A polyurethane resin, a polyurethane glove, and a method for preparing and using the same

Abstract

The application belongs to the technical field of polyurethane, and provides a polyurethane resin, a polyurethane glove and a preparation method and application thereof, raw materials for preparing the polyurethane resin include the following components in mass fraction: modified organosilicon polyol 5%-12.5%, bio-based polyol 5%-12.5%, isocyanate 5%-8%, antioxidant 0.01%-0.02%, catalyst 0.001%-0.002%, chain extender 1%-2%, polyether polyol 0.1%-0.7%, terminator 0.02%-0.05%, and solvent 71%-75%, and raw materials for preparing the modified organosilicon polyol include double-end hydroxyl organosilicon prepolymer and diacid. The polyurethane glove prepared by compounding the specific two kinds of polyol modified organosilicon polyol and bio-based polyol and other substances has good wear resistance and fingerprint-free characteristics, is easy to demould, and is suitable for the fields of automobile film and chip manufacturing.

Description

Technical Field

[0001] This invention belongs to the field of polyurethane technology, and particularly relates to a polyurethane resin, a polyurethane glove, its preparation method and application. Background Technology

[0002] Polyurethane synthetic leather, due to its excellent flexibility, abrasion resistance, comfortable feel, and good processing performance, has been widely used in various fields of daily life and industrial production, such as grip leather for badminton shafts, basketballs, car steering wheels, car seats, bathroom absorbent mats, and polyurethane gloves. Among them, polyurethane gloves have been developed into various types according to functional requirements, such as cut-resistant, oil-resistant, slip-resistant, anti-static, and abrasion-resistant, to meet the basic protection needs in different scenarios.

[0003] However, existing conventional polyurethane gloves are primarily designed for everyday general or basic industrial protection. They are unsuitable for high-end precision fields with extremely high cleanliness requirements, such as the semiconductor industry and high-end automotive window film applications. In the manufacturing, packaging, and testing of chips, even the slightest contamination can cause the expensive chip to malfunction. Fingerprints or other imperfections left on the chip surface by workers' gloves can become chemical contaminants or cause circuit corrosion. In the high-end automotive window film industry, fingerprints left on the inside of the film or paint surface by workers' gloves will be permanently sealed inside, forming an indelible flaw that severely affects the overall aesthetics of the vehicle.

[0004] Current research on polyurethane gloves mainly focuses on waterproof and breathable polyurethane gloves, bio-based gloves, and polyurethane gloves for work protection. CN114081222B discloses a waterproof and breathable polyurethane glove. Addressing the problem that conventional gloves in the prior art cannot effectively wick away sweat, the following solution is proposed: The lining is fitted onto a hand mold for a snug fit, a coagulant is impregnated, and after dripping, the mold is rotated and placed in a drying oven at 50-60°C for 10-20 minutes. This invention uses suitable viscosity and crosslinking agents to ensure uniform foaming and microchannels between the foam cells, facilitating the wicking of hand sweat to the outside of the glove and keeping hands dry. Furthermore, an impregnation molding process is used, with the first layer impregnated with a porous polyurethane coating and the second layer impregnated with a non-porous polyurethane coating. These two impregnation layers prevent contamination from dust, detergents, and other impurities that could clog the first porous coating. The composite between the two coatings also enhances the mechanical strength of the first coating, effectively reducing the decrease in moisture permeability caused by deformation of the foam cells in the first coating due to external forces.

[0005] CN113248904A discloses a large-scale bio-polyurethane glove, which comprises the following raw material formula in parts by weight: 80-100 parts of peppermint, 60-80 parts of tea leaves, 50-60 parts of olive oil, 8-15 parts of organic solvent, 60-80 parts of water, 1-9 parts of dimethylformamide, 40-50 parts of isocyanate groups, 25-35 parts of hydroxyl groups, 10-15 parts of colorant, 5-9 parts of diluent, and 7-11 parts of foaming agent. In this scheme, extracts of peppermint, tea leaves, and olive oil are added to the production of polyurethane gloves, so that the produced gloves have antibacterial effects and prevent long-term use of gloves from causing harm to the human body.

[0006] CN120271784A discloses a waterborne polyurethane for work gloves and its preparation method. The work gloves are made of waterborne polyurethane with a solid content between 45% and 50%, a viscosity maintained between 56 and 58 mPa·s, an average polyurethane particle size in the emulsion between 300 and 500 nm, and an emulsion potential between 35 mV and 50 mV. It has good dispersion stability and high solid content. After curing into a film, it has high strength and good flexibility. The waterborne polyurethane work gloves obtained by impregnating gloves with this waterborne polyurethane have excellent abrasion resistance, tear resistance, and puncture resistance.

[0007] However, there is limited research on polyurethane glove leather that meets the ultra-cleanliness requirement of "no fingerprint transfer" in existing technologies. Existing technologies either fail to fundamentally solve the oil transfer problem or sacrifice the necessary flexibility, breathability, and wearing comfort of the glove in pursuit of cleanliness. Therefore, developing a fingerprint-free polyurethane glove with good abrasion resistance while maintaining the inherent advantages of polyurethane material is a pressing technical problem to be solved in this field. Summary of the Invention

[0008] To address the shortcomings of existing technologies, the present invention aims to provide a polyurethane resin, polyurethane gloves, a preparation method thereof, and applications. The present invention prepares polyurethane gloves by compounding two specific polyols with organosilicon polyols and bio-based polyols, as well as other substances. The resulting polyurethane gloves have excellent wear resistance and fingerprint-resistant properties, making them suitable for automotive window tinting and chip manufacturing.

[0009] To achieve this objective, the present invention adopts the following technical solution:

[0010] In a first aspect, the present invention provides a polyurethane resin, wherein the raw materials for preparing the polyurethane resin comprise the following components by mass fraction:

[0011] Modified organosilicon polyols 5%-12.5%

[0012] Bio-based polyols 5%-12.5%

[0013] Isocyanates 5%-8%

[0014] Antioxidant 0.01%-0.02%

[0015] Catalyst 0.001%-0.002%

[0016] Chain extender 1%-2%

[0017] Polyether polyols 0.1%-0.7%

[0018] Terminator 0.02%-0.05%

[0019] Solvent 71%-75%

[0020] The raw materials for preparing the modified organosilicon polyol include a hydroxyl-terminated organosilicon prepolymer and a dicarboxylic acid.

[0021] In this invention, if the organosilicon prepolymer is directly applied to polyurethane resin, the foaming performance is poor. Therefore, the modified organosilicon polyol is obtained by condensing the double-hydroxyl-terminated organosilicon prepolymer and the dicarboxylic acid, which not only improves the foaming performance but also retains the wear resistance of the organosilicon itself. When applied to polyurethane gloves, it imparts good fingerprint-resistant properties, wear resistance and easy demolding.

[0022] The amount of the modified organosilicon polyol can be 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, or 12.5%, etc.

[0023] The amount of the bio-based polyol can be 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, or 12.5%, etc.

[0024] The amount of isocyanate used can be 5%, 6%, 7% or 8%, etc.

[0025] The amount of the antioxidant can be 0.01%, 0.015%, or 0.02%, etc.

[0026] The amount of catalyst used can be 0.001%, 0.0015%, or 0.002%, etc.

[0027] The amount of the chain extender can be 1%, 1.5%, or 2%, etc.

[0028] The amount of the polyether polyol can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, or 0.7%, etc.

[0029] The amount of the terminator can be 0.02%, 0.03%, 0.04%, or 0.05%, etc.

[0030] The amount of solvent used can be 71%, 72%, 73%, 74%, or 75%, etc.

[0031] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0032] Preferably, the dual-hydroxyl-terminated organosilicon prepolymer includes Guangzhou Silok 8812F2 and / or Guangzhou Silok 8802F2.

[0033] Preferably, the raw materials for preparing the bio-based polyol include bio-based succinic acid, bio-based 1,3-propanediol, and bio-based 1,4-butanediol.

[0034] Preferably, the bio-based polyol includes Asahikawa Chemical KJ-20005.

[0035] Preferably, the weight-average molecular weight of the bio-based polyol is 1800-2500, such as 1800, 1900, 2000, 2100, 2200, 2300, 2400 or 2500.

[0036] Preferably, the bio-based polyol is derived from corn cobs.

[0037] Preferably, the solid content of the polyurethane resin is 26wt%-28wt%, such as 26wt%, 26.5wt%, 27wt%, 27.5wt%, or 28wt%.

[0038] In this invention, if the solid content of the polyurethane resin is too high, there will be a greater number of small molecules in the polyurethane resin, which are more likely to be released, making the resulting polyurethane gloves prone to fingerprints. At the same time, a higher solid content will also make it more difficult to remove the solvent during the preparation of polyurethane gloves, resulting in poor mold release properties. If the solid content of the polyurethane resin is too low, the polyurethane resin will solidify too quickly, which can easily cause holes on the surface of the gloves, i.e., what is known in the industry as "glue leakage".

[0039] Preferably, the viscosity of the polyurethane resin at 25°C is 400,000-500,000 cps, such as 400,000 cps, 410,000 cps, 420,000 cps, 430,000 cps, 440,000 cps, 450,000 cps, 460,000 cps, 470,000 cps, 480,000 cps, 490,000 cps, or 500,000 cps.

[0040] In this invention, if the viscosity of the polyurethane resin is too low, the number of small molecules in the polyurethane resin will be too large, which will easily produce fingerprints and reduce the wear resistance; if the viscosity of the polyurethane resin is too high, the resin will foam too well, resulting in gloves with poor wear resistance.

[0041] Preferably, the weight-average molecular weight of the modified organosilicon polyol is 3500-4500, such as 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400 or 4500.

[0042] Preferably, the dicarboxylic acid includes adipic acid and / or succinic acid.

[0043] Preferably, the molar ratio of the hydroxyl-terminated organosilicon prepolymer to the diacid is (1.3-1.75):1, such as 1.3:1, 1.35:1, 1.4:1, 1.45:1, 1.5:1, 1.55:1, 1.6:1, 1.65:1, 1.7:1, or 1.75:1.

[0044] Preferably, the isocyanate comprises 4,4-diphenylmethane diisocyanate.

[0045] Preferably, the antioxidant comprises any one or a combination of at least two of the following: pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010), octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (antioxidant 1076), 4,4'-thiobis(6-tert-butyl-3-methylphenol) (antioxidant 300), 1,2-bis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine (antioxidant 1024), N,N'-(hexane-1,6-diyl)bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] (antioxidant 1098), or tris(2,4-di-tert-butylphenyl) phosphite (antioxidant B215).

[0046] Preferably, the catalyst comprises phosphoric acid.

[0047] Preferably, the chain extender comprises ethylene glycol.

[0048] Preferably, the polyether polyol includes any one or a combination of at least two of polyethylene glycol, polypropylene glycol, or polybutanediol.

[0049] Preferably, the weight-average molecular weight of the polyether polyol is 1000-2000, such as 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900 or 2000.

[0050] Preferably, the terminating agent comprises any one or a combination of at least two of ethylene glycol, 1,4-butanediol, or methylpropanediol.

[0051] Preferably, the solvent includes N,N-dimethylformamide.

[0052] Preferably, the preparation method of the modified organosilicon polyol includes the following steps:

[0053] The modified organosilicon polyol is obtained by reacting the hydroxyl-terminated organosilicon prepolymer and the dicarboxylic acid under the action of catalyst A.

[0054] Preferably, catalyst A comprises any one or a combination of at least two of tetraisopropyl titanate, tetraisobutyl titanate, toluenesulfonic acid, or stannous octaate.

[0055] Preferably, the preparation method of the modified organosilicon polyol specifically includes the following steps:

[0056] (1) Place the hydroxyl-terminated organosilicon prepolymer and the dicarboxylic acid in a reaction vessel, purge with nitrogen, heat to 140-160℃, keep at the temperature for 7-10h, continue heating to 220-230℃, keep at the temperature for 2-4h;

[0057] (2) Set the vacuum degree to -0.05MPa and evacuate for 4-6 hours; set the vacuum degree to -0.08MPa and evacuate for 8-10 hours.

[0058] (3) When the acid value of the system is between 20-30 mg KOH / g, catalyst A is added and the reaction is carried out at 220-230℃;

[0059] (4) Take samples every 1.4-1.6 hours. When the acid value is less than 0.5 mg KOH / g and the hydroxyl value is between 24-28 mg KOH / g, cool down and filter to obtain the modified organosilicon polyol.

[0060] Preferably, based on the total amount of raw materials for preparing the modified organosilicon polyol being 100%, the amount of catalyst A added is 50-80 ppm, such as 50 ppm, 60 ppm, 70 ppm, or 80 ppm.

[0061] Preferably, the flow rate of the nitrogen gas is 0.2-0.5 L / min, such as 0.2 L / min, 0.3 L / min, 0.4 L / min or 0.5 L / min.

[0062] Preferably, the 140-160℃ can be 140℃, 142℃, 144℃, 146℃, 148℃, 150℃, 152℃, 154℃, 156℃, 158℃, or 160℃, etc.

[0063] Preferably, the 7-10h can be 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, or 10h, etc.

[0064] Preferably, the 220-230℃ can be 220℃, 221℃, 222℃, 223℃, 224℃, 225℃, 226℃, 227℃, 228℃, 229℃, or 230℃, etc.

[0065] Preferably, the 2-4h can be 2h, 2.5h, 3h, 3.5h or 4h, etc.

[0066] Preferably, the 4-6h can be 4h, 4.5h, 5h, 5.5h, or 6h, etc.

[0067] Preferably, the 8-10h can be 8h, 8.5h, 9h, 9.5h, or 10h, etc.

[0068] Preferably, the acid value is 20-30 mg KOH / g, such as 20 mg KOH / g, 22 mg KOH / g, 24 mg KOH / g, 26 mg KOH / g, 28 mg KOH / g, or 30 mg KOH / g.

[0069] Preferably, the 1.4-1.6h can be 1.4h, 1.5h, or 1.6h, etc.

[0070] Preferably, the acid value is less than 0.5 mg KOH / g, such as 0.1 mg KOH / g, 0.2 mg KOH / g, 0.3 mg KOH / g, 0.4 mg KOH / g, or 0.5 mg KOH / g.

[0071] Preferably, the hydroxyl value is between 24 and 28 mg KOH / g, such as 24 mg KOH / g, 25 mg KOH / g, 26 mg KOH / g, 27 mg KOH / g, or 28 mg KOH / g.

[0072] In a second aspect, the present invention provides a method for preparing a polyurethane resin as described in the first aspect, the method comprising the following steps:

[0073] (1) Mix modified organosilicon polyol, bio-based polyol, antioxidant, catalyst, part of isocyanate and part of solvent, and react;

[0074] (2) Add some solvent, chain extender and polyether polyol, and continue the reaction;

[0075] (3) Add the remaining isocyanate, react, add the remaining solvent and terminator to obtain the polyurethane resin.

[0076] Preferably, in step (1), the viscosity of the mixture obtained from the reaction at 65°C is 220,000-260,000 cps, for example, 220,000 cps, 225,000 cps, 230,000 cps, 235,000 cps, 240,000 cps, 245,000 cps, 250,000 cps, 255,000 cps or 260,000 cps.

[0077] Preferably, in steps (1)-(3), the temperature of each reaction is independently 65-75℃, such as 65℃, 66℃, 67℃, 68℃, 69℃, 70℃, 71℃, 72℃, 73℃, 74℃ or 75℃.

[0078] Thirdly, the present invention provides a polyurethane glove, the polyurethane glove comprising the polyurethane resin described in the first aspect.

[0079] Preferably, the raw materials for preparing the polyurethane gloves include the following components by weight:

[0080] 90-110 parts of polyurethane resin

[0081] 150-180 parts of solvent

[0082] 3-5 parts color paste.

[0083] Preferably, the solvent includes N,N-dimethylformamide;

[0084] Preferably, the color paste includes a black color paste.

[0085] The amount of polyurethane resin used can be 90 parts, 92 parts, 94 parts, 96 parts, 98 parts, 100 parts, 102 parts, 104 parts, 106 parts, 108 parts, or 110 parts, etc.

[0086] The amount of solvent used can be 150 parts, 155 parts, 160 parts, 165 parts, 170 parts, 175 parts, or 180 parts, etc.

[0087] The amount of pigment used can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, or 5 parts, etc.

[0088] Fourthly, the present invention provides a method for preparing polyurethane gloves as described in the third aspect, the method comprising the following steps:

[0089] (1) Mix polyurethane resin, solvent and colorant to obtain a mixed solution;

[0090] (2) Immerse the glove core in the mixed solution, homogenize, solidify, dry, and demold to obtain the polyurethane glove.

[0091] Preferably, the glove core is heat-treated.

[0092] Preferably, the immersion time is 6-10 seconds, such as 6 seconds, 7 seconds, 8 seconds, 9 seconds, or 10 seconds.

[0093] Preferably, the homogenization time is 2-5 minutes, such as 2 minutes, 2.5 minutes, 3 minutes, 3.5 minutes, 4 minutes, 4.5 minutes, or 5 minutes.

[0094] Preferably, the material of the glove core is polyester.

[0095] Preferably, the coagulation process includes placing the glove core, after homogenization, into a mixed solvent and then immersing it in water.

[0096] Preferably, the mixed solvent comprises an aqueous solution of N,N-dimethylformamide.

[0097] Preferably, the mass percentage of N,N-dimethylformamide is 14%-18% based on 100% of the mass of the mixed solvent, for example, 14%, 15%, 16%, 17% or 18%.

[0098] Preferably, the soaking time is 1-1.5 hours, such as 1 hour, 1.1 hours, 1.2 hours, 1.3 hours, 1.4 hours, or 1.5 hours.

[0099] Preferably, the drying temperature is 110-120℃, such as 110℃, 111℃, 112℃, 113℃, 114℃, 115℃, 116℃, 117℃, 118℃, 119℃ or 120℃.

[0100] Preferably, the drying time is 40-50 min, such as 40 min, 41 min, 42 min, 43 min, 44 min, 45 min, 46 min, 47 min, 48 min, 49 min, or 50 min.

[0101] The preparation method specifically includes the following steps:

[0102] (1) Mix polyurethane resin, solvent and black paste, stir evenly, centrifuge to remove bubbles, and obtain a mixed solution;

[0103] (2) Place the glove core onto the glove mold and heat at 65-70℃ for 30-40 minutes; immerse the glove core in the mixed solution for 6-10 seconds and coat evenly for 2-5 minutes;

[0104] (3) Place the glove core after uniform coating into an aqueous solution of N,N-dimethylformamide and let it solidify for 15-20 minutes, then place it in water at 65-70℃ and soak for 1-1.5 hours;

[0105] (4) Place the glove core in an oven and dry at 110-120℃ for 40-50 minutes. Demold to obtain the polyurethane glove.

[0106] Compared with the prior art, the present invention has the following beneficial effects:

[0107] This invention obtains modified organosilicon polyols by condensing a double-hydroxyl-terminated organosilicon prepolymer with a diacid, which improves foaming performance while retaining the wear resistance of organosilicon itself. When compounded with other components, the resulting polyurethane gloves have fingerprint-free properties, good wear resistance (over 8500 wear cycles), and are easy to demold. Detailed Implementation

[0108] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0109] The information sources for some raw materials in the preparation examples and embodiments of this invention are as follows:

[0110] Bihydroxyl-terminated organosilicon prepolymer A: Guangzhou Silok 8812F2;

[0111] Bihydroxyl-terminated organosilicon prepolymer B: Guangzhou Silok 8802F2;

[0112] Bio-based polyols: Asahikawa Chemical KJ-20005;

[0113] Black paste: Dongguan Taichang Resin Co., Ltd. TC-007;

[0114] PTMG-1000: PTMG-1000 from Zhongshan Dixing Chemical Co., Ltd.

[0115] PEG-1000: PEG-1000 from Shandong Yousuo Chemical Technology Co., Ltd.;

[0116] PEBA-4000: Asahikawa Chemical XCPP-40013;

[0117] PPEG-1000: Dow polyether 1000LM.

[0118] Preparation Example 1

[0119] This preparation example provides a modified organosilicon polyol and its preparation method, the preparation method comprising the following steps:

[0120] (1) 1000 parts of double-hydroxyl-terminated organosilicon prepolymer A and 52.8 parts of adipic acid were put into a reaction flask, nitrogen gas was bubbled in, the nitrogen flow rate was set to 0.2 L / min, the temperature was heated to 140℃ and kept at the temperature for 10 h, and then the temperature was continued to be heated to 220℃ and kept at the temperature for 4 h.

[0121] (2) Set the vacuum degree to -0.05MPa and evacuate for 4 hours; set the vacuum degree to -0.08MPa and evacuate for 8 hours to remove moisture from the reaction flask;

[0122] (3) The acid value of the system was tested. When it dropped to 29 mg KOH / g, 0.06 parts of tetraisopropyl titanate were added and reacted at 220℃ and -0.08 MPa.

[0123] (4) Take samples every 1.5 hours. When the acid value is 0.5 mg KOH / g and the hydroxyl value is 24 mg KOH / g, cool down and filter to obtain modified organosilicon polyol A.

[0124] Preparation Example 2

[0125] This preparation example provides a modified organosilicon polyol and its preparation method, the preparation method comprising the following steps:

[0126] (1) 1000 parts of double-hydroxyl-terminated organosilicon prepolymer B and 121.1 parts of adipic acid were put into a reaction flask, nitrogen gas was bubbled in, the nitrogen flow rate was set to 0.3 L / min, the temperature was heated to 150℃ and kept at the temperature for 9 h, and then the temperature was continued to be heated to 225℃ and kept at the temperature for 3 h.

[0127] (2) Set the vacuum degree to -0.05MPa and evacuate for 5 hours; set the vacuum degree to -0.08MPa and evacuate for 9 hours to remove moisture from the reaction flask.

[0128] (3) The acid value of the system was tested. When it dropped to 27 mg KOH / g, 0.067 parts of toluenesulfonic acid were added and the reaction was carried out at 225 °C and -0.08 MPa.

[0129] (4) Take samples every 1.5 hours. When the acid value is 0.4 mg KOH / g and the hydroxyl value is 25 mg KOH / g, cool down and filter to obtain modified organosilicon polyol B.

[0130] Preparation Example 3

[0131] This preparation example provides a modified organosilicon polyol and its preparation method, the preparation method comprising the following steps:

[0132] (1) 1000 parts of double-hydroxyl-terminated organosilicon prepolymer A and 43.38 parts of succinic acid were put into a reaction flask, nitrogen gas was bubbled in, the nitrogen flow rate was set to 0.4 L / min, the temperature was heated to 155℃ and kept at the temperature for 8 hours, and then the temperature was continued to be heated to 225℃ and kept at the temperature for 3 hours.

[0133] (2) Set the vacuum degree to -0.05MPa and evacuate for 6 hours; set the vacuum degree to -0.08MPa and evacuate for 10 hours to remove moisture from the reaction flask;

[0134] (3) The acid value of the system was tested. When it dropped to 25 mg KOH / g, 0.073 parts of tetraisobutyl titanate were added and reacted at 225 °C and -0.08 MPa.

[0135] (4) Samples were taken every 1.5 hours. When the acid value was 0.35 mg KOH / g and the hydroxyl value was 26 mg KOH / g, the temperature was lowered and the sample was filtered to obtain modified organosilicon polyol C.

[0136] Preparation Example 4

[0137] This preparation example provides a modified organosilicon polyol and its preparation method, the preparation method comprising the following steps:

[0138] (1) 1000 parts of double-hydroxyl-terminated organosilicon prepolymer B and 99.3 parts of succinic acid were put into a reaction flask, nitrogen gas was bubbled in, the nitrogen flow rate was set to 0.5 L / min, the temperature was heated to 160℃ and kept at a constant temperature for 7 h, and then the temperature was continued to be heated to 230℃ and kept at a constant temperature for 2 h.

[0139] (2) Set the vacuum degree to -0.05MPa and evacuate for 5 hours; set the vacuum degree to -0.08MPa and evacuate for 9 hours to remove moisture from the reaction flask.

[0140] (3) The acid value of the system was tested. When it dropped to 28 mg KOH / g, 0.087 parts of stannous octaate were added and reacted at 230℃ and -0.08 MPa.

[0141] (4) Samples were taken every 1.5 hours. When the acid value was 0.33 mg KOH / g and the hydroxyl value was 27 mg KOH / g, the temperature was lowered and the sample was filtered to obtain modified organosilicon polyol D.

[0142] Example 1

[0143] This embodiment provides a polyurethane resin and a polyurethane glove. The raw materials for preparing the polyurethane resin include the following components by weight:

[0144] 81 parts of modified organosilicon polyol A;

[0145] 146 parts of bio-based polyols;

[0146] 88.93 MDI units;

[0147] Antioxidant 1010, 0.2 parts;

[0148] 0.02 parts of phosphoric acid;

[0149] 16.3 parts of chain extender ethylene glycol;

[0150] PPEG-1000 2.16 parts;

[0151] Terminating agent ethylene glycol 0.5 parts;

[0152] 953.8 copies of DMF;

[0153] (1) According to the above formula dosage, add modified organosilicon polyol A, bio-based polyol, antioxidant 1010, phosphoric acid, and 250.8 parts of DMF into the reaction bottle, stir evenly, add 22.67 parts of MDI, react at 65°C until the prepolymer viscosity reaches 220,000 cps (65°C).

[0154] (2) Add 158 parts of DMF for dilution, then add chain extender ethylene glycol and PPEG-1000, and continue the reaction;

[0155] (3) Add 66.26 parts of MDI and react. During the reaction, dilute with 545 parts of DMF. When the viscosity of the polyurethane resin reaches 400,000 cps at 25°C and the solid content is 26 wt%, add the terminator ethylene glycol and cool to obtain polyurethane resin A.

[0156] The raw materials for preparing the polyurethane gloves include the following components by weight:

[0157] 100 parts of polyurethane resin A;

[0158] 160 parts of 14wt% DMF aqueous solution;

[0159] 4 parts black paste;

[0160] The method for preparing the polyurethane gloves specifically includes the following steps:

[0161] (1) According to the above formula dosage, mix polyurethane resin A, 14wt% DMF aqueous solution and black paste, stir evenly, centrifuge to remove bubbles, and obtain a mixed solution;

[0162] (2) Place the glove core onto the glove mold and heat at 65°C for 30 minutes; immerse the glove core in the mixed solution for 6 seconds and coat evenly for 2 minutes, turning the glove core over continuously during the process.

[0163] (3) Place the glove core after uniform coating into DMF aqueous solution and let it solidify for 15 minutes, then place it in 65℃ water and soak for 1 hour;

[0164] (4) Place the glove core in an oven and dry at 120°C for 40 minutes. Demold to obtain the polyurethane glove.

[0165] Example 2

[0166] This embodiment provides a polyurethane resin and a polyurethane glove. The raw materials for preparing the polyurethane resin include the following components by weight:

[0167] 147 parts of modified organosilicon polyol B;

[0168] 84 parts of bio-based polyols;

[0169] 85.08 servings of MDI;

[0170] Antioxidant 300, 0.2 parts;

[0171] 0.02 parts of phosphoric acid;

[0172] 16.3 parts of chain extender ethylene glycol;

[0173] PTMG-1000 2.16 copies;

[0174] Terminating agent ethylene glycol 0.5 parts;

[0175] 908.8 copies of DMF;

[0176] (1) According to the above formula dosage, add modified organosilicon polyol B, bio-based polyol, antioxidant 300, phosphoric acid, and 250.8 parts of DMF into the reaction bottle, stir evenly, add 18.82 parts of MDI, react at 70°C until the prepolymer viscosity reaches 240,000 cps (65°C).

[0177] (2) Add 158 parts of DMF for dilution, then add chain extender ethylene glycol and PTMG-1000, and continue the reaction;

[0178] (3) Add 66.26 parts of MDI and react. During the reaction, dilute with 497 parts of DMF. When the viscosity of the polyurethane resin reaches 450,000 cps at 25°C and the solid content is 27wt%, add the terminator ethylene glycol and cool to obtain polyurethane resin B.

[0179] The raw materials for preparing the polyurethane gloves include the following components by weight:

[0180] 90 parts of polyurethane resin B;

[0181] 150 parts of 15wt% DMF aqueous solution;

[0182] Three parts black paste;

[0183] The method for preparing the polyurethane gloves specifically includes the following steps:

[0184] (1) According to the above formula dosage, mix polyurethane resin B, 15wt% DMF aqueous solution and black paste, stir evenly, centrifuge to remove bubbles, and obtain mixed solution;

[0185] (2) Place the glove core onto the glove mold and heat at 68°C for 40 minutes; immerse the glove core in the mixed solution for 7 seconds and coat evenly for 3 minutes, turning the glove core over continuously during the process.

[0186] (3) Place the glove core after uniform coating into the DMF aqueous solution and let it solidify for 20 minutes, then place it in 70℃ water and soak for 1.2 hours;

[0187] (4) Place the glove core in an oven and dry at 110°C for 50 minutes. Demold to obtain the polyurethane glove.

[0188] Example 3

[0189] This embodiment provides a polyurethane resin and a polyurethane glove. The raw materials for preparing the polyurethane resin include the following components by weight:

[0190] 114 parts of modified organosilicon polyol C;

[0191] 114 parts of bio-based polyols;

[0192] 88.27 servings of MDI;

[0193] Antioxidant 1076, 0.2 parts;

[0194] 0.02 parts of phosphoric acid;

[0195] 16.3 parts of chain extender ethylene glycol;

[0196] PEG-1000 6.44 parts;

[0197] Terminating agent ethylene glycol 0.5 parts;

[0198] 966.6 copies of DMF;

[0199] (1) According to the above formula dosage, add modified organosilicon polyol C, bio-based polyol, antioxidant 1076, phosphoric acid, and 250.8 parts of DMF into the reaction bottle, stir evenly, add 20.94 parts of MDI, react at 75°C until the prepolymer viscosity reaches 250,000 cps (65°C).

[0200] (2) Add 158 parts of DMF for dilution, then add chain extender ethylene glycol and PEG-1000, and continue the reaction;

[0201] (3) Add 67.33 parts of MDI and react. During the reaction, dilute with 465 parts of DMF. When the viscosity of the polyurethane resin reaches 500,000 cps at 25°C and the solid content is 28 wt%, add the terminator ethylene glycol and cool to obtain polyurethane resin C.

[0202] The raw materials for preparing the polyurethane gloves include the following components by weight:

[0203] 110 parts of polyurethane resin C;

[0204] 180 parts of 16wt% DMF aqueous solution;

[0205] Five parts black paste;

[0206] The method for preparing the polyurethane gloves specifically includes the following steps:

[0207] (1) According to the above formula dosage, mix polyurethane resin C, 16wt% DMF aqueous solution and black paste, stir evenly, centrifuge to remove bubbles, and obtain mixed solution;

[0208] (2) Place the glove core onto the glove mold and heat at 70°C for 30 minutes; immerse the glove core in the mixed solution for 8 seconds and homogenize for 4 minutes, turning the glove core over continuously during this period;

[0209] (3) Place the glove core after uniform coating into the DMF aqueous solution and let it solidify for 17 minutes, then place it in 68℃ water and soak for 1.5 hours;

[0210] (4) Place the glove core in an oven and dry at 115°C for 35 minutes. Demold to obtain the polyurethane glove.

[0211] Example 4

[0212] This embodiment provides a polyurethane resin and a polyurethane glove. The raw materials for preparing the polyurethane resin include the following components by weight:

[0213] 114 parts of modified organosilicon polyol D;

[0214] 114 parts of bio-based polyols;

[0215] 87.99 servings of MDI;

[0216] Antioxidant 1010, 0.2 parts;

[0217] 0.02 parts of phosphoric acid;

[0218] 16.3 parts of chain extender ethylene glycol;

[0219] PEG-1000 4.3 parts;

[0220] Terminating agent ethylene glycol 0.5 parts;

[0221] 866.8 copies of DMF;

[0222] (1) According to the above formula dosage, add modified organosilicon polyol D, bio-based polyol, antioxidant 1010, phosphoric acid, and 250.8 parts of DMF into the reaction bottle, stir evenly, add 21.19 parts of MDI, react at 75°C until the prepolymer viscosity reaches 260,000 cps (65°C).

[0223] (2) Add 158 parts of DMF for dilution, then add chain extender ethylene glycol and PEG-1000, and continue the reaction;

[0224] (3) Add 66.8 parts of MDI and react. During the reaction, dilute with 458 parts of DMF. When the viscosity of the polyurethane resin reaches 500,000 cps at 25°C and the solid content is 28wt%, add the terminator ethylene glycol and cool to obtain polyurethane resin D.

[0225] The raw materials for preparing the polyurethane gloves include the following components by weight:

[0226] 100 parts of polyurethane resin D;

[0227] 160 parts of 18wt% DMF aqueous solution;

[0228] 4 parts black paste;

[0229] The method for preparing the polyurethane gloves specifically includes the following steps:

[0230] (1) According to the above formula dosage, mix polyurethane resin D, 18wt% DMF aqueous solution and black paste, stir evenly, centrifuge to remove bubbles, and obtain mixed solution;

[0231] (2) Place the glove core onto the glove mold and heat at 65°C for 30 minutes; immerse the glove core in the mixed solution for 10 seconds and coat it evenly for 5 minutes, turning the glove core over continuously during this period;

[0232] (3) Place the glove core after uniform coating into DMF aqueous solution and let it solidify for 15 minutes, then place it in 65℃ water and soak for 1 hour;

[0233] (4) Place the glove core in an oven and dry at 120°C for 40 minutes. Demold to obtain the polyurethane glove.

[0234] Example 5

[0235] The only difference from Example 1 is that the solid content of the polyurethane resin is 32wt%, while the other components and preparation methods are the same as in Example 1.

[0236] Example 6

[0237] The only difference from Example 1 is that in step (3), the viscosity of the polyurethane resin at 25°C is 220,000 cps, and the other components and preparation methods are the same as in Example 1.

[0238] Comparative Example 1

[0239] The only difference from Example 1 is that equimolar amounts of polyethylene adipate diol (PEBA-4000) are used to replace the modified organosilicon polyol A and bio-based polyol in Example 1. All other components and preparation methods are the same as in Example 1.

[0240] Comparative Example 2

[0241] The only difference from Example 1 is that the amount of modified organosilicon polyol A is 40 parts (3.1%), the amount of bio-based polyol is 184.5 parts (14.3%), and the other components and preparation methods are the same as in Example 1.

[0242] Comparative Example 3

[0243] The only difference from Example 1 is that the amount of modified organosilicon polyol A is 185 parts (accounting for 14.3%), and the amount of bio-based polyol is 47.2 parts (accounting for 3.7%). The remaining components and preparation methods are the same as in Example 1.

[0244] Comparative Example 4

[0245] The only difference from Example 1 is that PPEG-1000 is not added to the raw materials for preparing polyurethane resin; the other components and preparation methods are the same as in Example 1.

[0246] Comparative Example 5

[0247] The only difference from Example 1 is that the amount of PPEG-1000 used is 21.46 parts (accounting for 1.6%), while the other components and preparation methods are the same as in Example 1.

[0248] Comparative Example 6

[0249] The only difference from Example 1 is that the modified organosilicon polyol A is replaced with an equimolar amount of commercially available organosilicon polyol GY6001 (Shaanxi Siyou Yunji New Materials Co., Ltd., weight average molecular weight 1600), and the other components and preparation methods are the same as in Example 1.

[0250] Comparative Example 7

[0251] The only difference from Example 1 is that the bio-based polyol is replaced with an equimolar amount of commercially available bio-based polyol H2400 (Daxiong Chemical, with a weight-average molecular weight of 2400), while the other components and preparation methods are the same as in Example 1.

[0252] Performance testing

[0253] (1) Abrasion resistance: The abrasion resistance of the polyurethane gloves of this invention was tested in accordance with GB 24541-2009 standard. The specific experimental steps are as follows: The sample was cut into a circle with a diameter of 38mm, and the abrasion resistance of Martindale was tested. The total mass of the loading block and the sample clamp assembly was 600g. The sample was checked for wear every 500 revolutions. If the sample was worn through, the test was stopped and the number of revolutions was recorded.

[0254] (2) Fingerprint detection: Wipe the phone screen clean with anhydrous ethanol to ensure that there is no dust or impurities on its surface. Wear the polyurethane gloves shown in the embodiments and comparative examples of this invention, press your fingers on the phone screen for 20 seconds, and then remove them. Observe whether there is a fingerprint on the phone screen.

[0255] (3) Demolding test: Take the polyurethane gloves out of the oven and let them cool to room temperature. Then pull the gloves off the mold. If the gloves can be pulled off smoothly and completely in one go without deliberate force, they are easy to demold. If you need to use both hands and there is a noticeable pause, you can hear a sticking sound or the polyurethane gloves are partially deformed, they are difficult to demold.

[0256] Following the above testing methods, the performance of the polyurethane gloves provided in the examples and comparative examples was tested, and the results are shown in Table 1:

[0257] Table 1

[0258]

[0259] As shown in Table 1, the polyurethane gloves in Examples 1-4 have good abrasion resistance, with an abrasion resistance of 8500-9500 cycles, are fingerprint-resistant, and are easy to demold.

[0260] As can be seen from the comparison between Example 1 and Example 5, the solid content of polyurethane resin in Example 5 is 32wt%, and the viscosity is the same as that in Example 1. Therefore, the polyurethane resin in Example 5 contains a large number of small molecules, which are more likely to be free on the surface of the polyurethane gloves and easily generate fingerprints. At the same time, the higher solid content will also make it more difficult to remove DMF during the preparation of polyurethane gloves, resulting in poor demolding performance.

[0261] As can be seen from the comparison between Example 1 and Example 6, the viscosity of polyurethane resin in Example 6 is only 220,000 cps (25°C), which is much lower than the viscosity of polyurethane resin in Example 1. The number of small molecules is significantly greater than that in Example 1. Therefore, the polyurethane gloves produce fingerprints and have poor wear resistance.

[0262] As can be seen from the comparison between Example 1 and Comparative Example 1, Comparative Example 1 did not use modified organosilicon polyols and bio-based polyols with excellent wear resistance. Therefore, the wear resistance of the polyurethane gloves deteriorated, and at the same time, the release properties also deteriorated.

[0263] As can be seen from the comparison between Example 1 and Comparative Examples 2-3, if the amount of modified organosilicon polyol and bio-based polyol exceeds the range defined in this invention, the wear resistance of the prepared polyurethane gloves will be reduced.

[0264] As can be seen from the comparison between Example 1 and Comparative Example 4, only ethylene glycol was added in the chain extension stage of Comparative Example 4, and no polyether polyol was used. Although the overall foaming property of the polyurethane resin was good, its wear resistance was poor.

[0265] As can be seen from the comparison between Example 1 and Comparative Example 5, the amount of polyether polyol used in Comparative Example 5 exceeds the range specified in this invention, which makes the crystallinity of polyurethane resin worse, foaming difficult, and demolding poor.

[0266] As can be seen from the comparison between Example 1 and Comparative Examples 6-7, the commercially available organosilicon polyols and commercially available bio-based polyols used in Examples 6 and 7 are not highly compatible with the material properties required by the present invention. Therefore, the polyurethane gloves prepared cannot simultaneously achieve excellent wear resistance, fingerprint-free properties and easy mold removal properties.

[0267] The above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A polyurethane resin, characterized in that, The raw materials for preparing the polyurethane resin include the following components by mass fraction: Modified organosilicon polyols 5%-12.5% Bio-based polyols 5%-12.5% Isocyanates 5%-8% Antioxidant 0.01%-0.02% Catalyst 0.001%-0.002% Chain extender 1%-2% Polyether polyols 0.1%-0.7% Terminator 0.02%-0.05% Solvent 71%-75% The raw materials for preparing the modified organosilicon polyol include a hydroxyl-terminated organosilicon prepolymer and a dicarboxylic acid. The weight-average molecular weight of the modified organosilicon polyol is 3500-4500. The molar ratio of the hydroxyl-terminated organosilicon prepolymer to the dicarboxylic acid is (1.3-1.75):1; The dicarboxylic acid includes adipic acid and / or succinic acid; The raw materials for preparing the bio-based polyol include bio-based succinic acid, bio-based 1,3-propanediol, and bio-based 1,4-butanediol. The viscosity of the polyurethane resin at 25°C is 400,000-500,000 cps; The solid content of the polyurethane resin is 26wt%-28wt%.

2. The polyurethane resin according to claim 1, characterized in that, The weight-average molecular weight of the bio-based polyol is 1800-2500.

3. The polyurethane resin according to claim 1, characterized in that, The isocyanate includes 4,4-diphenylmethane diisocyanate; And / or, the antioxidant comprises any one or a combination of at least two of the following: pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,4'-thiobis(6-tert-butyl-3-methylphenol), 1,2-bis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, N,N'-(hexane-1,6-diyl)bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], or tris(2,4-di-tert-butylphenyl) phosphite.

4. The polyurethane resin according to claim 1, characterized in that, The catalyst includes phosphoric acid; And / or, the chain extender includes ethylene glycol; And / or, the polyether polyol includes any one or a combination of at least two of polyethylene glycol, polypropylene glycol or polybutanediol; And / or, the weight-average molecular weight of the polyether polyol is 1000-2000; And / or, the terminating agent includes any one or a combination of at least two of ethylene glycol, 1,4-butanediol or methylpropanediol; And / or, the solvent includes N,N-dimethylformamide; And / or, the preparation method of the modified organosilicon polyol includes the following steps: The modified organosilicon polyol is obtained by reacting the hydroxyl-terminated organosilicon prepolymer and the dicarboxylic acid under the action of catalyst A. And / or, the catalyst A comprises any one or a combination of at least two of tetraisopropyl titanate, tetraisobutyl titanate, toluenesulfonic acid, or stannous octoate.

5. The method for preparing polyurethane resin according to any one of claims 1-4, characterized in that, The preparation method includes the following steps: (1) Mix the modified organosilicon polyol, bio-based polyol, antioxidant, catalyst, part of the isocyanate and part of the solvent, and react; (2) Add some solvent, chain extender and polyether polyol, and continue the reaction; (3) Add the remaining isocyanate, react, add the remaining solvent and terminator to obtain the polyurethane resin.

6. The preparation method according to claim 5, characterized in that, In step (1), the viscosity of the mixture obtained from the reaction is 220,000-260,000 cps at 65°C; And / or, in steps (1)-(3), the temperature of the reaction is independently 65-75°C.

7. A polyurethane glove, characterized in that, The polyurethane gloves comprise the polyurethane resin according to any one of claims 1-4.

8. The polyurethane glove according to claim 7, characterized in that, The raw materials for preparing the polyurethane gloves include the following components by weight: 90-110 parts of the polyurethane resin according to any one of claims 1-4 150-180 parts of solvent 3-5 parts colorant; And / or, the solvent includes N,N-dimethylformamide; And / or, the pigment includes black pigment.

9. A method for preparing a polyurethane glove as described in claim 7 or 8, characterized in that, The preparation method includes the following steps: (1) The polyurethane resin, solvent and colorant according to any one of claims 1-4 are mixed to obtain a mixed solution; (2) Immerse the glove core in the mixed solution, homogenize, solidify, dry, and demold to obtain the polyurethane glove.

10. The preparation method according to claim 9, characterized in that, The glove core is heat-treated; And / or, the immersion time is 6-10 seconds; And / or, the homogenization time is 2-5 minutes; And / or, the material of the glove core is polyester; And / or, the coagulation includes placing the homogenized glove core into a mixed solvent and then immersing it in water; And / or, the mixed solvent comprises an aqueous solution of N,N-dimethylformamide; And / or, based on the mass percentage of the mixed solvent being 100%, the mass percentage of N,N-dimethylformamide is 14%-18%; And / or, the soaking time is 1-1.5 hours; And / or, the drying temperature is 110-120°C; And / or, the drying time is 40-50 min.

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