Polyurethane-polyurea aqueous dispersion, method of preparation thereof, and use

Abstract

The present invention provides a polyurethane-polyurea aqueous dispersion, a method for preparing the same, and uses thereof. The polyurethane-polyurea aqueous dispersion contains units derived from component a, wherein component a contains at least one polyol having a functionality of 2 or more, and component a contains at least 40 wt% or more of a semi-crystalline polyester polyol obtained by reacting a dihydric alcohol with component I, wherein component I contains an aliphatic dicarboxylic acid and component II in a molar ratio of 2.1 to 10:1, and component II is an aromatic dicarboxylic acid and / or an aromatic dicarboxylic acid anhydride. The soft elastic products manufactured based on the polyurethane-polyurea aqueous dispersion according to the present invention can have comprehensive performances such as good elasticity, strength, water resistance, and wearing feeling.

Description

Technical Field

[0001] The present invention relates to the technical field of manufacturing soft elastic products (such as gloves, condoms, etc.), and particularly relates to a polyurethane-polyurea aqueous dispersion, a preparation method thereof, and use, which are advantageous for obtaining high-performance soft elastic products.

Background Art

[0002] Soft elastic products, such as disposable glove products, are widely applied in fields such as medical gloves, inspection gloves, household and industrial uses, etc. Currently, the materials used for manufacturing soft elastic products (such as disposable gloves, condoms, etc.) in the market mainly include natural latex, chloroprene rubber, nitrile rubber, PVC, etc. Since natural latex contains proteins, it is likely to cause allergic reactions in some people. In addition, products such as chloroprene rubber and nitrile rubber have problems such as strong odor and high production pollution degree. Comparatively, polyurethane dispersions are superior to the resins of several of the above materials in terms of mechanical strength, stretchability, air permeability, and environmental protection in the glove manufacturing process. Currently, there are several research reports on producing soft elastic products using polyurethane.

[0003] Patent document CN104725590B discloses a polyurethane dispersion with a low elastic modulus used for disposable gloves. The polyurethane dispersion employs poly(tetramethylene oxide) glycol, polypropylene glycol, and tolylene diisocyanate as raw materials. The manufactured gloves have performance similar to rubber products. However, the products manufactured with polypropylene glycol have problems such as poor water resistance. When exposed to water during use, the strength reduction is very significant, and there is no practical use value.

[0004] Patent document CN108864394A discloses gloves for medical use manufactured by compounding sulfonate polyester and polypropylene glycol, and states that they have excellent alcohol resistance. However, in reality, none of the systems using polypropylene glycol have achieved good alcohol resistance, and the overall strength of the gloves is low, making them unsuitable for many applications.

[0005] In patent document CN106188477B, a highly elastic polyurethane aqueous dispersion is synthesized using a polyether and a high molecular weight rebound elastic agent and used in the manufacture of gloves. However, the highly crosslinked structure in this polyurethane dispersion is unfavorable for elasticity, and the document only evaluates the mechanical properties of the resin and does not say anything about the manufacture or performance of the gloves. [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] The present invention provides a polyurethane-polyurea aqueous dispersion applicable to the manufacture of flexible elastic products, and enables the manufacture of flexible elastic products based on this polyurethane-polyurea aqueous dispersion, which can combine good overall performance such as elasticity, strength, water resistance, and wearability. [Means for solving the problem]

[0007] To achieve this objective, the present invention provides the following technical solutions.

[0008] The present invention The compound comprises units derived from component a, wherein component a contains at least one polyol with a functional value of 2 or higher, and component a contains at least 40 wt% of a semicrystalline polyester polyol obtained by reacting a dihydric alcohol with component I, of which component I comprises an aliphatic dicarboxylic acid and component II in a molar ratio of 2.1 to 10:1, and component II is an aromatic dicarboxylic acid and / or an aromatic dicarboxylic acid anhydride. We provide polyurethane-polyurea aqueous dispersions.

[0009] In some embodiments, the dihydric alcohol used in the preparation of the semicrystalline polyester polyol comprises at least one or more of 1,4-butanediol and 1,6-hexanediol, and may further comprise other dihydric alcohols having a relative molecular weight less than 150, wherein the other dihydric alcohol comprises one or more of ethylene glycol, 1,3-butanediol, neopentyl glycol, 1,5-pentanediol, propylene glycol, diethylene glycol, and dipropylene glycol, and the proportion of the other dihydric alcohols in the preparation of the semicrystalline polyester polyol is less than 50 wt%. and / or, the component II used in the preparation of the semicrystalline polyester polyol is one or more selected from phthalic acid and phthalic anhydride, preferably the phthalic acid is selected from isophthalic acid and / or orthophthalic acid, and more preferably the component II is isophthalic acid. and / or, the aliphatic dicarboxylic acid used in the preparation of the semicrystalline polyester polyol is adipic acid.

[0010] In some embodiments, the semicrystalline polyester polyol is an opaque, waxy solid at room temperature.

[0011] In some embodiments, the polyurethane-polyurea aqueous dispersion is Component a preferably contains at least one polyol with a functional value of 2 or more, and the proportion of the semicrystalline polyester polyol in component a is 40 wt% or more, and the proportion of the semicrystalline polyester polyol in component a is 70 to 100 wt%. Component b is a polyisocyanate. A hydrophilic compound containing 2 to 3 groups that are reactive with NCO, wherein the hydrophilic groups of the hydrophilic compound are hydrophilic compounds containing one or more types of ionic groups and latent ionic groups, component c Selectively, component d, which is an alcohol-based chain extender different from component a, Component f is a polyamine with a number-average molecular weight of 500 g / mol or less. It is prepared by reacting raw materials containing the following component.

[0012] In some embodiments, if the hydrophilic group of component c does not contain the ionic group, the raw material further comprises component e, which is a compound that can ionize component c. Preferably, when the raw material contains component e, the proportion of each component used in the preparation of the polyurethane-polyurea aqueous dispersion is as follows, based on the total weight of components a, b, c, d, e, and f: component a is 56-85 wt%, component b is 10-30 wt%, component c is 0.8-4 wt%, component d is 0-3 wt%, component f is 0.5-4 wt%, and component e is 0.6-4 wt%. Preferably, if the raw material does not contain component e, the proportion of each component used in the preparation of the polyurethane-polyurea dispersion, based on the total weight of components a, b, c, d, and f, is 56-85 wt% for component a, 10-30 wt% for component b, 0.8-4 wt% for component c, 0-3 wt% for component d, and 0.5-4 wt% for component f.

[0013] In some embodiments, in component a, the number average molecular weight of the polyol is preferably 500 to 15000 g / mol, the polyol preferably has a number average molecular weight of 800 to 10000 g / mol and a functional value of 2 to 4, and more preferably has a number average molecular weight of 1000 to 5000 g / mol and a functional value of 2 to 3. and / or, in component b, the polyisocyanate is one or more selected from aromatic, aliphatic, and alicyclic polyisocyanates, and it is preferable that the polyisocyanate has at least two isocyanate groups. and / or, in component c, the groups that are reactive with the NCO contained in the hydrophilic compound are hydroxyl groups and / or amino groups. and / or, in component c, the ionic group is preferably a carboxylate ion and / or a sulfonate ion, and the latent ionic group is preferably a carboxyl group. and / or, in component d, the alcohol-based chain extender different from component a is a small-molecule alcohol-based compound with a relative molecular weight less than 150. and / or, component e is triethylamine, And / or, component f is a polyamine with a relative molecular weight of 60 to 500, and is preferably one or more of ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-hexanediamine, 2-methylpentane-1,5-diamine, isophoronediamine, 4,4-diaminodicyclohexylmethane, piperazine, and diethylenetriamine.

[0014] In some embodiments, the hydrophilic compound as component c is one or more selected from dimethylolpropionic acid, dimethylolbutanoic acid, dihydroxysuccinic acid, N-(2-aminoethyl)-2-aminoethanesulfonic acid, N-(3-aminopropyl)-2-aminoethanesulfonic acid and its salts, wherein the salt comprises one or more of the corresponding alkali metal salts, alkaline earth metal salts, or ammonium salts, and component c is preferably dimethylolpropionic acid. and / or, the alcohol-based chain extender as component d is ethylene glycol, 1,2-propanediol, 1,3-propanediol, 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- The active ingredient is one or more selected from dodecanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and 2-ethyl-1,3-hexanediol, with one or more preferred from 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, and 1,4-cyclohexanedimethanol and 1,6-hexanediol.

[0015] In some embodiments, component a may contain other polyols different from the semicrystalline polyester polyol, the other polyol being one or more selected from polyester polyols, polycaprolactone polyols, polycarbonate polyols, and polyether polyols, and the proportion of the other polyol in component a being 0 to 60 wt%.

[0016] The present invention The polyurethane-polyurea aqueous dispersion is prepared by reacting a raw material containing component a. Preferably, the raw material further comprises component b, component c, a selective component d, and component f. However, if component b is a polyisocyanate, component c is a hydrophilic compound, the hydrophilic compound contains 2 to 3 groups that are reactive with NCO, component d is an alcohol-based chain extender different from component a, component f is a polyamine with a number average molecular weight of 500 g / mol or less, and component c does not contain an ionic group, then the raw material further contains component e, and component e is a compound that can ionize component c. Preferably, it includes a step of reacting at 60 to 90 °C to obtain a prepolymer of the blocked isocyanate. Furthermore, provided is a method for preparing the polyurethane-polyurea aqueous dispersion described above.

[0017] The present invention A soft elastic product manufactured by the polyurethane-polyurea aqueous dispersion described above, preferably including gloves and / or condoms. Furthermore, provided is a soft elastic product.

[0018] The present invention It includes a step of adding a raw material liquid containing the polyurethane-polyurea aqueous dispersion to a mold required for manufacturing a soft elastic product. Preferably, the soft elastic product includes gloves and / or condoms, and the polyurethane-polyurea aqueous dispersion employs the polyurethane-polyurea aqueous dispersion described above. Furthermore, provided is a method for manufacturing a soft elastic product.

Effects of the Invention

[0019] The technical solution according to the present invention has the following beneficial effects.

[0020] The polyurethane-polyurea dispersion according to the present invention is obtained by a polyol component (i.e., component a) containing at least 40 wt% or more of a semi-crystalline polyester polyol containing a benzene ring structure. The semi-crystalline polyester polyol is obtained by reacting a divalent alcohol with an aliphatic dicarboxylic acid and component II (aromatic dicarboxylic acid and / or aromatic dianhydride) in a specific molar ratio. Soft elastic products prepared with such a polyurethane-polyurea dispersion, such as gloves, condoms, etc., have excellent comprehensive performance and can combine good tensile strength, elongation rate, resilience, wearing comfort, and water resistance, and have excellent resistance to oxides and polar solvents. Based on the polyurethane-polyurea dispersion of the present invention, soft elastic products applicable to medical, household, and industrial uses, such as gloves, can be manufactured, and it is particularly applicable to the production of condoms.

Modes for Carrying Out the Invention

[0021] To facilitate understanding of the present invention, the invention will be further described below with reference to examples. It should be understood that the following examples are merely for the purpose of better understanding the present invention and do not imply that the invention is limited to these examples alone.

[0022] Unless otherwise specified, all technical or scientific terms used herein have the same meaning as those commonly understood by those skilled in the art. The terms “and / or” as used herein include any combination and all combinations of one or more related items listed.

[0023] Where specific experimental procedures or conditions are not specified in the examples, they should be carried out according to the operations or conditions of the corresponding standard experimental procedures in the art. Unless the manufacturer of the reagents or equipment used is specified, they are all standard products available on the market.

[0024] In one embodiment, the present invention provides a polyurethane-polyurea aqueous dispersion comprising a unit derived from component a, wherein component a comprises at least one polyol with a functional value of 2 or higher, and component a comprises at least 40 wt% of a semicrystalline polyester polyol obtained by reacting a dihydric alcohol with component I, of which component I comprises an aliphatic dicarboxylic acid and component II in a molar ratio of 2.1 to 10:1 (for example, molar ratios of 2.1:1, 2.5:1, 3:1, 4.5:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, etc.), and component II is an aromatic dicarboxylic acid and / or an aromatic dihydrohydride.

[0025] The present inventors have found that when preparing a polyurethane-polyurea aqueous dispersion, the polyol used (component a) comprises at least 40 wt% (e.g., 40 wt%, 42 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 90 wt%, 100%, etc.) of a semicrystalline polyester polyol, and that the semicrystalline polyester polyol is obtained by esterifying an aliphatic dicarboxylic acid and component II (aromatic dicarboxylic acid and / or aromatic dicarboxylic acid anhydride) with a dihydric alcohol in a molar ratio of 2.1 to 10:1, and that the dispersion is prepared according to the embodiment of the present invention. Polyurethane-polyurea dispersions can reduce the crystallinity of polyester, improve elasticity, and acquire good properties such as strength. When this polyurethane-polyurea aqueous dispersion is used in the manufacture of soft elastic products, the resulting polyurethane-polyurea aqueous dispersion is particularly applicable to the manufacture of soft elastic products, such as gloves and / or condoms. It has been found that when this polyurethane-polyurea aqueous dispersion is used in the manufacture of soft elastic products, the resulting soft elastic products have significantly improved overall performance, possessing good tensile strength, elongation, and rebound elasticity, resulting in a soft material with good elasticity and an improved wearing comfort. On the other hand, when semicrystalline polyester polyol is not used, or when the proportion of semicrystalline polyester polyol in the polyol (component a) is lower than 40 wt%, or when the semicrystalline polyester polyol is obtained from an aliphatic dicarboxylic acid and component II (aromatic dicarboxylic acid and / or aromatic dihydrohydride) that do not satisfy a molar ratio of 2.1 to 10:1, the resulting soft elastic products show a clear deterioration in performance and cannot possess good overall performance.

[0026] In a preferred embodiment, the proportion of the semicrystalline polyester polyol obtained by reacting the dihydric alcohol with component I in component a reaches 70-100 wt%, which is advantageous for obtaining a soft elastic product with better performance.

[0027] In some preferred embodiments, the dihydric alcohol used in the preparation of the semicrystalline polyester polyol comprises at least one or more of 1,4-butanediol and 1,6-hexanediol, and may further comprise other dihydric alcohols having a relative molecular weight less than 150, the other dihydric alcohols comprising one or more of ethylene glycol, 1,3-butanediol, neopentyl glycol, 1,5-pentanediol, propylene glycol, diethylene glycol, dipropylene glycol, etc., wherein the proportion of the other dihydric alcohols in the preparation of the semicrystalline polyester polyol is less than 50 wt%, i.e., the amount used is less than that of 1,4-butanediol and / or 1,6-hexanediol. When preparing the semicrystalline polyester polyol, those skilled in the art can easily determine the amount of dihydric alcohol used in the reaction system from the target molecular weight. When preparing semicrystalline polyester polyols, the dihydric alcohol used is preferably 1,4-butanediol and / or 1,6-hexanediol, or preferably 50 wt% (based on the total amount of dihydric alcohol) or more of 1,4-butanediol and / or 1,6-hexanediol, which can improve the performance of the resulting soft elastic product.

[0028] In some preferred embodiments, component II used in the preparation of the semicrystalline polyester polyol is one or more selected from phthalic acid and phthalic anhydride, preferably the phthalic acid is selected from isophthalic acid and / or orthophthalic acid, and more preferably component II is isophthalic acid. The use of isophthalic acid is preferable and advantageous for obtaining a soft elastic product with better performance.

[0029] In some preferred embodiments, the aliphatic dicarboxylic acid used in the preparation of the semicrystalline polyester polyol is adipic acid.

[0030] In some more preferred embodiments, the dihydric alcohol used in the preparation of the semicrystalline polyester polyol comprises at least one or more of 1,4-butanediol and 1,6-hexanediol, and the component II used is one or more selected from isophthalic acid, orthophthalic acid, and phthalic anhydride, with isophthalic acid being preferred, and the aliphatic dicarboxylic acid used is adipic acid, with a molar ratio of adipic acid to component II being 2.1 to 10:1. The polyurethane-polyurea aqueous dispersion prepared with the preferred semicrystalline polyester polyol can obtain better product performance, and the resulting product has significantly improved tensile strength, elongation, rebound elasticity, wearability, and water resistance. The semicrystalline polyester polyol obtained in this preferred manner is an opaque, waxy solid at room temperature, and the semicrystalline polyester polyol has a certain regularity, where room temperature refers to 25°C.

[0031] In the polyurethane-polyurea aqueous dispersion of the present invention, the semicrystalline polyester polyol used may be prepared by conventional polyester polyol preparation processes in the art, or a commercially available product that satisfies the above requirements may be directly adopted. Specifically, the semicrystalline polyester polyol can be prepared by a melt polycondensation method well known to those skilled in the art, which can be done by directly referring to existing processes, and exemplary, for example, by referring to the method for preparing polyester polyols in Patent CN110724249B, specifically by referring to the examples in said document. For example, the necessary amounts of aliphatic dicarboxylic acid, component II (aromatic dicarboxylic acid and / or aromatic dicarboxylic acid anhydride), and dihydric alcohol for the preparation of semicrystalline polyester polyol are placed in a reaction vessel, the system is heated to 130-180°C and reacted until the system becomes transparent, the system is heated to 200-230°C and reacted until the amount of water effluent approaches the theoretical amount (e.g., reacted for about 2-3 hours), then the catalyst is added, the system is heated to 235-250°C and the vacuum device is turned on (e.g., at a vacuum pressure of -0.095 MPa), the reaction is continued until the acid value of the system reaches 0.3 mg KOH / g or less, then the system is cooled (e.g., cooled to about 120°C), withdrawn, and packaged to obtain the desired semicrystalline polyester polyol. During the reaction process, a catalyst may be added to the reaction vessel as needed. For example, the catalyst may be one or more selected from organotin, organobismuth, organotitanium compounds (e.g., tetrabutyl titanate, tetraisopropyl titanate, etc.), and the amount of catalyst used may be 50 to 300 ppm of the total mass of the reactants. During the preparation process, the ratio of dibasic acid to dihydric alcohol can be determined from the molecular weight of the target polyester polyol, and typically, the amount of dihydric alcohol used may be 105 to 120% of the theoretical charge.

[0032] In some embodiments, component a may include other polyols different from the semicrystalline polyester polyol. In some embodiments, in component a, the number average molecular weight of the polyols (i.e., semicrystalline polyester polyols and selective other polyols) is 500 to 15000 g / mol, and the polyols are preferably polyols with a number average molecular weight of 800 to 10000 g / mol and a functional value of 2 to 4, and more preferably polyols with a number average molecular weight of 1000 to 5000 g / mol and a functional value of 2 to 3.

[0033] Here, the other polyol in component a may be one or more selected from polyester polyols, polycaprolactone polyols, polycarbonate polyols, and polyether polyols, and the proportion of the other polyol in component a is 0 to 60 wt%. There are no particular restrictions on the specific selection of the above other polyols, and polyols that can be normally added to polyurethane-polyurea aqueous dispersions can be used.

[0034] Specifically, among the other polyols mentioned above, polyester polyols can be obtained, for example, by reacting a polyol with a carboxylic acid and / or acid anhydride through a known preparation process, for example, by dehydration condensation of a polyol with an aliphatic, alicyclic, aromatic dicarboxylic acid or polycarboxylic acid or the corresponding acid anhydride. Examples of the carboxylic acid or acid anhydride include, but are not limited to, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, maleic acid, fumaric acid, malonic acid, trimellitic acid, phthalic anhydride, trimellitic anhydride, succinic anhydride, or mixtures thereof. Examples of the polyols include, but are not limited to, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,4-dihydroxycyclohexane, 1,4-dimethylolcyclohexane, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, or mixtures thereof. Selectively, polyols with higher functional values, such as trimethylolpropane, can be added. The polyester polyol may further contain a polyester containing fatty acids, having an average OH functional value of about 2, and may further contain transesterification products of castor oil and other oils. Preferably, the other polyol in component a is a polyester polyol whose structural components include a dibasic acid containing one or more of isophthalic acid, terephthalic acid, and adipic acid, and a dihydric alcohol containing one or more of neopentyl glycol, ethylene glycol, butanediol, and hexanediol.

[0035] Other polyester polyols may include lactone homopolymers or copolymers, which can be obtained by ring-opening a lactone or a mixture of lactones with a polyol having a suitable bifunctional and / or higher functional value.

[0036] Polycarbonates having hydroxyl groups prepared using diols and carbonates are also suitable as the other polyols in component a. Here, the diol used in the polycarbonate is preferably 1,4-butanediol and / or 1,6-hexanediol, and the carbonate may be diaryl carbonate and / or dialkyl carbonate, where diaryl carbonate is, for example, diphenyl carbonate and dialkyl carbonate is, for example, dimethyl carbonate.

[0037] Polyether polyols are also suitable as the other polyols in component a, and a preferred polyether polyol is polytetrahydrofuran polyol. When other polyols are added to component a, it is preferable that the other polyol is polytetrahydrofuran polyol, as this allows for the acquisition of suitable elasticity.

[0038] In some embodiments, polyurethane-polyurea aqueous dispersions are Component a contains at least one polyol with a functional value of 2 or higher, and the proportion of semicrystalline polyester polyol in component a is 40 wt% or more. Component b is a polyisocyanate. Component c is a hydrophilic compound containing 2-3 groups that are reactive with NCO. Selectively, component d, which is an alcohol-based chain extender different from component a, Component f is a polyamine with a number-average molecular weight of 500 g / mol or less. It is prepared by reacting raw materials containing the following component.

[0039] If the hydrophilic group of component c does not contain the ionic group, the raw material further contains component e, which is a compound that can ionize component c that does not contain an ionic group. If component c contains an ionic group, it is not necessary to add component e.

[0040] In some embodiments, when the raw material contains component e, the proportion of each component used in the preparation of the polyurethane-polyurea dispersion is 56-85 wt% for component a, 10-30 wt% for component b, 0.8-4 wt% for component c, 0-3 wt% for component d, 0.5-4 wt% for component f, and 0.6-4 wt% for component e, based on the total weight of components a, b, c, d, e, and f.

[0041] If the raw material does not contain component e, the proportion of each component used in the preparation of the polyurethane-polyurea dispersion, based on the total weight of components a, b, c, d, and f, is 56-85 wt% for component a, 10-30 wt% for component b, 0.8-4 wt% for component c, 0-3 wt% for component d, and 0.5-4 wt% for component f.

[0042] In component b, there are no particular restrictions on the specific selection of the polyisocyanate, and polyisocyanates commonly used in the art can be used. In some embodiments, the polyisocyanate may be one or more selected from aromatic, aliphatic, and alicyclic polyisocyanates, and a preferred polyisocyanate has at least two isocyanate groups. Preferably, the molecular formula of the polyisocyanate is Y(NCO)2, where Y represents a divalent aliphatic hydrocarbon group containing 4 to 12 carbon atoms, a divalent alicyclic hydrocarbon group containing 6 to 15 carbon atoms, a divalent aromatic hydrocarbon group containing 6 to 15 carbon atoms, or a divalent aromatic aliphatic hydrocarbon group containing 7 to 15 carbon atoms. In some embodiments, the polyisocyanate may be one or more of the following: tetramethylene diisocyanate, methylpentamethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 4,4'-dicyclohexylpropane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tole diisocyanate, 2,6-tole diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, p-xylylene diisocyanate, and p-isopropylidene diisocyanate. Component b may further contain a small amount of polyisocyanate with a higher functional value known in polyurethane chemistry, or a modified polyisocyanate containing, for example, a carbodiimide group, an allophanate group, an isocyanurate group, a urethane group, and / or a biuret group. Preferably, component b is one or more of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate, and tolylene diisocyanate.

[0043] In some embodiments, in component c, the group that is reactive with NCO contained in the hydrophilic compound is a hydroxyl group and / or an amino group. In some embodiments, in component c, the hydrophilic group of the hydrophilic compound includes one or more ionic groups and latent ionic groups, the ionic group is preferably a carboxylate ion and / or a sulfonate ion, and the latent ionic group is preferably a carboxyl group. In some embodiments, the hydrophilic compound as component c is one or more selected from dimethylolpropionic acid, dimethylolbutanoic acid, dihydroxysuccinic acid, N-(2-aminoethyl)-2-aminoethanesulfonic acid, N-(3-aminopropyl)-2-aminoethanesulfonic acid and its salts, the salt includes one or more of the corresponding alkali metal salts, alkaline earth metal salts or ammonium salts, and component c is preferably dimethylolpropionic acid.

[0044] In some embodiments, in component d, the alcohol-based chain extender, which is different from component a, is a small-molecule alcohol-based compound with a relative molecular weight less than 150. In some embodiments, the alcohol-based chain extender as component d is one or more selected from ethylene glycol, 1,2-propanediol, 1,3-propanediol, 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, and preferably one or more selected from 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, and 1,4-cyclohexanedimethanol, and 1,6-hexanediol.

[0045] In some embodiments, component e is a volatile tertiary amine compound, preferably triethylamine.

[0046] In some embodiments, component f is a polyamine with a relative molecular weight of 60 to 500, and is preferably one or more of ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-hexanediamine, 2-methylpentane-1,5-diamine, isophoronediamine, 4,4-diaminodicyclohexylmethane, piperazine, and diethylenetriamine, and is preferably one or two of ethylenediamine and isophoronediamine.

[0047] In this invention, unless otherwise specified, the meaning of "many" in "many types" and "multiple values" both refers to two or more.

[0048] The polyurethane-polyurea aqueous dispersion of the present invention can be prepared by referring to existing polyurethane-polyurea aqueous dispersion preparation processes in the art, and there are no particular requirements therefor. Specifically, the polyurethane-polyurea aqueous dispersion is prepared by reacting a raw material containing component a. More specifically, the raw material further comprises component b, component c, selective component d and component f. Thereafter, component b is a polyisocyanate, component c is a hydrophilic compound containing 2 to 3 groups that are reactive with NCO, component d is an alcohol-based chain extender different from component a, component f is a polyamine with a number average molecular weight of 500 g / mol or less, and if component c does not contain an ionic group, the raw material further comprises component e, which is a compound that can ionize component c. Preferably, the preparation method includes a step of reacting at 60 to 90°C to obtain a prepolymer of blocked isocyanate. For reference, if component c does not contain an ionic group, the specific preparation steps include reacting components a, b, c, and a selective component d at 60-90°C in the presence of a solvent (e.g., acetone) to obtain a prepolymer of blocked isocyanate, diluting with a solvent (e.g., acetone), adding component e to neutralize, dispersing (e.g., dispersing with water under high-speed stirring at 800-1000 r / min), adding component f to carry out a chain extension reaction, removing the solvent (acetone) after the reaction is complete to obtain a polyurethane-polyurea aqueous dispersion. If component c contains an ionic group, the specific preparation steps include reacting components a, b, and a selective component d at 60-90°C in the presence of a solvent (e.g., acetone) to obtain a prepolymer of blocked isocyanate, diluting with a solvent (e.g., acetone), adding components c and f to continue the reaction, then adding water to disperse, removing the solvent (acetone) to obtain a polyurethane-polyurea aqueous dispersion.

[0049] The components and other related details concerning the preparation of the polyurethane-polyurea aqueous dispersion in the above preparation method can be found in the description of the polyurethane-polyurea aqueous dispersion above, and are therefore omitted from this explanation.

[0050] In some embodiments, the polyurethane-polyurea aqueous dispersion prepared according to the present invention has a solid content of 35 wt% or more, preferably 35-40 wt%, a pH of 6-10, and an average particle size of, for example, 80-300 nm.

[0051] The present invention further provides a flexible elastic product, which is manufactured from the polyurethane-polyurea aqueous dispersion described above, and preferably the flexible elastic product may be a variety of products having flexibility and elastic properties, such as gloves and / or condoms, but is not limited thereto.

[0052] The present invention further provides a method for manufacturing a flexible elastic product, comprising the step of adding a raw material solution containing the polyurethane-polyurea aqueous dispersion of the present invention described above to a mold necessary for manufacturing a flexible elastic product, preferably the flexible elastic product including gloves and / or condoms. Specific steps of the method for manufacturing the flexible elastic product can be carried out by reference to existing corresponding conventional processes, but it is important to use the polyurethane-polyurea aqueous dispersion according to the present invention as the raw material solution. Any aspects of the method for manufacturing the flexible elastic product not specifically described can be carried out by reference to corresponding conventional processes for manufacturing flexible elastic products in the art. Taking the manufacture of gloves as an example, the exemplary manufacturing steps for reference include preparing a raw material solution with a polyurethane-polyurea aqueous dispersion according to the present invention and other auxiliary materials, such as water necessary for diluting the dispersion and a color paste or titanium white to be added according to the needs of the product; and immersing the glove mold in a coagulation solution (for example, an aqueous solution containing 10 wt% calcium chloride and 5 wt% release agent (for example, calcium stearate)), removing it and drying it, then immersing it in the raw material solution, removing it and drying it (the operation of immersing in the raw material solution and drying it can be repeated depending on the actual situation), immersing it in a glove coating agent as needed, removing it and drying it, then demolding it to obtain the finished glove.

[0053] The present invention will be described illustratively below with reference to specific examples.

[0054] A description of some of the raw materials used in the examples or comparative examples is as follows:

[0055] Here, polyols 1-3 and 7-8 were prepared according to the following synthesis method.

[0056] The necessary components I, dihydric alcohol, and catalyst were placed in a reaction vessel according to the proportions, the system was heated to 140°C and reacted until the system became transparent, then the system was heated to 210-220°C and reacted until the amount of water effluent was close to the theoretical amount (reacting for about 2-3 hours), then the system was heated to 235-240°C, the vacuum device was turned on, and the system was reacted under a vacuum pressure of -0.095 MPa to reduce the acid value of the system to 0.3 mg KOH / g or less, then the system was cooled to about 120°C, withdrawn, packaged, and polyester polyol was obtained.

[0057] Polyol 1 (semicrystalline polyester polyol): polyadipic acid / isophthalic acid / 1,4-butanediol ester (where the molar ratio of adipic acid to isophthalic acid used is 2.3:1), with a functional value of 2, Mn=2000, and is an opaque, waxy solid at room temperature. When polyol 1 was prepared, the molar ratio of 1,4-butanediol to component I was 1.21:1, and the catalyst used was tetrabutyl titanate at a concentration of 100 ppm.

[0058] Polyol 2 (semicrystalline polyester polyol): polyadipic acid / isophthalic acid / 1,6-hexanediol ester (where the molar ratio of adipic acid to isophthalic acid used is 3.0:1), with a functional value of 2, Mn=2000, and is an opaque waxy solid at room temperature. When polyol 2 was prepared, the molar ratio of 1,6-hexanediol to component I was 1.27:1, and the catalyst used was tetrabutyl titanate at a concentration of 100 ppm.

[0059] Polyol 3 (semicrystalline polyester polyol): polyadipic acid / isophthalic acid / 1,4-butanediol / neopentyl glycol ester (where the molar ratio of adipic acid to isophthalic acid is 4.5:1), with a functional value of 2, Mn=3000, and is an opaque waxy solid at room temperature. When polyol 3 was prepared, the molar ratio of the total amount of 1,4-butanediol and neopentyl glycol to component I was 1.17:1, the catalyst was tetraisopropyl titanate used at a concentration of 150 ppm, and the molar ratio of 1,4-butanediol to neopentyl glycol was 7:3.

[0060] The polyol 4 was polyadipic acid / 1,4-butanediol polyester / neopentyl glycol ester, with a functional value of 2, Mn=3000, semi-crystalline, and an opaque, waxy solid at room temperature. Its product name was WANTHANOL® WHP-3045.

[0061] The compound was polyol 5:polyadipic acid / neopentyl glycol ester, with a functional value of 2, Mn=2000, and amorphous nature. Its product name was WANTHANOL(registered trademark) WHP-205.

[0062] The polyol 6:polyadipic acid / neopentyl glycol / 1,6-hexanediol ester had a functional value of 2, Mn=1500, was manufactured by Wanhua Chemical Group Co., Ltd., was semicrystalline, an opaque waxy solid at room temperature, and its product name was WANTHANOL® WHP-1556.

[0063] Polyol 7 is a polyadipic acid / isophthalic acid / 1,4-butanediol ester (where the molar ratio of adipic acid to isophthalic acid is 1.7:1), has a functional value of 2, Mn=2000, is semi-crystalline, and is an opaque, waxy solid at room temperature. When polyol 7 was prepared, the molar ratio of 1,4-butanediol to component I was 1.25:1, and the catalyst used was tetrabutyl titanate at a concentration of 100 ppm.

[0064] Polyol 8 is a polyadipic acid / isophthalic acid / 1,4-butanediol ester (where the molar ratio of adipic acid to isophthalic acid is 0.8:1), has a functional value of 2, Mn=2000, is semi-crystalline, and is an opaque, waxy solid at room temperature. When polyol 8 was prepared, the molar ratio of 1,4-butanediol to component I was 1.235:1, and the catalyst used was tetrabutyl titanate at a concentration of 130 ppm.

[0065] Isophorone diamine, hexamethylene diisocyanate (HDI), 4,4'-dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI), 50% aqueous solution of sodium N-(2-aminoethyl)-2-aminoethanesulfonate, and neopentyl glycol were all derived from Wanhua Chemical Group Co., Ltd. Polycarbonate: Mn=2000, functional valency 2, manufactured by Nippon Polyurethane Co., Ltd. Poly(tetramethylene oxide) glycol: Mn=2000, functional value 2, manufactured by Mitsubishi Chemical Corporation. Polycaprolactone diol: Mn=2000, functional valency 2, manufactured by Daicel Corporation of Japan. Dimethylolpropionic acid (DMPA): Manufactured by Perstorp, 1,4-Butanediol, ethylenediamine, triethylamine: Manufactured by Guon Yao Chemical Reagents Co., Ltd.

[0066] [Example 1] 422.6 g of polyol 1, 78 g of polyol 3, 7.7 g of IPDI, 78 g of HDI, 7.16 g of DMPA, 4.0 g of 1,4-butanediol, and 110 g of acetone were placed in a 1 L four-necked round-bottom flask equipped with a nitrogen gas inlet and outlet. The mixture was stirred at 80-90°C until the NCO content reached 1.92 wt%. The mixture was cooled to 40-45°C, diluted with 500 g of acetone, then neutralized with 4.8 g of triethylamine for about 5 minutes. The mixture was then dispersed by adding 900 g of water, and 5 g of ethylenediamine was added while stirring to extend the rear chain. The reaction was carried out for 15 minutes. After separating the acetone by distillation, the obtained solvent-free dispersion had a solid content of 40 wt%, an average particle size of 148 nm, and a pH of 8.3.

[0067] [Example 2] 400g polyol, 48g IPDI, 60g HDI, 10g DMPA, 8.0g 1,4-butanediol, and 120g acetone were placed in a 1L four-necked round-bottom flask equipped with a nitrogen gas inlet and outlet. The mixture was stirred at 80-90°C until the NCO content reached 2.69 wt%. The mixture was cooled to 40-45°C, diluted with 500g of acetone, then neutralized with 7.0g of triethylamine for approximately 5 minutes. Subsequently, the mixture was dispersed by adding 800g of water, and 6.5g of ethylenediamine was added during stirring to extend the rear chain. The reaction was carried out for 15 minutes. After separating the acetone by distillation, the obtained solvent-free dispersion had a solid content of 40 wt%, an average particle size of 140 nm, and a pH of 8.3.

[0068] [Example 3] 400 g of polyol 1, 90 g of poly(tetramethylene oxide) glycol, 60 g of TDI, 30 g of HMDI, 10 g of DMPA, and 120 g of acetone were placed in a 1 L four-necked round-bottom flask equipped with a nitrogen gas inlet and outlet. The mixture was stirred at 80-90°C until the NCO content reached 1.63 wt%. The temperature was reduced to 40-45°C, and the mixture was diluted with 500 g of acetone. Then, 6.8 g of triethylamine was added and neutralized for about 5 minutes. Subsequently, 895 g of water was added to disperse the mixture. While stirring, 11.8 g of isophorone diamine was added to extend the rear chain, and the reaction was carried out for 15 minutes. After separating the acetone by distillation, the obtained solvent-free dispersion had a solid content of 40 wt%, an average particle size of 170 nm, and a pH of 7.80.

[0069] [Example 4] 300 g of polyol 2, 90 g of polyol 6, 55 g of TDI, 30 g of HMDI, 12 g of DMPA, and 90 g of acetone were placed in a 1 L four-necked round-bottom flask equipped with a nitrogen gas inlet and outlet. The mixture was stirred at 80-90°C until the NCO content reached 2.3 wt%. The temperature was lowered to 40-45°C, and 500 g of acetone was added for dilution. Then, 8.1 g of triethylamine was added and neutralized for approximately 5 minutes. Subsequently, 895 g of water was added to disperse the mixture. While stirring, 11 g of isophoronediamine was added to extend the rear chain, and the reaction was carried out for 15 minutes. After separating the acetone by distillation, the obtained solvent-free dispersion had a solid content of 40 wt%, an average particle size of 170 nm, and a pH of 8.0.

[0070] [Example 5] 350 g of polyol 2, 90 g of polycarbonate, 55 g of HDI, 30 g of HMDI, 8 g of DMPA, 3 g of neopentyl glycol, and 90 g of acetone were placed in a 1 L four-necked round-bottom flask equipped with a nitrogen gas inlet and outlet. The mixture was stirred at 80-90°C until the NCO content reached 1.75 wt%. The temperature was reduced to 40-45°C, and the mixture was diluted with 500 g of acetone. Then, 5.43 g of triethylamine was added and neutralized for about 5 minutes. Subsequently, the mixture was dispersed by adding 825 g of water, and 11 g of isophorone diamine was added while stirring to extend the rear chain. The reaction was carried out for 15 minutes. After separating the acetone by distillation, the obtained solvent-free dispersion had a solid content of 40 wt%, an average particle size of 170 nm, and a pH of 7.90.

[0071] [Example 6] 237.5 g of polyol 1, 328 g of polyol 4, 7.77 g of IPDI, 76 g of HDI, 8 g of DMPA, 4.0 g of 1,4-butanediol, and 110 g of acetone were placed in a 1 L four-necked round-bottom flask equipped with a nitrogen gas inlet and outlet. The mixture was stirred at 80-90°C until the NCO content reached 1.67 wt%. The temperature was reduced to 40-45°C, and 500 g of acetone was added for dilution. Then, 5.4 g of triethylamine was added and neutralized for about 5 minutes. Subsequently, 1000 g of water was added to disperse the mixture, and 4.6 g of ethylenediamine was added while stirring to extend the rear chain, and the reaction was carried out for 15 minutes. After separating the acetone by distillation, the obtained solvent-free dispersion had a solid content of 40 wt%, an average particle size of 138 nm, and a pH of 8.4.

[0072] [Example 7] 240 g of polyol 2, 135 g of polyol 6, 60 g of TDI, 29 g of HMDI, 12 g of DMPA, and 90 g of acetone were placed in a 1 L four-necked round-bottom flask equipped with a nitrogen gas inlet and outlet. The mixture was stirred at 80-90°C until the NCO content reached 2.28 wt%. The temperature was reduced to 40-45°C, and 500 g of acetone was added for dilution. Then, 8.1 g of triethylamine was added and neutralized for approximately 5 minutes. Subsequently, 895 g of water was added to disperse the mixture. While stirring, 13 g of isophoronediamine was added to extend the rear chain, and the reaction was allowed to proceed for 15 minutes. After separating the acetone by distillation, the obtained solvent-free dispersion had a solid content of 40 wt%, an average particle size of 188 nm, and a pH of 8.0.

[0073] [Example 8] 220 g of polyol 2, 220 g of polycarbonate, 55 g of HDI, 30 g of HMDI, 8 g of DMPA, 3 g of neopentyl glycol, and 90 g of acetone were placed in a 1 L four-necked round-bottom flask equipped with a nitrogen gas inlet and outlet. The mixture was stirred at 80-90°C until the NCO content reached 1.75 wt%. The temperature was reduced to 40-45°C, and the mixture was diluted with 500 g of acetone. Then, 5.43 g of triethylamine was added and neutralized for about 5 minutes. Subsequently, the mixture was dispersed by adding 825 g of water, and 11 g of isophorone diamine was added while stirring to extend the rear chain. The reaction was carried out for 15 minutes. After separating the acetone by distillation, the obtained solvent-free dispersion had a solid content of 40 wt%, an average particle size of 163 nm, and a pH of 8.0.

[0074] [Example 9] 450 g of polyol, 52.1 g of HDI, 30.2 g of IPDI, 2.6 g of neopentyl glycol, and 67 g of acetone were placed in a 1 L four-necked round-bottom flask equipped with a nitrogen gas inlet and outlet. The mixture was stirred at 80-90°C until the NCO content reached 2.8%, then cooled and diluted with 740 g of acetone. The mixture was then cooled to 40-50°C, and under stirring, 19 g of a 50 wt% aqueous solution of N-(2-aminoethyl)-2-aminoethanesulfonate diluted with 5 times the volume of water and 13 g of isophorone diamine were added. The mixture was reacted for approximately 15 minutes, and then 800 g of deionized water was added under stirring to disperse the mixture. After further separation of acetone by distillation, the obtained solvent-free dispersion had a solid content of 40 wt%, an average particle size of 218 nm, and a pH of 7.5.

[0075] [Example 10] 350 g of polyol, 250 g of poly(tetramethylene oxide) glycol, 69 g of HDI, 33 g of HMDI, and 87 g of acetone were placed in a 1 L four-necked round-bottom flask equipped with a nitrogen gas inlet and outlet. The mixture was stirred at 80-90°C until the NCO content reached 2.5 wt%, then cooled and diluted with 740 g of acetone. The mixture was then cooled to 40-50°C and, under rapid stirring, 22 g of a 50 wt% aqueous solution of N-(2-aminoethyl)-2-aminoethanesulfonate diluted with 5 times the volume of water and 10 g of isophorone diamine were added. The mixture was reacted for approximately 15 minutes, and then 900 g of deionized water was added under stirring to disperse the mixture. After further separation of acetone by distillation, the resulting solvent-free dispersion had a solid content of 40 wt%, an average particle size of 258 nm, and a pH of 7.2.

[0076] [Comparative Example 1] In Example 5, polyol 2 was replaced with polycarbonate, while the rest remained unchanged. It has a solid content of 40 wt%, an average particle size of 161 nm, and a pH of 7.90.

[0077] [Comparative Example 2] 150 g of polyol 1, 580 g of polyol 4, 48 g of IPDI, 60 g of HDI, 10 g of DMPA, 6.0 g of 1,4-butanediol, and 120 g of acetone were placed in a 1 L four-necked round-bottom flask equipped with a nitrogen gas inlet and outlet. The mixture was stirred at 80-90°C until the NCO content reached 1.39 wt%. The temperature was lowered to 40-45°C, and 500 g of acetone was added for dilution. Then, 6.7 g of triethylamine was added and neutralized for approximately 5 minutes. Subsequently, 1290 g of water was added to disperse the mixture. During stirring, 4.8 g of ethylenediamine was added to extend the rear chain, and the reaction was carried out for 15 minutes. After separating the acetone by distillation, the obtained solvent-free dispersion had a solid content of 40 wt%, an average particle size of 178 nm, and a pH of 8.3.

[0078] [Comparative Example 3] In Example 2, polyol 1 was replaced with polycaprolactone diol, while the rest remained unchanged. The resulting product has a solid content of 40 wt%, an average particle size of 140 nm, and a pH of 8.4.

[0079] [Comparative Example 4] In Example 2, polyol 1 was replaced with poly(tetramethylene oxide) glycol, while the rest remained unchanged. The resulting product has a solid content of 40 wt%, an average particle size of 130 nm, and a pH of 8.1.

[0080] [Comparative Example 5] In Example 2, polyol 1 was replaced with polyol 7, while the rest remained unchanged. The resulting product has a solid content of 40 wt%, an average particle size of 144 nm, and a pH of 8.2.

[0081] [Comparative Example 6] In Example 2, polyol 1 was replaced with polyol 8, while the rest remained unchanged. The resulting product has a solid content of 40 wt%, an average particle size of 151 nm, and a pH of 8.4.

[0082] Preparation of glove base resin (raw material liquid): Deionized water was added to the above-prepared dispersion to dilute it to a solid content of 15 wt%, then 0.5 wt% color paste and 5 wt% titanium white were added, and the mixture was stirred at low speed (rotation speed between 200 and 300 r / min) for 30 minutes.

[0083] Preparation of the coagulation solution: An aqueous solution containing 10 wt% CaCl2 and 5 wt% release agent (calcium stearate) was prepared by mixing deionized water and stirring for 1 hour.

[0084] Glove manufacturing: 1) The glove molds, which had been thoroughly cleaned, were placed in a 100°C oven to dry. 2) Remove the glove-shaped mold, let it cool to 60°C, immerse it in the coagulation solution for about 8 seconds, then remove it and dry it in an oven at 120-140°C. 3) Remove the dried glove mold, lower the temperature to 60°C, and immerse it in the prepared base resin for about 8 seconds. After removing it, it was baked in a 130°C oven for about 4 minutes, then removed again and dipped in the prepared base resin for about 8 seconds, and then baked in the oven for another 20 minutes. 4) After removing the glove mold from the firing process, it was dipped in a glove coating agent, then removed and allowed to air dry, and finally released from the mold to obtain the finished gloves.

[0085] Performance testing: Tensile strength and elongation testing: A portion of the palm of the glove was selected and cut into a dumbbell shape measuring 6 mm in width and 115 mm in length. The tensile strength was tested using a tensile testing machine, and the elongation was also measured. Water resistance test: 800g of water was poured into the gloves, and they were turned upside down. The deformation and appearance of the gloves were observed. Oxidation resistance: A 30 wt% hydrogen peroxide solution was injected into the gloves and left for 10 minutes, and the presence or absence of leakage or seepage was observed. Polarity-resistant solvents: A 75 wt% alcohol solution was injected into gloves and left for 10 minutes, and the presence or absence of leakage or seepage was observed. Rebound elasticity and wearing comfort: Referring to the "commercially available latex gloves" shown in Table 1, the rebound elasticity and wearing comfort of the gloves obtained in each example and comparative example were evaluated.

[0086] Refer to Table 1 for performance detection results. [Table 1]

[0087] As can be seen from the table, gloves manufactured based on the polyurethane-polyurea aqueous dispersion of the present invention are clearly superior to the comparative example and commercially available nitrile rubber gloves in terms of overall performance in terms of tensile strength, elongation, rebound elasticity, wearing comfort, and water resistance, and are clearly superior to commercially available latex gloves in terms of tensile strength and water resistance.

[0088] The above embodiments are merely examples given for illustrative purposes and it will be readily apparent that the present invention is not limited thereto. Those skilled in the art will know that other different forms of variations or modifications are possible based on the above description. It is not possible, nor is it necessary, to comprehensively enumerate all embodiments here. Any obvious changes or variations resulting therefrom still fall within the scope of protection created by the present invention.

Claims

1. The material contains units derived from component a, wherein component a contains at least one polyol with a functional value of 2 or more, and component a contains at least 40 wt% or more of a semicrystalline polyester polyol obtained by reacting a dihydric alcohol with component I, of which component I contains an aliphatic dicarboxylic acid and component II in a molar ratio of 2.1 to 10:1, and component II is an aromatic dicarboxylic acid and / or an aromatic dicarboxylic acid anhydride. Polyurethane-polyurea aqueous dispersions are Component a comprises at least one polyol with a functional value of 2 or more, and the proportion of the semicrystalline polyester polyol in component a is 70 to 100 wt%. Component b is a polyisocyanate. A hydrophilic compound containing two to three groups that are reactive with NCO, wherein the hydrophilic groups of the hydrophilic compound are hydrophilic compounds containing one or more types of ionic groups and latent ionic groups, component c Component d is an alcohol-based chain extender that is different from component a. Component f is a polyamine with a number-average molecular weight of 500 g / mol or less. It is prepared by reacting raw materials containing the following component: A polyurethane-polyurea aqueous dispersion characterized by the following features.

2. The dihydric alcohol used in the preparation of the semicrystalline polyester polyol comprises at least one or more of 1,4-butanediol and 1,6-hexanediol. and / or, the component II used in the preparation of the semicrystalline polyester polyol is one or more selected from phthalic acid and phthalic anhydride. and / or, the aliphatic dicarboxylic acid used in the preparation of the semicrystalline polyester polyol is adipic acid. The polyurethane-polyurea aqueous dispersion according to feature 1.

3. The aforementioned semicrystalline polyester polyol is an opaque, waxy solid at room temperature. The polyurethane-polyurea aqueous dispersion according to feature 1.

4. The polyurethane-polyurea aqueous dispersion according to Claim 1, characterized in that the raw material satisfies either (1) or (2) below, (1) The hydrophilic group of component c does not contain the ionic group, and further comprises component e, which is a compound capable of ionizing component c. Based on the total weight of components a, b, c, d, e, and f, the proportion of each component used in the preparation of the polyurethane-polyurea aqueous dispersion is 56-85 wt% for component a, 10-30 wt% for component b, 0.8-4 wt% for component c, 0-3 wt% for component d (excluding 0 wt%), 0.5-4 wt% for component f, and 0.6-4 wt% for component e. (2) Based on the total weight of components a, b, c, d, and f, the proportion of each component used in the preparation of the polyurethane-polyurea aqueous dispersion is as follows: component a: 56-85 wt%, component b: 10-30 wt%, component c: 0.8-4 wt%, component d: 0-3 wt% (excluding 0 wt%), and component f: 0.5-4 wt%. The polyurethane-polyurea aqueous dispersion according to feature 1.

5. In component a, the polyol has a number-average molecular weight of 800 to 10000 g / mol and a functional value of 2 to 4. and / or, in component b, the polyisocyanate is one or more selected from aromatic, aliphatic, and alicyclic polyisocyanates. and / or, in component c, the group that is reactive with the NCO contained in the hydrophilic compound is a hydroxyl group and / or an amino group. and / or, in component c, the ionic group is a carboxylate ion and / or a sulfonate ion, and the latent ionic group is a carboxyl group, and / or, in component d, the alcohol-based chain extender different from component a is a small-molecule alcohol-based compound with a relative molecular weight less than 150. and / or, component e is triethylamine, and / or, component f is one or more selected from ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-hexanediamine, 2-methylpentane-1,5-diamine, isophoronediamine, 4,4-diaminodicyclohexylmethane, piperazine, and diethylenetriamine. The polyurethane-polyurea aqueous dispersion according to feature 4.

6. The hydrophilic compound as component c is one or more selected from dimethylolpropionic acid, dimethylolbutanoic acid, dihydroxysuccinic acid, N-(2-aminoethyl)-2-aminoethanesulfonic acid, N-(3-aminopropyl)-2-aminoethanesulfonic acid and its salts, and the salt comprises one or more of the corresponding alkali metal salts, alkaline earth metal salts, or ammonium salts. and / or, the alcohol-based chain extender as component d is one or more selected from ethylene glycol, 1,2-propanediol, 1,3-propanediol, 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. The polyurethane-polyurea aqueous dispersion according to feature 5.

7. The component a contains another polyol different from the semicrystalline polyester polyol, the other polyol being one or more selected from polyester polyol, polycaprolactone polyol, polycarbonate polyol, and polyether polyol, and the proportion of the other polyol in component a being 0 to 60 wt%. The polyurethane-polyurea aqueous dispersion according to feature 5.

8. The polyurethane-polyurea aqueous dispersion is prepared by reacting a raw material containing component a. The raw material further comprises component b, component c, component d, and component f. However, if component b is a polyisocyanate, component c is a hydrophilic compound, the hydrophilic compound contains 2 to 3 groups that are reactive with NCO, component d is an alcohol-based chain extender different from component a, component f is a polyamine with a number average molecular weight of 500 g / mol or less, and component c does not contain an ionic group, then the raw material further contains component e, and component e is a compound that can ionize component c. The step includes reacting at 60-90°C to obtain a prepolymer of blocked isocyanate, A method for preparing a polyurethane-polyurea aqueous dispersion according to any one of claims 1 to 7.

9. A polyurethane-polyurea aqueous dispersion produced according to any one of claims 1 to 7, A soft, elastic product characterized by the following features.

10. The process includes adding a raw material liquid containing a polyurethane-polyurea aqueous dispersion to a mold necessary for the manufacture of a flexible elastic product, wherein the polyurethane-polyurea aqueous dispersion is the polyurethane-polyurea aqueous dispersion described in any one of claims 1 to 7. A method for manufacturing a soft, elastic product characterized by the following:

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