Net-shaped dry-wet rubbing fastness improver and preparation method thereof

Abstract

The invention belongs to the technical field of textile printing and dyeing, and particularly relates to a reticular dry-wet rubbing fastness improver and a preparation method thereof. The reticular dry-wet rubbing fastness improver provided by the invention is mainly prepared from polyether polyol, trifunctional isocyanate, bifunctional isocyanate, a catalyst, a hydrophilic chain extender, a cationic chain extender, organic silicon, a solvent, neutralizing acid and deionized water. According to the net-shaped dry-wet rubbing fastness improver prepared by the preparation method disclosed by the invention, the film forming continuity, the film forming strength and the film forming durability of a polyurethane film are enhanced through a net-shaped structure of molecules, and the crosslinking degree of a film formed on the surface of a fiber is higher than that of a film formed by a traditional straight-chain waterborne polyurethane polymer by virtue of a hydrogen bond; the fibers and the dye can be more firmly wrapped, and the dry and wet rubbing fastness is remarkably improved.

Description

Technical Field

[0001] This invention belongs to the field of textile printing and dyeing technology, specifically relating to a mesh-like dry and wet rubbing fastness improver and its preparation method. Background Technology

[0002] Reactive dyes are commonly used for dyeing cellulosic fibers due to their comprehensive color spectrum, low price, and good dye penetration. However, because reactive dyes contain both water-soluble and reactive groups, hydrolysis and bonding reactions occur simultaneously during the dyeing and printing process. This results in some reactive dyes hydrolyzing or failing to form strong covalent bonds with the fibers. This excess dye accumulates on the fiber surface after dyeing, forming loose dye. Under significant external force, especially when wet, it easily transfers to the rubbing cloth, leading to poor wet and dry rubbing fastness. Wet and dry rubbing fastness is a crucial indicator for evaluating the dyeing performance of dark-colored cellulosic fibers. Common methods to improve wet and dry rubbing fastness include removing loose dye with soap or water and using softeners to reduce the surface friction coefficient of the fibers. However, these methods have limited effectiveness in improving wet and dry rubbing fastness and also affect the color and feel. Therefore, improving the wet and dry rubbing fastness of dyed fibers remains a technical challenge for the dyeing and finishing industry.

[0003] In recent years, the rapid development of waterborne polyurethane has provided an opportunity for the synthesis of high-performance dry and wet rubbing fastness improvers. Patent document CN102432801A discloses a cationic waterborne polyurethane synthesized from polyisocyanate, polyether polyol, small molecule chain extender, and blocking agent. This polyurethane can undergo a deblocking reaction at a certain temperature during fabric finishing, releasing reactive functional groups protected by the blocking agent. These groups react with active hydrogen on the fabric, solidifying to form a polymeric network structure that coats dye molecules and colored fiber particles, preventing their detachment and significantly improving dry and wet rubbing fastness.

[0004] Patent document CN104862980A discloses a wet rubbing fastness improver made of copper microcapsules using a micro-suspension polymerization method. This wet rubbing fastness improver utilizes the property of copper powder and other nanomaterials to form a smooth protective layer on the surface of the friction solid under frictional conditions, reducing the coefficient of friction on the surface of dyed fabrics and improving the dry and wet rubbing properties of the dyed fabrics. Patent document CN108301235A discloses a cationic waterborne polyurethane, which improves the dry and wet rubbing properties of dyed fabrics by using a cationic emulsifier and introducing cationic monomer copolymerization to achieve ionic bonding of anionic groups between latex particles, fibers, and dyes.

[0005] However, most waterborne polyurethane dry and wet rubbing fastness improvers currently on the market exist in a linear form, mainly relying on hydrogen bonding between urethane groups on adjacent molecules to crosslink and form a thin film on the fiber surface. The protective film formed by the crosslinking of linear polyurethane lacks film-forming continuity, film strength, and film durability, and exhibits significant performance degradation after multiple washes. Furthermore, fabrics treated with most traditional linear waterborne polyurethanes tend to feel stiff to the touch.

[0006] Therefore, developing a dry and wet friction fastness improver with good film-forming properties and high bonding strength with fibers remains a problem to be solved in the industry. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention provides a network-like dry and wet rubbing fastness improver and its preparation method. This invention provides a cationic aqueous polyurethane with a network molecular structure. Through its positively charged properties, it can enhance the physical adsorption between dyes and fibers. Simultaneously, the network structure of the molecules itself can effectively enhance the film-forming continuity, film-forming strength, and film-forming durability of the polyurethane film, further binding fibers and dyes more firmly together and significantly improving dry and wet rubbing fastness.

[0008] To achieve the above objectives, the technical solution of the present invention is as follows: This invention provides a mesh-like dry and wet rubbing fastness improver, wherein the content of each component is based on the mass percentage of all comonomers, and includes the following components and their contents: The composition includes: 60-68% polyether polyol, 12-18% trifunctional isocyanate, 12-18% difunctional isocyanate, 0.05-0.2% catalyst, 1.8-2.8% hydrophilic chain extender, 2-3.3% cationic chain extender, 6-10% organosilicon, 50-65% solvent, 4.5-8% neutralizing acid, and 100-300% deionized water.

[0009] The total mass of all comonomers in the system before water addition and acid emulsification is 100%. All polymers refer to high molecular weight polyurethane polymers linked by polyether polyols, isocyanates, hydrophilic chain extenders, cationic chain extenders, and organosilicones through urethane groups.

[0010] Furthermore, the molecular weight of the polyether polyol is 600-1500. A mixture of polyether polyols within this molecular weight range can better meet the softness requirements of the polyurethane film after formation.

[0011] Furthermore, the polyether polyol is composed of polypropylene glycol (PPG) and polyethylene glycol (PEG) mixed in a molar ratio of 1:(0.8~1.2). Preferably, the optimal molar ratio of PPG to PEG is 1:1. PPG helps improve the dry and wet rubbing effect of dyed fabrics, but it is highly hydrophobic. An excessively high proportion of PPG increases the risk of subsequent gelation with hexamethylene diisocyanate trimer. When the molar ratio of PPG to PEG is 1:1, the rheological properties of the system can be guaranteed while ensuring superior performance.

[0012] Furthermore, the trifunctional isocyanate is a hexamethylene diisocyanate trimer (HDI trimer) or an isophorone diisocyanate homopolymer (IPDI trimer).

[0013] Furthermore, the difunctional isocyanate is one or a combination of two or more of toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), and diphenylmethane diisocyanate (MDI).

[0014] Further, the molar ratio of the trifunctional isocyanate to the difunctional isocyanate is 1:(2~4). Preferably, the optimal molar ratio of the trifunctional isocyanate to the difunctional isocyanate is 1:3.

[0015] Furthermore, the catalyst is one of bismuth neodecanoate, bismuth isooctanoate, and bismuth naphthenate. The catalyst is an organobismuth catalyst, which is more environmentally friendly than traditional organotin catalysts.

[0016] Furthermore, the hydrophilic chain extender is one or a combination of dimethylolpropionic acid (DMPA) and dimethylolbutyric acid (DMBA); the cationic chain extender is one or a combination of N-methyldiethanolamine (MDEA) and diethylenetriamine (DETA). This hydrophilic chain extender can improve the water solubility of polyurethane by introducing a carboxyl group.

[0017] Furthermore, the organosilicon is an aminosilane coupling agent (KH-550). The solvent is one or a combination of ethylene glycol diacetate (EGDA) and acetone (AC); the addition of the solvent to the system prevents gelation due to excessive viscosity during the reaction. The neutralizing acid is one or a combination of acetic acid and citric acid; the neutralizing acid is mainly used to neutralize the cationic chain extender, protonating the tertiary amines on the chain segments and making them positively charged.

[0018] In addition, the present invention also provides a method for preparing a mesh-like dry and wet rubbing fastness improving agent, comprising the following steps: Step S1: Dehydrate the polyether polyol at a temperature of 110~120 ℃ and a vacuum of -0.1 MPa for 1~1.5 h. After dehydration, cool it to 50~70 ℃ to obtain dehydrated polyether polyol. Step S2: Add 10-20% v / v solvent to the dehydrated polyether polyol obtained in step S1, and stir at 180-220 r / min for 4-6 min. Then add trifunctional isocyanate and catalyst, raise the temperature, and react at 80-85 ℃ and 180-220 r / min for 1-1.5 h. After the reaction is completed, lower the reaction temperature to 65-70 ℃, then add difunctional isocyanate, raise the temperature, and react at 75-80 ℃ and 180-220 r / min for 1-1.5 h. After the reactions in steps S3 and S2 are completed, add 10-20% v / v of solvent to the reaction system, then add a hydrophilic chain extender, and react for 2-3 h at a temperature of 75-80 ℃ and a rotation speed of 180-220 r / min. After the reaction is completed, lower the temperature to 55-60 ℃, add a cationic chain extender and 30-40% v / v of solvent, and react for 30-60 min at a temperature of 58-62 ℃ and a rotation speed of 80-120 r / min under medium-low stirring. After the reactions in steps S4 and S3 are completed, add organosilicon and 30-40% v / v solvent to the reaction system and react at 58-62 °C for 30-60 min. Then add neutralizing acid and deionized water and emulsify at 220-280 r / min for 2-4 h to obtain the final product.

[0019] Specifically, the preparation method of the mesh-like dry and wet friction fastness improving agent of the present invention includes the following steps: Step S1: Dehydrate the polyether polyol at 110~120 ℃ and a vacuum of -0.1 MPa for 1~1.5 h. After dehydration, cool down to below 70 ℃ to obtain dehydrated polyether polyol. Step S2: Add 10-20% v / v solvent to the dehydrated polyether polyol obtained in Step S1 to prevent excessively high viscosity in the subsequent nonionic stage reaction. Stir at 180-220 r / min for 4-6 min. Then add trifunctional isocyanate and catalyst. The reaction will rapidly exothermize. Finally, set the temperature to maintain the system temperature at 80-85 °C and react at 180-220 r / min for 1-1.5 h. Use infrared spectroscopy to determine if the remaining NCO groups have reached the specified value. If they have, proceed to the next step; otherwise, continue the reaction. The overall R value (n(-NCO):n(-OH)) is 1.03-1.15. After the reaction, lower the reaction temperature to 70 °C and add difunctional isocyanate. The temperature will rise again. Adjust the temperature to stabilize at 75-80 °C and react at 180-220 r / min for 1-1.5 h. h; Determine whether the remaining NCO groups have reached the specified value by di-n-butylamine titration. If they have, proceed to the next step; otherwise, continue the reaction. After the nonionic stage reactions in steps S3 and S2 are completed, maintain the temperature at 75-80 °C, add 10-20% v / v solvent and hydrophilic chain extender, and react for 2-3 h at a rotation speed of 180-220 r / min. Determine whether the remaining NCO groups have reached the specified value by di-n-butylamine titration. If they have, proceed to the next step; otherwise, continue the reaction. After the reaction is complete, lower the temperature to about 60 °C, add cationic chain extender and 30-40% v / v solvent. The stirring process will also rapidly release heat. Maintain the reaction temperature at 58-62 °C and react for 30-60 min at a rotation speed of 80-120 r / min. The viscosity of this reaction system will increase rapidly. After the viscosity of the system stabilizes and the infrared spectrum shows no significant change, proceed to the next step. After the reactions in steps S4 and S3 are completed, maintain the temperature at 58~62 ℃, add organosilicon and 30~40% v / v solvent, and react for 30~60 min. The NCO groups can be determined by infrared spectroscopy to see if they have been completely consumed. Once the NCO groups are confirmed to be completely consumed, add neutralizing acid and deionized water, and emulsify for 2~4 h at a speed of 220~280 r / min to obtain the final product.

[0020] The method for preparing the dry and wet rubbing fastness improver provided by this invention involves first polymerizing a trifunctional isocyanate with excess polyether in the presence of a catalyst to obtain a trifunctional polymer with terminal hydroxyl groups. Simultaneously, due to the large number of ether bonds within the polymer, it exhibits good hydrophilicity. Specifically, the trifunctional polymer with terminal hydroxyl groups is obtained by polymerizing HDI trimer with excess polyether, and the resulting molecular structure is as follows: R1 is the PPG 1000 or PEG1000 polyether segment after reaction with the NCO group.

[0021] Next, the difunctional isocyanate is added to the system and undergoes a crosslinking reaction with the trifunctional polymer terminated with hydroxyl groups and the remaining polyether in the system to form a network macromolecular polymer with HDI trimer or IPDI trimer as branch points. Because the difunctional isocyanate is in excess, the intermediate at this point has NCO groups at the end. Specifically, the crosslinking reaction of toluene diisocyanate (TDI) difunctional isocyanate with the trifunctional polymer terminated with hydroxyl groups and the remaining polyether in the system results in the following network polymer unit structure: R2 is -NH-CO-R1-CO-NH-, which is a polyether segment containing two urethane bonds. The TDI used contains 80% 2,4-substituted isocyanate and 20% 2,6-substituted isocyanate.

[0022] After the reaction was complete, a hydrophilic chain extender and a cationic chain extender were added sequentially to carry out the chain extension reaction. Finally, the aminosilane coupling agent KH-550 was grafted and modified. The structural formula of the aminosilane coupling agent is as follows: This invention introduces organosilicon into the polymer chain ends or side chains, which on the one hand improves the crosslinking of the polymer to achieve good film-forming properties, and on the other hand reduces the surface energy of the fiber fabric, lowers the coefficient of friction, makes the hand feel smoother, and improves dry and wet rubbing fastness. After the reaction is complete, neutralizing acid and deionized water are added, and the mixture is emulsified under high-speed stirring. The dry and wet rubbing fastness improver prepared by this invention has a network structure, which can form a more wear-resistant and continuous film on the fiber surface, and can more effectively encapsulate dyes, thereby improving dry and wet rubbing fastness.

[0023] Compared with the prior art, the mesh-like dry and wet friction fastness improving agent provided by the present invention has the following advantages: (1) The mesh-like dry and wet rubbing fastness improver provided by the present invention has a mesh structure. The film formed on the fiber surface has a higher degree of cross-linking than the film formed by hydrogen bonding of traditional linear waterborne polyurethane polymers, and has better wear resistance and continuity. It can more effectively encapsulate dyes and improve dry and wet rubbing fastness.

[0024] (2) The mesh dry and wet rubbing fastness improver provided by the present invention is a cationic improver after acid neutralization. It can be firmly combined with anionic reactive dyes and cellulose fibers that are usually negatively charged in water, so that the polyurethane film has strong ionic electrostatic adsorption between the dye and the fiber, which helps to fix the dye on the fiber surface.

[0025] (3) The alkoxy groups on the terminal silicon atoms of the mesh-like wet and dry rubbing fastness improver provided by the present invention will hydrolyze in an aqueous environment to generate silanols. During subsequent fabric surface treatment, the silanols can dehydrate with the hydroxyl groups on the cellulose macromolecules to form silicon-oxygen-carbon covalent bonds (-Si-OC-), and can also condense with adjacent silanols to improve the crosslinking of the polymer. At the same time, the introduction of organosilicon can also reduce the surface energy of the finished fiber fabric, thereby reducing the coefficient of friction and making the hand feel smoother.

[0026] (4) Compared with traditional dry and wet rubbing fastness improvers, the mesh dry and wet rubbing fastness improver provided by the present invention uses a single PEG synthesis. The mixed use of PPG and PEG can appropriately adjust the hydrophilicity of the film and improve the fastness and color fastness to perspiration in wet conditions. Detailed Implementation

[0027] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0028] Example 1: A mesh-like dry and wet friction fastness improving agent The mesh-like dry and wet friction fastness improver consists of the following components and their contents: The composition includes 49 g of polyether polyol, 10.24 g of hexamethylene diisocyanate trimer (HDI trimer), 14.13 g of toluene diisocyanate (TDI), 0.09 g of bismuth neodecanoate, 2.05 g of dimethylolpropionic acid (DMPA), 2.52 g of N-methyldiethanolamine (MDEA), 3 g of aminosilane coupling agent (KH-550), 46 g of ethylene glycol diacetate (EGDA), 6 g of acetic acid, and 150 g of deionized water; the polyether polyol is composed of polypropylene glycol 1000 (PPG1000) and polyethylene glycol 1000 (PEG1000) mixed in a molar ratio of 1:1.

[0029] Preparation method: Step S1: Mix PEG 1000 and PPG 1000 at a molar ratio of 1:1 to obtain a polyether polyol mixture. Add 49 g of the polyether polyol mixture to a four-necked flask equipped with a thermometer and a stirrer. Connect one neck to a vacuum oil pump and control the temperature throughout the process using an oil bath. Heat the mixture to 110~120 ℃ and dehydrate the system under a vacuum of -0.1 MPa for 1 h. After dehydration, cool the mixture to 70 ℃ to obtain dehydrated polyether polyol. Step S2: Add 8 g of ethylene glycol diacetate solvent to the dehydrated polyether polyol obtained in step S1, and stir for 5 min at 200 r / min. Then add 10.24 g of HDI trimer and 0.09 g of bismuth neodecanoate. The system begins to heat up exothermically. Adjust the temperature to stabilize the system at 80-85 °C, and react for 1.5 h at 200 r / min. Use infrared spectroscopy to determine that the NCO groups are basically consumed. Lower the temperature to 70 °C, add 14.13 g of toluene diisocyanate, and adjust the temperature to stabilize at 75-80 °C. React for 1.5 h at 200 r / min. Use di-n-butylamine titration to determine that the remaining NCO is 4.51%, and the reaction ends. After steps S3 and S2 are completed, 8 g of ethylene glycol diacetate solvent and 2.05 g of dimethylolpropionic acid are added to the reaction system. The temperature is maintained at 75-80 °C, and the reaction is carried out for 2.5 h at a rotation speed of 200 r / min. The remaining NCO is determined to be 2.54% by di-n-butylamine titration. After the reaction is completed, the reaction system is cooled to 60 °C, 15 g of ethylene glycol diacetate solvent and 2.52 g of N-methyldiethanolamine are added, and the reaction is carried out for 40 min at a rotation speed of 100 r / min. The viscosity of the system is basically stable and there is no significant change in the infrared spectrum. The reaction is then complete. After the reactions in steps S4 and S3 are completed, the reaction system is cooled to 60 °C. 15 g of ethylene glycol diacetate solvent and 3 g of aminosilane coupling agent KH-550 are added to the reaction system. The reaction is allowed to proceed for 40 min until infrared spectroscopy shows that the NCO groups have basically reacted completely. Then, 6 g of acetic acid and 150 g of deionized water are added for neutralization. The mixture is then emulsified for 2.5 h at a rotation speed of 250 r / min. The product is then discharged.

[0030] Example 2: A mesh-like dry and wet friction fastness improving agent The mesh-like dry and wet friction fastness improver consists of the following components and their contents: The composition includes 49 g of polyether polyol, 8.89 g of hexamethylene diisocyanate trimer (HDI trimer), 9.2 g of toluene diisocyanate (TDI), 0.09 g of bismuth neodecanoate, 2.05 g of dimethylolpropionic acid (DMPA), 2.52 g of N-methyldiethanolamine (MDEA), 3.9 g of aminosilane coupling agent (KH-550), 46 g of ethylene glycol diacetate (EGDA), 6 g of acetic acid, and 150 g of deionized water; the polyether polyol is composed of polypropylene glycol 1000 (PPG1000) and polyethylene glycol 1000 (PEG1000) mixed in a molar ratio of 1:1.

[0031] Preparation method: Step S1: Mix PEG 1000 and PPG 1000 at a molar ratio of 1:1 to obtain a polyether polyol mixture. Add 49 g of the polyether polyol mixture to a four-necked flask equipped with a thermometer and a stirrer. Connect one neck to a vacuum oil pump and control the temperature throughout the process using an oil bath. Heat the mixture to 110~120 ℃ and dehydrate the system under a vacuum of -0.1 MPa for 1 h. After dehydration, cool the mixture to 70 ℃ to obtain dehydrated polyether polyol. Step S2: Add 8 g of ethylene glycol diacetate solvent to the dehydrated polyether polyol obtained in step S1, and stir for 5 min at 200 r / min. Then add 8.89 g of HDI trimer and 0.09 g of bismuth neodecanoate. The system begins to heat up exothermically. Adjust the temperature to stabilize the system at 80-85 °C, and react for 1.5 h at 200 r / min. Use infrared spectroscopy to determine that the NCO groups are basically consumed. Lower the temperature to 70 °C, add 9.2 g of toluene diisocyanate, and adjust the temperature to stabilize at 75-80 °C. React for 1.5 h at 200 r / min. Use di-n-butylamine titration to determine that the remaining NCO is 4.97%, and the reaction ends. After steps S3 and S2 are completed, 8 g of ethylene glycol diacetate solvent and 2.05 g of dimethylolpropionic acid are added to the reaction system. The temperature is maintained at 75-80 °C, and the reaction is carried out for 2.5 h at a rotation speed of 200 r / min. The remaining NCO is determined to be 2.92% by di-n-butylamine titration. After the reaction is completed, the reaction system is cooled to 60 °C, 15 g of ethylene glycol diacetate solvent and 2.52 g of N-methyldiethanolamine are added, and the reaction is carried out for 40 min at a rotation speed of 100 r / min. The viscosity of the system is basically stable and there is no significant change in the infrared spectrum. The reaction is then complete. After the reactions in steps S4 and S3 are completed, the reaction system is cooled to 60 °C. 15 g of ethylene glycol diacetate solvent and 3.9 g of aminosilane coupling agent KH-550 are added to the reaction system. The reaction is allowed to proceed for 40 min until infrared spectroscopy shows that the NCO groups have basically reacted completely. Then, 6 g of acetic acid and 150 g of deionized water are added for neutralization. The mixture is then emulsified for 2.5 h at a rotation speed of 250 r / min. The product is then discharged.

[0032] Example 3: A mesh-like dry and wet friction fastness improving agent The mesh-like dry and wet friction fastness improver consists of the following components and their contents: The composition includes 49 g of polyether polyol, 11.46 g of hexamethylene diisocyanate trimer (HDI trimer), 11.2 g of toluene diisocyanate (TDI), 0.09 g of bismuth isooctanoate, 2.05 g of dimethylolpropionic acid (DMPA), 2.52 g of N-methyldiethanolamine (MDEA), 4.2 g of aminosilane coupling agent (KH-550), 46 g of ethylene glycol diacetate (EGDA), 6 g of acetic acid, and 150 g of deionized water; the polyether polyol is composed of polypropylene glycol 1000 (PPG1000) and polyethylene glycol 1000 (PEG1000) mixed in a molar ratio of 1:1.

[0033] Preparation method: Step S1: Mix PEG 1000 and PPG 1000 at a molar ratio of 1:1 to obtain a polyether polyol mixture. Add 49 g of the polyether polyol mixture to a four-necked flask equipped with a thermometer and a stirrer. Connect one neck to a vacuum oil pump and control the temperature throughout the process using an oil bath. Heat the mixture to 110~120 ℃ and dehydrate the system under a vacuum of -0.1 MPa for 1 h. After dehydration, cool the mixture to 70 ℃ to obtain dehydrated polyether polyol. Step S2: Add 8 g of ethylene glycol diacetate solvent to the dehydrated polyether polyol obtained in step S1, and stir for 5 min at 200 r / min. Then add 11.46 g of HDI trimer and 0.09 g of bismuth isooctanoate. The system begins to heat up exothermically. Adjust the temperature to stabilize the system at 80-85 °C and react for 1.5 h at 200 r / min. Use infrared spectroscopy to determine that the NCO groups are basically consumed. Lower the temperature to 70 °C, add 11.2 g of toluene diisocyanate, and adjust the temperature to stabilize at 75-80 °C. React for 1.5 h at 200 r / min. Use di-n-butylamine titration to determine that the remaining NCO is 4.78%, and the reaction ends. After steps S3 and S2 are completed, 8 g of ethylene glycol diacetate solvent and 2.05 g of dimethylolpropionic acid are added to the reaction system. The temperature is maintained at 75-80 °C, and the reaction is carried out for 2.5 h at a rotation speed of 200 r / min. The remaining NCO is determined to be 2.85% by di-n-butylamine titration. After the reaction is completed, the reaction system is cooled to 60 °C, 15 g of ethylene glycol diacetate solvent and 2.52 g of N-methyldiethanolamine are added, and the reaction is carried out for 40 min at a rotation speed of 100 r / min. The viscosity of the system is basically stable and there is no significant change in the infrared spectrum. The reaction is then complete. After the reactions in steps S4 and S3 are completed, the reaction system is cooled to 60 °C. 15 g of ethylene glycol diacetate solvent and 4.2 g of aminosilane coupling agent KH-550 are added to the reaction system. The reaction is allowed to proceed for 40 min until infrared spectroscopy shows that the NCO groups have basically reacted completely. Then, 6 g of acetic acid and 150 g of deionized water are added for neutralization. The mixture is then emulsified for 2.5 h at a speed of 250 r / min. The product is then discharged.

[0034] Example 4: A mesh-like dry and wet friction fastness improving agent The mesh-like dry and wet friction fastness improver consists of the following components and their contents: The composition includes 49 g of polyether polyol, 12.11 g of hexamethylene diisocyanate trimer (HDI trimer), 16 g of toluene diisocyanate (TDI), 0.12 g of bismuth naphthenate, 2.05 g of dimethylolpropionic acid (DMPA), 2.52 g of N-methyldiethanolamine (MDEA), 4.5 g of aminosilane coupling agent (KH-550), 46 g of ethylene glycol diacetate (EGDA), 6 g of acetic acid, and 150 g of deionized water; the polyether polyol is composed of polypropylene glycol 1000 (PPG1000) and polyethylene glycol 1000 (PEG1000) mixed in a molar ratio of 1:1.

[0035] Preparation method: Step S1: Mix PEG 1000 and PPG 1000 at a molar ratio of 1:1 to obtain a polyether polyol mixture. Add 49 g of the polyether polyol mixture to a four-necked flask equipped with a thermometer and a stirrer. Connect one neck to a vacuum oil pump and control the temperature throughout the process using an oil bath. Heat the mixture to 110~120 ℃ and dehydrate the system under a vacuum of -0.1 MPa for 1 h. After dehydration, cool the mixture to 70 ℃ to obtain dehydrated polyether polyol. Step S2: Add 8 g of ethylene glycol diacetate solvent to the dehydrated polyether polyol obtained in step S1, and stir for 5 min at 200 r / min. Then add 12.11 g of HDI trimer and 0.12 g of bismuth naphthenate. The system begins to heat up exothermically. Adjust the temperature to stabilize the system at 80-85 °C and react for 1.5 h at 200 r / min. Use infrared spectroscopy to determine that the NCO groups are basically consumed. Lower the temperature to 70 °C, add 16 g of toluene diisocyanate, and adjust the temperature to stabilize at 75-80 °C. React for 1.5 h at 200 r / min. Use di-n-butylamine titration to determine that the remaining NCO is 4%, and the reaction ends. After steps S3 and S2 are completed, 8 g of ethylene glycol diacetate solvent and 2.05 g of dimethylolpropionic acid are added to the reaction system. The temperature is maintained at 75-80 °C, and the reaction is carried out for 2.5 h at a rotation speed of 200 r / min. The remaining NCO is determined to be 2.54% by di-n-butylamine titration. After the reaction is completed, the reaction system is cooled to 60 °C, 15 g of ethylene glycol diacetate solvent and 2.52 g of N-methyldiethanolamine are added, and the reaction is carried out for 40 min at a rotation speed of 100 r / min. The viscosity of the system is basically stable and there is no significant change in the infrared spectrum. The reaction is then complete. After the reactions in steps S4 and S3 are completed, the reaction system is cooled to 60 °C. 15 g of ethylene glycol diacetate solvent and 4.5 g of aminosilane coupling agent KH-550 are added to the reaction system. The reaction is allowed to proceed for 40 min until infrared spectroscopy shows that the NCO groups have basically reacted completely. Then, 6 g of acetic acid and 150 g of deionized water are added for neutralization. The mixture is then emulsified for 2.5 h at a speed of 250 r / min. The product is then discharged.

[0036] Example 5: A mesh-like dry and wet friction fastness improving agent The mesh-like dry and wet friction fastness improver consists of the following components and their contents: The composition includes 49 g of polyether polyol, 12.07 g of hexamethylene diisocyanate trimer (HDI trimer), 12.5 g of toluene diisocyanate (TDI), 0.09 g of bismuth naphthenate, 1.85 g of dimethylolbutyric acid (DMBA), 2.42 g of diethylenetriamine (DETA), 4.6 g of aminosilane coupling agent (KH-550), 46 g of ethylene glycol diacetate (EGDA), 6 g of acetic acid, and 150 g of deionized water; the polyether polyol is composed of polypropylene glycol 1000 (PPG1000) and polyethylene glycol 1000 (PEG1000) mixed in a molar ratio of 1:1.

[0037] Preparation method: Step S1: Mix PEG 1000 and PPG 1000 at a molar ratio of 1:1 to obtain a polyether polyol mixture. Add 49 g of the polyether polyol mixture to a four-necked flask equipped with a thermometer and a stirrer. Connect one neck to a vacuum oil pump and control the temperature throughout the process using an oil bath. Heat the mixture to 110~120 ℃ and dehydrate the system under a vacuum of -0.1 MPa for 1 h. After dehydration, cool the mixture to 70 ℃ to obtain dehydrated polyether polyol. Step S2: Add 8 g of ethylene glycol diacetate solvent to the dehydrated polyether polyol obtained in step S1, and stir for 5 min at 200 r / min. Then add 12.07 g of HDI trimer and 0.09 g of bismuth naphthenate. The system begins to heat up exothermically. Adjust the temperature to stabilize the system at 80-85 °C and react for 1.5 h at 200 r / min. Use infrared spectroscopy to determine that the NCO groups are basically consumed. Lower the temperature to 70 °C, add 12.5 g of toluene diisocyanate, and adjust the temperature to stabilize at 75-80 °C. React for 1.5 h at 200 r / min. Use di-n-butylamine titration to determine that the remaining NCO is 4.13%, and the reaction ends. After steps S3 and S2 are completed, 8 g of ethylene glycol diacetate solvent and 1.85 g of dimethylolbutyric acid are added to the reaction system. The temperature is maintained at 75-80 °C, and the reaction is carried out at 200 r / min for 2.5 h. The remaining NCO is determined to be 2.74% by di-n-butylamine titration. After the reaction is completed, the reaction system is cooled to 60 °C, and 15 g of ethylene glycol diacetate solvent and 2.42 g of diethylenetriamine are added. The reaction is carried out at 100 r / min for 40 min. The viscosity of the system is basically stable and the infrared spectrum shows no significant change. The reaction is then complete. After the reactions in steps S4 and S3 are completed, the reaction system is cooled to 60 °C. 15 g of ethylene glycol diacetate solvent and 4.6 g of aminosilane coupling agent KH-550 are added to the reaction system. The reaction is allowed to proceed for 40 min until infrared spectroscopy shows that the NCO groups have basically reacted completely. Then, 6 g of acetic acid and 150 g of deionized water are added for neutralization. The mixture is then emulsified for 2.5 h at a rotation speed of 250 r / min. The product is then discharged.

[0038] Test Example 1: Friction Fastness Test of Mesh Dry and Wet Friction Fastness Improver 1. Test method: The rubbing fastness of the mesh-like dry and wet rubbing fastness improvers prepared in Examples 1, 2, 3, 4, and 5 was tested. The mesh-like dry and wet rubbing fastness improver was used at a dosage of 30 g / L, and the process involved two dips and two rubs (pressure 2 kg / cm²). 2→ Drying at 100℃ → Setting (150℃ for 2 min) → Testing dry / wet rubbing fastness, hand feel, and dry / wet rubbing fastness after 3 washes (standard detergent 1 g / L, liquor ratio 1:30, 40℃ for 12 min, 3 washes in total). Color fastness to rubbing was determined according to GB / T3920-2008 "Textiles - Tests for Color Fastness: Color Fastness to Rubbing", and the grade was determined using the GB / T251-280 Grey Scale for Staining. Test fabrics: pure cotton woven fabric (bright red, black), polyester-cotton knitted fabric (bright red, black).

[0039] 2. Test Results: 2.1 The wet and dry rubbing fastness of pure cotton woven fabric before and after washing is shown in Table 1 and Table 2 below.

[0040] 2.2 The dry and wet rubbing fastness of polyester-cotton knitted fabrics before and after washing is shown in Tables 3 and 4 below.

[0041] Table 1. Test results of rubbing fastness of various examples of pure cotton woven fabric (bright red).

[0042] Table 2. Test results of rubbing fastness of various examples of pure cotton woven fabric (black).

[0043] Table 3. Rubbing fastness test results of various examples of polyester-cotton knitted fabric (bright red).

[0044] Table 4. Rubbing fastness test results of various examples of polyester-cotton knitted fabric (black).

[0045] As shown in Tables 1 to 4, the mesh-like dry and wet rubbing fastness improvers prepared in Examples 1 and 4 exhibit significant dry and wet rubbing fastness improvement effects on both pure cotton woven fabrics and polyester-cotton knitted fabrics. Although the mesh-like dry and wet rubbing fastness improvers prepared in Examples 2, 3, and 5 have slightly worse performance, the performance fluctuations after washing are relatively small, proving that the fiber surface film has good wash resistance.

[0046] In addition, the inventors also conducted a softness test on the fabric treated with the mesh dry and wet rubbing fastness improver prepared in Examples 1 to 5. The results showed that the fabric treated with the mesh dry and wet rubbing fastness improver prepared in Examples 1 to 5 of this invention felt softer and smoother than the fabric before treatment, which improved the problem of fabric hardening that occurred after the fabric was treated with traditional dry and wet film rubbing fastness improvers.

[0047] Test Example 2: Color fastness to perspiration of a mesh-like dry and wet rubbing fastness improver 1. Test method: The color fastness to perspiration of the mesh-like dry and wet rubbing fastness improvers prepared in Examples 1 and 4 was tested. The amount of the mesh-like dry and wet rubbing fastness improver was 30 g / L, and the test was conducted according to GB / T3922-2013 "Textiles - Tests for color fastness - Color fastness to perspiration".

[0048] 2. Test Results: The experimental results are shown in Table 5.

[0049] Table 5 Results of color fastness to perspiration of the mesh-based dry and wet rubbing fastness improver

[0050] As shown in Table 5, the mesh-like dry and wet rubbing fastness improver provided by the present invention also has good color fastness to perspiration.

[0051] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A mesh-like dry and wet rubbing fastness improving agent, characterized in that, The content of each component is expressed as a percentage of the total mass of all comonomers, including the following components and their contents: The composition includes: 60-68% polyether polyol, 12-18% trifunctional isocyanate, 12-18% difunctional isocyanate, 0.05-0.2% catalyst, 1.8-2.8% hydrophilic chain extender, 2-3.3% cationic chain extender, 6-10% organosilicon, 50-65% solvent, 4.5-8% neutralizing acid, and 100-300% deionized water.

2. The mesh-like dry and wet rubbing fastness improver as described in claim 1, characterized in that, The molecular weight of the polyether polyol is 600~1500.

3. The mesh-like dry and wet rubbing fastness improver as described in claim 2, characterized in that, The polyether polyol is composed of polypropylene glycol and polyethylene glycol mixed in a molar ratio of 1:(0.8~1.2).

4. The mesh-like dry and wet rubbing fastness improver as described in claim 1, characterized in that, The trifunctional isocyanate is a hexamethylene diisocyanate trimer or an isophorone diisocyanate homopolymer.

5. The mesh-like dry and wet rubbing fastness improver as described in claim 1, characterized in that, The difunctional isocyanate is one or a combination of two or more of toluene diisocyanate, isophorone diisocyanate, and diphenylmethane diisocyanate.

6. The mesh-like dry and wet rubbing fastness improver as described in claim 1, characterized in that, The molar ratio of the trifunctional isocyanate to the difunctional isocyanate is 1:(2~4).

7. The mesh-like dry and wet rubbing fastness improver as described in claim 1, characterized in that, The catalyst is one of bismuth neodecanoate, bismuth isooctanoate, and bismuth naphthenate.

8. The mesh-like dry and wet rubbing fastness improving agent as described in claim 1, characterized in that, The hydrophilic chain extender is one or a combination of dimethylolpropionic acid and dimethylolbutyric acid; the cationic chain extender is one or a combination of N-methyldiethanolamine and diethylenetriamine.

9. The mesh-like dry and wet rubbing fastness improving agent as described in claim 1, characterized in that, The organosilicon is an aminosilane coupling agent; the solvent is one or a combination of ethylene glycol diacetate and acetone; the neutralizing acid is one or a combination of acetic acid and citric acid.

10. The method for preparing the mesh-like dry and wet rubbing fastness improving agent according to any one of claims 1 to 9, characterized in that, Includes the following steps: Step S1: Dehydrate the polyether polyol at a temperature of 110~120 ℃ and a vacuum of -0.1 MPa for 1~1.5 h. After dehydration, cool it to 50~70 ℃ to obtain dehydrated polyether polyol. Step S2: Add 10-20% v / v solvent to the dehydrated polyether polyol obtained in step S1, and stir at 180-220 r / min for 4-6 min. Then add trifunctional isocyanate and catalyst, raise the temperature, and react at 80-85℃ and 180-220 r / min for 1-1.5 h. After the reaction is completed, lower the reaction temperature to 65-70℃, then add difunctional isocyanate, raise the temperature, and react at 75-80℃ and 180-220 r / min for 1-1.5 h. After the reactions in steps S3 and S2 are completed, add 10-20% v / v of solvent to the reaction system, then add a hydrophilic chain extender, and react for 2-3 h at a temperature of 75-80 ℃ and a rotation speed of 180-220 r / min. After the reaction is completed, lower the temperature to 55-60 ℃, add a cationic chain extender and 30-40% v / v of solvent, and react for 30-60 min at a temperature of 58-62 ℃ and a rotation speed of 80-120 r / min under medium-low stirring. After the reactions in steps S4 and S3 are completed, add organosilicon and 30-40% v / v solvent to the reaction system and react at 58-62 °C for 30-60 min. Then add neutralizing acid and deionized water and emulsify at 220-280 r / min for 2-4 h to obtain the final product.

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