metal compound is sodium hydroxide and / or sodium carbonate.

[0156] The alkali metal compound can be added directly to the polyurethane-polyurea aqueous dispersion without an inert solvent in solid form. Alternatively, the alkali metal compound can be added to the polyurethane-polyurea aqueous dispersion without an inert solvent in solution form.

[0157] The applicant has discovered that by reacting a polyurethane prepolymer containing terminal isocyanate groups with a polyamine and a compound reactive with isocyanate and containing a single amino group selected from a primary or secondary amino group or a hydroxyl group and multiple carboxyl groups, a polyurethane-polyurea polymer having multiple carboxyl functional groups or carboxyl salts thereof (e.g., sodium carboxylate) at the ends of its chain segments is obtained. This prevents metal ions from a coagulant solution from damaging the stability of the rubber compound containing the polyurethane-polyurea polymer used to prepare the gloves during the preparation of the gloves, while simultaneously improving the mechanical properties of the prepared gloves, such as having improved elongation and excellent tensile strength.

[0158] Uses of polyurethane-polyurea aqueous dispersions

[0159] In a third aspect, the present disclosure provides use of the polyurethane-polyurea aqueous dispersion of the first aspect of the present disclosure or the polyurethane-polyurea aqueous dispersion prepared by the method of the second aspect of the present disclosure for preparing a flocculation-processed aqueous polyurethane glove slurry or a polyurethane glove.

[0160] In the present disclosure, “polyurethane gloves,” “polyurethane-polyurea gloves,” “polyurethane-polyurea polymer gloves,” and “polyurethane-polyurea copolymer gloves” have the same meaning, which all refer to gloves comprising the polyurethane-polyurea copolymer described in relation to the first aspect of the present disclosure as a constituent component (e.g., a constituent layer), and are used interchangeably herein.

[0161] Polyurethane slurry

[0162] In a fourth aspect, the present disclosure provides a polyurethane slurry comprising the polyurethane-polyurea aqueous dispersion of the first aspect of the present disclosure or the polyurethane-polyurea aqueous dispersion prepared by the method of the second aspect of the present disclosure, a crosslinker, an optional ion sequestering agent, and optionally additional water.

[0163] The additional water means water other than the water contained in the polyurethane-polyurea aqueous dispersion.

[0164] The cross-linking agent that can be used in the present disclosure is not particularly limited. In a preferred embodiment of the present disclosure, the cross-linking agent comprises one or more of polyfunctional aziridine, carbodiimide, amino resin, and sorbitol polyglycidyl ether.

[0165] The cross-linking agent that can be used in the present disclosure is not particularly limited. In one embodiment of the present disclosure, the ion chelating agent comprises one or more of sodium gluconate, sodium tartrate, disodium ethylenediaminetetraacetate, and sodium diethylenetriaminepentaacetate.

[0166] In a preferred embodiment of the present disclosure, the weight ratio of the polyurethane-polyurea aqueous dispersion, the crosslinking agent, the ion chelating agent and the additional water is 100:0.3-1.2:0.01-0.5:100-200.

[0167] For example, based on 100 parts by weight of the polyurethane-polyurea aqueous dispersion, the content of the crosslinking agent may be 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2 parts by weight, or a range limited by any two thereof.

[0168] For example, based on 100 parts by weight of the polyurethane-polyurea aqueous dispersion, the content of the ion chelating agent may be 0.01, 0.02, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50 parts by weight, or a range limited by any two of them.

[0169] For example, based on 100 parts by weight of the polyurethane-polyurea aqueous dispersion, the additional water content can be 100, 110, 120, 130, 140, 150 parts by weight, or 160 parts by weight, or 170 parts by weight, or 180 parts by weight, or 190 parts by weight, or 200 parts by weight.

[0170] Method for preparing polyurethane gloves

[0171] In a fifth aspect, the present disclosure provides a method for preparing a polyurethane glove, the method comprising the step of preparing a polyurethane layer using the slurry according to the fourth aspect of the present disclosure.

[0172] In the present disclosure, "polyurethane layer", "polyurethane-polyurea layer", "polyurethane-polyurea polymer layer" and "polyurethane-polyurea copolymer layer" have the same meaning and all refer to the layer formed by the polyurethane-polyurea (copolymer) described with respect to the polyurethane-polyurea aqueous dispersion of the first aspect of the present disclosure.

[0173] In a non-limiting embodiment, the method of the fifth aspect of the present disclosure comprises the following steps:

[0174] S1: dipping the optionally cleaned hand mold in a coagulant solution, and optionally drying it thereafter, to obtain a first-treated hand mold;

[0175] S2: dipping the hand mold subjected to the first treatment into the slurry of the fourth aspect of the present disclosure, and optionally drying the hand mold; optionally repeating the dipping and drying process one or more times to obtain a hand mold subjected to the second treatment;

[0176] S3: Optionally, cleaning the second treated hand mold with water, and optionally drying it thereafter, to obtain a third treated hand mold;

[0177] S4: Optionally, dipping the hand mold subjected to the second treatment or the hand mold subjected to the third treatment into a slippery coating liquid;

[0178] S5: curling, plasticizing, and demoulding to obtain polyurethane gloves.

[0179] In one embodiment, the hand mold is cleaned before being immersed in the coagulant solution. The cleaning can be performed by known means in the art and is not particularly limited. For example, the cleaning can be performed by immersing the hand mold in an acid solution (e.g., nitric acid), then immersing the hand mold in an aqueous alkali solution (e.g., sodium hydroxide), then washing with water, and then drying.

[0180] The coagulant that can be used in the present disclosure is not particularly limited. For example, the coagulant solution includes a soluble salt, a release agent, and water.

[0181] The soluble salt has a divalent or higher valent cation, such as but not limited to: Mg 2+ , Ca 2+ 、Al 3+ In a preferred embodiment, the soluble salt may be chloride, nitrate, etc. In a more preferred embodiment, the soluble salt may be selected from one or more of calcium nitrate, calcium chloride, magnesium nitrate, magnesium chloride, zinc nitrate and zinc chloride.

[0182] The release agent that can be used in the present disclosure can be any release agent known to those skilled in the art, such as calcium stearate, zinc stearate, magnesium stearate, starch, etc. The release agent can be commercially obtained, for example, under the brand names ZK-40 and LU-101.

[0183] In one embodiment of the present disclosure, the weight ratio of the soluble salt, the release agent and water may be 15 to 30 (15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, or a range defined by any two thereof): 8 to 20 (8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, or a range defined by any two thereof): 150 to 250 (150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, or a range defined by any two thereof).

[0184] In one embodiment, the handform is dried after being dipped in the coagulant solution.

[0185] In one embodiment, the process of dipping the first treated hand mold in the slurry of the fourth aspect of the present disclosure, and optionally drying it, in step S2 is performed once. Alternatively, the process can be performed multiple times (e.g., 2, 3, or more times) depending on the desired thickness of the polyurethane layer. In one embodiment, drying is performed after dipping the first treated hand mold in the slurry of the fourth aspect of the present disclosure.

[0186] In one embodiment, step S3 may not be performed.

[0187] In one embodiment, step S3 is performed, that is, cleaning the second treated hand form with water, and optionally drying it, to obtain a third treated hand form. In one embodiment, drying is performed after cleaning the second treated hand form with water.

[0188] The method may optionally include a step of immersing the handform in a slippery coating liquid (to form a slippery coating). When step S3 is not performed, the second-treated handform is directly immersed in the slippery coating liquid. When step S3 is performed, the third-treated handform is immersed in the slippery coating liquid. In one embodiment of the present disclosure, the slippery coating liquid comprises one or more of a polyurethane (PU) coating, an acrylic coating, a corn starch coating, and a talc coating. In a preferred embodiment, the slippery coating liquid is a polyurethane (PU) coating.

[0189] In step S5, curling, plasticizing, and demoulding are performed to obtain polyurethane gloves.

[0190] The curling, plasticizing and demoulding can be performed by any suitable method known in the art and are not particularly limited.

[0191] The drying in steps S1 to S3 can each be independently performed by any known method and is not particularly limited.

[0192] In one embodiment, in step S2, the hand mold may be dried after being taken out of the dipping process. The drying may be performed, for example, by oven drying.

[0193] Drying can be carried out in any equipment known to those skilled in the art, such as but not limited to a forced air oven or a vacuum oven.

[0194] In a preferred embodiment of the present disclosure, when the dipping and drying process is repeated multiple times in S2, drying is performed after each dipping step.

[0195] The drying conditions can be selected according to the impregnation process. Preferably, the drying can be performed at a temperature of 80-150° C. For example, the drying can be performed at a temperature of 80, 90, 100, 110, 120, 130, 140, 150° C., or a range defined by any two of these.

[0196] The plasticization in step S5 can be performed by methods known to those skilled in the art, such as, but not limited to, baking. In some embodiments of the present disclosure, the plasticization can be performed at a temperature of 110 to 140° C., for example, at a temperature of 115° C., 120° C., 125° C., 130° C., 135° C., or 140° C. The duration of plasticization can be adjusted according to the raw materials used. In some embodiments, the plasticization can last for 20 to 40 minutes, for example, 20, 25, 30, 35, or 40 minutes.

[0197] Polyurethane gloves

[0198] In a sixth aspect, the present disclosure provides a polyurethane glove comprising a polyurethane layer prepared using the slurry of the fourth aspect as a raw material.

[0199] Preferably, the polyurethane gloves are prepared using the method of the fifth aspect of the present disclosure.

[0200] The gloves may only comprise a polyurethane layer prepared using the slurry of the fourth aspect as a raw material. The gloves may also further comprise other layers, such as a slippery coating, as required.

[0201] By introducing a polycarboxyl group structure at the end of the polyurethane-polyurea polymer chain, the stability of the polyurethane-polyurea aqueous dispersion under high electrolyte conditions is improved. By using the polyurethane-polyurea aqueous dispersion disclosed herein, even without adding an additional metal chelating agent to the glove slurry formulation, the destructive effects of metal ions such as calcium ions from the coagulant solution on the rubber compound containing the polyurethane-polyurea aqueous dispersion used to make gloves can be effectively reduced, extending the service life of the rubber compound. Furthermore, the mechanical properties of the gloves produced can be improved, such as enhanced elongation and excellent tensile strength.

[0202] The applicants of the present disclosure have further discovered that, unexpectedly, if a chelating agent is further included in the polyurethane-polyurea aqueous dispersion, the chelating agent can produce a synergistic effect with the polyurethane-polyurea molecules, further significantly extending the service life of the rubber compound and improving the mechanical properties of the prepared gloves, such as having improved elongation and excellent tensile strength.

[0203] Example

[0204] The following examples further illustrate the technical solutions provided by the present disclosure, but the present disclosure is not limited to the listed examples.

[0205] Main raw materials

[0206] Poly(neopentyl adipate) glycol, OH value = 56 mg KOH / g, brand WHP205, Wanhua Chemical;

[0207] Poly(hexanediol-neopentyl glycol-adipate diol), OH value = 56 mg KOH / g, brand WHP2056, Wanhua Chemical;

[0208] Poly(methyl propylene glycol adipate), OH value = 56 mg KOH / g, brand WHP208, Wanhua Chemical;

[0209] Poly(ethylene glycol adipate), OH value = 56 mg KOH / g, WHP207, Wanhua Chemical;

[0210] Polytetramethylene glycol, PTMEG 2000, OH value = 56 mgKOH / g, Mitsubishi Chemical, Japan;

[0211] 4,4'-dicyclohexylmethane diisocyanate (HMDI), from Wanhua Chemical;

[0212] Isophorone diisocyanate (IPDI), from Wanhua Chemical;

[0213] Neopentyl glycol (NPG), from Wanhua Chemical;

[0214] Butanediol was from Sinopharm Chemical Reagent Company;

[0215] triethylamine, from Sinopharm Chemical Reagent Company;

[0216] Ethylenediamine, from Sinopharm Chemical Reagent Company;

[0217] diethanolamine, from Sinopharm Chemical Reagent Company;

[0218] Ethylenediaminetriacetic acid was from Sinopharm Chemical Reagent Company;

[0219] Dihydroxypropionic acid (DMPA), Sinopharm Chemical Reagent Company

[0220] Sodium gluconate, Sinopharm Chemical Reagent Company

[0221] Etherified amino resin crosslinker, CYMEL 385 from Allnex

[0222] PU coating, Stahl WF-78-923

[0223] Release agent, Zhukun ZK-40

[0224] Characterization methods

[0225] Average particle size Dv50: The polyurethane dispersion was diluted with water to a concentration of 0.5 wt % and measured using a Malvern Nano-ZS90;

[0226] pH value: measured using a Metrohm 6173 pH meter;

[0227] -NCO determination: The -NCO content in the polyurethane synthesis process is determined according to the chemical industry standard "HG / T2409-92 Determination of Isocyanate Group Content in Polyurethane Prepolymers".

[0228] Terminal carboxyl content: obtained through theoretical calculation based on raw materials.

[0229] Tensile strength: measured using a universal testing machine (model: GT-7005-A2LT, from High Speed ​​Rail Testing Instruments (Dongguan) Co., Ltd.) at a temperature of 24-26°C and a humidity of 40-50%.

[0230] Elongation: measured using a universal testing machine (model: GT-7005-A2LT, from High Speed ​​Rail Testing Instruments (Dongguan) Co., Ltd.) at a temperature of 24-26°C and a humidity of 40-50%.

[0231] Calcium ion content: tested by inductively coupled plasma optical emission spectrometer (purchased from Thermo Fisher Scientific, USA).

[0232] Example 1

[0233] 400 g of WHP205, 78 g of IPDI, 8 g of DMPA (dimethylolpropionic acid), and 60 g of acetone were added to a 1 L four-necked round-bottom flask equipped with a nitrogen inlet and outlet. The mixture was stirred at 80°C until the NCO content reached 1.40 wt%. The mixture was cooled to 40°C and diluted with 330 g of acetone. 6.0 g of triethylamine was added for neutralization for 5 minutes. 900 g of deionized water was added with high-speed stirring for 10 minutes. Post-chain extension was performed by adding 3 g of ethylenediamine and 6.0 g of ethylenediaminetriacetic acid for 15 minutes. After removing the acetone by distillation, a solvent-free polyurethane-polyurea aqueous dispersion was obtained. The resulting polyurethane-polyurea aqueous dispersion had a solids content of 35 wt%, an average particle size of 200 nm, and a pH of 8.3. The terminal carboxyl group content of the resulting polyurethane-polyurea was 15.35 mmol / 100 g (the terminal carboxyl group content is calculated relative to the total weight of the polyurethane-polyurea, the same applies hereinafter).

[0234] Gloves were prepared using the polyurethane-polyurea aqueous dispersion prepared in the above example (weight of the polyurethane-polyurea aqueous dispersion: 1000 g):

[0235] 100 parts by weight of polyurethane-polyurea aqueous dispersion, 1.2 parts by weight of etherified amino resin crosslinking agent, 0.1 parts by weight of sodium gluconate, and 100 parts by weight of deionized water were mixed and stirred for 2 hours to obtain a slurry.

[0236] Pre-treat the glove formers: first clean the glove formers in a nitric acid solution with a pH value of 3, then clean them in an aqueous sodium hydroxide solution with a pH value of 12, then rinse them clean and dry them in an oven at 75°C.

[0237] Prepare a coagulant solution: add 18 parts by weight of calcium nitrate, 10 parts by weight of a release agent, and 170 parts by weight of deionized water into a mixing barrel, and stir evenly to obtain a coagulant solution.

[0238] Prepare the coating solution: add 5 parts by weight of PU coating and 95 parts by weight of deionized water into a mixing barrel, stir evenly, and obtain a coating aqueous solution.

[0239] The pretreated glove former was immersed in a coagulant solution at 75°C for 20 seconds, dried at 100°C, then immersed in the slurry at 25°C for 10 seconds, dried at 110°C, immersed in the slurry at 25°C for 10 seconds again, dried at 100°C, leached, dipped in a coating solution, crimped, placed in an oven at 125°C, heated for 25 minutes, and demolded to obtain a polyurethane glove.

[0240] Example 2

[0241] 450 g of WHP207, 125 g of HMDI, 16 g of DMPA, 2 g of NPG, and 70 g of acetone were added to a 1 L four-necked round-bottom flask equipped with a nitrogen inlet and outlet. The mixture was stirred at 85°C until the NCO content reached 1.43 wt%. The mixture was cooled to 40°C and diluted with 477 g of acetone. 12.0 g of triethylamine was then added for neutralization over approximately 5 minutes. Subsequently, 1210 g of deionized water was added with high-speed stirring for dispersion over approximately 10 minutes. 2 g of ethylenediamine and 13 g of ethylenediaminetriacetic acid were then added for post-chain extension over approximately 15 minutes. The acetone was then removed by distillation to yield a solvent-free polyurethane-polyurea aqueous dispersion having a solids content of 35 wt%, an average particle size of 78 nm, and a pH of 8.7. The resulting polyurethane-polyurea had a terminal carboxyl group content of 26.82 mmol / 100 g.

[0242] Gloves were prepared using the polyurethane-polyurea aqueous dispersion prepared in the above example (weight of the polyurethane-polyurea aqueous dispersion: 1000 g):

[0243] 100 parts by weight of polyurethane-polyurea aqueous dispersion, 1.0 part by weight of amino resin crosslinking agent, 0.3 part by weight of sodium gluconate, and 120 parts by weight of deionized water were mixed and stirred for 2 hours to obtain a slurry.

[0244] Pre-treat the glove formers: first clean the glove formers in a nitric acid solution with a pH value of 3, then clean them in an aqueous sodium hydroxide solution with a pH value of 12, then rinse them clean and dry them in an oven at 75°C.

[0245] Prepare a coagulant solution: add 20 parts by weight of calcium nitrate, 15 parts by weight of a release agent, and 200 parts by weight of deionized water into a mixing barrel, and stir evenly to obtain a coagulant solution.

[0246] Prepare the coating solution: add 5 parts by weight of PU coating and 95 parts by weight of deionized water into a mixing barrel, stir evenly, and obtain a coating aqueous solution.

[0247] The pretreated glove former was immersed in a coagulant solution at 75°C for 20 seconds, dried at 100°C, then immersed in the slurry at 25°C for 10 seconds, dried at 100°C, immersed in the slurry at 25°C for 10 seconds again, dried at 100°C, leached, dipped in a coating solution, crimped, placed in an oven at 135°C, heated for 30 minutes, and demolded to obtain a polyurethane glove.

[0248] Example 3

[0249] 428g of WHP2056, 69g of IPDI, 45g of HMDI, 10g of DMPA, 3.5g of butanediol, and 80g of acetone were added to a 1L four-necked round-bottom flask equipped with a nitrogen inlet and outlet. The mixture was stirred at 80°C until the NCO content reached 2.04% by weight. The mixture was cooled to 40°C and diluted with 449g of acetone. 7.55g of triethylamine was then added for neutralization over approximately 5 minutes. Subsequently, 1141g of deionized water was added with high-speed stirring for dispersion over approximately 10 minutes. Post-chain extension was then performed by adding 6g of ethylenediamine and 1.2g of ethylenediaminetriacetic acid over approximately 15 minutes. A solvent-free polyurethane-polyurea aqueous dispersion was obtained after removing the acetone by distillation. The resulting polyurethane-polyurea aqueous dispersion had a solids content of 35% by weight, an average particle size of 169nm, and a pH of 8.3. The terminal carboxyl group content of the resulting polyurethane-polyurea was 13.46mmol / 100g.

[0250] Gloves were prepared using the polyurethane-polyurea aqueous dispersion prepared in the above example (weight of the polyurethane-polyurea aqueous dispersion: 1000 g):

[0251] 100 parts by weight of polyurethane-polyurea aqueous dispersion, 0.8 parts by weight of etherified amino resin crosslinking agent, 0.3 parts by weight of sodium gluconate, and 130 parts by weight of deionized water were mixed and stirred for 2 hours to obtain a slurry.

[0252] Pre-treat the glove formers: first clean the glove formers in a nitric acid solution with a pH value of 3, then clean them in an aqueous sodium hydroxide solution with a pH value of 12, then rinse them clean and dry them in an oven at 75°C.

[0253] Prepare a coagulant solution: add 22 parts by weight of calcium nitrate, 11 parts by weight of a release agent, and 200 parts by weight of deionized water into a mixing barrel, and stir evenly to obtain a coagulant solution.

[0254] Prepare the coating solution: add 5 parts by weight of talc and 95 parts by weight of deionized water into a mixing barrel, stir evenly, and obtain a coating aqueous solution.

[0255] The pretreated glove former was immersed in a coagulant solution at 75°C for 20 seconds, dried at 100°C, then immersed in the slurry at 25°C for 10 seconds, dried at 120°C, immersed in the slurry at 25°C for 10 seconds again, dried at 120°C, leached, dipped in a coating solution, crimped, placed in an oven at 130°C, heated for 35 minutes, and demolded to obtain a polyurethane glove.

[0256] Example 4

[0257] 500g of PTMEG2000, 107g of IPDI, 13g of DMPA, and 78g of acetone were added to a 1L four-necked round-bottom flask equipped with a nitrogen inlet and outlet. The mixture was stirred at 80°C until the NCO content reached 1.61% by weight. The mixture was cooled to 40°C and diluted with 548g of acetone. 8.8g of triethylamine was then added for neutralization over approximately 5 minutes. 1270g of deionized water was then added with high-speed stirring for dispersion over approximately 10 minutes. 6g of ethylenediamine and 4.5g of ethylenediaminetriacetic acid were then added for post-chain extension over approximately 15 minutes. The acetone was then removed by distillation to yield a solvent-free polyurethane-polyurea aqueous dispersion. The resulting polyurethane-polyurea aqueous dispersion had a solids content of 35% by weight, an average particle size of 109nm, and a pH of 8.5. The resulting polyurethane-polyurea contained 9.10mmol / 100g of terminal carboxyl groups.

[0258] Gloves were prepared using the polyurethane-polyurea aqueous dispersion prepared in the above example (weight of the polyurethane-polyurea aqueous dispersion: 1000 g):

[0259] 100 parts by weight of polyurethane-polyurea aqueous dispersion, 0.9 parts by weight of amino resin crosslinking agent, 0.2 parts by weight of sodium gluconate, and 100 parts by weight of deionized water were mixed and stirred for 2 hours to obtain a slurry.

[0260] Pre-treat the glove formers: first clean the glove formers in a nitric acid solution with a pH value of 3, then clean them in an aqueous sodium hydroxide solution with a pH value of 12, then rinse them clean and dry them in an oven at 75°C.

[0261] Prepare a coagulant solution: add 21 parts by weight of calcium nitrate, 15 parts by weight of a release agent, and 223 parts by weight of deionized water into a mixing barrel and stir evenly to obtain a coagulant solution.

[0262] Prepare coating solution: add 5 parts by weight of PU coating and 95 parts by weight of deionized water into a mixing barrel, stir evenly, and obtain a coating aqueous solution.

[0263] The pretreated glove former was immersed in a coagulant solution at 75°C for 20 seconds, dried at 100°C, then immersed in the slurry at 25°C for 10 seconds, dried at 100°C, immersed in the slurry at 25°C for 10 seconds again, dried at 100°C, leached, dipped in a coating solution, crimped, placed in an oven at 125°C, heated for 25 minutes, and demolded to obtain a polyurethane glove.

[0264] Example 5

[0265] The chelating agent sodium gluconate is not added to the gloves of this embodiment.

[0266] 500g of PTMEG2000, 107g of IPDI, 13g of DMPA, and 78g of acetone were added to a 1L four-necked round-bottom flask equipped with a nitrogen inlet and outlet. The mixture was stirred at 80°C until the NCO content reached 1.61% by weight. The mixture was cooled to 40°C and diluted with 548g of acetone. 8.8g of triethylamine was then added for neutralization over approximately 5 minutes. Subsequently, 1270g of deionized water was added with high-speed stirring for dispersion over approximately 10 minutes. Subsequently, 6g of ethylenediamine and 4.5g of ethylenediaminetriacetic acid were added for post-chain extension over approximately 15 minutes. The acetone was then removed by distillation to yield a solvent-free polyurethane-polyurea aqueous dispersion having a solids content of 35% by weight, an average particle size of 109nm, and a pH of 8.5. The resulting polyurethane-polyurea contained 9.10mmol / 100g of terminal carboxyl groups.

[0267] Gloves were prepared using the polyurethane-polyurea aqueous dispersion prepared in the above example (weight of the polyurethane-polyurea aqueous dispersion: 1000 g):

[0268] 100 parts by weight of polyurethane-polyurea aqueous dispersion, 0.9 parts by weight of amino resin crosslinking agent, and 100 parts by weight of deionized water were mixed and stirred for 2 hours to obtain a slurry.

[0269] Pre-treat the glove formers: first clean the glove formers in a nitric acid solution with a pH value of 3, then clean them in an aqueous sodium hydroxide solution with a pH value of 12, then rinse them clean and dry them in an oven at 75°C.

[0270] Prepare a coagulant solution: add 21 parts by weight of calcium nitrate, 15 parts by weight of a release agent, and 223 parts by weight of deionized water into a mixing barrel and stir evenly to obtain a coagulant solution.

[0271] Prepare the coating solution: add 5 parts by weight of PU coating and 95 parts by weight of deionized water into a mixing barrel, stir evenly, and obtain a coating aqueous solution.

[0272] The pretreated glove former was immersed in a coagulant solution at 75°C for 20 seconds, dried at 100°C, then immersed in the slurry at 25°C for 10 seconds, dried at 100°C, immersed in the slurry at 25°C for 10 seconds again, dried at 100°C, leached, dipped in a coating solution, crimped, placed in an oven at 125°C, heated for 25 minutes, and demolded to obtain a polyurethane glove.

[0273] Comparative Example 1

[0274] The ethylenediaminetriacetic acid in Example 1 was replaced with an equal molar amount of diethanolamine, with all other modifications remaining unchanged. The resulting polyurethane-polyurea aqueous dispersion had a solids content of 35 wt%, an average particle size of 207 nm, a pH of 8.3, and a terminal carboxyl group content of 0 mmol / 100 g.

[0275] Gloves were prepared using the polyurethane-polyurea aqueous dispersion prepared in the above example (weight of the polyurethane-polyurea aqueous dispersion: 1000 g):

[0276] 100 parts by weight of polyurethane-polyurea aqueous dispersion, 3 parts by weight of amino resin crosslinking agent, and 100 parts by weight of deionized water were mixed and stirred for 2 hours to obtain a slurry.

[0277] Pre-treat the glove formers: first clean the glove formers in a nitric acid solution with a pH value of 3, then clean them in an aqueous sodium hydroxide solution with a pH value of 12, then rinse them clean and dry them in an oven at 75°C.

[0278] Prepare a coagulant solution: add 12 parts by weight of calcium nitrate, 10 parts by weight of a release agent, and 170 parts by weight of deionized water into a mixing barrel, and stir evenly to obtain a coagulant solution.

[0279] Prepare the coating solution: add 5 parts by weight of PU coating and 95 parts by weight of deionized water into a mixing barrel, stir evenly, and obtain a coating aqueous solution.

[0280] The pretreated glove former was immersed in a coagulant solution at 75°C for 20 seconds, dried at 100°C, then immersed in the slurry at 25°C for 10 seconds, dried at 100°C, immersed in the slurry at 25°C for 10 seconds again, dried at 100°C, leached, dipped in a coating solution, crimped, placed in an oven at 125°C, heated for 25 minutes, and demolded to obtain a polyurethane glove.

[0281] Comparative Example 2

[0282] The half mole of ethylenediaminetriacetic acid in Example 4 was replaced by an equal mole of diethanolamine.

[0283] 500g of PTMEG2000, 107g of IPDI, 13g of DMPA, and 78g of acetone were added to a 1L four-necked round-bottom flask equipped with a nitrogen inlet and outlet. The mixture was stirred at 80°C until the NCO content reached 1.61% by weight. The mixture was cooled to 40°C and diluted with 548g of acetone. 8.8g of triethylamine was then added for neutralization for approximately 5 minutes. The mixture was then dispersed in 1270g of deionized water with high-speed stirring for approximately 10 minutes. Post-chain extension was then performed by adding 6g of ethylenediamine, 2.25g of ethylenediaminetriacetic acid, and 1.0g of diethanolamine for approximately 15 minutes. The acetone was then removed by distillation to obtain a solvent-free polyurethane-polyurea aqueous dispersion. The resulting polyurethane-polyurea aqueous dispersion had a solids content of 35% by weight, an average particle size of 109nm, a pH of 8.5, and a terminal carboxyl group content of 4.55mmol / 100g.

[0284] Gloves were prepared using the polyurethane-polyurea aqueous dispersion prepared in the above example (weight of the polyurethane-polyurea aqueous dispersion: 1000 g):

[0285] 100 parts by weight of polyurethane-polyurea aqueous dispersion, 3 parts by weight of amino resin crosslinking agent, 0.05 parts by weight of sodium gluconate, and 100 parts by weight of deionized water were mixed and stirred for 2 hours to obtain a slurry.

[0286] Pre-treat the glove formers: first clean the glove formers in a nitric acid solution with a pH value of 3, then clean them in an aqueous sodium hydroxide solution with a pH value of 12, then rinse them clean and dry them in an oven at 75°C.

[0287] Prepare a coagulant solution: add 21 parts by weight of calcium nitrate, 15 parts by weight of a release agent, and 223 parts by weight of deionized water into a mixing barrel and stir evenly to obtain a coagulant solution.

[0288] Prepare coating solution: add 5 parts by weight of PU coating and 95 parts by weight of deionized water into a mixing barrel, stir evenly, and obtain a coating aqueous solution.

[0289] The pretreated glove former was immersed in a coagulant solution at 75°C for 20 seconds, dried at 100°C, then immersed in the slurry at 25°C for 10 seconds, dried at 100°C, immersed in the slurry at 25°C for 10 seconds again, dried at 100°C, leached, dipped in a coating solution, crimped, placed in an oven at 125°C, heated for 25 minutes, and demolded to obtain a polyurethane glove.

[0290] Comparative Example 3

[0291] Example 4 was repeated except that ethylenediaminetriacetic acid was replaced by an equal molar amount of diethanolamine.

[0292] Comparative Example 4

[0293] Example 5 was repeated except that ethylenediaminetriacetic acid was replaced by an equal molar amount of diethanolamine.

[0294] Glove performance testing:

[0295] The palm area of ​​the prepared polyurethane gloves was cut according to ASTM D412, and the tensile strength and elongation of the sliced ​​samples were tested. At the same time, the calcium ion content in the prepared latex was tested when the gloves were continuously dipped for 200 times. The test results are shown in Table 1.

[0296] Table 1. Performance test results

[0297] As can be seen from Table 1 above, the presence of terminal polycarboxyl structures in the polyurethane-polyurea aqueous dispersion and the introduction of metal ion chelators in the glove formula can effectively reduce the enrichment of calcium ions in the rubber compound, improve the stability of the latex during continuous operation of the production line, and at the same time enhance the strength of the gloves.

[0298] In addition, by comparing Examples 4-5 and Comparative Example 3 with Comparative Example 4, it can be found that:

[0299] - In terms of composition, the difference between Example 4 and Comparative Example 4 is equivalent to the sum of (the difference between Example 5 and Comparative Example 4) and (the difference between Comparative Example 3 and Comparative Example 4).

[0300] Example 5 differs from Comparative Example 4 in that the polyurethane-polyurea polymer in Example 5 contains terminal carboxyl groups, but no metal ion chelating agent is added to the polyurethane-polyurea aqueous dispersion. The results in Table 3 show that compared to Comparative Example 4, Example 5 maintains the same tensile strength, increases elongation by 7%, and reduces the amount of calcium ions in the rubber compound by 238 ppm.

[0301] Comparative Example 3 differs from Comparative Example 4 in that the polyurethane-polyurea polymer in Comparative Example 3 lacks terminal carboxyl groups, but the polyurethane-polyurea aqueous dispersion contains an additional metal ion chelating agent. The results in Table 3 show that compared to Comparative Example 4, Example 4 exhibits essentially unchanged tensile strength, a -40% increase in elongation, and a -110 ppm reduction in calcium ion content.

[0302] Example 4 differs from Comparative Example 4 in that the polyurethane-polyurea polymer in Example 4 contains terminal carboxyl groups, and the polyurethane-polyurea aqueous dispersion contains an additional metal ion chelating agent. The results in Table 3 show that compared to Comparative Example 4, Example 4 exhibits essentially unchanged tensile strength, a 10% increase in elongation, and a 250 ppm reduction in calcium ion content. Both values ​​are greater than the sum of the changes in Example 5 relative to Comparative Example 4 and the changes in Comparative Example 3 relative to Comparative Example 4.

[0303] It can be seen that when the polyurethane-polyurea containing terminal carboxyl groups is used in combination with another metal chelating agent, the effect of the combination of the terminal carboxyl groups and the metal chelating agent in increasing the elongation of the product and reducing the calcium ion content in the rubber compound is greater than the sum of the technical effects produced by the terminal carboxyl groups and the metal chelating agent alone.

[0304] Therefore, in the polyurethane-polyurea aqueous dispersion of the present disclosure, the carboxyl or carboxylate groups at the ends of the polyurethane-polyurea polymers and the additionally added metal chelating agent achieve a synergistic effect in improving the elongation of the product and reducing the calcium ion content in the latex, while achieving this synergistic effect without compromising the tensile strength of the product. Thus, the present disclosure avoids the destabilization of the rubber compound by metal ions while improving the mechanical properties of the resulting gloves, such as improved elongation and excellent tensile strength.

[0305] The foregoing description is merely an exemplary embodiment of the present disclosure and is not intended to limit the scope of protection of the present disclosure. The scope of protection of the present disclosure is determined by the appended claims.

Claims

1. A polyurethane-polyurea aqueous dispersion, characterized in that: The polyurethane-polyurea aqueous dispersion comprises a polyurethane-polyurea having terminal polycarboxylic acid and / or carboxylate groups dispersed in water.

2. The polyurethane-polyurea aqueous dispersion according to claim 1, characterized in that The content of the terminal polycarboxylic acid and / or carboxylate groups is 7-30 mmol / 100 g, for example 9 to 27 mmol / 100 g, based on the total weight of the polyurethane-polyurea.

3. The polyurethane-polyurea aqueous dispersion according to any one of claims 1 to 2, characterized in that: The polyurethane-polyurea is prepared by reacting raw materials comprising the following components: Component a: one or more polyether or polyester polyols, wherein the number average molecular weight of the polyether or polyester polyol is greater than 500 g / mol; Component b: one or more polyisocyanates; Component c: one or more hydrophilic compounds, wherein the hydrophilic compound contains 2-3 groups reactive with NCO, and the hydrophilic groups of the hydrophilic compound include ionic groups and / or potential ionic groups; Optional component d: one or more alcohol chain extenders different from component a, having a number average molecular weight of 300 g / mol or less; Component e: one or more compounds that ionize the potentially ionic groups in component c, having the structural formula R1R2R3N, wherein R1-R3 are the same as or different from each other and are independently selected from H, or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, or C5-C6 cycloalkyl groups that are unsubstituted or substituted with OH; Component f: one or more polyamines containing at least two amino groups selected from primary and / or secondary amino groups, having a number average molecular weight of 500 g / mol or less; Component g: one or more compounds reactive with isocyanate containing a single amino group selected from primary or secondary amino groups or a hydroxyl group and containing multiple carboxyl groups; The terminal polycarboxylic acid and / or carboxylate groups in the polyurethane-polyurea are introduced by component g.

4. The polyurethane-polyurea aqueous dispersion according to any one of claims 1 to 3, characterized in that - Component a is one or more of diol, triol and tetraol, preferably diol, preferably component a has a number average molecular weight of 500 to 6000 g / mol, for example 500 to 5000 g / mol / mole; and / or - Component b is one or more of aromatic, aliphatic and alicyclic polyisocyanates having at least two, preferably two, isocyanate groups; and / or - Component c is one or more selected from dimethylolpropionic acid, dimethylolbutanoic acid, and aminosulfonates, more preferably dimethylolpropionic acid; and / or - the component d is selected from one or more of 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, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and 2-ethyl-1,3-hexanediol; preferably, component d is selected from one or more of 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol and 1,4-cyclohexanedimethanol; and / or - the component e is an organic tertiary amine, such as triethylamine, dimethylethanolamine, triisopropylamine, or ammonia, preferably component e is triethylamine; and / or - the component f is a polyamine having a number average molecular weight of 60 to 500 g / mol, preferably component f is selected from 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 component f is ethylenediamine and / or isophoronediamine; and / or - The number of carboxyl groups in the component g is 2 or more, for example 3 or more, and preferably the component g is ethylenediaminetriacetic acid.

5. The polyurethane-polyurea aqueous dispersion according to any one of claims 1 to 4, characterized in that Based on the total weight of component ag being 100%, the weight proportion of component ag is as follows: Component a: 72-85 wt%; Component b: 10-23 wt%; Component c: 1.5-4 wt%; Component d: 0-3 wt%; Component e: 0.1-3 wt%; Component f: 0-3 wt%; Component g: 0.4-2.5% by weight.

6. The polyurethane-polyurea aqueous dispersion according to any one of claims 1 to 5, characterized in that The content of the polyurethane-polyurea in the polyurethane-polyurea aqueous dispersion is 35% by weight or more, based on the total weight of the polyurethane-polyurea aqueous dispersion.

7. A method for preparing the polyurethane-polyurea aqueous dispersion according to any one of claims 1 to 6, characterized in that: The preparation method comprises preparing the polyurethane-polyurea by: A prepolymer containing terminal isocyanate groups, preferably at least two terminal isocyanate groups, is reacted with a polyamine containing at least two amine groups selected from primary and / or secondary amine groups and an isocyanate-reactive compound containing a single amine group selected from primary or secondary amine groups or a hydroxyl group and containing multiple carboxyl groups.

8. The method according to claim 7, wherein The preparation method comprises the following steps: - reacting component a, component b, component c, and optionally component d in a first inert solvent to obtain a prepolymer containing terminal isocyanate groups, preferably at least two terminal isocyanate groups; - optionally diluting with a second inert solvent; - Add component e to neutralize, then add water to disperse evenly to obtain a dispersion containing an inert solvent; - Add components f and g to the dispersion containing an inert solvent and continue the reaction; - removing the inert solvent to obtain a polyurethane-polyurea aqueous dispersion free of inert solvent; - optionally, converting the terminal carboxyl groups in the polyurethane-polyurea into carboxylate groups, The second inert solvent is the same as or different from the first inert solvent.

9. The method according to claim 7 or 8, characterized in that The step of converting the terminal carboxyl groups in the polyurethane-polyurea into carboxylate groups is performed by adding a basic compound, preferably an alkali metal compound, more preferably sodium hydroxide and / or sodium carbonate, to the polyurethane-polyurea aqueous dispersion containing no inert solvent.

10. Use of the polyurethane-polyurea aqueous dispersion according to any one of claims 1 to 6, or the polyurethane-polyurea aqueous dispersion prepared by the method according to any one of claims 7 to 9, in preparing a slurry for flocculation-processed water-based polyurethane gloves, or polyurethane gloves.

11. A slurry comprising the polyurethane-polyurea aqueous dispersion according to any one of claims 1 to 6 or prepared by the preparation method according to any one of claims 7 to 9, a crosslinking agent, an optional ion chelating agent, and optionally additional water.

12. The slurry according to claim 11, characterized in that The cross-linking agent comprises one or more of multifunctional aziridine, carbodiimide, amino resin, and sorbitol polyglycidyl ether; And / or, the ion chelating agent comprises one or more of sodium gluconate, sodium tartrate, disodium ethylenediaminetetraacetate, and sodium diethylenetriaminepentaacetate; Preferably, the weight ratio of the polyurethane-polyurea aqueous dispersion, the crosslinking agent, the ion chelating agent and the additional water is 100:0.3-1.2:0.01-0.5:100-200.

13. A method for preparing a polyurethane glove comprising a polyurethane layer, characterized in that: The method comprises the step of preparing a polyurethane layer using the slurry according to any one of claims 11 to 12.

14. The method of claim 13, wherein the method comprises the steps of: S1: dipping the optionally cleaned hand mold in a coagulant solution, and optionally drying it thereafter, to obtain a first-treated hand mold; S2: dipping the first treated hand mold in the slurry according to any one of claims 11 to 12, and optionally drying the hand mold; optionally repeating the dipping and drying process one or more times to obtain a second treated hand mold; S3: Optionally, cleaning the second treated hand mold with water, and optionally drying it thereafter, to obtain a third treated hand mold; S4: Optionally, dipping the hand mold subjected to the second treatment or the hand mold subjected to the third treatment into a slippery coating liquid; S5: curling, plasticizing, and demoulding to obtain polyurethane gloves.

15. The method according to claim 14, characterized in that The coagulant solution comprises a soluble salt, a release agent and water; Preferably, the soluble salt is selected from one or more of calcium nitrate, calcium chloride, magnesium nitrate, magnesium chloride, zinc nitrate and zinc chloride; Preferably, the weight ratio of the soluble salt, the release agent and water is 15-30:8-20:150-250; And / or, the slippery coating liquid comprises one or more of PU coating, acrylic coating, corn starch coating, and talcum powder coating; And / or, the dipping and drying process in step S2 is performed at least twice, and the drying in step S2 is oven drying; preferably, the oven drying temperature is 80-150° C., preferably 90-140° C.; And / or, the plasticizing in step S5 is performed by baking at a temperature of 110 to 140° C. for 20 to 40 minutes.

16. Polyurethane gloves, comprising a polyurethane layer prepared using the slurry according to claim 11 or 12 as a raw material, preferably the gloves are obtained by the method according to any one of claims 13 to 15.

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