Composition containing polyurethane-polyurea aqueous dispersion and preparation method and application thereof

Abstract

The invention provides a composition containing a polyurethane-polyurea aqueous dispersion as well as a preparation method and application of the composition. The composition comprises a polyurethane-polyurea aqueous dispersion, a butyronitrile emulsion and a vulcanizing agent, wherein the polyurethane-polyurea aqueous dispersion is formed by polymerizing raw materials including macromolecular polyol, polyisocyanate, a chain extender containing a carbon-carbon double bond and a hydrophilic chain extender; the carbon-carbon double bond of the chain extender containing the carbon-carbon double bond is positioned on a side chain of a polyurethane chain segment, and the content of the carbon-carbon double bond is 4.5-25mmol / 100g. The composition is used for preparing gloves by a flocculation method, side chain double bonds contained in the waterborne polyurethane-polyurea aqueous dispersion and carbon-carbon double bonds in the butyronitrile emulsion can be crosslinked at high temperature in the presence of a vulcanizing agent, and the two resins form chemical bond combination. According to the method, the strength and elongation of the glove can be improved, and the wearing hand feeling of the glove is further improved.

Description

Technical Field

[0001] The invention belongs to the field of polyurethane-polyurea dispersions, and specifically relates to a composition containing polyurethane-polyurea aqueous dispersions, and a preparation method and application thereof. Background Art

[0002] Soft elastic products such as disposable gloves are widely used in medical gloves, examination gloves, household and industrial fields. The materials currently used to prepare soft elastic products (such as disposable gloves, condoms, etc.) on the market mainly include nitrile rubber, natural latex, chloroprene rubber, PVC, etc. Nitrile gloves are widely used, but have low extensibility, low tear strength, and hard feel, and the experience is poor during use. There are literature reports on the use of aqueous polyurethane emulsions to mix nitrile latex to improve the strength and feel of nitrile, such as CN112794972A, CN112812261B, CN112778480B, CN112143154B, but still cannot solve the problem of glove strength and feel.

[0003] Therefore, there is an urgent need in the art for a product solution that can simultaneously improve the strength, elongation, and wearing feel of nitrile gloves. Summary of the invention

[0004] One of the purposes of the present invention is to provide a composition containing a polyurethane-polyurea aqueous dispersion, which can improve the strength and elongation of gloves by mixing with a nitrile emulsion, and further improve the wearing feel of the gloves.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] A composition containing a polyurethane-polyurea aqueous dispersion, the composition comprising a polyurethane-polyurea aqueous dispersion, a nitrile emulsion, and a vulcanizing agent;

[0007] The polyurethane-polyurea aqueous dispersion is formed by polymerizing raw materials including macromolecular polyol, polyisocyanate, chain extender containing carbon-carbon double bonds, and hydrophilic chain extender;

[0008] Preferably, the carbon-carbon double bond of the chain extender containing a carbon-carbon double bond is located on the side chain of the polyurethane segment, and the content of the carbon-carbon double bond is 4.5-25 mmol / 100g;

[0009] Wherein, the nitrile emulsion is a carboxyl nitrile emulsion;

[0010] Under the action of high temperature, the polyurethane-polyurea in the composition forms a chemical bond with the nitrile.

[0011] The inventors found in their research that the existing compounding scheme is actually unable to effectively improve the strength and elongation of nitrile. Polyurethane is mixed in nitrile as a plasticizer because polyurethane does not form a good link with nitrile. The inventors further found that using a substance with a carbon-carbon double bond structure as a reactant to introduce a carbon-carbon double bond into the polyurethane chain segment, the double bond can be opened during the subsequent vulcanization and cross-linking of nitrile and connected to nitrile through a carbon-carbon bond, which can significantly improve the strength and feel of nitrile.

[0012] The polyurethane-polyurea dispersion in the coating combination provided by the present invention can be cross-linked with nitrile latex during the vulcanization process by introducing a carbon-carbon double bond structure into the polyurethane chain segment, and the two substances are effectively combined together in the form of covalent bonds, thereby changing the physical blending previously used, which cannot achieve effective synergistic effect of the two substances. The polyurethane with this structure can effectively improve the strength and elongation of the nitrile latex, and make the nitrile gloves have a soft and elastic wearing feel.

[0013] In one embodiment of the present invention, the ratio of each component in the composition is as follows:

[0014] 80-100 parts of nitrile resin based on solid parts,

[0015] 10-30 parts of polyurethane-polyurea based on solid parts,

[0016] 2-7 parts of vulcanizing agent;

[0017] Optionally, the composition further comprises the following components:

[0018] 1-4 parts of additives,

[0019] The color paste is 0.5-2 parts based on solid content, and the titanium dioxide is 0.5-2 parts based on solid content. The auxiliary agents and their usage amounts are all commonly used auxiliary agents and usage amounts in the art.

[0020] In one embodiment of the present invention, the vulcanizing agent is a disulfide compound, preferably sulfur. The vulcanizing agent and its dosage are commonly used additives and dosages for preparing crosslinking systems.

[0021] In one embodiment of the present invention, the auxiliary agent is a metal oxide and / or a metal hydroxide, preferably ZnO and / or KOH. The auxiliary agent and the amount used are the common auxiliary agents and amounts used in preparing a crosslinking system.

[0022] Another object of the present invention is to provide a method for preparing a composition containing a polyurethane-polyurea aqueous dispersion.

[0023] A method for preparing a composition containing a polyurethane-polyurea aqueous dispersion, wherein the composition is the above-mentioned composition, and the preparation method comprises: diluting the polyurethane-polyurea aqueous dispersion and nitrile emulsion with water, adding a vulcanizing agent, and optionally color paste, titanium dioxide, and an auxiliary agent, stirring, and degassing.

[0024] In one embodiment of the present invention, the preparation method is performed by diluting the resin until the solid content of the whole resin is 18-20%.

[0025] Another object of the present invention is to provide a use of a composition containing a polyurethane-polyurea aqueous dispersion.

[0026] A use of a composition containing a polyurethane-polyurea aqueous dispersion, wherein the composition is the above composition, or a composition prepared by the above preparation method, and the composition is used for preparing soft elastic products, preferably for preparing gloves.

[0027] Another object of the present invention is to provide a method for preparing gloves.

[0028] A method for preparing gloves, the method using the above composition, or a composition prepared by the above preparation method, the method comprising the following steps:

[0029] S1: prepare coagulation solution;

[0030] S2: preparing a liquid from a composition containing a polyurethane-polyurea aqueous dispersion;

[0031] S2: The glove mold is immersed in the coagulation liquid, the material liquid and the finishing agent, and the glove product is obtained by demoulding.

[0032] In one embodiment of the present invention, the coagulation liquid in S1 comprises water, a flocculant, and a release agent; preferably, the ratio of water, flocculant, and release agent is 100:8-10:5-10. Preferably, the flocculant is a metal ion salt compound, preferably calcium nitrate; preferably, the release agent is a long carbon chain fatty acid salt, preferably calcium stearate. The above coagulation liquid components and ratios are commonly used in the art.

[0033] In one embodiment of the present invention, the slurry S2 comprises 100 parts of nitrile resin based on solid content, 10-30 parts of polyurethane-polyurea based on solid content, 2-7 parts of vulcanizing agent, optionally, 1-4 parts of auxiliary agent, 0.5-1.5 parts of color paste based on solid content, and 0.5-1.5 parts of titanium dioxide.

[0034] In one embodiment of the present invention, the immersion in the coagulation liquid and the slurry liquid in S3 is followed by drying, and the preferred drying temperature is 100-150°C.

[0035] Another object of the present invention is to provide a glove.

[0036] A pair of gloves, wherein the gloves are made of the above composition, or a composition prepared by the above preparation method, or are prepared by the above preparation method, and the strength of the gloves is 27-36MPa, and the elongation is 277-350%.

[0037] Another object of the present invention is to provide a polyurethane-polyurea aqueous dispersion.

[0038] A polyurethane-polyurea aqueous dispersion, which is used for the above-mentioned composition, or for the composition prepared by the above-mentioned preparation method, or for the dispersion used in the above-mentioned preparation method, or for the dispersion of the above-mentioned gloves. The polyurethane-polyurea aqueous dispersion is formed by polymerizing raw materials including macromolecular polyol, polyisocyanate, chain extender containing carbon-carbon double bonds, and hydrophilic chain extender.

[0039] In one embodiment of the present invention, the chain extender containing carbon-carbon double bonds has the following structure:

[0040]

[0041] Among them, R1 is one of an alkyl group, an alkoxy group, or a group containing an aromatic ring having 2 to 10 carbon atoms, preferably one of an ethyl group, a butyl group, a bisphenol A structure, or a diethylene glycol structure; R2 is hydrogen or an alkyl group, preferably a methyl group.

[0042] In one embodiment of the present invention, the chain extender containing carbon-carbon double bonds is the product of the reaction of acrylic acid or methacrylic acid with polyglycidyl ether; preferably, the polyglycidyl ether contains 2-3 epoxy groups, preferably one or more of ethylene glycol diglycidyl ether, butanediol diglycidyl ether, diethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, and trimethylolpropane triglycidyl ether; preferably, the molar ratio of the epoxy group of the polyglycidyl ether to the carboxyl group of acrylic acid or methacrylic acid is 1:(1.95-2.05).

[0043] In one embodiment of the present invention, the reaction temperature is 105-110°C and the reaction time is 4-6h.

[0044] Another object of the present invention is to provide a method for preparing the polyurethane-polyurea aqueous dispersion.

[0045] A method for preparing a polyurethane-polyurea aqueous dispersion, wherein the dispersion is used for the above-mentioned composition, or for the composition prepared by the above-mentioned preparation method, or for the dispersion used in the above-mentioned preparation method, or for the dispersion of the above-mentioned gloves, or is the above-mentioned dispersion, and the dispersion is prepared by reacting raw materials comprising the following components:

[0046] Component a: macromolecular polyol,

[0047] Component b: polyisocyanate,

[0048] Component c: a hydrophilic compound containing 2-3 reactive groups with NCO,

[0049] Component d: chain extender containing carbon-carbon double bonds,

[0050] Optional component e: a small molecule alcohol chain extender different from component d,

[0051] Component f: a compound that ionizes the latent groups in component c.

[0052] Component g: a polyamine having a number average molecular weight not exceeding 500 g / mol.

[0053] In one embodiment of the present invention, the mass fractions of the components of the dispersion are as follows:

[0054] Component A: 65-80,

[0055] Component B: 12-25,

[0056] Component c: 1-2.5,

[0057] Component d: 3-10,

[0058] Component e: 0-3,

[0059] Component f: 0.6-2,

[0060] Component g: 0.5-3.

[0061] In one embodiment of the present invention, the component a is one or more of diols, triols and tetraols having a number average molecular weight of 500-6000 g / mol; preferably one or more of polyester polyols, polyether polyols, polycarbonate polyols and polycaprolactone polyols having a number average molecular weight of 500-5000 g / mol and a functionality of 2-3.

[0062] In one embodiment of the present invention, the component b is one or more of aromatic, aliphatic and alicyclic polyisocyanates, preferably one or more of aromatic, aliphatic and alicyclic polyisocyanates having at least two isocyanate groups.

[0063] In one embodiment of the present invention, the component c contains 2 to 3 NCO-reactive groups, preferably dimethylolpropionic acid and / or dimethylolbutanoic acid.

[0064] In one embodiment of the present invention, the component d is a hydroxy compound containing a double bond structure, preferably a product of acrylic acid or alkyl acrylic acid and an epoxy compound; more preferably, an esterification product of acrylic acid or alkyl acrylic acid and a polyglycidyl compound.

[0065] In one embodiment of the present invention, the component e is selected from polyhydroxy small molecule alcohols, preferably one or more of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-dihydroxycyclohexane, 1,4-dimethylolcyclohexane, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and 2-ethyl-1,3-hexanediol, more preferably one or more of 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol and 1,4-cyclohexanedimethanol.

[0066] In one embodiment of the present invention, the component f is an organic base, preferably one or more of triethylamine, dimethylethanolamine, and aqueous ammonia, more preferably triethylamine.

[0067] In one embodiment of the present invention, the component g is a polyamine having a number average molecular weight of 60-500 g / mol, preferably one or more of ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-hexanediamine, 2-methyl-1,5-diamine, isophoronediamine, 4,4-diaminodicyclohexylmethane, piperazine and diethylenetriamine, more preferably ethylenediamine and / or isophoronediamine.

[0068] Compared with the prior art, the positive effects of the present invention are:

[0069] The two substances are effectively combined together by forming a covalent bond, which changes the previous physical blending that could not achieve effective synergistic effect of the two substances. The polyurethane with this structure can effectively improve the strength and elongation of nitrile latex and make nitrile gloves have a soft and elastic wearing feel. BRIEF DESCRIPTION OF THE DRAWINGS

[0070] Attached Figure 1 This is the IR spectrum of component d prepared in Example 1. DETAILED DESCRIPTION

[0071] In order to facilitate the understanding of the present invention, the present invention will be further described below in conjunction with examples. It should be understood that the following examples are only for a better understanding of the present invention and do not mean that the present invention is limited to the following examples.

[0072] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which the invention belongs. The term "and / or" as may be used herein includes any and all combinations of one or more of the associated listed items.

[0073] Where specific experimental steps or conditions are not specified in the examples, the corresponding conventional experimental steps or conditions in the art can be used. The reagents or instruments used without specifying the manufacturer are all conventional products that can be purchased commercially.

[0074] Hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), Wanhua Chemical

[0075] Polyester polyol 1: polyadipic acid-neopentyl glycol polyester, Mn=2000, functionality 2, Wanhua Chemical;

[0076] Polyester polyol 2: poly(1,4-butanediol-adipate-isophthalate) polyester, Mn=2000, functionality 2, Wanhua Chemical;

[0077] Polyester polyol 3: polyadipic acid-neopentyl glycol-hexanediol polyester, Mn=1500, functionality 2, Wanhua Chemical;

[0078] Polyether polyol: polytetramethylene glycol Mn=2000, functionality 2, Mitsubishi Chemical, Japan;

[0079] Dimethylolpropionic acid (DMPA): Perstorp;

[0080] Neopentyl glycol (NPG): Wanhua Chemical;

[0081] Ethylenediamine (EDA), triethylamine (TEA), methacrylic acid, acrylic acid, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, bisphenol A diglycidyl ether, trimethylolpropane triglycidyl ether, p-hydroxyanisole, triphenylphosphine: Sinopharm Chemical Reagent Company.

[0082] Nitrile emulsion: (solid content 45%, PH=10, butadiene acrylonitrile methacrylate terpolymer emulsion, carboxyl content 5%), Lanfan Medical Co., Ltd.

[0083] Sulfur, zinc oxide, potassium hydroxide (KOH): Blue Sail Medical Co., Ltd.

[0084] pH value: measured using a Metrohm 6173 pH meter.

[0085] Average particle size: The polyurethane dispersion was diluted with water to a concentration of 0.5 wt % and measured using a Malvern Nano-ZS90.

[0086] -NCO determination: The -NCO content in the polyurethane synthesis process is determined according to the chemical industry standard of the People's Republic of China "HG / T2409-92 Determination of isocyanate content in polyurethane prepolymers". Use the NCO tester from Swiss Metrohm.

[0087] Infrared spectrum measurement: Fourier transform infrared spectrometer, model IRPrestige-21, riben SHIMATSU was used.

[0088] The calculation formula of the theoretical double bond content is: 1000*(molar amount of acrylic acid or methacrylic acid) / [(total mass of reactants) / 100], and is given by Example 1 as follows:

[0089] 1000*(163.8 / 72) / [(100+163.8+0.082+0.4) / 100]=860, where 72 is the molecular weight of acrylic acid.

[0090] Example 1

[0091] Preparation of component d: 100 g of ethylene glycol diglycidyl ether, 163.8 g of acrylic acid, 0.082 g of p-hydroxyanisole and 0.4 g of triphenylphosphine were added to a 500 mL four-necked flask, reacted at 105 ° C for 6 h in a nitrogen atmosphere, and filtered after cooling to obtain the target product, with an acid value of 0.2 mgKOH / g, a theoretical hydroxyl value of 243 mgKOH / g, and a carbon-carbon double bond content on the chain of 860 mmol / 100 g.

[0092] The infrared spectrum of the product is shown in the attached figure, 1634cm -1 The absorption peak of carbon-carbon double bond is at 3400cm -1 The absorption peak of hydroxyl is at 910cm -1 The epoxy absorption peak at has disappeared.

[0093] Example 2

[0094] Preparation of component d: 100 g of butanediol diglycidyl ether, 170.3 g of methacrylic acid, 0.085 g of p-hydroxyanisole and 0.4 g of triphenylphosphine were added to a 500 mL four-necked flask, reacted at 105° C. for 4.5 h in a nitrogen atmosphere, and filtered after cooling to obtain the target product, with an acid value of 0.15 mgKOH / g and a theoretical hydroxyl value of 205 mgKOH / g. The content of carbon-carbon double bonds on the side chain was 730 mmol / 100 g.

[0095] Example 3

[0096] Preparation of component d: 100g of bisphenol A diglycidyl ether, 101g of methacrylic acid, 0.05g of p-hydroxyanisole and 0.4g of triphenylphosphine were added to a 500mL four-necked flask, reacted at 110°C for 5h in a nitrogen atmosphere, and filtered after cooling to obtain the target product, with an acid value of 0.23mgKOH / g and a theoretical hydroxyl value of 163mgKOH / g. The content of carbon-carbon double bonds on the side chain was 580mmol / 100g.

[0097] Example 4

[0098] Preparation of component d: 100g of trimethylolpropane triglycidyl ether, 116.6g of methacrylic acid, 0.058g of p-hydroxyanisole and 0.4g of triphenylphosphine were added to a 500mL four-necked flask, reacted at 107°C for 5.5h in a nitrogen atmosphere, and filtered after cooling to obtain the target product, with an acid value of 0.11mgKOH / g and a theoretical + hydroxyl value of 170.9mgKOH / g. The content of carbon-carbon double bonds on the side chain was 620mmol / 100g.

[0099] Example 5

[0100] 310g of polyester polyol 1, 28.5g of IPDI, 28.5g of HDI, 5.2g of DMPA and 58.4g of acetone were added to a 1L four-necked round-bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 80°C until the NCO reached 2.1wt% (theoretical value 2.1wt%), cooled to 50°C, added, cooled to 45°C, 14g of component d prepared in Example 1 and 38.9g of acetone were added, and the temperature was continued to rise to 80°C for reaction until the NCO reached 1.33wt% (theoretical value 1.33wt%), cooled to 45°C, 350g of acetone was added to dilute evenly, and cooled to below 40°C, and then 3. 92 g of triethylamine was neutralized for 5 min, 723 g of deionized water was added under high-speed stirring at 1000 r / min for dispersion for 15 min, a 50% aqueous solution containing 3.1 g of ethylenediamine was added and continued to be stirred for chain extension for 15 min, and acetone was separated by reduced pressure distillation at 55° C. and a vacuum degree of 0.09 MPa to obtain a solvent-free dispersion having a solid content of 35 wt%, an average particle size of 213 nm, a pH value of 8.1, and a carbon-carbon double bond content on the side chain of 15.47 mmol / 100 g.

[0101] Example 6

[0102] 310 g of polyester polyol 2, 78 g of IPDI, 6.2 g of DMPA, 1.0 g of neopentyl glycol and 42 g of acetone were added to a 1 L four-necked round-bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 80° C. until the NCO reached 2.87 wt % (theoretical value 2.87 wt %), cooled to 50° C., added, cooled to 45° C., 25 g of component d prepared in Example 2 and 42 g of acetone were added, and the temperature was continued to rise to 80° C. to react until the NCO reached 1.56 wt % (theoretical value 1.56 wt %), cooled to 45° C., 381 g of acetone was added to dilute evenly, and the temperature was cooled to below 40° C., and then added 4.68 g of triethylamine was added for neutralization for 5 min, 787 g of deionized water was added for dispersion under high-speed stirring at 1000 r / min for 15 min, a 50% concentration aqueous solution containing 3.95 g of ethylenediamine was added and the chain was continued to be stirred for 15 min, and acetone was separated by reduced pressure distillation at 55° C. and a vacuum degree of 0.09 MPa to obtain a solvent-free dispersion having a solid content of 35 wt%, an average particle size of 203 nm, a pH value of 8.2, and a carbon-carbon double bond content on the side chain of 21.35 mmol / 100 g.

[0103] Example 7

[0104] 288 g of polyester polyol 3, 90 g of IPDI, 6.9 g of DMPA and 42 g of acetone were added to a 1 L four-necked round-bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 80° C. until the NCO reached 3.17 wt % (theoretical value 3.17 wt %), cooled to 50° C., added 35 g of component d prepared in Example 3 and 42 g of acetone were cooled to 45° C., and the temperature was continued to rise to 80° C. to react until the NCO reached 1.83 wt % (theoretical value 1.83 wt %), cooled to 45° C., added 382 g of acetone, diluted evenly, cooled to below 40° C., and then added 5.2 1g of triethylamine was neutralized for 5min, 788g of deionized water was added under high-speed stirring at 1000r / min for dispersion for 15min, a 50% concentration aqueous solution containing 4.64g of ethylenediamine was added and continued to be stirred for chain extension for 15min, and acetone was separated by reduced pressure distillation at 55°C and a vacuum degree of 0.09Mpa to obtain a solvent-free dispersion having a solid content of 35wt%, an average particle size of 183nm, a pH value of 8.3, and a carbon-carbon double bond content on the side chain of 23.67mmol / 100g.

[0105] Example 8

[0106] 280 g of polyether polyol, 56 g of IPDI, 28.5 g of HDI, 6.8 g of DMPA, 6.0 g of neopentyl glycol and 38 g of acetone were added to a 1 L four-necked round-bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 80° C. until the NCO reached 3.48 wt % (theoretical value 3.48 wt %), cooled to 50° C., added, cooled to 45° C., 6 g of component d prepared in Example 4 and 38 g of acetone were added, and the temperature was continued to rise to 80° C. to react until the NCO reached 1.88 wt % (theoretical value 1.88 wt %), cooled to 45° C., 348 g of acetone was added to dilute evenly, and the temperature was cooled to below 40° C., and then added 5.13 g of triethylamine was added for neutralization for 5 min, 719 g of deionized water was added for dispersion under high-speed stirring at 1000 r / min for 15 min, a 50% concentration aqueous solution containing 4.33 g of ethylenediamine was added and the chain was continued to be stirred for 15 min, and acetone was separated by reduced pressure distillation at 55° C. and a vacuum degree of 0.09 MPa to obtain a solvent-free dispersion having a solid content of 35 wt%, an average particle size of 187 nm, a pH value of 8.2, and a carbon-carbon double bond content of 4.65 mmol / 100 g on the side chain.

[0107] Comparative Example 1

[0108] Compared with Example 8, the difference is that less component d is added.

[0109] 280 g of polyether polyol, 56 g of IPDI, 28.5 g of HDI, 6.8 g of DMPA, 6.0 g of neopentyl glycol and 38 g of acetone were added to a 1 L four-necked round-bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 80° C. until the NCO reached 3.48 wt % (theoretical value 3.48 wt %), cooled to 50° C., added, cooled to 45° C., 3 g of component d prepared in Example 4 and 38 g of acetone were added, and the temperature was continued to rise to 80° C. to react until the NCO reached 1.97 wt % (theoretical value 1.97 wt %), cooled to 45° C., 348 g of acetone was added to dilute evenly, and the temperature was cooled to below 40° C., and then added 5.13 g of triethylamine was added for neutralization for 5 min, 719 g of deionized water was added for dispersion under high-speed stirring at 1000 r / min for 15 min, a 50% concentration aqueous solution containing 4.52 g of ethylenediamine was added and the chain was continued to be stirred for 15 min, and acetone was separated by reduced pressure distillation at 55° C. and a vacuum degree of 0.09 MPa to obtain a solvent-free dispersion having a solid content of 35 wt%, an average particle size of 185 nm, a pH value of 8.2, and a carbon-carbon double bond content on the side chain of 2.37 mmol / 100 g.

[0110] Comparative Example 2

[0111] Compared with Example 8, the difference is that more component d is added.

[0112] 280 g of polyether polyol, 56 g of IPDI, 28.5 g of HDI, 6.8 g of DMPA, 1.3 g of neopentyl glycol and 41 g of acetone were added to a 1 L four-necked round-bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 80° C. until the NCO reached 3.45 wt % (theoretical value 3.45 wt %), cooled to 50° C., added, cooled to 45° C., 38 g of component d prepared in Example 4 and 41 g of acetone were added, and the temperature was continued to rise to 80° C. to react until the NCO reached 1.69 wt % (theoretical value 1.69 wt %), cooled to 45° C., 373 g of acetone was added to dilute evenly, and the temperature was cooled to below 40° C., and then added 5.13 g of triethylamine was added for neutralization for 5 min, 770 g of deionized water was added for dispersion under high-speed stirring at 1000 r / min for 15 min, a 50% concentration aqueous solution containing 4.18 g of ethylenediamine was added and the chain was continued to be stirred for 15 min, and acetone was separated by reduced pressure distillation at 55° C. and a vacuum degree of 0.09 MPa to obtain a solvent-free dispersion having a solid content of 35 wt%, an average particle size of 191 nm, a pH value of 8.2, and a carbon-carbon double bond content on the side chain of 27.92 mmol / 100 g.

[0113] The dispersions of the above examples and comparative examples were used to prepare the following liquid:

[0114]

[0115] Liquid preparation method:

[0116] A certain weight portion of nitrile emulsion, polyurethane-polyurea water dispersion, titanium dioxide, color paste, vulcanizing agent and additives are added into a dispersion barrel and stirred for 24 hours to obtain a feed liquid.

[0117] The glove former was pretreated by first cleaning the glove former in a nitric acid solution with a pH value of 3, then cleaning it in an aqueous solution of sodium hydroxide with a pH value of 12, then rinsing it and drying it in an oven at 75°C.

[0118] Prepare a coagulant solution: add 20 parts by weight of calcium nitrate, 15 parts by weight of a release agent and 200 parts by weight of deionized water into a mixing barrel, stir evenly, and obtain a coagulant solution.

[0119] Process 1: The pretreated glove model is immersed in a coagulant solution at 75°C for 20 seconds, dried at 100°C, then immersed in the slurry at 25°C for 10 seconds, dried at 100°C, immersed in the slurry at 25°C for 10 seconds again, dried at 100°C, leached, placed in an oven at 135°C, heated for 30 minutes, and demoulded to obtain a glove.

[0120] Process 2: The pretreated glove model is immersed in a coagulant solution at 75°C for 20 seconds, dried at 100°C, then immersed in the slurry at 25°C for 10 seconds, dried at 110°C, immersed in the slurry at 25°C for 10 seconds again, dried at 110°C, leached, placed in an oven at 140°C, heated for 30 minutes, and demoulded to obtain a glove.

[0121] Performance Test:

[0122] Tensile Strength / Elongation Test:

[0123] The palm part of the glove was cut into a dumbbell shape with a width of 6mm and a length of 115mm, and the tensile strength was tested on a tensile machine. The tensile tester of the high-speed rail company was used for the test, and the tensile rate was 200mm / min. The performance test results are shown in the table below.

[0124] Among them, 1#, 2#, 3#, 4#, 6# and 7# liquids are prepared by process 1, and 5#, 8# and 9# liquids are prepared by process 2.

[0125] Liquid No. Tensile strength / Mpa Elongation / % Resilience 1# Nitrile emulsion 23 200 Difference 2# Liquid 27 277 excellent 3# Liquid 31 289 excellent 4# Liquid 33 309 excellent 5# Liquid 35 350 excellent 6# Liquid 35 311 excellent 7# Liquid 36 323 excellent 8# Liquid 23 245 good 9# Liquid 40 230 good

[0126] It can be seen from the table that adding the polyurethane-polyurea aqueous dispersion of the present invention can significantly improve the mechanical strength and elongation of nitrile gloves, and the prepared gloves have good resilience. It is easy to understand that the above embodiments are only examples for clear explanation, and do not mean that the present invention is limited to them. For ordinary technicians in the field, other different forms of changes or modifications can be made on the basis of the above description. It is not necessary and impossible to list all the embodiments here. The obvious changes or modifications derived from this are still within the protection scope of the present invention.

Claims

1. A composition containing a polyurethane-polyurea aqueous dispersion, characterized in that: The composition comprises a polyurethane-polyurea aqueous dispersion, a nitrile emulsion, and a vulcanizing agent; The polyurethane-polyurea aqueous dispersion is formed by polymerizing raw materials including macromolecular polyol, polyisocyanate, chain extender containing carbon-carbon double bonds, and hydrophilic chain extender; Preferably, the carbon-carbon double bond of the chain extender containing a carbon-carbon double bond is located on the side chain of the polyurethane segment, and the content of the carbon-carbon double bond is 4.5-25 mmol / 100g; Wherein, the nitrile emulsion is a carboxyl nitrile emulsion; Under the action of high temperature, the polyurethane-polyurea in the composition forms a chemical bond with the nitrile.

2. The composition according to claim 1, characterized in that The proportions of the components in the composition are as follows: 60-80 parts of nitrile resin based on solid parts, 10-30 parts of polyurethane-polyurea based on solid parts, 2-7 parts of vulcanizing agent; Optionally, the composition further comprises the following components: 1-5 parts of additives, 0.5-2 parts of color paste based on solid content, 0.5-2 parts of titanium dioxide based on solid content.

3. The composition according to claim 1 or 2, characterized in that The vulcanizing agent is a disulfide compound, preferably sulfur; And / or, the auxiliary agent is a metal oxide and / or a metal hydroxide, preferably ZnO and / or KOH.

4. A method for preparing a composition containing a polyurethane-polyurea aqueous dispersion, wherein the composition is the composition according to any one of claims 1 to 3, characterized in that: The preparation method comprises: diluting a polyurethane-polyurea aqueous dispersion and a nitrile emulsion with water, adding a vulcanizing agent, and optionally color paste, titanium dioxide, and an auxiliary agent, stirring, and degassing.

5. The preparation method according to claim 4, characterized in that: In the preparation method, the resin is diluted to have a solid content of 18-20%.

6. Use of a composition containing a polyurethane-polyurea aqueous dispersion, wherein the composition is the composition according to any one of claims 1 to 3, or is a composition prepared by the preparation method according to claim 4 or 5, and the composition is used to prepare soft elastic products, preferably gloves.

7. A method for preparing gloves, the method using the composition according to any one of claims 1 to 3, or the composition prepared by the preparation method according to claim 4 or 5, characterized in that: The method comprises the following steps: S1: prepare coagulation solution; S2: preparing a liquid from a composition containing a polyurethane-polyurea aqueous dispersion; S2: The glove mold is immersed in the coagulation liquid, the material liquid and the finishing agent, and the glove product is obtained by demoulding.

8. The preparation method according to claim 7, characterized in that: The coagulation liquid in S1 includes water, flocculant, and release agent; Preferably, the ratio of water, flocculant and release agent is 100:8-10:5-10.

9. The preparation method according to claim 7, characterized in that: S2 The slurry comprises 100 parts of nitrile resin based on solid content, 10-30 parts of polyurethane-polyurea based on solid content, 2-7 parts of vulcanizing agent, optionally, 1-4 parts of auxiliary agent, 0.5-1.5 parts of color paste based on solid content, and 0.5-1.5 parts of titanium dioxide.

10. The preparation method according to claim 7, characterized in that: S3: drying after immersing in coagulation liquid and feed liquid, preferably at a drying temperature of 100-150°C.

11. A glove, wherein the glove is made of the composition according to any one of claims 1 to 3, or a composition prepared by the preparation method according to claim 4 or 5, or a composition prepared by the preparation method according to any one of claims 7 to 10, characterized in that: The gloves have a strength of 27-36 MPa and an elongation of 277-350%.

12. A polyurethane-polyurea aqueous dispersion, which is used for the composition according to any one of claims 1 to 3, or for the composition prepared by the preparation method according to claim 4 or 5, or for the dispersion used in the preparation method according to any one of claims 7 to 10, or for the dispersion of the gloves according to claim 11, wherein the polyurethane-polyurea aqueous dispersion is formed by polymerizing raw materials including macromolecular polyol, polyisocyanate, chain extender containing carbon-carbon double bonds, and hydrophilic chain extender.

13. The dispersion according to claim 12, characterized in that The chain extender containing carbon-carbon double bonds has the following structure: Among them, R1 is one of an alkyl group, an alkoxy group, or a group containing an aromatic ring having 2 to 10 carbon atoms, preferably one of an ethyl group, a butyl group, a bisphenol A structure, or a diethylene glycol structure; R2 is hydrogen or an alkyl group, preferably a methyl group.

14. The dispersion according to claim 12 or 13, characterized in that The chain extender containing carbon-carbon double bonds is a product of the reaction of acrylic acid or methacrylic acid with polyglycidyl ether; Preferably, the polyglycidyl ether contains 2-3 epoxy groups, preferably one or more of ethylene glycol diglycidyl ether, butanediol diglycidyl ether, diethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, and trimethylolpropane triglycidyl ether; Preferably, the molar ratio of the epoxy group of the polyglycidyl ether to the carboxyl group of acrylic acid or methacrylic acid is 1:(1.95-2.05); And / or, the reaction temperature is 105-110° C., and the reaction time is 4-6 hours.

15. A method for preparing a polyurethane-polyurea aqueous dispersion, wherein the dispersion is used for the composition according to any one of claims 1 to 3, or for the composition prepared by the preparation method according to claim 4 or 5, or for the dispersion used in the preparation method according to any one of claims 7 to 10, or for the dispersion of the gloves according to claim 11, or for the dispersion according to any one of claims 12 to 14, wherein the dispersion is prepared by reacting raw materials comprising the following components: Component a: macromolecular polyol, Component b: polyisocyanate, Component c: a hydrophilic compound containing 2-3 reactive groups with NCO, Component d: chain extender containing carbon-carbon double bonds, Optional component e: a small molecule alcohol chain extender different from component d, Component f: a compound that ionizes the latent groups in component c. Component g: a polyamine having a number average molecular weight not exceeding 500 g / mol.

16. The method according to claim 15, characterized in that The mass fractions of the various components of the dispersion are as follows: Component A: 65-80, Component B: 12-25, Component c: 1-2.5, Component d: 3-10, Component e: 0-3, Component f: 0.6-2, Component g: 0.5-3.

17. The method according to claim 15 or 16, characterized in that The component a is one or more of diols, triols and tetraols with a number average molecular weight of 500-6000 g / mol; preferably one or more of polyester polyols, polyether polyols, polycarbonate polyols and polycaprolactone polyols with a number average molecular weight of 500-5000 g / mol and a functionality of 2-3; and / or, the component b is one or more of aromatic, aliphatic and alicyclic polyisocyanates, preferably one or more of aromatic, aliphatic and alicyclic polyisocyanates having at least two isocyanate groups; And / or, the component c contains 2-3 reactive groups with NCO, preferably dimethylolpropionic acid and / or dimethylolbutanoic acid; And / or, the component d is a hydroxy compound containing a double bond structure, preferably a product of acrylic acid or alkyl acrylic acid and an epoxy compound; more preferably an esterification product of acrylic acid or alkyl acrylic acid and a polyglycidyl compound; And / or, the component e is selected from a polyhydroxy small molecule alcohol, preferably one or more of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-dihydroxycyclohexane, 1,4-dimethylolcyclohexane, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and 2-ethyl-1,3-hexanediol, more preferably one or more of 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol and 1,4-cyclohexanedimethanol; and / or, the component f is an organic base, preferably one or more of triethylamine, dimethylethanolamine, and aqueous ammonia, more preferably triethylamine; And / or, the component g is a polyamine having a number average molecular weight of 60-500 g / mol, preferably one or more of ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-hexanediamine, 2-methyl-1,5-diamine, isophoronediamine, 4,4-diaminodicyclohexylmethane, piperazine and diethylenetriamine, more preferably ethylenediamine and / or isophoronediamine.

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