A water-based self-lubricating wet friction fastness enhancer and preparation method thereof

Abstract

The invention discloses a wet friction fastness improver with excellent hydrophilicity and good self-lubricating performance. The wet friction fastness improver is composed of a self-made hydrophilic prepolymer and a self-lubricating functional monomer combined by a multi-arm bridging agent. Experimental results show that the water-based self-lubricating wet friction fastness improver has good hydrophilicity and can be effectively adsorbed to the surface of a fabric; at the same time, the wet friction fastness improver has good self-lubricating performance and can effectively reduce friction and improve the wet friction grade in a wet state.

Description

Technical Field

[0001] The invention relates to the technical field of textiles, and in particular to a water-based self-lubricating wet friction fastness improving agent and a preparation method thereof. Background Art

[0002] Cotton fabrics are popular among consumers because they are non-irritating to the skin, harmless to the human body, and have the advantages of good moisture absorption, breathability, and environmental protection. Reactive dyes are the preferred dyes for cotton fabrics because of their complete color spectrum, good dyeing penetration, low dyeing cost, bright colors, and easy use. The complementary combination of the two has brought more choices and convenience to the market and consumers, but the only drawback is that the wet friction fastness of cotton fabrics dyed with reactive dyes is often unsatisfactory, generally only level 1-2. Domestic customers generally require the wet friction fastness of dyed fabrics to reach level 2-3, while foreign customers often require wet friction fastness to reach level 3 or even higher. Effectively improving the wet friction fastness grade of cotton fabrics is an important issue in the auxiliary industry.

[0003] At present, there are several methods to improve the wet friction fastness of cotton fabrics: first, starting from the dye and process, the dye with high solubility, high fixation rate and moderate directness is selected; the process is to improve the quality of singeing and mercerization; but it is difficult to improve the wet friction fastness of fabrics from the dye performance and dyeing process. Secondly, starting from the pre-treatment, the cotton fabric is fully soaped to remove the floating color on the cotton fiber as much as possible. However, too many soaping times will destroy the dyed dye, cause bond breaking, and lead to a decrease in dyeing effect. In addition, it is not practical to clean the dyed fabric thoroughly in large-scale production. The most suitable and effective method is to properly finish the cotton fabric, that is, mainly by using a wet friction fastness enhancer to improve the wet friction fastness of the fabric. Therefore, the research and development of a wet friction fastness enhancer with excellent performance is of great significance to the dye auxiliary industry and even the entire textile industry. Summary of the invention

[0004] The purpose of the present invention is to provide a wet friction fastness improver with excellent working fluid stability, not easy to produce fixed color spots, good self-lubricating performance, and effectively improve the wet friction fastness grade, in view of the fact that the current wet friction fastness improver has a poor wet friction effect on dark cotton fabrics and is prone to precipitation in the working liquid state, resulting in the risk of fixed color spots. The present invention also provides a method for preparing a water-based self-lubricating wet friction fastness improver.

[0005] The technical solution of the present invention to solve the technical problem is: a water-based self-lubricating wet friction fastness improver, which is obtained by free radical reaction of a homemade hydrophilic prepolymer with unsaturated functional groups and a self-lubricating functional monomer with unsaturated functional groups to obtain a wet friction fastness improver with good hydrophilicity and self-lubricating properties, and the components include the following raw materials in parts by weight:

[0006]

[0007] The self-made hydrophilic prepolymer part is firstly prepared from oligomer polyol and polyisocyanate through polyester reaction to obtain polyester, then reacted with a multi-arm bridging agent, and finally quaternized to obtain a hydrophilic prepolymer with unsaturated functional groups.

[0008] The oligomer polyol is a mixture of one or more of polyethylene glycol and polyoxypropylene glycol.

[0009] The number average molecular weight Mn of polyethylene glycol (PEG) is preferably 1000, 2000 and 2500; the number average molecular weight Mn of polyoxypropylene glycol (PPG) is preferably 400, 600 and 1000.

[0010] The polyisocyanate is a mixture of one or more of L-lysine ethyl diisocyanate, dimer acid diisocyanate, 1,4-butanediisocyanate and 1,5-naphthalene diisocyanate.

[0011] The multi-arm bridging agent is a mixture of one or more of N,N-vinylbisacrylamide, 2-(diallylamino)ethylamine, diallylammonium, and N,N-dimethylallylamine.

[0012] The quaternizing agent is a mixture of one or more of dimethyl sulfate, diethyl sulfate, epichlorohydrin, benzyl chloride and methyl iodide.

[0013] The self-lubricating functional monomer is a mixture of one or more of methacryloylethyl sulfobetaine, 2-methacryloyloxyethyl phosphorylcholine, [3-(methacryloylamino)propyl]dimethyl(3-thiopropyl)ammonium hydroxide inner salt, N,N-dimethyl-N-acrylamidopropyl-N-propane sulfonic acid inner salt, di(methacryloyloxyethyl) hydrogen phosphate, and polyphosphorylcholine glycol acrylate.

[0014] The initiator is a mixture of one or more of ammonium persulfate, potassium persulfate, azobisisobutylamidine hydrochloride (AIBA), azobisisobutylimidazoline hydrochloride (AIBI), azobiscyanovaleric acid (ACVA), and azobisisopropylimidazoline (AIP).

[0015] The defoaming agent is one or more of organic siloxanes and polyoxyenolamine ethers.

[0016] A method for preparing a water-based self-lubricating wet friction fastness improving agent comprises the following steps:

[0017] (1) Add oligomer polyol to the reaction kettle, raise the temperature to 100-130° C., dehydrate for 1.0-2.0 h under vacuum conditions of -0.85-0.1 MPa, evacuate the air to normal pressure with nitrogen, and then cool to 40-50° C.;

[0018] (2) According to the ratio, add polyisocyanate under nitrogen protection, keep the temperature at 50-65°C for 1.5-2.0 hours, then raise the temperature to 80-95°C and continue to keep the temperature for 1.5-2.0 hours;

[0019] (3) Turn on the circulating cooling water, control the temperature below 40°C, add the multi-arm bridging agent dropwise, add at a constant speed over 30 minutes, raise the temperature to 50-60°C and continue to keep the temperature for 1.0-2.0 hours;

[0020] (4) At 40-90°C, under nitrogen protection, add the quaternary ammonium reagent dropwise, and continue to keep warm for 1.0-2.0 hours after the addition is completed at a constant speed of 30 minutes; then add an appropriate amount of deionized water to adjust the viscosity;

[0021] (5) Add self-lubricating functional monomer, vacuum at -0.85~-0.1MPa → pass nitrogen, repeat three times, add initiator under nitrogen protection, control the temperature at 70~90℃, keep warm for reaction, viscosity ≥10×10 3 mPa.s. Stop the reaction. Add deionized water according to the ratio, adjust the speed to 500-800r / min, stir at 40-60℃ for 60-90min, add defoamer after emulsification, stir evenly, filter and pack the material to obtain the water-based self-lubricating wet friction fastness enhancer.

[0022] The beneficial effects of the present invention are:

[0023] 1. The water-based self-lubricating wet friction fastness improver of the present invention has good water holding capacity. The wet friction fastness improver has good stability in the working fluid and is resistant to temperature changes, pH changes, and Ca in the water. 2+ Mg 2+ Both plasma and electrolytes have good tolerance, which greatly reduces the risk of precipitation and color fixation during use.

[0024] 2. The water-based self-lubricating wet friction fastness enhancer of the present invention has strong cationicity, can effectively combine with anionic dyes on cotton fabrics, effectively adsorb on the fabric surface, and form a good polymer film.

[0025] 3. The water-based self-lubricating wet friction fastness improver of the present invention has good self-lubricating properties, can effectively reduce the friction coefficient of the fabric surface, reduce the friction force, effectively reduce the short fibers and debris being rubbed off, and effectively improve the wet friction grade.

[0026] 4. The water-based self-lubricating wet friction fastness improver of the present invention has good co-bath performance and can be finished with silicone oil, film, and color fixing agent in the same bath. The working liquid has good stability. After the same bath finishing, the wet friction effect is significantly improved, and the finishing time can be effectively shortened. DETAILED DESCRIPTION

[0027] The present invention is described in detail below through examples. It is necessary to point out that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Those skilled in the art can make some non-essential improvements and adjustments based on the contents of the present invention, which still fall within the scope of protection of the present invention.

[0028] Example 1

[0029] The reactor was dried, 26.7 parts of PEG2000, 15.2 parts of PEG1000 and 4 parts of PPG600 were added to the reactor, the temperature was raised to 115°C, dehydrated for 1.0 h under -0.1 MPa vacuum conditions, the air was evacuated to normal pressure with nitrogen, and the temperature was lowered to 50°C;

[0030] Start nitrogen protection, add 7.5 parts of L-lysine ethyl ester diisocyanate and 19 parts of dimer acid diisocyanate into the reactor, keep the temperature at 60°C for 2.0 hours, then raise the temperature to 80°C and continue to keep the temperature for 1.0 hour;

[0031] Start circulating cooling water, control the temperature below 40°C, add 3.6 parts of bridging agent diallylamine and 6.3 parts of bridging agent N,N-vinylbisacrylamide into the dropping funnel, add at a constant speed of 30 minutes, then raise the temperature to 55°C and continue to keep the reaction for 1.5 hours;

[0032] Turn on nitrogen protection, raise the temperature to 70°C, take 8 parts of quaternary ammonium reagent dimethyl sulfate and add it to the dropping funnel, add it dropwise at a constant speed of 30 minutes, and continue to keep the temperature for 1.5 hours; then add 50 parts of deionized water and stir evenly;

[0033] Add 85 parts of 2-methacryloyloxyethyl phosphorylcholine and 20 parts of methacryloylethyl sulfobetaine, vacuumize at -0.85MPa → pass nitrogen, repeat three times, add 1.5 parts of initiator ammonium persulfate and 1 part of azobisisobutylamidine hydrochloride under nitrogen protection, control the temperature at 80-85℃ to keep the reaction, the viscosity is ≥10×10 3mPa.s, stop the reaction, add 403 parts of deionized water, adjust the speed to 800r / min, stir for 90min at 50℃, add 0.76 parts of organosiloxane defoamer, stir evenly, and filter and package the discharged material.

[0034] Performance Test:

[0035] The wet rubbing fastness enhancer in the embodiment is prepared into working solutions with concentrations of 30 g / L and 50 g / L and is bathed with different silicone oils, films and fixing agents; a padding process is adopted, and the process flow is: dyeing fabric → padding wet rubbing fastness enhancer (rolling rate 70-80%) → drying (150°C, 2 min);

[0036] The test was conducted according to the national standard GB / T 3920-2008 "Textiles - Tests for colour fastness - Colour fastness to rubbing". The test results are shown in Table 1.

[0037] Table 1 Product performance test results obtained in Example 1

[0038]

[0039] Example 2

[0040] The reactor was dried, 33.5 parts of PEG2000, 15 parts of PEG1000 and 5 parts of PPG1000 were added to the reactor, the temperature was raised to 125°C, dehydrated under -0.1 MPa vacuum conditions for 2.0 h, the air was evacuated to normal pressure with nitrogen, and the temperature was lowered to 50°C;

[0041] Start nitrogen protection, add 16 parts of dimer acid diisocyanate and 5.4 parts of 1,4-butanediisocyanate into the reactor, keep the temperature for reaction for 2.0 hours, then raise the temperature to 80°C and continue to keep the temperature for reaction for 1.5 hours;

[0042] Start circulating condensed water, control the temperature below 40°C, add 10.8 parts of bridging agent N,N-vinylbisacrylamide and 6 parts of 2-(diallylamino)ethylamine into the dropping funnel, add at a constant speed of 30 minutes, then raise the temperature to 45°C and continue to keep the reaction for 2.0 hours;

[0043] Turn on nitrogen protection, raise the temperature to 85°C, take 6.2 parts of quaternary ammonium reagent epichlorohydrin and add it to the dropping funnel, add it dropwise at a constant speed of 30 minutes and continue to keep warm and react for 1.5 hours; then add 100 parts of deionized water and stir evenly;

[0044] Add 87 parts of self-lubricating functional monomer 2-methacryloyloxyethyl phosphorylcholine and 29 parts of [3-(methacryloylamino)propyl]dimethyl(3-thiopropyl)ammonium hydroxide inner salt, -0.95MPa vacuum → nitrogen, repeat three times, add 2 parts of initiator potassium persulfate and 1 part of azobisisobutylimidazoline hydrochloride (AIBI) under nitrogen protection, control the temperature at 85-90℃ to keep the reaction, the viscosity is ≥10×10 3 mPa.s, stop the reaction. Add 403 parts of deionized water, adjust the speed to 700r / min, stir for 70 minutes at 60°C, add 1.4 parts of polyoxyenolamine ether defoamer, stir evenly, and filter and package the material.

[0045] The performance test method is the same as the performance test method in Example 1, and the test results are shown in Table 2.

[0046] Table 2 Product performance test results obtained in Example 2

[0047]

[0048] Example 3

[0049] The reactor was dried, 13.5 parts of PEG2000, 21 parts of PEG1000 and 3 parts of PPG400 were added to the reactor, the temperature was raised to 105°C, dehydrated under -0.1 MPa vacuum conditions for 1.5 h, the air was evacuated to normal pressure with nitrogen, and the temperature was lowered to 50°C;

[0050] Start nitrogen protection, add 4.4 parts of 1,4-butanediisocyanate and 7 parts of 1,5-naphthalenediisocyanate into the reactor, keep the temperature for reaction for 2.0 hours, then raise the temperature to 80°C and continue to keep the temperature for reaction for 2.0 hours;

[0051] Turn on the condensing water, control the temperature below 40°C, take 4.1 parts of bridging agent diallylamine and 5.7 parts of N,N-dimethylallylamine and add them into the dropping funnel. Add them over 30 minutes, then raise the temperature to 50°C and continue to keep the temperature for 1.5 hours;

[0052] Turn on nitrogen protection, raise the temperature to 90°C, add 5.8 parts of quaternary ammonium reagent epichlorohydrin into the dropping funnel, add dropwise for 30 minutes, and continue to keep warm and react for 2.0 hours; then add 50 parts of deionized water and stir evenly;

[0053] Add 46 parts of self-lubricating functional monomer 2-methacryloyloxyethyl phosphorylcholine and 41 parts of N,N-dimethyl-N-acrylamidopropyl-N-propanesulfonic acid inner salt, vacuum at -0.9MPa → nitrogen, repeat three times, add 1 part of initiator ammonium persulfate and 1 part of azobiscyanovaleric acid (ACVA) under nitrogen protection, control the temperature at 70-75℃ to keep the reaction, the viscosity is ≥10×10 3mPa.s, stop the reaction. Add 278 parts of deionized water, adjust the speed to 600r / min, stir for 60 minutes at 60°C, add 0.6 parts of organosiloxane defoamer, stir evenly, and filter and package the material.

[0054] The performance test method is the same as the performance test method in Example 1, and the test results are shown in Table 3.

[0055] Table 3 Product performance test results obtained in Example 3

[0056]

[0057] Example 4

[0058] The reactor was dried, 25 parts of PEG2500, 18.5 parts of PEG2000 and 11 parts of PEG1000 were added to the reactor, the temperature was raised to 120°C, dehydrated under -0.1 MPa vacuum condition for 2.0 h, the air was evacuated to normal pressure with nitrogen, and the temperature was lowered to 50°C;

[0059] Start nitrogen protection, add 3.6 parts of L-lysine ethyl ester diisocyanate and 4.2 parts of 1,4-butane diisocyanate into the reactor, keep the temperature for 2.0 hours, then raise the temperature to 80°C and continue to keep the temperature for 1.5 hours;

[0060] Turn on the condensing water, control the temperature below 40°C, add 5.6 parts of bridging agent diallylamine and 3.4 parts of N,N-dimethylallylamine into the dropping funnel, add them over 30 minutes, then raise the temperature to 55°C and continue to keep the reaction for 1.0 hour;

[0061] Turn on nitrogen protection, raise the temperature to 55°C, add 6.4 parts of quaternary ammonium reagent benzyl chloride into the dropping funnel, add dropwise for 30 minutes, and continue to keep warm and react for 1.5 hours; then add 60 parts of deionized water and stir evenly;

[0062] Add 37 parts of self-lubricating functional monomer 2-methacryloyloxyethyl phosphorylcholine, 24 parts of methacryloylethyl sulfobetaine and 37 parts of di(methacryloyloxyethyl) hydrogen phosphate, vacuumize at -0.95MPa → pass nitrogen, repeat three times, add 1.5 parts of initiator ammonium persulfate and 1 part of azodiisopropylimidazoline under nitrogen protection, control the temperature at 75-80℃ and keep the reaction, the viscosity is ≥10×10 3 mPa.s, stop the reaction. Add 330 parts of deionized water, adjust the speed to 800r / min, stir for 80min at 50℃, add 1 part of polyoxyenolamine ether defoamer, stir evenly, filter and package the material.

[0063] The performance test method is the same as the performance test method in Example 1, and the test results are shown in Table 4.

[0064] Table 4 Product performance test results obtained in Example 4

[0065]

[0066] Example 5

[0067] The reactor was dried, 45 parts of PEG2500 and 4.5 parts of PPG400 were added to the reactor, the temperature was raised to 110°C, dehydrated for 1.5 h under -0.1 MPa vacuum conditions, the air was evacuated to normal pressure with nitrogen, and the temperature was lowered to 45°C;

[0068] Start nitrogen protection, add 16 parts of dimer acid diisocyanate and 8.6 parts of 1,5-naphthalene diisocyanate into the reactor, keep the temperature for reaction for 1.5 hours, then raise the temperature to 80°C and continue to keep the temperature for reaction for 1.5 hours;

[0069] Turn on the condensing water, control the temperature below 40°C, take 4 parts of bridging agent 2-(diallylamino)ethylamine and 8 parts of N,N-dimethylallylamine and add them into the dropping funnel. Add them over 30 minutes, then raise the temperature to 60°C and continue to keep the temperature for 2.0 hours;

[0070] Turn on nitrogen protection, raise the temperature to 60°C, add 8.5 parts of quaternary ammonium reagent iodomethane into the dropping funnel, add it dropwise for 30 minutes, and continue to keep warm and react for 1.5 hours; then add 80 parts of deionized water and stir evenly;

[0071] Add 75 parts of self-lubricating functional monomer 2-methacryloyloxyethyl phosphorylcholine and 35 parts of polyphosphorylcholine glycol acrylate, vacuum at -1.0MPa → nitrogen, repeat three times, add 2 parts of initiator ammonium persulfate and 1 part of azodiisopropylimidazoline under nitrogen protection, control the temperature at 80-85℃ to keep the reaction, the viscosity is ≥10×10 3 mPa.s, stop the reaction. Add 405 parts of deionized water, adjust the speed to 700r / min, stir for 90 minutes at a material temperature of 50°C, add 0.9 parts of organosiloxane defoamer, stir evenly, and filter and package the material.

[0072] The performance test method is the same as the performance test method in Example 1, and the test results are shown in Table 5.

[0073] Table 5 Product performance test results obtained in Example 5

[0074]

[0075]

[0076] The above examples are used to illustrate the present invention. It is necessary to point out that the above examples are only used to further illustrate the present invention and do not limit the protection scope of the present invention. Some non-essential modifications and adjustments made by others based on the present invention still fall within the protection scope of the present invention.

Claims

1. A water-based self-lubricating wet friction fastness improving agent, characterized in that: A wet friction fastness enhancer with good hydrophilicity and self-lubricating properties is obtained by free radical reaction of a homemade hydrophilic prepolymer with an unsaturated functional group and a self-lubricating functional monomer with an unsaturated functional group. The components include the following raw materials in parts by weight: 60~100 parts of self-made hydrophilic prepolymer 80 ~120 parts of self-lubricating functional monomer Initiator 2.0 ~5.0 parts 300 ~530 parts of deionized water Defoaming agent 0.5~1.5 parts The self-made hydrophilic prepolymer part is firstly prepared from the oligomer polyol and polyisocyanate through polyester reaction to obtain polyester, then reacted with a multi-arm bridging agent, and finally quaternized to obtain a hydrophilic prepolymer with unsaturated functional groups; The oligomer polyol is a mixture of one or more of polyethylene glycol and polypropylene glycol; The polyisocyanate is a mixture of one or more of L-lysine ethyl diisocyanate, dimer acid diisocyanate, biomatrix 1,4-butanediisocyanate and biomatrix 1,5-pentanedimethyl diisocyanate; The multi-arm bridging agent is a mixture of multiple types selected from N,N-vinylbisacrylamide, 2-(diallylamino)ethylamine, diallylammonium, and N,N-dimethylallylamine; The self-lubricating functional monomer is a mixture of one or more of methacryloylethyl sulfobetaine, 2-methacryloyloxyethyl phosphorylcholine, [3-(methacrylamido)propyl]dimethyl(3-thiopropyl)ammonium hydroxide inner salt, N,N-dimethyl-N-acrylamidopropyl-N-propane sulfonic acid inner salt, di(methacryloyloxyethyl) hydrogen phosphate, and polyphosphorylcholine glycol acrylate.

2. The water-based self-lubricating wet friction fastness improving agent according to claim 1, characterized in that: The quaternizing agent is a mixture of one or more of dimethyl sulfate, diethyl sulfate, epichlorohydrin, benzyl chloride and methyl iodide.

3. The water-based self-lubricating wet friction fastness improving agent according to claim 1, characterized in that: The initiator is a mixture of one or more of ammonium persulfate, potassium persulfate, azobisisobutylamidine hydrochloride (AIBA), azobisisobutylimidazoline hydrochloride (AIBI), azobiscyanovaleric acid (ACVA), and azobisisopropylimidazoline (AIP).

4. The water-based self-lubricating wet friction fastness improving agent according to claim 1, characterized in that: The defoaming agent is one or more of organic siloxanes and polyoxyenolamine ethers.

5. The method for preparing the water-based self-lubricating wet friction fastness improving agent according to claim 1, characterized in that: The following steps are involved: (1) Add oligomer polyol to the reaction kettle, heat it to 100-130°C, dehydrate it under vacuum conditions of -0.85-0.1MPa for 1.0-2.0h, exhaust the air to normal pressure with nitrogen, and then cool it to 40-50°C; (2) According to the ratio, add polyisocyanate under nitrogen protection, keep the temperature at 50-65°C for 1.5-2.0h, then heat it to 80-95°C and continue to keep the temperature for 1.5-2.0h; (3) Start the circulating cooling water, control the temperature below 40°C, and add multi-arm bridged (4) At 40-90°C, under nitrogen protection, add quaternary ammonium reagent, and after 30 minutes of uniform dropwise addition, continue to keep the temperature for 1.0-2.0 hours; then add appropriate amount of deionized water to adjust the viscosity; (5) Add self-lubricating functional monomer, vacuumize at -0.85 to -0.1 MPa → pass nitrogen, repeat three times, add initiator under nitrogen protection, control the temperature at 70-90°C, keep the temperature for reaction, and the viscosity is ≥10×10 3 mPa.s, stop the reaction, add deionized water according to the ratio, adjust the speed to 500-800r / min, stir at 40-60℃ for 60-90min, add defoamer after emulsification and stir evenly, filter and package the material to obtain the water-based self-lubricating wet friction fastness improver.

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