Water-soluble bio-based polyurethane resin and application thereof in ink
By introducing water-soluble bio-based polyurethane resin, the problems of nozzle clogging and slow-drying solvents have been solved, achieving high fluidity and low-carbon environmental protection in different printing environments.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-19
- Publication Date
- 2026-04-07
AI Technical Summary
Existing waterborne polyurethane resins are prone to drying and causing printhead clogging in inkjet printing. Furthermore, the extensive use of slow-drying solvents leads to issues such as backflow, smoke, and high SVOCs, while also limiting their use in non-UV environments and in high-temperature and low-humidity conditions.
Water-soluble bio-based polyurethane resin is used, and nonionic polyether polyol, bio-based polyol, nonionic polyester polyol, hydrophilic chain extender and hydroxyl-containing diamine chain extender are introduced to form a polymer with good water solubility, avoiding drying and reducing the use of slow-drying solvents.
It solves the problem of printhead clogging, reduces dependence on petroleum resources, meets the needs of low-carbon and environmental protection, and maintains high smoothness in different printing environments.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of waterborne polyurethane resin technology, specifically to a water-soluble bio-based polyurethane resin and its application in inks. Background Technology
[0002] Currently, water-based polyurethane inks for coating-type digital inkjet printing are all dispersions. However, dispersions are prone to drying and are not water-soluble, making them easy to clog printheads during printing. Existing technologies typically add large amounts of slow-drying solvents to the ink to delay drying, but this easily leads to problems such as ink backflow, excessive smoke during baking, high levels of semi-volatile organic compounds (SVOCs), and ink runaway. Furthermore, the addition of large amounts of slow-drying solvents also significantly consumes petroleum resources.
[0003] Existing technology discloses a UV-curable bio-based waterborne resin, which, by weight percentage, comprises: 10%-35% bio-based polyol, 0-25% non-bio-based polyol, 5%-25% diisocyanate, 0.005-0.1% catalyst, 0.5%-6% sulfonate hydrophilic chain extender, 0.2%-5% hydroxyacrylate, 0.2%-1% neutralizer, 0.5%-3% hydroxydiamine chain extender, with deionized water to make up the balance. Although this balances the solid content, hydrophilicity, and viscosity of the waterborne resin and avoids the use of petroleum-based resins and petroleum-based high-boiling-point solvents, this resin is a waterborne UV resin, requiring UV curing during the curing process, thus limiting its use in non-UV environments. Furthermore, since the polymer is not completely water-soluble, there is still a risk of nozzle clogging in some extreme high-temperature and low-humidity environments. Summary of the Invention
[0004] This invention provides a bio-based polyurethane resin to solve the problem of nozzle clogging caused by the drying of existing resins.
[0005] In a first aspect, the present invention provides a water-soluble bio-based polyurethane resin, wherein, by weight, the raw materials of the water-soluble bio-based polyurethane resin include: 0-10 parts of nonionic polyether polyol, 3-13 parts of bio-based polyol, 0.5-3 parts of nonionic polyester polyol, 5-12 parts of diisocyanate, 0.005-0.05 parts of catalyst, 2-6 parts of hydrophilic chain extender, 0.3-1.5 parts of neutralizer, 70-82 parts of deionized water, and 1-3 parts of hydroxyl-containing diamine chain extender.
[0006] In some optional embodiments, the solids content of the water-soluble bio-based polyurethane resin is 15%-28%.
[0007] It should be noted that the solid component of water-soluble bio-based polyurethane resin refers to the solid obtained after drying the water-soluble bio-based polyurethane resin.
[0008] In some alternative embodiments, the hydrophilic chain extender accounts for 7wt%-40wt% of the solids content in the water-soluble bio-based polyurethane resin.
[0009] As an example, the hydrophilic chain extender accounts for 7 wt%, 10 wt%, 13 wt%, 16 wt%, 19 wt%, 22 wt%, 25 wt%, 28 wt%, 31 wt%, 34 wt%, 37 wt%, and 40 wt% of the solids in the water-soluble bio-based polyurethane resin.
[0010] In some optional embodiments, the nonionic polyester polyol accounts for 1.5wt%-20wt% of the solids content in the water-soluble bio-based polyurethane resin.
[0011] As an example, the nonionic polyester polyol accounts for 1.5wt%, 4wt%, 6wt%, 8wt%, 10wt%, 12wt%, 14wt%, 16wt%, 18wt%, and 20wt% of the solids in the water-soluble bio-based polyurethane resin.
[0012] In some alternative embodiments, the nonionic polyester polyol has a molecular weight of 500-1000.
[0013] As an example, the molecular weight of the nonionic polyester polyol is 500, 600, 700, 800, 900, or 1000.
[0014] In some alternative embodiments, the nonionic polyether polyol includes at least one of polypropylene glycol, polyethylene glycol, and polytetrahydrofuran glycol.
[0015] In some alternative embodiments, the hydrophilic chain extender includes at least one of sulfonates and carboxylates.
[0016] In some alternative embodiments, the hydrophilic chain extender is a sulfonate, and the sulfonate is 4-6 parts by weight.
[0017] In some optional embodiments, the hydrophilic chain extender is a carboxylate, and the carboxylate is 2-4 parts by weight.
[0018] In some alternative embodiments, the bio-based content of the water-soluble bio-based polyurethane resin is >10%.
[0019] In some alternative embodiments, the bio-based polyol includes at least one of bio-based polycarbonate diol, bio-based polyether diol, and bio-based polyester diol.
[0020] In some optional embodiments, the hydroxyl-containing diamine chain extender includes at least one of N-(2-hydroxyethyl)ethylenediamine, N,N-bis(2-hydroxyethyl)ethylenediamine, and hydroxyethylethylenediamine.
[0021] In some alternative embodiments, the sulfonate includes at least one of sulfonate diol, sulfonate diamine, and triethylamine dihydroxypropanesulfonate.
[0022] In some alternative embodiments, the carboxylate includes at least one of 2,2-dimethylolpropionic acid and 2,2-dimethylolbutyric acid.
[0023] In some alternative embodiments, the neutralizing agent includes at least one of N,N-dimethylethanolamine, potassium hydroxide, and sodium hydroxide.
[0024] In some alternative embodiments, the diisocyanate includes at least one selected from toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), 1,6-hexane diisocyanate (HDI), and dicyclohexylmethane diisocyanate (HMDI).
[0025] In some alternative embodiments, the catalyst includes at least one of bismuth octanoate, bismuth octanoate, zinc octanoate, and bismuth isooctanoate.
[0026] It should be noted that the preparation method of the water-soluble bio-based polyurethane resin specifically includes the following steps: (1) After dehydrating nonionic polyether polyol, bio-based polyol and nonionic polyester polyol, dehydrated polyol is obtained; (2) The diisocyanate, catalyst and the dehydrated polyol are mixed to carry out the first reaction, and then a hydrophilic chain extender is added to carry out the second reaction to obtain the prepolymer; (3) After mixing the prepolymer and neutralizing agent, a third reaction is carried out, and then deionized water and a hydroxyl-containing diamine chain extender are added to carry out a fourth reaction to obtain the product.
[0027] Furthermore, the dehydration temperature is 80℃-120℃.
[0028] Furthermore, the temperature of the first reaction is 60℃-85℃, and the time is 3h-4h.
[0029] Furthermore, the temperature of the second reaction is 50℃-85℃, and the time is 2h-3h.
[0030] Furthermore, in step (3), the temperature of the prepolymer is 30℃-45℃.
[0031] Furthermore, the duration of the third reaction is 5-60 minutes.
[0032] In a second aspect, the present invention provides an application of the water-soluble bio-based polyurethane resin described in the first aspect in inks.
[0033] Furthermore, the water-soluble bio-based polyurethane resin prepared by this invention can be used directly as ink, or it can be mixed with a crosslinking agent to formulate ink.
[0034] In some alternative embodiments, the crosslinking agent includes at least one of aqueous blocked isocyanate, aqueous amino resin, and silane coupling agent.
[0035] In some alternative embodiments, the water-soluble bio-based polyurethane resin is present in an amount of 5 wt% to 95 wt% in the ink.
[0036] It should be noted that the ink provided by this invention includes a water-soluble bio-based polyurethane resin and a water-based crosslinking agent. After printing, the ink undergoes a crosslinking reaction with the hydroxyl groups in the resin through heating, forming an ink layer that is insoluble in water. This not only solves the problem of printhead clogging due to drying, but also does not affect other functions of the ink. It can significantly reduce the use of slow-drying solvents in the ink and avoid various problems caused by slow-drying solvents.
[0037] The technical solution of this invention has the following advantages: 1. The water-soluble bio-based polyurethane resin provided by the present invention comprises, by weight parts: 0-10 parts of nonionic polyether polyol, 3-13 parts of bio-based polyol, 0.5-3 parts of nonionic polyester polyol, 5-12 parts of diisocyanate, 0.005-0.05 parts of catalyst, 2-6 parts of hydrophilic chain extender, 0.3-1.5 parts of neutralizer, 70-82 parts of deionized water, and 1-3 parts of hydroxyl-containing diamine chain extender. This invention uses hydrophilic ether bonds as the main chain, while introducing a large amount of hydrophilic chain extenders and hydroxyl-containing diamine chain extenders, along with nonionic polyether polyols and nonionic polyester polyols, to give the polymer excellent water solubility. Even if the ink droplets around the printhead dry out, they can still dissolve back into the ink during continuous printing, thus solving the problem of printhead clogging caused by drying in resin-based digital inkjet inks, and significantly reducing the use of slow-drying solvents in the ink. At the same time, the introduction of bio-based polyols can reduce the ink industry's heavy dependence on petroleum resources, meeting the demand for low-carbon and environmentally friendly practices while ensuring performance and economy.
[0038] 2. The water-soluble bio-based polyurethane resin provided by the present invention, by controlling the solid content in the water-soluble bio-based polyurethane resin within the range of 15%-28%, can improve the water solubility of the bio-based polyurethane resin.
[0039] 3. The water-soluble bio-based polyurethane resin provided by the present invention controls the content of hydrophilic chain extender in the solids of the water-soluble bio-based polyurethane resin to be 7wt%-40wt%, and the content of hydrophilic groups is relatively large, which further improves the water solubility of the bio-based polyurethane resin.
[0040] 4. The water-soluble bio-based polyurethane resin provided by this invention also contains a certain amount of bio-based components (bio-based content > 10%), which can significantly reduce the use of petroleum resources at both the resin and ink ends, achieving true low-carbon and environmentally friendly results. This resin has a wide range of applications and can meet the high fluidity requirements of various printing media such as films, paper, textiles, and leather for inks in different printheads and printing environments. Detailed Implementation
[0041] The following embodiments are provided to better understand the present invention, but the following embodiments do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the scope of protection of the present invention.
[0042] Unless otherwise specified, all experimental steps or conditions in the examples were performed according to conventional experimental procedures and conditions in the art. Reagents or instruments whose manufacturers are not specified are all commercially available products.
[0043] Sources of raw materials used in the examples and comparative examples: Polytetrahydrofuran ether, with the option of at least one of PolyTHF® 2000 and PTMG 1000; Polyethylene glycol, with PEG2000 as an option; Bio-based polyether diols, with models selectable from at least one of BioPTMG1000 and BioPTMG650; Bio-based polycarbonate diol, model Mofltive® HBE2000 is available; Bio-based castor oil polyols, purchased from Vantrus, with Polycin® D-2000 as an option; Nonionic polyester diol, purchased from BASF, model Capromer™ PD4-05, molecular weight 550; 1,6-Hexanediisocyanate, purchased from Covestro, available under the model name Desmodur H; Dicyclohexylmethane diisocyanate, purchased from Covestro, available under the model DESMODUR W; Isophorone diisocyanate, purchased from Covestro, model DESMODUR I is available; Bismuth isooctanoate was purchased from Shanghai Manhaigao Schmidt Chemical Co., Ltd., and the model TMG722 is available. Triethylamine dihydroxypropanesulfonic acid salt, model MS-09 is available.
[0044] Example 1 This embodiment provides a water-soluble bio-based polyurethane resin, comprising, by weight: 10 parts of polytetrahydrofuran ether PolyTHF® 2000, 3 parts of bio-based polyether diol BioPTMG1000, 1.0 parts of nonionic polyester diol Capromer™ PD4-05, 5.0 parts of 1,6-hexamethylene diisocyanate, 0.02 parts of bismuth isooctanoate, 2.3 parts of 2,2-dimethylolpropionic acid, 1.0 part of sodium hydroxide, 75.7 parts of deionized water, and 2 parts of N,N-bis(2-hydroxyethyl)ethylenediamine; A method for preparing water-soluble bio-based polyurethane resin includes the following steps: (1) 10 parts of polytetrahydrofuran ether PolyTHF® 2000, 3 parts of bio-based polyether diol BioPTMG1000 and 1 part of nonionic polyester diol Capromer™ PD4-05 were dehydrated at 100°C to obtain the dehydrated polyol. (2) Add 5 parts of 1,6-hexamethylene diisocyanate and 0.02 parts of bismuth isooctanoate to the dehydrated polyol, react at 80°C for 3 hours, then add 2.3 parts of 2,2-dimethylolpropionic acid, and continue to react at 80°C for 3 hours to obtain an NCO-terminated prepolymer containing bio-based components. (3) Cool the prepolymer to 40°C, add 1.0 part of sodium hydroxide for neutralization reaction for 15 min, then add 75.7 parts of deionized water for emulsification, then add 2 parts of N,N-bis(2-hydroxyethyl)ethylenediamine for chain extension, filter, and obtain water-soluble bio-based polyurethane resin.
[0045] Example 2 This embodiment provides a water-soluble bio-based polyurethane resin, comprising, by weight: 13 parts of bio-based polyether polyol BioPTMG1000, 0.5 parts of nonionic polyester diol Capromer™ PD4-05, 12 parts of dicyclohexylmethane diisocyanate, 0.02 parts of bismuth isooctanoate, 2 parts of 2,2-dimethylolpropionic acid, 0.8 parts of potassium hydroxide, 70.68 parts of deionized water, and 1 part of hydroxyethyl ethylenediamine; A method for preparing water-soluble bio-based polyurethane resin includes the following steps: (1) 13 parts of bio-based polyether diol BioPTMG1000 and 0.5 parts of nonionic polyester diol Capromer™ PD4-05 were dehydrated at 100°C to obtain the dehydrated polyol. (2) 12 parts of dicyclohexylmethane diisocyanate and 0.02 parts of bismuth isooctanoate were added dropwise to the dehydrated polyol and reacted at 80°C for 3 hours. Then 2 parts of 2,2-dihydroxymethylpropionic acid were added and the reaction was continued at 80°C for 3 hours to obtain an NCO-terminated prepolymer containing bio-based components. (3) Cool the prepolymer to 40°C, add 0.8 parts of potassium hydroxide for neutralization reaction for 15 min, then add 70.68 parts of deionized water for emulsification, then add 1 part of hydroxyethyl ethylenediamine for chain extension, filter, and obtain water-soluble bio-based polyurethane resin.
[0046] Example 3 This embodiment provides a water-soluble bio-based polyurethane resin, comprising, by weight: 3 parts of polytetrahydrofuran ether PolyTHF® 2000, 4 parts of bio-based polycarbonate diol Mofltive® HBE2000, 2 parts of nonionic polyester diol Capromer™ PD4-05, 8 parts of isophorone diisocyanate, 0.02 parts of bismuth isooctanoate, 6 parts of triethylamine dihydroxypropanesulfonic acid, 0.3 parts of N,N-dimethylethanolamine, 73.68 parts of deionized water, and 3 parts of N,N-bis(2-hydroxyethyl)ethylenediamine. A method for preparing water-soluble bio-based polyurethane resin includes the following steps: (1) 3 parts of polytetrahydrofuran ether PolyTHF® 2000, 4 parts of bio-based polycarbonate diol Mofltive® HBE2000 and 2 parts of nonionic polyester diol Capromer™ PD4-05 were dehydrated at 100°C to obtain the dehydrated polyol; (2) Add 8 parts of isophorone diisocyanate and 0.02 parts of bismuth isooctanoate to the dehydrated polyol, react at 80°C for 3 hours, then add 6 parts of triethylamine dihydroxypropanesulfonic acid salt, and continue to react at 60°C for 3 hours to obtain an NCO-terminated prepolymer containing bio-based components. (3) Cool the prepolymer to 40°C, add 0.3 parts of N,N-dimethylethanolamine for neutralization reaction for 15 min, then add 73.68 parts of deionized water for emulsification, and then add 3 parts of N,N-bis(2-hydroxyethyl)ethylenediamine for chain extension. Filter to obtain water-soluble bio-based polyurethane resin.
[0047] Example 4 This embodiment provides a water-soluble bio-based polyurethane resin, comprising, by weight: 2.0 parts polyethylene glycol PEG2000, 3 parts bio-based castor oil polyol Polycin® D-2000, 0.5 parts nonionic polyester diol Capromer™ PD4-05, 6.5 parts 1,6-hexamethylene diisocyanate, 0.02 parts bismuth isooctanoate, 4 parts 2,2-dimethylolbutyric acid, 1.5 parts N,N-dimethylethanolamine, 80.48 parts deionized water, and 2 parts N,N-bis(2-hydroxyethyl)ethylenediamine; A method for preparing water-soluble bio-based polyurethane resin includes the following steps: (1) Two parts of polyethylene glycol PEG2000, three parts of bio-based castor oil polyol Polycin® D-2000 and 0.5 parts of nonionic polyester diol Capromer™ PD4-05 were dehydrated at 100°C to obtain the dehydrated polyol; (2) 6.5 parts of 1,6-hexamethylene diisocyanate and 0.02 parts of bismuth isooctanoate were added dropwise to the dehydrated polyol and reacted at 80°C for 3 hours. Then 4 parts of 2,2-dihydroxymethylbutyric acid were added and the reaction was continued at 80°C for 3 hours to obtain an NCO-terminated prepolymer containing bio-based components. (3) Cool the prepolymer to 40°C, add 1.5 parts of N,N-dimethylethanolamine for neutralization reaction for 15 min, then add 80.48 parts of deionized water for emulsification, and finally add 2 parts of N,N-bis(2-hydroxyethyl)ethylenediamine for chain extension, filter, and obtain water-soluble bio-based polyurethane resin.
[0048] Example 5 This embodiment provides a water-soluble bio-based polyurethane resin, comprising, by weight: 2 parts of polytetrahydrofuran ether PTMG 1000, 4 parts of bio-based polyether diol BioPTMG650, 3 parts of nonionic polyester diol Capromer™ PD4-05, 10 parts of dicyclohexylmethane diisocyanate, 0.05 parts of bismuth isooctanoate, 4 parts of triethylamine dihydroxypropanesulfonic acid, 0.8 parts of N,N-dimethylethanolamine, 74.15 parts of deionized water, and 2 parts of N,N-bis(2-hydroxyethyl)ethylenediamine. A method for preparing water-soluble bio-based polyurethane resin includes the following steps: (1) Two parts of polytetrahydrofuran ether PTMG 1000, four parts of bio-based polyether diol BioPTMG650 and three parts of nonionic polyester diol Capromer™ PD4-05 were dehydrated at 100°C to obtain the dehydrated polyol. (2) 10 parts of dicyclohexylmethane diisocyanate and 0.05 parts of bismuth isooctanoate were added dropwise to the dehydrated polyol and reacted at 80°C for 3 hours. Then, 4 parts of triethylamine dihydroxypropanesulfonate were added and reacted at 60°C for 3 hours to obtain an NCO-terminated prepolymer containing bio-based components. (3) Cool the prepolymer to 40°C, add 0.8 parts of N,N-dimethylethanolamine for neutralization reaction for 15 min, then add 74.15 parts of deionized water for emulsification, and then add 2 parts of N,N-bis(2-hydroxyethyl)ethylenediamine for chain extension. Filter to obtain water-soluble bio-based polyurethane resin.
[0049] Comparative Example 1 This comparative example provides a water-soluble bio-based polyurethane resin, comprising, by weight: 4 parts of polytetrahydrofuran ether PTMG 1000, 4.5 parts of bio-based polyol BioPTMG650, 0.5 parts of nonionic polyester diol Capromer™ PD4-05, 10 parts of isophorone diisocyanate, 0.05 parts of bismuth isooctanoate, 3 parts of 2,2-dimethylolbutyric acid, 1.5 parts of N,N-dimethylethanolamine, 75.75 parts of deionized water, and 0.7 parts of ethylenediamine; A method for preparing water-soluble bio-based polyurethane resin includes the following steps: (1) 4 parts of polytetrahydrofuran ether PTMG 1000, 4.5 parts of bio-based polyether polyol BioPTMG650 and 0.5 parts of nonionic polyester diol Capromer™ PD4-05 were dehydrated at 100°C to obtain the dehydrated polyol. (2) 10 parts of isophorone diisocyanate and 0.05 parts of bismuth isooctanoate were added dropwise to the dehydrated polyol and reacted at 80°C for 3 hours. Then 3 parts of 2,2-dihydroxymethylbutyric acid were added and the reaction was continued at 80°C for 3 hours to obtain an NCO-terminated prepolymer containing bio-based components. (3) Cool the prepolymer to 40°C, add 1.5 parts of N,N-dimethylethanolamine for neutralization reaction for 15 min, then add 75.75 parts of deionized water for emulsification, and then add 0.7 parts of ethylenediamine for chain extension. Filter to obtain water-soluble bio-based polyurethane resin.
[0050] Comparative Example 2 This comparative example provides a water-soluble bio-based polyurethane resin, comprising, by weight: 4 parts of polytetrahydrofuran ether PolyTHF® 2000, 5 parts of bio-based polyether polyol BioPTMG650, 7.0 parts of isophorone diisocyanate, 0.02 parts of bismuth isooctanoate, 1.5 parts of 2,2-dimethylolbutyric acid, 0.5 parts of N,N-dimethylethanolamine, 75.98 parts of deionized water, and 2 parts of N,N-bis(2-hydroxyethyl)ethylenediamine; A method for preparing water-soluble bio-based polyurethane resin includes the following steps: (1) Dehydrate 4 parts of polytetrahydrofuran ether PolyTHF® 2000 and 5 parts of bio-based polyether polyol BioPTMG650 to obtain the dehydrated polyol; (2) 7.0 parts of isophorone diisocyanate and 0.02 parts of bismuth isooctanoate were added dropwise to the dehydrated polyol and reacted at 80°C for 3 hours. Then 1.5 parts of 2,2-dihydroxymethylbutyric acid were added and reacted at 60°C for 3 hours to obtain NCO-terminated prepolymer. (3) Cool the prepolymer to 40°C, add 0.5 parts of N,N-dimethylethanolamine for neutralization reaction for 15 min, then add 75.98 parts of deionized water for emulsification, and finally add 2 parts of N,N-bis(2-hydroxyethyl)ethylenediamine for chain extension, filter, and obtain water-soluble bio-based polyurethane resin.
[0051] Comparative Example 3 This comparative example provides a water-soluble bio-based polyurethane resin, comprising, by weight: 11 parts of polytetrahydrofuran ether PolyTHF® 2000, 1 part of nonionic polyester diol Capromer™ PD4-05, 6 parts of dicyclohexylmethane diisocyanate, 0.02 parts of bismuth isooctanoate, 1 part of triethylamine dihydroxypropanesulfonic acid, 0.3 parts of N,N-dimethylethanolamine, 79.68 parts of deionized water, and 1 part of ethylenediamine; A method for preparing water-soluble bio-based polyurethane resin includes the following steps: (1) Dehydrate 11 parts of polytetrahydrofuran ether PolyTHF® 2000 and 1 part of nonionic polyester diol Capromer™ PD4-05 to obtain the dehydrated polyol; (2) Add 6 parts of dicyclohexylmethane diisocyanate and 0.02 parts of bismuth isooctanoate to the dehydrated polyol, react at 80°C for 3 hours, then add 1 part of triethylamine dihydroxypropanesulfonate, and continue to react at 60°C for 3 hours to obtain NCO-terminated prepolymer. (3) Cool the prepolymer to 40°C, add 0.3 parts of N,N-dimethylethanolamine for neutralization reaction for 15 min, then add 79.68 parts of deionized water for emulsification, and finally add 1 part of ethylenediamine for chain extension. Filter to obtain water-soluble bio-based polyurethane resin.
[0052] Comparative Example 4 This comparative example provides a water-soluble bio-based polyurethane resin, comprising, by weight: 5 parts of polytetrahydrofuran ether PTMG 1000, 4 parts of bio-based polyether polyol BioPTMG650, 1 part of nonionic polyester diol Capromer™ PD4-05, 10 parts of isophorone diisocyanate, 0.05 parts of bismuth isooctanoate, 0.5 parts of 2,2-dimethylolbutyric acid, 0.5 parts of triethylamine, 78.35 parts of deionized water, and 0.6 parts of ethylenediamine; A method for preparing water-soluble bio-based polyurethane resin includes the following steps: (1) Five parts of polytetrahydrofuran ether PTMG 1000, four parts of bio-based polyether polyol BioPTMG650 and one part of nonionic polyester diol Capromer™ PD4-05 were dehydrated at 100°C to obtain the dehydrated polyol. (2) 10 parts of isophorone diisocyanate and 0.05 parts of bismuth isooctanoate were added dropwise to the dehydrated polyol and reacted at 80°C for 3 hours. Then 0.5 parts of 2,2-dihydroxymethylbutyric acid were added dropwise and the reaction was continued at 80°C for 3 hours to obtain an NCO-terminated prepolymer containing bio-based components. (3) Cool the prepolymer to 40°C, add 0.5 parts of triethylamine for neutralization reaction for 15 min, then add 78.35 parts of deionized water for emulsification, and finally add 0.6 parts of ethylenediamine for chain extension. Filter to obtain water-soluble bio-based polyurethane resin.
[0053] Comparative Example 5 This comparative example provides a water-soluble bio-based polyurethane resin, comprising, by weight: 7 parts of polytetrahydrofuran ether PolyTHF® 2000, 2 parts of nonionic polyester diol Capromer™ PD4-05, 7.5 parts of isophorone diisocyanate, 0.02 parts of bismuth isooctanoate, 5 parts of triethylamine dihydroxypropanesulfonic acid, 0.5 parts of N,N-dimethylethanolamine, 77.18 parts of deionized water, and 0.8 parts of ethylenediamine; A method for preparing water-soluble bio-based polyurethane resin includes the following steps: (1) After dehydrating 7 parts of polytetrahydrofuran ether PolyTHF® 2000 and 2 parts of nonionic polyester diol Capromer™ PD4-05, the dehydrated polyol was obtained. (2) 7.5 parts of isophorone diisocyanate and 0.02 parts of bismuth isooctanoate were added dropwise to the dehydrated polyol and reacted at 80°C for 3 hours. Then, 5 parts of triethylamine dihydroxypropanesulfonic acid salt were added and reacted at 60°C for 3 hours to obtain the NCO-terminated prepolymer. (3) Cool the prepolymer to 40°C, add 0.5 parts of N,N-dimethylethanolamine for neutralization reaction for 15 minutes, then add 77.18 parts of deionized water for emulsification, and finally add 0.8 parts of ethylenediamine for chain extension. Filter to obtain water-soluble bio-based polyurethane resin.
[0054] Comparative Example 6 This comparative example provides a water-soluble bio-based polyurethane resin, which follows essentially the same steps as Example 2, except that the weight of the nonionic polyester diol Capromer™ PD4-05 is 0.2.
[0055] Comparative Example 7 This comparative example provides a water-soluble bio-based polyurethane resin, which follows essentially the same steps as Example 2, except that the weight of the nonionic polyester diol Capromer™ PD4-05 is 4 parts.
[0056] Performance testing The bio-based polyurethane resins prepared in Examples 1-5 and Comparative Examples 1-7 were subjected to water solubility tests, solids content tests according to GB / T 1725, bio-based content tests according to ASTM D6866, and hydroxyl value (relative solids content) tests according to GB / T 31412. The results are shown in Table 1. Water solubility test: Take 2g of the bio-based polyurethane resin obtained in Examples 1-5 and Comparative Examples 1-7 respectively and place it in an I-shaped mold. Dry it at room temperature for 24h, then bake it at 60℃ for 72h, then adjust it at 25℃ and 50% humidity for 24h, and finally immerse it in deionized water. If the paint film cannot maintain the complete I-shaped shape in the water within 1min, then the film condition is rated.
[0057] The criteria for evaluating water solubility are as follows: Level 5: Can break down the paint film into more than 10 small blocks or flocculent particles; Level 0: The paint film can still maintain its intact I-shaped shape in water within 10 minutes.
[0058] Table 1 Performance tests of bio-based polyurethane resins prepared in each example and comparative example
[0059] Application examples Ink was prepared by mixing 35g of the bio-based polyurethane resin prepared in Examples 1-5 and Comparative Examples 1-7, 5g of blocked isocyanate Bayhydur®BL XP 2706, and 35g of deionized water. The washing fastness was tested according to GB / T 3921 and the wet rubbing fastness was tested according to GB / T 3920. The results are shown in Table 2.
[0060] Printability test: Bidirectional continuous printing was performed on a uniform medium using an Epson I3200 printhead, with a printing area of 30m². 2 The printing environment was 35℃ and 40% humidity. Then, we observed for defects such as broken lines, clogged nozzles, ink flow, and ink bleeding. The results are shown in Table 2.
[0061] Table 2 Performance tests of inks prepared in each example and comparative example
[0062] As can be seen from Tables 1 and 2, the bio-based polyurethane resins prepared in Examples 1-5 have a bio-based content >10%, a hydroxyl value of 20mgKOH / g-90mgKOH / g, and good water solubility (grade 5). The inks prepared using Examples 1-5 have good wash fastness and rub fastness, and function normally during printing. However, in Comparative Example 1, ethylenediamine was used to replace the hydroxyl-containing diamine chain extender, resulting in a hydroxyl value of 0 in the bio-based polyurethane resin, leading to a wash fastness and wet rub fastness of 0 in the ink. Comparative Example 2 omitted the addition of nonionic polyester polyol and had a small amount of hydrophilic chain extender, resulting in poor water solubility and line breakage and clogging during printing. In Comparative Example 3, the amount of polyether polyol added was large, the addition of bio-based polyol was omitted, the amount of hydrophilic chain extender was small, and ethylenediamine was used to replace the hydroxyl-containing diamine chain extender, resulting in a bio-based polyurethane resin with a bio-based content and hydroxyl value of 0, and a water solubility grade of 0. The resulting ink exhibited poor wash fastness and wet rubbing fastness, and numerous line breaks and nozzle clogging occurred during printing. In Comparative Example 4, the amount of hydrophilic chain extender was low, triethylamine was used as the neutralizer, and ethylenediamine was used instead of hydroxyl-containing diamine chain extenders, resulting in a hydroxyl value of 0 and a water solubility grade of 0 in the bio-based polyurethane resin. Consequently, the prepared ink also exhibited poor wash fastness and wet rubbing fastness, and numerous line breaks and nozzle clogging occurred during printing. In Comparative Example 5, the addition of bio-based polyol was omitted, and ethylenediamine was used instead of hydroxyl-containing diamine chain extenders, resulting in a bio-based content and hydroxyl value of 0 in the bio-based polyurethane resin. Consequently, the prepared ink also exhibited poor wash fastness and wet rubbing fastness. In Comparative Example 6, the amount of nonionic polyester polyol was low, resulting in poor water solubility of the bio-based polyurethane resin, and numerous line breaks and nozzle clogging occurred during printing. In Comparative Example 7, the amount of nonionic polyester polyol was high, but the hydroxyl content was low, resulting in poor crosslinking density and poor wash fastness and wet rubbing fastness.
[0063] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.
Claims
1. A water-soluble bio-based polyurethane resin, characterized in that, The raw materials of the water-soluble bio-based polyurethane resin, by weight, include: 0-10 parts of nonionic polyether polyol, 3-13 parts of bio-based polyol, 0.5-3 parts of nonionic polyester polyol, 5-12 parts of diisocyanate, 0.005-0.05 parts of catalyst, 2-6 parts of hydrophilic chain extender, 0.3-1.5 parts of neutralizer, 70-82 parts of deionized water, and 1-3 parts of hydroxyl-containing diamine chain extender.
2. The water-soluble bio-based polyurethane resin according to claim 1, characterized in that, The solids content of the water-soluble bio-based polyurethane resin is 15%-28%.
3. The water-soluble bio-based polyurethane resin according to claim 2, characterized in that, The hydrophilic chain extender accounts for 7wt%-40wt% of the solids in the water-soluble bio-based polyurethane resin.
4. The water-soluble bio-based polyurethane resin according to claim 2, characterized in that, The nonionic polyester polyol accounts for 1.5wt%-20wt% of the solids in the water-soluble bio-based polyurethane resin.
5. The water-soluble bio-based polyurethane resin according to claim 4, characterized in that, The molecular weight of the nonionic polyester polyol is 500-1000.
6. The water-soluble bio-based polyurethane resin according to claim 1, characterized in that, The nonionic polyether polyol includes at least one of polypropylene glycol, polyethylene glycol, and polytetrahydrofuran glycol.
7. The water-soluble bio-based polyurethane resin according to claim 1, characterized in that, The hydrophilic chain extender includes at least one of sulfonates and carboxylates; Optionally, the hydrophilic chain extender is a sulfonate, and the sulfonate is 4-6 parts by weight; Optionally, the hydrophilic chain extender is a carboxylate, and the carboxylate is 2-4 parts by weight.
8. The water-soluble bio-based polyurethane resin according to claim 1, characterized in that, The bio-based content of the water-soluble bio-based polyurethane resin is >10%.
9. The water-soluble bio-based polyurethane resin according to any one of claims 1-8, characterized in that, The bio-based polyols include at least one of bio-based polycarbonate diols, bio-based polyether diols, and bio-based polyester diols; And / or, the hydroxyl-containing diamine chain extender includes at least one of N-(2-hydroxyethyl)ethylenediamine, N,N-bis(2-hydroxyethyl)ethylenediamine, and hydroxyethylethylenediamine; And / or, the sulfonate includes at least one of sulfonate diol, sulfonate diamine, and triethylamine dihydroxypropanesulfonate; And / or, the carboxylate includes at least one of 2,2-dimethylolpropionic acid and 2,2-dimethylolbutyric acid; And / or, the neutralizing agent includes at least one of N,N-dimethylethanolamine, potassium hydroxide, and sodium hydroxide.
10. The use of the water-soluble bio-based polyurethane resin according to any one of claims 1-9 in inks.