Organic silicon modified waterborne polyurethane resin, preparation method thereof and digital ink-jet ink

Abstract

The invention provides organic silicon modified waterborne polyurethane resin, a preparation method thereof and digital ink-jet ink. The organic silicon modified waterborne polyurethane resin is prepared from the following raw material components in parts by mass: 10 to 30 parts of polyol polymer, 0.5 to 15 parts of hydroxyl-terminated polydimethylsiloxane, 5 to 20 parts of diisocyanate, 0.005 to 0.1 part of tin-free catalyst, 0.5 to 4 parts of sulfonate hydrophilic chain extender, 0.5 to 3 parts of diamine chain extender and 0.2 to 1 part of neutralizer, and 50-60 parts by mass of water. The organic silicon modified waterborne polyurethane resin provided by the invention has the characteristics of low viscosity and high hydrophilicity, so that relatively high solid content can be realized while relatively low viscosity is maintained.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of polyurethane materials, and particularly relates to a silicone-modified waterborne polyurethane resin and a preparation method thereof and a digital inkjet ink. BACKGROUND

[0002] With the progress of society and the enhancement of environmental awareness, the limitation of volatile organic compound (VOC) emission and harmful solvent content is becoming increasingly strict, which promotes the wide application of waterborne resins in many fields. Among them, water-based ink as a key material for packaging printing has the advantages of small influence on the health of operating personnel, low environmental pollution, high safety, etc. by replacing 30%-70% of toxic organic solvents in traditional inks with water, and has become an important type of environmentally friendly ink.

[0003] In the field of digital inkjet printing, the ink needs to meet the stringent requirements of printing smoothness, low viscosity and high color hiding power. Therefore, a large amount of humectant and high pigment content color paste are often added to the waterborne resin ink. However, the currently marketed waterborne resins for inkjet printing generally have performance limitations: when the viscosity is less than 20 cP, the solid content is usually low (<35)%;when the solid content is increased to the range of 35%-40%, the viscosity is significantly increased to more than 200 cP. This technical contradiction of "high solid high viscosity" seriously restricts the actual amount of waterborne resin as an effective film-forming material in the ink. Due to the insufficient proportion of effective resin components, the final ink is difficult to improve the key performance after film formation, including hand feeling, wear resistance (dry / wet rub fastness), water resistance (soaping fastness), color density and elongation at break, etc., which cannot meet the demand for quality and durability of high-end applications.

[0004] Therefore, there is an urgent need in the prior art for a new resin material that can significantly increase the solid content of the resin while maintaining a low viscosity suitable for inkjet printing, thereby substantially increasing the effective resin component while keeping the apparent amount of resin in the ink formula unchanged, and thus systematically improving the overall performance of the ink. SUMMARY

[0005] In view of the deficiencies of the prior art, the present application provides a silicone-modified waterborne polyurethane resin and a preparation method thereof, and a digital inkjet ink. The silicone-modified waterborne polyurethane resin has the characteristics of low viscosity and high hydrophilicity, so that it can achieve a high solid content while maintaining a low viscosity. Based on this, when the resin is applied to a digital inkjet ink, it can significantly increase the proportion of effective resin components in the formula without affecting the printing smoothness, so that the obtained ink exhibits excellent hand feeling, color development, water resistance (soaping fastness) and wear resistance (dry / wet rub fastness) after film formation, and can be widely used for high-performance printing of various printing media such as films, paper, textiles and leather.

[0006] To achieve the above object, in one aspect, the present application provides a silicone-modified waterborne polyurethane resin, raw materials for preparing the silicone-modified waterborne polyurethane resin comprising the following components: 10-30 parts by mass of a polyol polymer, 0.5-15 parts by mass of a hydroxyl-terminated polydimethylsiloxane, 5-20 parts by mass of a diisocyanate, 0.005-0.1 parts by mass of a tin-free catalyst, 0.5-4 parts by mass of a sulfonate hydrophilic chain extender, 0.5-3 parts by mass of a diamine chain extender, 0.2-1 parts by mass of a neutralizing agent, and 50-60 parts by mass of water.

[0007] Optionally, the polyol polymer comprises at least one of a polyester polyol, a polyether polyol, and a polycarbonate polyol.

[0008] Optionally, the hydroxyl-terminated polydimethylsiloxane is at least one of a mono-terminal monohydroxy polydimethylsiloxane, a double-terminal dihydroxy polydimethylsiloxane, and a mono-terminal dihydroxy polydimethylsiloxane. The mono-terminal monohydroxy polydimethylsiloxane has a structure as shown in Formula I: ; The double-terminal dihydroxy polydimethylsiloxane has a structure as shown in Formula II: ; The mono-terminal dihydroxy polydimethylsiloxane has a structure as shown in Formula III: .

[0009] Optionally, the hydroxyl-terminated polydimethylsiloxane is at least one of a mono-terminal dihydroxy polydimethylsiloxane and a mono-terminal monohydroxy polydimethylsiloxane.

[0010] Optionally, the diisocyanate comprises at least one of toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), 1,6-hexane diisocyanate (HDI), and dicyclohexylmethane diisocyanate (HMDI). The tin-free catalyst comprises at least one of bismuth octoate, bismuth isooctoate, bismuth octylate, and zinc octoate.

[0011] Optionally, the sulfonate hydrophilic chain extender comprises at least one of a sulfonate diol, a sulfonate diamine, triethylamine 2-hydroxypropane sulfonate, or other alcohol or amine sulfonate. The diamine chain extender comprises at least one of ethylenediamine, isophorone diamine, N-(2-hydroxyethyl)ethylenediamine, 2N,N-bis(2-hydroxyethyl)ethylenediamine, and other diamine chain extenders. The neutralizing agent comprises at least one of triethylamine and N,N-dimethylethanolamine.

[0012] Optionally, the solid content of the organosilicon-modified waterborne polyurethane resin is 40%-47.5%; And / or; the viscosity of the organosilicon-modified waterborne polyurethane resin is less than 100 cP; And / or; the molecular weight of the terminal hydroxyl polydimethylsiloxane is 500-15000.

[0013] On the other hand, the present invention also provides a method for preparing the above-mentioned organosilicon-modified waterborne polyurethane resin, which includes the following steps: (1) Dehydrate 10-30 parts by weight of polyol polymer and 0.5-15 parts by weight of terminal hydroxyl polydimethylsiloxane to obtain a dehydrated mixture; (2) 5-20 parts by mass of diisocyanate and the dehydrated mixture are reacted with 0.005-0.1 parts by mass of tin-free catalyst, and then reacted with 0.5-4 parts by mass of sulfonate hydrophilic chain extender to obtain NCO-terminated prepolymer A containing organosilicon segments; (3) The NCO-terminated prepolymer A containing organosilicon segments is mixed with 0.2-1 parts by weight of neutralizing agent to carry out a neutralization reaction, then mixed with 50-60 parts by weight of water for emulsification, and then 0.5-3 parts by weight of diamine chain extender is added for chain extension to obtain the organosilicon-modified waterborne polyurethane resin.

[0014] Optionally, the dehydration in step (1) is heat dehydration at a temperature of 80-120 ℃; In step (2), the diisocyanate is reacted with the dehydrated polyol from step (1) under the catalysis of a tin-free catalyst at a temperature of 60-85 °C for 3-4 h; subsequently, it is reacted with a sulfonate hydrophilic chain extender at a temperature of 50-85 °C for 2-3 h. The chain extension reaction temperature for adding the diamine chain extender in step (3) is 20-35 °C and the time is 0.5-1 h.

[0015] Furthermore, the present invention also provides the application of the above-mentioned silicone-modified waterborne polyurethane resin or the silicone-modified waterborne polyurethane resin prepared by the above method in digital inkjet inks.

[0016] Compared with the prior art, the present invention has the following beneficial effects: (1) Significantly improved overall performance and effective improvement of application defects: By introducing hydroxyl-terminated polydimethylsiloxane as a key component into the polymer backbone, deep organosilicon modification of the resin is achieved. This structural design enables the final ink coating to have excellent hand feel, outstanding water resistance, and abrasion resistance (high dry / wet rub fastness), effectively improving the core problems of rough hand feel and insufficient durability of existing resin-based digital inkjet inks.

[0017] (2) Excellent printing performance, achieving an ideal balance of high solids and low viscosity: The resin system obtained by this invention can maintain a stable dispersion state with low viscosity and small particle size while achieving a high solids content of 40%-47.5%. At the same time, the higher proportion of effective resin components directly improves the adhesion and color development of the ink on various media.

[0018] (3) Significant advantages in raw materials and processes, and wide applicability: The hydroxyl-terminated polydimethylsiloxane used has no special requirements for the viscosity of the raw materials, which facilitates the proportion control and cost optimization in industrial production. In addition, the resin emulsion has good slow-drying characteristics, which provides a longer leveling time for the ink droplets after printing, helps to form a denser and smoother ink film, effectively improves the nozzle clogging and printing defects caused by fast drying, and makes it widely applicable to various printing media such as films, paper, textiles and leather. Detailed Implementation

[0019] To make the technical problems solved, the technical solutions, and the beneficial effects of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

[0020] This invention provides a silicone-modified waterborne polyurethane resin. The raw materials for preparing the silicone-modified waterborne polyurethane resin include the following components: 10-30 parts by weight of polyol polymer, 0.5-15 parts by weight of hydroxyl-terminated polydimethylsiloxane, 5-20 parts by weight of diisocyanate, 0.005-0.1 parts by weight of tin-free catalyst, 0.5-4 parts by weight of sulfonate hydrophilic chain extender, 0.5-3 parts by weight of diamine chain extender, 0.2-1 parts by weight of neutralizing agent, and 50-60 parts by weight of water.

[0021] In this embodiment of the invention, by using hydroxyl-terminated polydimethylsiloxane to modify the main chain of waterborne polyurethane, the resulting organosilicon-modified waterborne polyurethane resin has better feel, water resistance and abrasion resistance, thereby effectively solving the problems of poor feel, insufficient water resistance and abrasion resistance of conventional resin-based digital inkjet inks.

[0022] Simultaneously, by introducing sulfonate hydrophilic chain extenders, the resin acquires both excellent hydrophilicity and low viscosity characteristics, thereby achieving a high solids content while maintaining low viscosity. This characteristic allows for an increase in the proportion of effective resin components without affecting the dosage of other components in the ink formulation, thereby enhancing the ink's adhesion. Furthermore, this high solids content also helps improve the ink's color development.

[0023] Therefore, by combining organosilicon modification with hydrophilic chain extension technology of sulfonate, this silicone-modified waterborne polyurethane resin significantly improves the ink's feel, water resistance, abrasion resistance, and color development performance while reducing viscosity and increasing solid content.

[0024] In some embodiments, the polyol polymer includes at least one of polyester polyol, polyether polyol, and polycarbonate polyol.

[0025] These polyester polyols, polyether polyols, or polycarbonate polyols are selected as soft segment units, which together with diisocyanates form the flexible skeleton of polyurethane, jointly affecting the final properties of the resin, and providing the necessary structural basis for organosilicon functional groups to play their role in improving feel, water resistance, etc.

[0026] In some embodiments, the hydroxyl-terminated polydimethylsiloxane is at least one of monohydroxyl-terminated polydimethylsiloxane, dihydroxyl-terminated polydimethylsiloxane, and monohydroxyl-terminated polydimethylsiloxane. The single-terminated monohydroxyl polydimethylsiloxane has the structure shown in Formula I: ; The dual-terminated dihydroxyl polydimethylsiloxane has the structure shown in Formula II: ; The single-terminated dihydroxyl polydimethylsiloxane has the structure shown in Formula III: .

[0027] In a preferred embodiment, the hydroxyl-terminated polydimethylsiloxane is at least one of single-terminated dihydroxyl polydimethylsiloxane and single-terminated monohydroxyl polydimethylsiloxane.

[0028] In some embodiments, the diisocyanate is at least one selected from isophorone diamine, toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), 1,6-hexane diisocyanate (HDI), and dicyclohexylmethane diisocyanate (HMDI).

[0029] In some embodiments, the tin-free catalyst is at least one of bismuth octoate, bismuth isooctanoate, bismuth octanoate, and zinc octoate.

[0030] The selection of these Wuxi catalysts is a key measure to ensure a safer and more environmentally friendly resin production process and final product while ensuring high-efficiency catalysis. They are especially suitable for high-end water-based product applications with strict requirements on toxicity and ecology.

[0031] In some embodiments, the sulfonate hydrophilic chain extender includes at least one of sulfonate diol, sulfonate diamine, triethylamine dihydroxypropanesulfonate, or other alcohols or amine sulfonates; The diamine chain extender includes at least one of ethylenediamine, isophorone diamine, N-(2-hydroxyethyl)ethylenediamine, 2N,N-bis(2-hydroxyethyl)ethylenediamine, and other diamine chain extenders; The neutralizing agent includes at least one of triethylamine and N,N-dimethylethanolamine.

[0032] In some embodiments, the solid content of the silicone-modified waterborne polyurethane resin is 40%-47.5%; And / or; the viscosity of the silicone-modified waterborne polyurethane resin is less than 100 cP, and in the exemplary examples, it can be 5 cP, 10 cP, 15 cP, 21 cP, 32 cP, 39 cP, 45 cP, 53 cP, 60 cP, 67 cP, 75 cP, 85 cP, 93 cP, or 99 cP; And / or; the molecular weight of the terminal hydroxyl polydimethylsiloxane is 500-15000.

[0033] This application also provides a method for preparing the above-mentioned organosilicon-modified waterborne polyurethane resin, which includes the following steps: (1) Dehydrate 10-30 parts by weight of polyol polymer and 0.5-15 parts by weight of terminal hydroxyl polydimethylsiloxane to obtain a dehydrated mixture; (2) 5-20 parts by mass of diisocyanate and the dehydrated mixture are reacted with 0.005-0.1 parts by mass of tin-free catalyst, and then reacted with 0.5-4 parts by mass of sulfonate hydrophilic chain extender to obtain NCO-terminated prepolymer A containing organosilicon segments; (3) The NCO-terminated prepolymer A containing organosilicon segments is mixed with 0.2-1 parts by weight of neutralizing agent to carry out a neutralization reaction, then mixed with 50-60 parts by weight of water for emulsification, and then 0.5-3 parts by weight of diamine chain extender is added for chain extension to obtain the organosilicon-modified waterborne polyurethane resin.

[0034] In some embodiments, the dehydration in step (1) is heating dehydration at a temperature of 80-120 °C. Within this temperature range, polyol polymers and hydroxyl-terminated polydimethylsiloxanes can effectively remove water.

[0035] In some embodiments, in step (2), the diisocyanate is reacted with the dehydrated polyol from step (1) under the catalysis of a tin-free catalyst at a temperature of 60-85 °C for 2-5 h, preferably 3-4 h; subsequently, the reaction with the sulfonate hydrophilic chain extender is carried out at a temperature of 50-85 °C for 2-5 h, preferably 2-3 h.

[0036] The chain extension reaction temperature for adding the diamine chain extender in step (3) is 20-35 °C, and the time is 0.5-2 h, preferably 0.5-1 h.

[0037] Furthermore, embodiments of this application also provide the application of the above-mentioned silicone-modified waterborne polyurethane resin or the silicone-modified waterborne polyurethane resin prepared by the above method in digital inkjet inks.

[0038] To further illustrate the technical effects of the present invention, the following specific embodiments are also provided.

[0039] In this embodiment, the polycarbonate diol is purchased from Tosoh Corporation of Japan, and the model can be at least one of NIPPOLLAN® 982 and NIPPOLLAN® 963.

[0040] In this embodiment, the polyether diol was purchased from BASF and the model can be PolyTHF® 2000.

[0041] In this embodiment, the polytetrahydrofuran ether has a weight-average molecular weight of 2000.

[0042] In this embodiment, the polyester diol was purchased from Changxing Chemical, and the model can be UNIPOL-2530.

[0043] In this embodiment, the weight-average molecular weight of the polyester polyol is 3000.

[0044] In this embodiment, the hydroxyl-terminated polydimethylsiloxane is purchased from Silok®. The single-terminated monohydroxyl polydimethylsiloxane can be selected as Silok® 8821F2, the double-terminated dihydroxyl polydimethylsiloxane can be selected as at least one of Silok® 8847 and Silok® 8847F5, and the single-terminated dihydroxyl polydimethylsiloxane can be selected as Silok® 8822F2.

[0045] In this embodiment, the weight-average molecular weight of the single-ended dihydroxyl polydimethylsiloxane is 1400.

[0046] In this embodiment, 1,6-hexamethylene diisocyanate was purchased from Covestro, and the model number can be Desmodur H.

[0047] In this embodiment, dicyclohexylmethane diisocyanate was purchased from Covestro, and the model can be DESMODURW.

[0048] In this embodiment, isophorone diisocyanate was purchased from Covestro, and the model can be DESMODUR I.

[0049] In this embodiment, bismuth isooctanoate was purchased from Shanghai Manhai Gaoschmit Chemical Co., Ltd., and the model can be TMG722.

[0050] In this embodiment, triethylamine dihydroxypropanesulfonic acid salt was purchased from Beijing Baiyuan Chemical Co., Ltd., and the model can be MS-09.

[0051] Example 1 provides a high-solids, low-viscosity silicone-modified waterborne polyurethane resin for digital inkjet printing, comprising the following components: A. Polycarbonate polyol, 26.0 parts by weight; B. 3.0 parts by weight of single-terminated dihydroxyl polydimethylsilane; 11.0 parts by weight of C diisocyanate; 0.02 parts by mass of catalyst D; 3.0 parts by weight of E sulfonate hydrophilic chain extender; Neutralizing agent F, 0.3 parts by weight; 55.68 parts by weight of deionized water; 1.0 parts by weight of H-diamine chain extender.

[0052] Includes the following steps: S1. 26 parts by weight of polycarbonate diol NIPPOLLAN® 982 and 3 parts by weight of mono-dihydroxyl-terminated polydimethylsilane Silok® 8822F2 were dehydrated at 110 °C to obtain the dehydrated polyol; S2. 11 parts by mass of diisocyanate DESMODUR W and 0.02 parts by mass of catalyst TMG722 were added dropwise to the dehydrated polyol and reacted at 80 °C for 3 hours. Then, 3.0 parts by mass of triethylamine dihydroxypropanesulfonic acid chain extender MS-09 were added dropwise and the reaction was continued at 65 °C for 3 hours to obtain an NCO-terminated prepolymer containing organosilicon. S3. Cool the prepolymer to 35 °C, add 0.3 parts by mass of triethylamine as a neutralizing agent and neutralize for 15 minutes, then add 55.68 parts by mass of deionized water for emulsification, and finally add 1.0 parts by mass of isophorone diamine for chain extension. After filtration, the high-solids, low-viscosity silicone-modified waterborne polyurethane resin N1 for digital inkjet printing is obtained.

[0053] Example 2 provides a high-solids, low-viscosity silicone-modified waterborne polyurethane resin for digital inkjet printing, comprising the following components: A. Polycarbonate polyol, 30.0 parts by weight; B. 1.0 parts by weight of monohydroxyl-terminated polydimethylsiloxane; 8.0 parts by weight of C diisocyanate; 0.1 parts by mass of catalyst D; 4.0 parts by weight of E sulfonate hydrophilic chain extender; Neutralizing agent F, 1.0 parts by weight; 54.9 parts by weight of deionized water; 1.0 parts by weight of H-diamine chain extender.

[0054] Includes the following steps: S1. 30 parts by weight of polycarbonate diol NIPPOLLAN® 982 and 1 part by weight of monohydroxyl-terminated polydimethylsiloxane Silok® 8821F2 were dehydrated at 120 °C to obtain the dehydrated polyol. S2. 8 parts by mass of diisocyanate DESMODUR H and 0.1 parts by mass of catalyst TMG722 were added dropwise to the dehydrated polyol and reacted at 70 °C for 4 hours. Then, 4.0 parts by mass of triethylamine dihydroxypropanesulfonic acid chain extender MS-09 were added dropwise, and the reaction was continued at 60 °C for 3 hours to obtain an NCO-terminated prepolymer containing organosilicon. S3. Cool the prepolymer to 30 °C, add 1.0 part by weight of neutralizing agent N,N-dimethylethanolamine for neutralization reaction for 15 minutes, then add 54.9 parts by weight of deionized water for emulsification, and finally add 1.0 part by weight of hydroxyethyl ethylenediamine for chain extension. After filtration, the high solids and low viscosity organosilicon modified waterborne polyurethane resin N2 for digital inkjet is obtained.

[0055] Example 3 provides a high-solids, low-viscosity silicone-modified waterborne polyurethane resin for digital inkjet printing, comprising the following components: A. 10.0 parts by weight of polyether polyol; B. 15.0 parts by weight of dihydroxyl-terminated polydimethylsiloxane; 15.0 parts by weight of C diisocyanate; 0.05 parts by weight of catalyst D; 2.0 parts by weight of E sulfonate hydrophilic chain extender; Neutralizing agent F, 0.5 parts by weight; 56.45 parts by weight of deionized water; 1.0 parts by weight of H-diamine chain extender.

[0056] Includes the following steps: S1. 10 parts by weight of polytetrahydrofuran ether PolyTHF® 2000 and 15 parts by weight of dihydroxyl-terminated polydimethylsiloxane Silok® 8847 were dehydrated at 90 °C to obtain the dehydrated polyol. S2. 15 parts by mass of diisocyanate DESMODUR W and 0.05 parts by mass of catalyst TMG722 were added dropwise to the dehydrated polyol and reacted at 85 °C for 3 hours. Then, 2.0 parts by mass of triethylamine dihydroxypropanesulfonic acid chain extender MS-09 were added dropwise and the reaction was continued at 80 °C for 3 hours to obtain an NCO-terminated prepolymer containing organosilicon. S3. Cool the prepolymer to 25 °C, add 0.5 parts by mass of triethylamine as a neutralizing agent and neutralize for 15 minutes, then add 56.45 parts by mass of deionized water for emulsification, and finally add 1.0 parts by mass of hydroxyethyl ethylenediamine for chain extension. After filtration, the high-solids, low-viscosity silicone-modified waterborne polyurethane resin N3 for digital inkjet printing is obtained.

[0057] Example 4 provides a high-solids, low-viscosity silicone-modified waterborne polyurethane resin for digital inkjet printing, comprising the following components: A. Polyester polyol, 20.0 parts by weight; 10.0 parts by weight of B polycarbonate polyol; 0.5 parts by weight of C-terminated dihydroxy polydimethylsiloxane; 5.0 parts by weight of D diisocyanate; E catalyst 0.1 parts by mass; 2.0 parts by weight of F sulfonate hydrophilic chain extender; 0.5 parts by weight of neutralizing agent G; 58.9 parts by weight of deionized water; 3.0 parts by weight of 1-diamine chain extender.

[0058] Includes the following steps: S1. 20 parts by weight of polyester polyol UNIPOL-2530, 10 parts by weight of polycarbonate diol NIPPOLLAN® 963 and 0.5 parts by weight of single-terminated dihydroxy polydimethylsiloxane Silok® 8822F2 were dehydrated at 110 °C to obtain the dehydrated polyol. S2. Five parts by mass of diisocyanate DESMODUR H and 0.1 parts by mass of catalyst TMG722 were added dropwise to the dehydrated polyol and reacted at 70 °C for 4 hours. Then, 2.0 parts by mass of triethylamine dihydroxypropanesulfonic acid chain extender MS-09 were added dropwise and the reaction was continued at 55 °C for 4 hours to obtain an NCO-terminated prepolymer containing organosilicon. S3. Cool the prepolymer to 35 °C, add 0.5 parts by weight of triethylamine as a neutralizing agent and neutralize for 15 minutes, then add 58.9 parts by weight of deionized water for emulsification, and finally add 3.0 parts by weight of isophorone diamine for chain extension. After filtration, the high-solids, low-viscosity silicone-modified waterborne polyurethane resin N4 for digital inkjet printing is obtained.

[0059] Example 5 provides a high-solids, low-viscosity silicone-modified waterborne polyurethane resin for digital inkjet printing, comprising the following components: A. 20.0 parts by weight of polyether polyol; B. 15.0 parts by weight of dihydroxyl-terminated polydimethylsiloxane; 10.0 parts by weight of C diisocyanate; 0.1 parts by mass of catalyst D; 2.0 parts by weight of E sulfonate hydrophilic chain extender; Neutralizing agent F, 0.2 parts by weight; 52.2 parts by weight of deionized water; 0.5 parts by weight of H-diamine chain extender.

[0060] Includes the following steps: S1. 20 parts by weight of polytetrahydrofuran ether PolyTHF® 2000 and 15 parts by weight of dihydroxyl-terminated polydimethylsiloxane Silok® 8847 were dehydrated at 120 °C to obtain the dehydrated polyol. S2. 10 parts by mass of diisocyanate DESMODUR W and 0.1 parts by mass of catalyst TMG722 were added dropwise to the dehydrated polyol and reacted at 80 °C for 3 hours. Then, 2.0 parts by mass of triethylamine dihydroxypropanesulfonic acid chain extender MS-09 were added dropwise and the reaction was continued at 65 °C for 3 hours to obtain an NCO-terminated prepolymer containing organosilicon. S3. Cool the prepolymer to 30 °C, add 0.2 parts by mass of triethylamine as a neutralizing agent and neutralize for 15 minutes, then add 52.2 parts by mass of deionized water for emulsification, and finally add 0.5 parts by mass of ethylenediamine for chain extension. After filtration, the high-solids, low-viscosity silicone-modified waterborne polyurethane resin N5 for digital inkjet printing is obtained.

[0061] Example 6 provides a high-solids, low-viscosity silicone-modified waterborne polyurethane resin for digital inkjet printing, comprising the following components: A. 20.0 parts by weight of polyether polyol; B. 13.0 parts by weight of dihydroxyl-terminated polydimethylsiloxane; C single-terminated monohydroxy polydimethylsiloxane 2.0 parts by weight; 10.0 parts by weight of D diisocyanate; E catalyst 0.1 parts by mass; 2.0 parts by weight of F sulfonate hydrophilic chain extender; G neutralizing agent 0.2 parts by weight; 52.2 parts by weight of deionized water; 0.5 parts by weight of 1-diamine chain extender.

[0062] Includes the following steps: S1. 20 parts by weight of polytetrahydrofuran ether PolyTHF® 2000, 13 parts by weight of dihydroxyl-terminated polydimethylsiloxane Silok® 8847 and 2 parts by weight of monohydroxyl-terminated polydimethylsiloxane Silok® 8821F2 were dehydrated at 105°C to obtain the dehydrated polyol; S2. 10 parts by mass of diisocyanate DESMODUR W and 0.1 parts by mass of catalyst TMG722 were added dropwise to the dehydrated polyol and reacted at 70 °C for 4 hours. Then, 2.0 parts by mass of triethylamine dihydroxypropanesulfonic acid chain extender MS-09 were added dropwise and the reaction was continued at 60 °C for 3 hours to obtain an NCO-terminated prepolymer containing organosilicon. S3. Cool the prepolymer to 35 °C, add 0.2 parts by mass of triethylamine as a neutralizing agent and neutralize for 15 minutes, then add 52.2 parts by mass of deionized water for emulsification, and finally add 0.5 parts by mass of ethylenediamine for chain extension. After filtration, the high-solids, low-viscosity silicone-modified waterborne polyurethane resin N6 for digital inkjet printing is obtained.

[0063] Comparative Example 1 provides a water-based polyurethane resin for digital inkjet printing, comprising the following components: A. Polyester polyol, 20.0 parts by weight; 10.0 parts by weight of B polycarbonate polyol; 5.0 parts by weight of C diisocyanate; 0.1 parts by mass of catalyst D; 2.0 parts by weight of E sulfonate hydrophilic chain extender; Neutralizing agent F, 0.5 parts by weight; 58.9 parts by weight of deionized water; 3.0 parts by weight of H-diamine chain extender.

[0064] Includes the following steps: S1. 20 parts by weight of polyester polyol UNIPOL-2530 and 10 parts by weight of polycarbonate diol NIPPOLLAN® 963 were dehydrated at 110 °C to obtain the dehydrated polyol. S2. 5 parts by mass of diisocyanate DESMODUR H and 0.1 parts by mass of catalyst TMG722 were added dropwise to the dehydrated polyol and reacted at 70 °C for 4 hours. Then, 2.0 parts by mass of triethylamine dihydroxypropanesulfonic acid chain extender MS-09 were added dropwise and the reaction was continued at 55 °C for 4 hours to obtain NCO-terminated prepolymer. S3. Cool the prepolymer to 35 °C, add 0.5 parts by weight of triethylamine as a neutralizing agent and neutralize for 15 minutes, then add 58.9 parts by weight of deionized water for emulsification, and finally add 3.0 parts by weight of isophorone diamine for chain extension. After filtration, the waterborne polyurethane resin for digital inkjet printing is obtained.

[0065] Comparative Example 2 provides a water-based polyurethane resin for digital inkjet printing, comprising the following components: A. Polycarbonate polyol, 35.0 parts by weight; 10.0 parts by weight of β diisocyanate; 0.1 parts by mass of C catalyst; 3.0 parts by weight of D-sulfonate hydrophilic chain extender; E neutralizing agent 0.5 parts by weight; F 50.9 parts by weight of deionized water; 0.5 parts by weight of G diamine chain extender.

[0066] Includes the following steps: S1. 35 parts by weight of polycarbonate diol NIPPOLLAN® 963 were dehydrated at 100 °C to obtain the dehydrated polyol; S2. 10 parts by mass of diisocyanate DESMODUR H and 0.1 parts by mass of catalyst TMG722 were added dropwise to the dehydrated polyol and reacted at 80 °C for 3 hours. Then, 3.0 parts by mass of triethylamine dihydroxypropanesulfonic acid chain extender MS-09 were added dropwise and the reaction was continued at 60 °C for 3 hours to obtain NCO-terminated prepolymer. S3. Cool the prepolymer to 40 °C, add 0.5 parts by mass of triethylamine as a neutralizing agent and neutralize for 15 minutes, then add 50.9 parts by mass of deionized water for emulsification, and finally add 0.5 parts by mass of ethylenediamine for chain extension. After filtration, the waterborne polyurethane resin for digital inkjet printing is obtained.

[0067] Comparative Example 3 provides a silicone-modified waterborne polyurethane resin for digital inkjet printing, comprising the following components: A. 3.0 parts by weight of polycarbonate polyol; B. 26.0 parts by weight of single-terminated dihydroxyl polydimethylsiloxane; 11.0 parts by weight of C diisocyanate; 0.02 parts by mass of catalyst D; 3.0 parts by weight of E sulfonate hydrophilic chain extender; Neutralizing agent F, 0.3 parts by weight; 55.68 parts by weight of deionized water; 1.0 parts by weight of H-diamine chain extender.

[0068] Includes the following steps: S1. Three parts by weight of polycarbonate diol NIPPOLLAN® 982 and 26 parts by weight of mono-dihydroxyl-terminated polydimethylsiloxane Silok® 8822F2 were dehydrated at 110 °C to obtain the dehydrated polyol. S2. 11 parts by mass of diisocyanate DESMODUR W and 0.02 parts by mass of catalyst TMG722 were added dropwise to the dehydrated polyol and reacted at 80 °C for 3 hours. Then, 3.0 parts by mass of triethylamine dihydroxypropanesulfonic acid chain extender MS-09 were added dropwise and the reaction was continued at 65 °C for 3 hours to obtain an NCO-terminated prepolymer containing organosilicon. S3. Cool the prepolymer to 35 °C, add 0.3 parts by mass of triethylamine as a neutralizing agent and neutralize for 15 minutes, then add 55.68 parts by mass of deionized water for emulsification, and finally add 1.0 parts by mass of isophorone diamine for chain extension. After filtration, the silicone-modified waterborne polyurethane resin for digital inkjet printing is obtained.

[0069] Comparative Example 4 provides a silicone-modified waterborne polyurethane resin for digital inkjet printing, comprising the following components: A. Polycarbonate polyol, 26.0 parts by weight; B. 3.0 parts by weight of single-terminated dihydroxyl polydimethylsilane; 11.0 parts by weight of C diisocyanate; 0.02 parts by mass of catalyst D; E small molecule alcohol chain extender 1.0 parts by weight; 3.0 parts by weight of F sulfonate hydrophilic chain extender; Neutralizing agent G, 0.3 parts by weight; 54.68 parts by weight of deionized water; 1.0 parts by weight of diamine chain extender.

[0070] Includes the following steps: S1. 26 parts by weight of polycarbonate diol NIPPOLLAN® 982 and 3 parts by weight of mono-dihydroxyl-terminated polydimethylsiloxane Silok® 8822F2 were dehydrated at 110 °C to obtain the dehydrated polyol. S2. 11 parts by mass of diisocyanate DESMODUR W and 0.02 parts by mass of catalyst TMG722 were added dropwise to the dehydrated polyol and reacted at 80 °C for 3 hours. Then, 1.0 parts by mass of 1,4-butanediol and 3.0 parts by mass of triethylamine dihydroxypropanesulfonic acid chain extender MS-09 were added dropwise, and the reaction was continued at 65 °C for 3 hours to obtain an NCO-terminated prepolymer containing organosilicon. S3. Cool the prepolymer to 35 °C, add 0.3 parts by mass of triethylamine as a neutralizing agent and neutralize for 15 minutes, then add 54.68 parts by mass of deionized water for emulsification, and finally add 1.0 parts by mass of ethylenediamine for chain extension. After filtration, the silicone-modified waterborne polyurethane resin for digital inkjet printing is obtained.

[0071] Comparative Example 5 provides a water-based polyurethane resin for digital inkjet printing, comprising the following components: A. Polycarbonate polyol, 30.0 parts by weight; B. 1.0 parts by weight of monohydroxyl-terminated polydimethylsiloxane; 8.0 parts by weight of C diisocyanate; 0.1 parts by mass of catalyst D; 4.0 parts by weight of E carboxylate hydrophilic chain extender; Neutralizing agent F, 1.0 parts by weight; 54.9 parts by weight of deionized water; 1.0 parts by weight of H-diamine chain extender.

[0072] Includes the following steps: S1. 30 parts by weight of polycarbonate diol NIPPOLLAN® 982 and 1 part by weight of monohydroxyl-terminated polydimethylsiloxane Silok® 8821F2 were dehydrated at 100 °C to obtain the dehydrated polyol. S2. Add 8 parts by mass of diisocyanate DESMODUR H and 0.1 parts by mass of catalyst TMG722 dropwise to the dehydrated polyol and react at 80 °C for 3 hours. Then add 4.0 parts by mass of 2,2-dihydroxypropionic acid chain extender DMPA dropwise and continue to react at 60 °C for 4 hours to obtain NCO-terminated prepolymer. S3. Cool the prepolymer to 35 °C, add 1.0 part by weight of neutralizing agent N,N-dimethylethanolamine for neutralization reaction for 15 minutes, then add 54.9 parts by weight of deionized water for emulsification, and finally add 1.0 part by weight of hydroxyethyl ethylenediamine for chain extension. After filtration, the silicone-modified waterborne polyurethane resin for digital inkjet printing is obtained.

[0073] The performance of the waterborne polyurethane resins for digital inkjet printing prepared in Examples 1-6 and Comparative Examples 1-5 was determined, and the results are listed in Table 1 below.

[0074] Table 1 Test Results

[0075] Note: (1) Feel (AATCC 202) 0-100 points, the higher the score, the better the feel; (2) Wash fastness (GB / T 3921), dry rubbing fastness (GB / T 3920), and wet rubbing fastness (GB / T 3920) are divided into 0-5 grades, with grade 5 being the best; (3) Printability test: Bidirectional continuous printing was performed on a uniform medium using an Epson I3200 printhead, with a printing area of ​​30 m². 2 Then observe for defects such as broken lines, clogged nozzles, ink flow, and ink seepage.

[0076] As shown in Table 1, the silicone-modified waterborne polyurethane resins provided in Examples 1-6, while achieving a high solids content of 40%-47.5%, still maintain a stable dispersion state with low viscosity and small particle size. Furthermore, the final ink coating exhibits excellent hand feel, outstanding water resistance, and abrasion resistance (high dry / wet rub fastness).

[0077] Compared with Example 1, if terminal hydroxyl polydimethylsiloxane (Comparative Example 1 and Comparative Example 2) is not added, the viscosity of the prepared waterborne polyurethane resin increases, and the hand feel, soap wash fastness, dry rub fastness, and wet rub fastness decrease significantly.

[0078] Compared with Example 1, if the weight fraction of terminal hydroxyl polydimethylsiloxane is higher (Comparative Example 3), the viscosity of the prepared silicone-modified waterborne polyurethane resin increases sharply and the printing performance decreases significantly.

[0079] Compared with Example 1, if a small molecule alcohol chain extender (Comparative Example 4) is added, the viscosity of the prepared silicone-modified waterborne polyurethane resin increases sharply, and the feel and printing performance decrease significantly.

[0080] Compared with Example 2, if the triethylamine dihydroxypropanesulfonic acid chain extender MS-09 is replaced with the same mass of 2,2-dihydroxypropionic acid chain extender DMPA (Comparative Example 5), the viscosity of the prepared silicone-modified waterborne polyurethane resin increases sharply, and the hand feel, washing fastness, dry rubbing fastness, wet rubbing fastness and printing performance decrease significantly.

[0081] Compared with the prior art, the present invention has the following beneficial effects: (1) Significantly improved performance: By introducing terminal hydroxyl polydimethylsiloxane for organosilicon modification, the ink coating has excellent feel, water resistance and abrasion resistance, effectively improving the problems of rough feel and insufficient durability of existing products. (2) Superior printing performance: While achieving a high solid content of 40%-47.5%, it maintains a stable dispersion state with low viscosity and small particle size, improving ink adhesion and color development. (3) Strong process adaptability: The raw materials have no special viscosity requirements, which is convenient for industrial production and cost control; the slow drying characteristics of the emulsion help ink leveling, reduce printhead clogging and printing defects, and are suitable for various media such as films, paper, textiles and leather.

[0082] The specific embodiments of the present invention have been described above. It should be understood that the scope of protection of the present invention is not limited thereto. Those skilled in the art should understand that any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention fall within the scope of protection and disclosure of the present invention.

Claims

1. An organosilicon-modified waterborne polyurethane resin, characterized in that, The raw materials for preparing the organosilicon-modified waterborne polyurethane resin include the following components: 10-30 parts by weight of polyol polymer, 0.5-15 parts by weight of hydroxyl-terminated polydimethylsiloxane, 5-20 parts by weight of diisocyanate, 0.005-0.1 parts by weight of tin-free catalyst, 0.5-4 parts by weight of sulfonate hydrophilic chain extender, 0.5-3 parts by weight of diamine chain extender, 0.2-1 parts by weight of neutralizing agent, and 50-60 parts by weight of water.

2. The organosilicon-modified waterborne polyurethane resin according to claim 1, characterized in that, The polyol polymer includes at least one of polyester polyol, polyether polyol, and polycarbonate polyol.

3. The organosilicon-modified waterborne polyurethane resin according to claim 1, characterized in that, The hydroxyl-terminated polydimethylsiloxane is at least one of monohydroxyl-terminated polydimethylsiloxane, dihydroxyl-terminated polydimethylsiloxane, and monohydroxyl-terminated polydimethylsiloxane. The single-terminated monohydroxyl polydimethylsiloxane has the structure shown in Formula I: ； The dual-terminated dihydroxyl polydimethylsiloxane has the structure shown in Formula II: ； The single-terminated dihydroxyl polydimethylsiloxane has the structure shown in Formula III: 。 4. The organosilicon-modified waterborne polyurethane resin according to claim 1, characterized in that, The hydroxyl-terminated polydimethylsiloxane is at least one of single-terminated dihydroxyl polydimethylsiloxane and single-terminated monohydroxyl polydimethylsiloxane.

5. The organosilicon-modified waterborne polyurethane resin according to claim 1, characterized in that, The diisocyanate includes at least one of toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), 1,6-hexanediisocyanate (HDI), and dicyclohexylmethane diisocyanate (HMDI). The tin-free catalyst includes at least one of bismuth octanoate, bismuth isooctanoate, bismuth octanoate, and zinc octanoate.

6. The organosilicon-modified waterborne polyurethane resin according to claim 1, characterized in that, The sulfonate hydrophilic chain extender includes at least one of sulfonate diol, sulfonate diamine, triethylamine dihydroxypropanesulfonate, or other alcohol or amine sulfonates; The diamine chain extender includes at least one of ethylenediamine, isophorone diamine, N-(2-hydroxyethyl)ethylenediamine, 2N,N-bis(2-hydroxyethyl)ethylenediamine, and other diamine chain extenders; The neutralizing agent includes at least one of triethylamine and N,N-dimethylethanolamine.

7. The organosilicon-modified waterborne polyurethane resin according to claim 1, characterized in that, The solid content of the organosilicon-modified waterborne polyurethane resin is 40%-47.5%; And / or; the viscosity of the organosilicon-modified waterborne polyurethane resin is less than 100 cP; And / or; the molecular weight of the terminal hydroxyl polydimethylsiloxane is 500-15000.

8. A method for preparing an organosilicon-modified waterborne polyurethane resin, characterized in that, include: (1) Dehydrate 10-30 parts by weight of polyol polymer and 0.5-15 parts by weight of terminal hydroxyl polydimethylsiloxane to obtain a dehydrated mixture; (2) 5-20 parts by mass of diisocyanate and the dehydrated mixture are reacted with 0.005-0.1 parts by mass of tin-free catalyst, and then reacted with 0.5-4 parts by mass of sulfonate hydrophilic chain extender to obtain NCO-terminated prepolymer A containing organosilicon segments; (3) The NCO-terminated prepolymer A containing organosilicon segments is mixed with 0.2-1 parts by weight of neutralizing agent to carry out a neutralization reaction, then mixed with 50-60 parts by weight of water for emulsification, and then 0.5-3 parts by weight of diamine chain extender is added for chain extension to obtain the organosilicon-modified waterborne polyurethane resin.

9. The preparation method according to claim 8, characterized in that, The dehydration in step (1) is a heated dehydration at a temperature of 80-120 ℃; In step (2), the diisocyanate is reacted with the dehydrated polyol from step (1) under the catalysis of a tin-free catalyst at a temperature of 60-85 °C for 3-4 h; subsequently, it is reacted with a sulfonate hydrophilic chain extender at a temperature of 50-85 °C for 2-3 h. The chain extension reaction temperature for adding the diamine chain extender in step (3) is 20-35 °C and the time is 0.5-1 h.

10. A digital inkjet ink, characterized in that, include: The silicone-modified waterborne polyurethane resin as described in any one of claims 1-7, or the silicone-modified waterborne polyurethane resin prepared by the preparation method as described in any one of claims 8-9.

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