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

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 uses thereof, 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 to manufacture soft elastic products (such as disposable gloves, condoms, etc.) 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 strong odors and serious production pollution problems. 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 for use in disposable gloves. The polyurethane dispersion employs poly(tetramethylene oxide) glycol, polypropylene glycol, and toluene diisocyanate as raw materials, and the produced gloves have performance similar to rubber products. However, products manufactured with polypropylene glycol have the problem of poor water resistance. When exposed to water during use, the strength reduction is very significant, and they have no practical use value.

[0004] Patent Document CN108864394A discloses gloves for medical use manufactured by compounding a sulfonate polyester and polypropylene glycol, and is described as having excellent alcohol resistance. However, in reality, systems using polypropylene glycol cannot achieve good alcohol resistance, and moreover, the strength of the entire glove is low and the applicability is not strong.

[0005] In Patent Document CN106188477B, a polyurethane aqueous dispersion having high elasticity is synthesized using a polyether and a high molecular weight repulsive elastic agent and used in the manufacture of gloves. However, the crosslinked structure in the polyurethane dispersion is disadvantageous to elasticity, and this document only evaluates the mechanical properties of the resin and does not mention anything about the manufacture and performance of gloves.

Summary of the Invention

Problems to be Solved by the Invention

[0006] The present invention provides a polyurethane-polyurea aqueous dispersion applicable to the manufacture of soft elastic products, manufactures a soft elastic product based on the polyurethane-polyurea aqueous dispersion, and can have comprehensive properties such as good elasticity, strength, water resistance and wearing feeling.

Means for Solving the Problems

[0007] In order to achieve this object, the present invention provides the following technical solutions.

[0008] The present invention 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 anhydride. provides a polyurethane-polyurea aqueous dispersion.

[0009] In some embodiments, the dihydric alcohol used in the preparation of the semi-crystalline polyester polyol comprises at least one or more of 1,4-butanediol and 1,6-hexanediol, and may further contain other dihydric alcohols having a relative molecular weight lower than 150. The other dihydric alcohols include one or more of ethylene glycol, 1,3-butanediol, neopentyl glycol, 1,5-pentanediol, propylene glycol, diethylene glycol, and dipropylene glycol. Among the dihydric alcohols used in the preparation of the semi-crystalline polyester polyol, the proportion of the other dihydric alcohols is lower than 50 wt%. And / or, the component II used in the preparation of the semi-crystalline 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. More preferably, the component II is isophthalic acid. And / or, the aliphatic dicarboxylic acid used in the preparation of the semi-crystalline polyester polyol is adipic acid.

[0010] In some embodiments, the semi-crystalline polyester polyol is an opaque wax-like solid at room temperature.

[0011] In some embodiments, the polyurethane-polyurea aqueous dispersion contains at least one polyol having a functionality of 2 or more, and the proportion of the semi-crystalline polyester polyol in component a is 40 wt% or more, and preferably the proportion of the semi-crystalline polyester polyol in component a is 70 to 100 wt%, component a component b, which is a polyisocyanate component c, which is a hydrophilic compound containing 2 to 3 groups reactive with NCO, and the hydrophilic group of the hydrophilic compound contains one or more of an ionic group and a latent ionic group Optionally, component d, which is an alcohol-based chain extender different from component a, Component f, which is a polyamine with a number average molecular weight of 500 g / mol or less, It is prepared by reacting a raw material containing such components.

[0012] In some embodiments, when the hydrophilic group of component c does not contain the ionic group, the raw material further includes component e, which is a compound capable of ionizing component c, Preferably, when the raw material contains component e, based on the total weight of components a, b, c, d, e, and f, the proportion of the usage amount of each of the following components used in the preparation of the polyurethane-polyurea aqueous dispersion is: 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, when the raw material does not contain component e, based on the total weight of components a, b, c, d, and f, the proportion of the usage amount of each of the following components used in the preparation of the polyurethane-polyurea dispersion is: 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%, and component f is 0.5 - 4 wt%.

[0013] In some embodiments, in component a, the number average molecular weight of the polyol is 500 - 15000 g / mol, and the polyol preferably has a number average molecular weight of 800 - 10000 g / mol and a functionality of 2 - 4. More preferably, the polyol has a number average molecular weight of 1000 - 5000 g / mol and a functionality of 2 - 3. And / or, in component b, the polyisocyanate is one or more selected from aromatic, aliphatic, and alicyclic polyisocyanates, and preferably the polyisocyanate has at least two isocyanate groups. And / or, in component c, the group reactive with NCO contained in the hydrophilic compound is a hydroxy group and / or an amino group. And / or, in the component c, the ionic group is preferably a carboxylic acid ion and / or a sulfonic acid ion, and the latent ionic group is preferably a carboxyl group, And / or, in the component d, the alcohol-based chain extender different from the component a is a small molecule alcohol-based compound having a relative molecular weight of less than 150, And / or, the component e is triethylamine, And / or, the component f is a polyamine having a relative molecular weight of 60 to 500, and is preferably 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.

[0014] In some embodiments, the hydrophilic compound as the 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 salts thereof, the salts include one or more of corresponding alkali metal salts, alkaline earth metal salts or ammonium salts, and the component c is preferably dimethylolpropionic acid, And / or, the alcohol-based chain extender as the 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 one or more of 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and 1,6-hexanediol are preferred.

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

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

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

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

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 (an aromatic dicarboxylic acid and / or an aromatic dianhydride) in a specific molar ratio. Flexible 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, flexible 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] For the sake of easier understanding of the present invention, the present invention will be further described below with reference to examples. It should be understood that the following examples are merely for better understanding of the present invention and do not mean that the present invention is limited only to the following examples.

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

[0023] For parts where specific experimental procedures or conditions in the examples are not specified, they may be carried out according to the operations or conditions of the corresponding normal experimental procedures in the technical field. Those for which the manufacturer of the reagents or equipment used is not specified are all ordinary products that can be purchased on the market.

[0024] In one aspect, the present invention provides a polyurethane-polyurea aqueous dispersion, which contains units derived from component a. 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. Among them, component I contains 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 dianhydride.

[0025] When the present inventor prepares a polyurethane-polyurea aqueous dispersion, the polyol (component a) used contains at least 40 wt% or more (for example, 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 semi-crystalline polyester polyol, and the semi-crystalline polyester polyol is obtained by subjecting an aliphatic dicarboxylic acid and component II (aromatic dicarboxylic acid and / or aromatic dicarboxylic anhydride) and a dihydric alcohol to an esterification reaction at a molar ratio of 2.1 to 10:1. The polyurethane-polyurea dispersion prepared based on the form of the present invention can reduce the crystallinity of the polyester, improve the elasticity, and obtain properties such as good strength. When the polyurethane-polyurea aqueous dispersion is used in the production of a soft elastic product, the obtained polyurethane-polyurea aqueous dispersion is particularly applicable to the production of soft elastic products such as gloves and / or condoms. When the polyurethane-polyurea aqueous dispersion is used in the production of a soft elastic product, the obtained soft elastic product has significantly improved comprehensive performance and can have good tensile strength, elongation rate, resilience, etc. It has been found that the material is soft and elastic, bringing an improved wearing feeling. On the other hand, when a semi-crystalline polyester polyol is not used, or when the proportion of the semi-crystalline polyester polyol in the polyol (component a) is less than 40 wt%, or when the semi-crystalline polyester polyol is obtained by an aliphatic dicarboxylic acid and component II (aromatic dicarboxylic acid and / or aromatic diacid anhydride) that does not satisfy the molar ratio of 2.1 to 10:1, the obtained soft elastic product has obvious deterioration in performance and cannot have good comprehensive performance.

[0026] In a preferred embodiment, in component a, the proportion of the semi-crystalline polyester polyol obtained by reacting the dihydric alcohol with component I reaches 70 to 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 semi-crystalline polyester polyol includes at least one or more of 1,4-butanediol and 1,6-hexanediol, and may further include other dihydric alcohols having a relative molecular weight lower than 150. The other dihydric alcohols include one or more of ethylene glycol, 1,3-butanediol, neopentyl glycol, 1,5-pentanediol, propylene glycol, diethylene glycol, dipropylene glycol, etc. Among the dihydric alcohols used in the preparation of the semi-crystalline polyester polyol, the proportion of the other dihydric alcohols is lower than 50 wt%, that is, the usage amount is less than that of 1,4-butanediol and / or 1,6-hexanediol. When preparing the semi-crystalline polyester polyol, those skilled in the art can easily determine the usage amount of the dihydric alcohol in the reaction system from the target molecular weight. When preparing the semi-crystalline polyester polyol, the dihydric alcohol used is preferably 1,4-butanediol and / or 1,6-hexanediol, or preferably adopts 1,4-butanediol and / or 1,6-hexanediol of 50 wt% or more (based on the total amount of the dihydric alcohol), which can improve the performance of the finally obtained soft elastic product.

[0028] In some preferred embodiments, Component II used in the preparation of the semi-crystalline polyester polyol is one or more selected from phthalic acid and phthalic anhydride. Preferably, phthalic acid is selected from isophthalic acid and / or orthophthalic acid. More preferably, Component II is isophthalic acid. It is preferable to adopt isophthalic acid, which is 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 semi-crystalline polyester polyol is adipic acid.

[0030] In some more preferred embodiments, the dihydric alcohol used in the preparation of the semi-crystalline polyester polyol contains at least one or more of 1,4-butanediol and 1,6-hexanediol, the component II used is one or more selected from isophthalic acid, phthalic acid, and phthalic anhydride, isophthalic acid is preferred, the aliphatic dicarboxylic acid used is adipic acid, and the molar ratio of adipic acid to component II is 2.1 to 10:1. The polyurethane-polyurea aqueous dispersion prepared from the preferred semi-crystalline polyester polyol can obtain better product performance, and the resulting product has significantly improved tensile strength, elongation at break, resilience, wearing comfort, and water resistance. The semi-crystalline polyester polyol obtained in the preferred manner is an opaque wax-like solid at room temperature, and the semi-crystalline 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 semi-crystalline polyester polyol used may be prepared by the usual polyester polyol preparation process in this field, or a commercial product satisfying the above requirements may be directly adopted. Specifically, the semi-crystalline polyester polyol can be prepared by the melt polycondensation method well known to those skilled in the art, and can be directly carried out with reference to the existing process. Exemplarily, for example, it can be prepared with reference to the preparation method of polyester polyol in Patent CN110724249B, specifically, referring to the examples of this document. Exemplarily, for example, the compounding amounts of aliphatic dicarboxylic acid, Component II (aromatic dicarboxylic acid and / or aromatic dicarboxylic anhydride), and dihydric alcohol required for the preparation of the semi-crystalline polyester polyol are put into a reaction kettle, the temperature of the system is raised to 130-180°C and reacted until the system becomes transparent, the temperature of the system is raised to 200-230°C and reacted until the water output is close to the theoretical water output (for example, reacted for about 2-3 h), then a catalyst is added and the temperature is raised to 235-250°C and the vacuum device is turned on (for example, at a vacuum pressure of -0.095 Mpa), and the reaction is continued until the acid value of the system reaches 0.3 mg KOH / g or less. Then, the temperature is lowered (for example, lowered to about 120°C) and taken out and packaged to obtain the target semi-crystalline polyester polyol. During the reaction process, a catalyst can also be added to the reaction kettle as needed. For example, the catalyst is one or more selected from organotin, organobismuth, organic titans (for example, tetrabutyl titanate, tetraisopropyl titanate, etc.), and the usage amount of the catalyst may be 50-300 ppm of the total mass of the reactants. During the preparation process, the ratio of the usage amounts of the dibasic acid and the dihydric alcohol can be determined from the molecular weight of the target polyester polyol. Usually, the usage amount of the dihydric alcohol may be 105-120% of the theoretical charging amount.

[0032] In some embodiments, component a may include other polyols different from the semi-crystalline polyester polyol. In some embodiments, in component a, the number average molecular weight of the polyol (i.e., the semi-crystalline polyester polyol and optional other polyols) is 500 to 15,000 g / mol, and the polyol is preferably a polyol having a number average molecular weight of 800 to 10,000 g / mol and a functionality of 2 to 4, and more preferably a polyol having a number average molecular weight of 1,000 to 5,000 g / mol and a functionality of 2 to 3.

[0033] Here, the other polyol for 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 usually be added to the polyurethane-polyurea aqueous dispersion can be employed.

[0034] Specifically, the polyester polyol among the other polyols can be obtained, for example, by reacting a carboxylic acid and / or an acid anhydride with a polyol according to a known preparation process. For example, it can be obtained by dehydrative condensation of an aliphatic, alicyclic, aromatic dicarboxylic acid or polyvalent carboxylic acid or the corresponding acid anhydride, etc. with a polyol. Examples of the carboxylic acid or acid anhydride include, but are not limited to, succinic acid, methyl succinic 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 a mixture thereof. Examples of the polyol 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 a mixture thereof. Optionally, a polyol with a higher functionality number, such as trimethylolpropane, can be added. The polyester polyol may further contain a polyester containing a fatty acid, may have an average OH functionality number of about 2, and may further contain a transesterification reaction product of castor oil and other oils other than castor oil. Preferably, the other polyol in component a is a polyester polyol having as a structural component a dibasic acid containing one or more of isophthalic acid, terephthalic acid, adipic acid, and a dihydric alcohol containing one or more of neopentyl glycol, ethylene glycol, butanediol, hexanediol.

[0035] Among other polyols, the polyester polyol may be a homopolymer or copolymer of lactone, which can be obtained by ring-opening a lactone or a mixture of lactones with a suitable polyol having a functionality of 2 and / or more than 2.

[0036] The hydroxy group-containing polycarbonate prepared using a diol and a carbonate is also suitable as the other polyol in component a. Here, the diol used for the polycarbonate is preferably 1,4-butanediol and / or 1,6-hexanediol, and the carbonate may be a diaryl carbonate and / or a dialkyl carbonate. The diaryl carbonate is, for example, diphenyl carbonate, and the dialkyl carbonate is, for example, dimethyl carbonate.

[0037] The polyether polyol is also suitable as the other polyol in component a, and a preferred polyether polyol is polytetrahydrofuran polyol. When adding other polyols to component a, it is preferable that the other polyol is polytetrahydrofuran polyol, and suitable elasticity can be obtained.

[0038] In some embodiments, the polyurethane-polyurea aqueous dispersion Component a containing at least one polyol having a functionality of 2 or more and having a proportion of semi-crystalline polyester polyol in component a of 40 wt% or more, Component b which is a polyisocyanate, Component c which is a hydrophilic compound containing 2 to 3 groups reactive with NCO, Optionally, component d which is an alcohol-based chain extender different from component a, Component f which is a polyamine having a number average molecular weight of 500 g / mol or less, is prepared by reacting a raw material containing the above components.

[0039] When the hydrophilic group of the component c does not contain the ionic group, the raw material further includes a component e which is a compound capable of ionizing the component c that does not contain the ionic group. When the component c contains the ionic group, it is not necessary to add the component e.

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

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

[0042] In the component b, there are no particular restrictions on the specific selection of the polyisocyanate, and polyisocyanates commonly used in this field can be used. In some embodiments, the polyisocyanate may be one or more selected from aromatic, aliphatic, and alicyclic polyisocyanates. Preferred polyisocyanates have 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 araliphatic hydrocarbon group containing 7 to 15 carbon atoms. In some embodiments, the polyisocyanate may be one or more of 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-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, p-xylylene diisocyanate, p-isopropylidene diisocyanate. Component b may further contain a small amount of polyisocyanates with higher functionality known in polyurethane chemistry, or modified polyisocyanates containing, for example, carbodiimide groups, allophanate groups, isocyanurate groups, urethane groups, and / or biuret groups. Preferably, component b is preferably one or more of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate, and tolylene diisocyanate.

[0043] In some embodiments, in component c, the groups in the hydrophilic compound that are reactive with NCO are hydroxy groups and / or amino groups. In some embodiments, in component c, the hydrophilic groups of the hydrophilic compound include one or more of ionic groups and potential ionic groups, and the ionic group is preferably a carboxylate ion and / or a sulfonate ion, and the potential 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 salts thereof, the salts include one or more of 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 different from component a is a small molecule alcohol-based compound having a relative molecular weight smaller 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 of 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and 1,6-hexanediol.

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

[0046] In some embodiments, component f is a polyamine having a relative molecular weight of 60 to 500, 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 preferably one or two of ethylenediamine and isophoronediamine.

[0047] In the present invention, unless otherwise specified, the meaning of "multiple" and "polyvalent" in relation to "multiple types" and "polyvalent" both refer to two or more.

[0048] The polyurethane-polyurea aqueous dispersion of the present invention can be prepared with reference to the existing preparation processes of polyurethane-polyurea aqueous dispersions in this field, and there are no particular requirements for this. Specifically, the raw materials containing component a are reacted to prepare the polyurethane-polyurea aqueous dispersion. More specifically, the raw materials therein further include component b, component c, optional component d, and component f. Among them, the component b is a polyisocyanate, the component c is a hydrophilic compound, the hydrophilic compound contains 2 to 3 groups reactive with NCO, the component d is an alcohol chain extender different from component a, the component f is a polyamine with a number average molecular weight of 500 g / mol or less. When the component c does not contain an ionic group, the raw materials further include component e, and the component e is a compound capable of ionizing the component c. Preferably, the preparation method includes a step of reacting at 60 to 90 °C to obtain a prepolymer of blocked isocyanate. By reference, when the component c does not contain an ionic group, the specific preparation steps are as follows: Component a, component b, component c, and optional component d are reacted at 60 to 90 °C in the presence of a solvent (such as acetone) to obtain a prepolymer of blocked isocyanate, diluted with a solvent (such as acetone), then component e is added for neutralization and dispersion (for example, water is added for dispersion under high-speed stirring at 800 to 1000 r / min), component f is added to carry out a chain extension reaction. After the reaction is completed, the solvent (acetone) is removed to obtain a polyurethane-polyurea aqueous dispersion. When the component c contains an ionic group, the specific preparation steps are as follows: Component a, component b, and optional component d are reacted at 60 to 90 °C in the presence of a solvent (such as acetone) to obtain a prepolymer of blocked isocyanate, diluted with a solvent (such as acetone), then component c and component f are added to continue the reaction, then water is added for dispersion, the solvent (acetone) is removed to obtain a polyurethane-polyurea aqueous dispersion.

[0049] For each component or other related content regarding the preparation of the polyurethane-polyurea aqueous dispersion in the above preparation method, reference can be made to the description of the polyurethane-polyurea aqueous dispersion above, and the description is omitted here.

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

[0051] The present invention further provides a soft elastic product, which is manufactured by the above-mentioned polyurethane-polyurea aqueous dispersion. Preferably, the soft elastic product may be various products having flexibility and elastic attributes, for example, gloves and / or condoms, but is not limited thereto.

[0052] The present invention further provides a method for manufacturing a soft elastic product, which includes the step of adding a raw material liquid containing the above-mentioned polyurethane-polyurea aqueous dispersion of the present invention to a mold required for manufacturing the soft elastic product. Preferably, the soft elastic product includes gloves and / or condoms. For the specific steps of the method for manufacturing the soft elastic product, reference can be made to the existing corresponding normal processes. However, it is important to use the polyurethane-polyurea aqueous dispersion according to the present invention as the raw material liquid. For points not specifically described in the method for manufacturing the soft elastic product, those skilled in the art can all refer to the normal processes for manufacturing the corresponding soft elastic products in this field. Taking the manufacture of gloves as an example, the exemplary manufacturing steps for reference are to prepare in the raw material liquid the polyurethane-polyurea aqueous dispersion according to the present invention and other auxiliary materials, such as water required for diluting the dispersion and color pastes, titanium white, etc. added according to the needs of the product, and after immersing the glove mold in a coagulating liquid (for example, an aqueous solution containing 10 wt% calcium chloride and 5 wt% release agent (for example, calcium stearate)), taking it out and drying it, then immersing it in the above-mentioned raw material liquid, taking it out and drying it (the operation of immersing in the raw material liquid and drying can be repeated according to the actual situation), and if necessary, immersing it in a glove coating agent, taking it out and drying it, and then demolding to obtain the finished glove.

[0053] Hereinafter, the present invention will be illustratively described by way of specific examples.

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

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

[0056] According to the compounding amount, the corresponding necessary component I, dihydric alcohol, and catalyst were put into a reaction kettle. 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 water output was close to the theoretical water output (reacted for about 2 - 3 h). After that, the temperature was raised to 235 - 240 °C, the vacuum device was turned on, and the acid value of the system was reacted to 0.3 mgKOH / g or less at a vacuum pressure of -0.095 Mpa. The temperature was lowered to about 120 °C and taken out for packaging to obtain a polyester polyol.

[0057] Polyol 1 (semicrystalline polyester polyol): Poly(adipic acid / isophthalic acid / 1,4 - butanediol ester) (here, the molar ratio of the usage amounts of adipic acid and isophthalic acid is 2.3:1), with a functionality of 2, Mn = 2000, and an opaque wax - like solid at room temperature. When preparing Polyol 1, the molar ratio of 1,4 - butanediol to component I was 1.21:1, the catalyst was tetrabutyl titanate, and the usage amount was 100 ppm.

[0058] Polyol 2 (semicrystalline polyester polyol): Poly(adipic acid / isophthalic acid / 1,6 - hexanediol ester) (here, the molar ratio of the usage amounts of adipic acid and isophthalic acid is 3.0:1), with a functionality of 2, Mn = 2000, and an opaque wax - like solid at room temperature. When preparing Polyol 2, the molar ratio of 1,6 - hexanediol to component I was 1.27:1, the catalyst was tetrabutyl titanate, and the usage amount was 100 ppm.

[0059] Polyol 3 (semicrystalline polyester polyol): Poly(adipic 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 functionality of 2, Mn = 3000, an opaque wax-like solid at room temperature. When preparing Polyol 3, the molar ratio of the total amount of 1,4-butanediol and neopentyl glycol to Component I is 1.17:1, the catalyst is tetra-isopropyl titanate with a usage amount of 150 ppm, and the molar ratio of 1,4-butanediol to neopentyl glycol is 7:3.

[0060] Polyol 4: Poly(adipic acid / 1,4-butanediol polyester / neopentyl glycol ester), with a functionality of 2, Mn = 3000, semicrystalline, an opaque wax-like solid at room temperature, and the product name was WANTHANOL® WHP-3045.

[0061] Polyol 5: Poly(adipic acid / neopentyl glycol ester), with a functionality of 2, Mn = 2000, amorphous, and the product name was WANTHANOL® WHP-205.

[0062] Polyol 6: Poly(adipic acid / neopentyl glycol / 1,6-hexanediol ester), with a functionality of 2, Mn = 1500, manufactured by Wanhua Chemical Group Co., Ltd., semicrystalline, an opaque wax-like solid at room temperature, and the product name was WANTHANOL® WHP-1556.

[0063] Polyol 7: Poly(adipic acid / isophthalic acid / 1,4-butanediol ester) (where the molar ratio of adipic acid to isophthalic acid is 1.7:1), with a functionality of 2, Mn = 2000, semicrystalline, an opaque wax-like solid at room temperature. When preparing Polyol 7, the molar ratio of 1,4-butanediol to Component I is 1.25:1, the catalyst is tetrabutyl titanate with a usage amount of 100 ppm.

[0064] Polyol 8: Poly(adipic acid / isophthalic acid / 1,4-butanediol ester) (where the molar ratio of adipic acid to isophthalic acid is 0.8:1), with a functionality of 2, Mn = 2000, semi-crystalline, an opaque wax-like solid at room temperature. When preparing the polyol 8, the molar ratio of 1,4-butanediol to Component I was 1.235:1, and the catalyst was tetrabutyl titanate with a usage amount of 130 ppm.

[0065] Isophoronediamine, hexamethylene diisocyanate (HDI), 4,4'-dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI), 50% aqueous solution of sodium N-(2-aminoethyl)-2-aminoethanesulfonate, neopentyl glycol, all originated from Wanhua Chemical Group Co., Ltd. Polycarbonate: Mn = 2000, functionality of 2, manufactured by Nippon Polyurethane Company, Poly(tetramethylene oxide) glycol: Mn = 2000, functionality of 2, manufactured by Mitsubishi Chemical Corporation of Japan, Polycaprolactone diol: Mn = 2000, functionality of 2, manufactured by Daicel Corporation of Japan, Dimethylolpropionic acid (DMPA): Manufactured by Perstorp, 1,4-Butanediol, ethylenediamine, triethylamine: Manufactured by Guoyao Chemical Reagent Company.

[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. At 80 - 90 °C, the mixture was stirred until the NCO reached 1.92 wt%. The temperature was lowered to 40 - 45 °C, diluted by adding 500 g of acetone, then 4.8 g of triethylamine was added and neutralized for about 5 min. Thereafter, the mixture was dispersed by adding 900 g of water, and 5 g of ethylenediamine was added during stirring for post - chain extension and reacted for 15 min. Then, the solvent - free dispersion obtained after separating acetone by distillation had a solid content of 40 wt%, an average particle size of 148 nm, and a pH of 8.3.

[0067] [Example 2] 400 of polyol 1, 48 g of IPDI, 60 g of HDI, 10 g of DMPA, 8.0 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. At 80 - 90 °C, the mixture was stirred until the NCO reached 2.69 wt%. The temperature was lowered to 40 - 45 °C, diluted by adding 500 g of acetone, then 7.0 g of triethylamine was added and neutralized for about 5 min. Thereafter, the mixture was dispersed by adding 800 g of water, and 6.5 g of ethylenediamine was added during stirring for post - chain extension and reacted for 15 min. Then, the solvent - free dispersion obtained after separating acetone by distillation 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 reached 1.63 wt%. The temperature was lowered to 40 - 45 °C, diluted by adding 500 g of acetone, then 6.8 g of triethylamine was added and neutralized for about 5 min. Thereafter, the mixture was dispersed by adding 895 g of water, and 11.8 g of isophoronediamine was added during stirring for post-chain extension and reacted for 15 min. Thereafter, the solvent-free dispersion obtained after separating acetone by distillation 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 reached 2.3 wt%. The temperature was lowered to 40 - 45 °C, diluted by adding 500 g of acetone, then 8.1 g of triethylamine was added and neutralized for about 5 min. Thereafter, the mixture was dispersed by adding 895 g of water, and 11 g of isophoronediamine was added during stirring for post-chain extension and reacted for 15 min. Thereafter, the solvent-free dispersion obtained after separating acetone by distillation 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 reached 1.75 wt%. After cooling the temperature to 40 - 45 °C, 500 g of acetone was added for dilution, then 5.43 g of triethylamine was added and neutralized for about 5 min. Thereafter, the mixture was dispersed by adding 825 g of water, and 11 g of isophoronediamine was added during stirring for post-chain extension and reacted for 15 min. After that, the solvent-free dispersion obtained after separating acetone by distillation 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 reached 1.67 wt%. After cooling the temperature to 40 - 45 °C, 500 g of acetone was added for dilution, then 5.4 g of triethylamine was added and neutralized for about 5 min. Thereafter, the mixture was dispersed by adding 1000 g of water, and 4.6 g of ethylenediamine was added during stirring for post-chain extension and reacted for 15 min. After that, the solvent-free dispersion obtained after separating acetone by distillation 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 reached 2.28 wt%. After cooling the temperature to 40 - 45 °C, it was diluted by adding 500 g of acetone. Then, 8.1 g of triethylamine was added and neutralized for about 5 min. Thereafter, the mixture was dispersed by adding 895 g of water. During stirring, 13 g of isophoronediamine was added for post-chain extension and reacted for 15 min. After that, the solvent-free dispersion obtained after separating acetone by distillation 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 reached 1.75 wt%. After cooling the temperature to 40 - 45 °C, it was diluted by adding 500 g of acetone. Then, 5.43 g of triethylamine was added and neutralized for about 5 min. Thereafter, the mixture was dispersed by adding 825 g of water. During stirring, 11 g of isophoronediamine was added for post-chain extension and reacted for 15 min. After that, the solvent-free dispersion obtained after separating acetone by distillation 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 1, 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 reached 2.8%. The temperature was lowered, and 740 g of acetone was added for dilution. The temperature was further lowered to 40 - 50 °C, and under stirring, 19 g of an aqueous solution of sodium N-(2-aminoethyl)-2-aminoethanesulfonate with a concentration of 50 wt% diluted with 5 volumes of water and 13 g of isophoronediamine were added. The reaction was carried out for about 15 min, and 800 g of deionized water was added under stirring for dispersion. Further, after separating acetone by distillation, the solvent-free dispersion obtained 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 1, 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 reached 2.5 wt%. The temperature was lowered, and 740 g of acetone was added for dilution. The temperature was further lowered to 40 - 50 °C, and under rapid stirring, 22 g of an aqueous solution of sodium N-(2-aminoethyl)-2-aminoethanesulfonate with a concentration of 50 wt% diluted with 5 volumes of water and 10 g of isophoronediamine were added. The reaction was carried out for about 15 min, and 900 g of deionized water was added under stirring for dispersion. Further, after separating acetone by distillation, the solvent-free dispersion obtained had a solid content of 40 wt%, an average particle size of 258 nm, and a pH of 7.2.

[0076] [Comparative Example 1] The polyol 2 in Example 5 was replaced with polycarbonate, and the rest remained unchanged. It had 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, and the mixture was stirred at 80 - 90 °C until the NCO reached 1.39 wt%. After cooling the temperature to 40 - 45 °C, it was diluted by adding 500 g of acetone, then 6.7 g of triethylamine was added and neutralized for about 5 min. Thereafter, the mixture was dispersed by adding 1290 g of water, and 4.8 g of ethylenediamine was added during stirring for post-chain extension, and the reaction was carried out for 15 min. Then, after separating acetone by distillation, the solvent-free dispersion obtained 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, and the rest remained unchanged. It had 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, and the rest remained unchanged. It had 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, and the rest remained unchanged. It had 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, and the rest remained unchanged. It had a solid content of 40 wt%, an average particle size of 151 nm, and a pH of 8.4.

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

[0083] Formulation of coagulating liquid: An aqueous solution containing 10 wt% of CaCl2 and 5 wt% of mold release agent (calcium stearate) was formulated with deionized water and continuously stirred for 1 h to prepare.

[0084] Manufacture of gloves: 1) The glove mold that had been cleaned was put into an oven at 100 °C and dried. 2) The glove mold was taken out, cooled to 60 °C, immersed in the coagulating liquid for about 8 s, taken out, and put into an oven at 120 - 140 °C and dried. 3) The dried glove mold was taken out, cooled to 60 °C, immersed in the prepared base resin for about 8 s, after being taken out, put into an oven at 130 °C and baked for about 4 min, taken out, immersed in the prepared base resin again for about 8 s, and then put into the oven and baked continuously for about 20 min. 4) After taking out the glove mold after baking, it was immersed in the glove coating agent, taken out, dried naturally, and demolded to obtain the finished glove.

[0085] Performance test: Test of tensile strength and elongation: The palm part of the glove was selected and cut into a dumbbell shape with a width of 6 mm and a length of 115 mm, and the tensile strength was tested with a tensile testing machine and the elongation was obtained. Water resistance test: 800 g of water was injected into the glove and it was turned upside down, and the deformation and appearance of the glove were observed. Resistance to oxides: 30 wt% hydrogen peroxide solution was injected into the glove and left for 10 min, and the presence or absence of leakage or seepage was observed. Resistance to polar solvents: 75 wt% alcohol solution was injected into the glove and left for 10 min, and the presence or absence of leakage or seepage was observed. Rebound elasticity and wearing comfort: With reference to the "commercially available latex gloves" shown in Table 1, the expression of the rebound elasticity and wearing comfort of the gloves obtained in each example and comparative example was evaluated.

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

Table 1

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

[0088] It is easily understood that the above examples are merely examples given for clear explanation and do not mean that the present invention is limited thereto. For those skilled in the art, based on the above description, other different forms of changes or modifications are further possible. Here, it is not possible to list all the embodiments comprehensively, nor is it necessary. The obvious changes or variations generated thereby are still included within the protection scope created by the present invention.

Claims

1. It 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. Among them, 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 anhydride. A polyurethane-polyurea aqueous dispersion characterized by the above.

2. The dihydric alcohol used in the preparation of the semi-crystalline polyester polyol contains at least one or more of 1,4-butanediol and 1,6-hexanediol, and may further contain other dihydric alcohols having a relative molecular weight lower than 150. The other dihydric alcohols include one or more of ethylene glycol, 1,3-butanediol, neopentyl glycol, 1,5-pentanediol, propylene glycol, diethylene glycol, and dipropylene glycol. Among the dihydric alcohols used in the preparation of the semi-crystalline polyester polyol, the proportion of the other dihydric alcohols is lower than 50 wt%. And / or, component II used in the preparation of the semi-crystalline 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. More preferably, component II is isophthalic acid. And / or, the aliphatic dicarboxylic acid used in the preparation of the semi-crystalline polyester polyol is adipic acid. The polyurethane-polyurea aqueous dispersion according to claim 1, characterized by the above.

3. The semi-crystalline polyester polyol is an opaque wax-like solid at room temperature. The polyurethane-polyurea aqueous dispersion according to claim 1 or 2, characterized by the above.

4. The polyurethane-polyurea aqueous dispersion contains at least one polyol having a functionality of 2 or more, and the proportion of the semi-crystalline polyester polyol in component a is 40 wt% or more. Component a in which the proportion of the semi-crystalline polyester polyol in component a is preferably 70 to 100 wt%. Component b which is a polyisocyanate A hydrophilic compound containing 2 to 3 groups reactive with NCO, wherein the hydrophilic group of the hydrophilic compound contains one or more of an ionic group and a latent ionic group, component c Optionally, component d, which is an alcohol chain extender different from component a Component f, which is a polyamine having a number average molecular weight of 500 g / mol or less It is prepared by reacting a raw material containing such components The polyurethane-polyurea aqueous dispersion according to any one of claims 1 to 4, characterized in that

5. When the hydrophilic group of component c does not contain the ionic group, the raw material further contains component e, which is a compound capable of ionizing component c Preferably, when the raw material contains component e, based on the total weight of components a, b, c, d, e and f, the proportion of the usage amount of each of the following components used in the preparation of the polyurethane-polyurea aqueous dispersion is: component a is 56 to 85 wt%, component b is 10 to 30 wt%, component c is 0.8 to 4 wt%, component d is 0 to 3 wt%, component f is 0.5 to 4 wt%, and component e is 0.6 to 4 wt% Preferably, when the raw material does not contain component e, based on the total weight of components a, b, c, d and f, the proportion of the usage amount of each of the following components used in the preparation of the polyurethane-polyurea dispersion is: component a is 56 to 85 wt%, component b is 10 to 30 wt%, component c is 0.8 to 4 wt%, component d is 0 to 3 wt%, and component f is 0.5 to 4 wt% The polyurethane-polyurea aqueous dispersion according to claim 4, characterized in that

6. In component a, the number average molecular weight of the polyol is 500 to 15000 g / mol, and the polyol preferably has a number average molecular weight of 800 to 10000 g / mol and a functionality of 2 to 4. More preferably, the polyol has a number average molecular weight of 1000 to 5000 g / mol and a functionality of 2 to 3 And / or in component b, the polyisocyanate is one or more selected from aromatic, aliphatic, and alicyclic polyisocyanates, and preferably the polyisocyanate has at least two isocyanate groups And / or in component c, the group reactive with NCO contained in the hydrophilic compound is a hydroxy group and / or an amino group And / or, in the component c, the ionic group is preferably a carboxylic acid ion and / or a sulfonic acid ion, and the latent ionic group is preferably a carboxyl group, And / or, in the component d, the alcohol-based chain extender different from the component a is a small molecule alcohol-based compound having a relative molecular weight of less than 150, And / or, the component e is triethylamine, And / or, the component f is a polyamine having a relative molecular weight of 60 to 500, and is preferably 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 claim 5, characterized in that.

7. The hydrophilic compound as the 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 salts thereof, the salts include one or more of the corresponding alkali metal salts, alkaline earth metal salts or ammonium salts, and the component c is preferably dimethylolpropionic acid, And / or, the alcohol-based chain extender as the 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 one or more of 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and 1,6-hexanediol are preferred. The polyurethane-polyurea aqueous dispersion according to claim 6, characterized in that.

8. The component a may contain other polyols different from the semi-crystalline polyester polyol, and the other polyols are one or more selected from polyester polyols, polycaprolactone polyols, polycarbonate polyols, and polyether polyols, and the proportion of the other polyols in the component a is 0 to 60 wt%. The polyurethane-polyurea aqueous dispersion according to claim 6, characterized in that.

9. Reacting a raw material containing component a to prepare the polyurethane-polyurea aqueous dispersion. Preferably, the raw material further contains component b, component c, optional component d, and component f. However, the component b is a polyisocyanate, the component c is a hydrophilic compound, the hydrophilic compound contains 2 to 3 groups reactive with NCO, the component d is an alcohol-based chain extender different from component a, the component f is a polyamine having a number average molecular weight of 500 g / mol or less, and when the component c does not contain an ionic group, the raw material further contains component e, and the component e is a compound capable of ionizing the component c. Preferably, it includes the step of reacting at 60 to 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 8, characterized in that...

10. A soft elastic product produced from the polyurethane-polyurea aqueous dispersion according to any one of claims 1 to 8, preferably including gloves and / or condoms. A soft elastic product, characterized in that...

11. A method for producing a soft elastic product, comprising the step of adding a raw material liquid containing a polyurethane-polyurea aqueous dispersion to a mold required for the production of the 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 according to any one of claims 1 to 8. A method for producing a soft elastic product, characterized in that...

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