Wet-friction-resistant fibrillation-resistant auxiliary agent and preparation method thereof

Abstract

The invention belongs to the technical field of fabric finishing, and relates to a wet-friction-resistant fibrillation-resistant auxiliary agent and a preparation method thereof. The anti-fibrillation auxiliary agent is prepared from the following raw materials: 0 to 25 percent of polyhydric alcohol, 8 to 10 percent of diisocyanate, 0.01 to 0.1 percent of a catalyst, 0 to 4 percent of a solvent, 1 to 2 percent of a chain extender, 0 to 2 percent of an end-capping reagent, 1 to 2 percent of a salt-forming agent and 60 to 70 percent of water. The method disclosed by the invention is simple in synthesis process, green and environment-friendly, low in cost, good in water solubility and good in stability. The cellulose fabric dyed by the reactive dye finished by the aid of the aid has the characteristics of excellent dry and wet rubbing fastness resistance, fibrillation resistance, soft handfeel, no yellowing, small color change of fabric color and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of fabric finishing and relates to a wet-abrasion-resistant anti-fibrillation auxiliary agent and a preparation method thereof. Background Art

[0002] Fibrillation is manifested as a single fiber splitting into fine fibers layer by layer along the length of the fiber. It is more likely to occur when the fiber is swollen and mechanically acted on at the same time, resulting in the formation of "white spots", "frost flowers" and entanglement into balls on the fabric. Fibrillation is a common feature of all cellulose fibers, and Lyocell fibers are more significant. The fibrillation performance of Lyocell fibers depends on the highly oriented and highly crystallized fiber structure formed in the spinning stage. These structures give the fiber excellent strength, gloss, drape, hygroscopicity and other characteristics.

[0003] At present, the problem of Lyocell fibrillation is mainly solved by regulating the spinning process, cross-linking treatment in the spinning stage, cellulase washing, cross-linking treatment after the filaments are formed, or resin finishing. CN118441367A discloses that by adjusting the discharge speed of the spinning mixture from the nozzle and the pulling speed of the fiber, a low-crystallinity Lyocell fiber with anti-fibrillation is obtained. WO95 / 28516A discloses a cross-linking agent with multiple acrylamide groups, preferably 1,3,5-triacryl-hexahydrotriazine, which effectively reduces the fibrillation tendency of solvent-spun cellulose fibers. By using acid cellulase to decompose the microfibrils on the surface of the fabric, the fibrillation of the fabric will reappear after washing again, and the cellulase will reduce the fiber. CN114457591A discloses that by adding an aldehyde-free cross-linking agent glycidyl ether type epoxy resin resin during the spinning or post-treatment of cellulose fibers, cellulose fibers with anti-fibrillation are cross-linked. CN103306136A discloses using a composition of oligomeric polyacid and C2-C6 polyacid as a crosslinking agent to improve the anti-fibrillation performance of fibers by high temperature heating. The above patent can achieve the anti-fibrillation effect, but there are also some problems, such as complex process, expensive crosslinking agent and poor water solubility, yellowing of the finished fiber or fabric, decreased mechanical properties, and poor hand feel.

[0004] At present, cross-linking agents with excellent anti-fibrillation effect are used in the stage of filament formation, while the fibrillation formed in the dyeing and finishing process of fabrics is an industry problem that needs to be solved urgently. Therefore, it is necessary to develop a versatile, green and efficient anti-fibrillation finishing agent. Summary of the invention

[0005] In view of the shortcoming that lyocell fabric is prone to fibrillation when wet and subjected to mechanical action, the object of the present invention is to provide a wet abrasion-resistant anti-fibrillation auxiliary agent and a preparation method thereof.

[0006] The first aspect of the present invention discloses a moisture-resistant and anti-fibrillation auxiliary agent, which is prepared from the following raw materials by mass fraction: 1-25% polyol, 8-10% diisocyanate, 0.8-1% carbon nanotube nanoparticles, 0.01-0.1% catalyst, 0-4% solvent, 1-2% chain extender, 0-2% end-capping agent, 1-2% salt-forming agent, and 60-70% water.

[0007] The general formula of the prepared anti-fibrillation agent is shown in Formula 1: .

[0008] Preferably, the polyol is at least one of polyethylene glycol 400, polyethylene glycol 1000, polyethylene glycol 1500 and polyethylene glycol 2000.

[0009] Preferably, the solvent is at least one of propylene glycol methyl ether acetate, acetone, methyl ethyl ketone, dioxane, N-methylpyrrolidone, and N,N-dimethylformamide.

[0010] Preferably, the chain extender is a small molecule polyol containing a tertiary amino group, selected from at least one of N-methyldiethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, 3-dimethylamino-1,2-propylene glycol, and N,N-dimethyl-2-(dihydroxymethyl)butylamine.

[0011] Preferably, the end-capping agent is at least one of acetanilide, butanone oxime, sodium bisulfite and phenol.

[0012] Preferably, the salt-forming agent is at least one of glacial acetic acid, hydrochloric acid, epichlorohydrin, oxalic acid and methyl iodide.

[0013] The second aspect of the present invention discloses a method for preparing the above-mentioned anti-fibrillation auxiliary agent, comprising the following steps: S1. Add a certain amount of polyol into a reaction vessel and perform a decompression dehydration treatment at 120°C for 3 hours; S2, cool down to 50-60℃, add catalyst, and stir evenly for 5-15min; S3, add diisocyanate dropwise, raise the temperature to 70-80°C after the addition is completed, and react at a constant temperature for 1-3 hours to make NCO reach the theoretical value to obtain a polyurethane prepolymer; S4, cool down to 60-65℃, add solvent, and stir evenly for 5-15min; S5, add chain extender dropwise, raise the temperature to 70-80°C, and react at constant temperature for 0.5-2h; S6. Add a certain amount of end-capping agent to cap the residual NCO, and react at a constant temperature for 0.5-1h; S7, the temperature is controlled at 50-70°C, a salt-forming agent is added, and the reaction is carried out at a constant temperature for 5-30 minutes; S8. Control the temperature at 30-70°C, slowly add water, and emulsify and disperse for 1 hour to obtain an anti-fibrillation agent with a content of 30-40%.

[0014] Wherein, the diisocyanate is isophorone diisocyanate IPDI, and the molar ratio of the diisocyanate -NCO to the polyol -OH is 1.6-2.2:1; The amount of the solvent is 0-4%, the amount of the chain extender is 2%-6%, the molar ratio of the end-capping agent to the residual NCO is 0-1.5:1, and the molar ratio of the salt-forming agent to the chain extender is 0.5-1:1.

[0015] The anti-fibrillation auxiliary agent of the present invention is a cationic aqueous polyurethane solution, the chain extender used is a hydrophilic chain extender containing tertiary amino groups, the Coulomb attraction formed by the protonated polyurethane and the negative charge on the fiber is utilized, and at the same time, because the -NCO on the polyurethane structure can undergo a cross-linking reaction with the -OH on the cellulose fiber, the reactivity of the polyurethane and the fiber is improved, and the polyurethane can also form a dense film on the surface of the fabric, thereby enhancing the friction resistance, and in addition, the polyurethane is mixed with carbon nanotube nanoparticles to prepare a cross-linking liquid, and the nanoparticles are dispersed in the cross-linked film to form a composite structure, thereby enhancing the film's resistance to dry and wet friction fastness. The anti-fibrillation auxiliary agent comprehensively improves the anti-fibrillation performance of lyocell cellulose through multiple effects of adsorption, cross-linking, and film formation.

[0016] Compared with the prior art, the present invention has the following advantages: The method is not only simple in synthesis process and green and environmentally friendly, but also low in cost, good in water solubility and good in stability. Cellulose fabrics dyed with reactive dyes finished with the auxiliary agent have excellent dry and wet friction fastness and anti-fibrillation performance, and the treated fabrics are soft to the touch, not yellowish, and the color of the fabrics is reduced. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the existing methods and experiments, the following is a brief introduction to the drawings required for use in the embodiments. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without paying creative work.

[0018] Figure 1 The diagram shows the effect of the lyocell fabric in Examples 1-4 after multiple washings. DETAILED DESCRIPTION

[0019] The technical scheme of the present invention is described in detail below in conjunction with the accompanying drawings and embodiments, but the present invention is not limited to the scope of the embodiments. The experimental methods and techniques in the following embodiments without specifying specific conditions are usually carried out according to conventional conditions in the field or according to the conditions recommended by the manufacturer.

[0020] Example 1 S1, 25g of PEG1000 was added to the reaction vessel and dehydrated under reduced pressure at 120°C for 3h; S2, cool to 60°C, add 0.1 g of dibutyltin dilaurate, and stir evenly for 7 min; S3, add 11.27 g of isophorone diisocyanate dropwise, raise the temperature to 70° C. after the addition is completed, and react at this temperature for 3 hours to obtain a polyurethane prepolymer; S4, add 1.48 g N-methyldiethanolamine dropwise, raise the temperature to 70°C, and react at this constant temperature for 1 hour; S5, cool to 50°C, add 0.53 g of glacial acetic acid, and react at constant temperature for 10 min; S6, cooling to room temperature, slowly adding water, and performing emulsification and dispersion for 1 hour to obtain an anti-fibrillation auxiliary agent.

[0021] Example 2 S1, add 25 g of PEG1000 into the reaction vessel and perform decompression dehydration treatment at 120°C for 3 h; S2, cool to 60°C, add 0.1 g of dibutyltin dilaurate, and stir evenly for 7 min; S3, dropwise adding 11.27 g of isophorone diisocyanate and 1.1 g of carbon nanotube nanoparticles, raising the temperature to 70° C. after the dropwise addition, and reacting at the constant temperature for 3 h to obtain a polyurethane prepolymer; S4, add 1.48 g N-methyldiethanolamine dropwise, raise the temperature to 70°C, and react at this constant temperature for 1 hour; S5, cool to 50°C, add 0.53 g of glacial acetic acid, and react at constant temperature for 10 min; S6, cooling to room temperature, slowly adding water, and performing emulsification and dispersion for 1 hour to obtain an anti-fibrillation auxiliary agent.

[0022] Example 3 S1, add 25 g of PEG1000 into the reaction vessel and perform decompression dehydration treatment at 120°C for 3 h; S2, cool to 55°C, add 0.1 g of dibutyltin dilaurate, and stir evenly for 10 min; S3, add 10.58 g of isophorone diisocyanate dropwise, raise the temperature to 70° C. after the addition is completed, and react at this temperature for 3 hours to obtain a polyurethane prepolymer; S4, cool to 60°C, add 4.12 g acetone, and stir evenly for 10 min; S5, add 1.51 g of N-methyldiethanolamine dropwise, raise the temperature to 70°C, and react at this constant temperature for 1 hour; S6, temperature 70°C, add 2.21g butanone oxime to cap the residual NCO, and react at constant temperature for 0.5h; S7, cool to 50°C, add 0.77g glacial acetic acid, and react at constant temperature for 30min; S8, cool to room temperature, slowly add water, and emulsify and disperse for 1 hour to obtain an anti-fibrillation agent.

[0023] Example 4 S1, add 25 g of PEG1000 into the reaction vessel and perform decompression dehydration treatment at 120°C for 3 h; S2, cool to 55°C, add 0.1 g of dibutyltin dilaurate, and stir evenly for 10 min; S3, adding 10.58 g of isophorone diisocyanate and 1.1 g of carbon nanotube nanoparticles dropwise, raising the temperature to 70° C. after the addition is completed, and reacting at this temperature for 3 h to obtain a polyurethane prepolymer; S4, cool to 60°C, add 4.12 g acetone, and stir evenly for 10 min; S5, add 1.51 g of N-methyldiethanolamine dropwise, raise the temperature to 70°C, and react at this constant temperature for 1 hour; S6, temperature 70°C, add 2.21g butanone oxime to cap the residual NCO, and react at constant temperature for 0.5h; S7, cool to 50°C, add 0.77g glacial acetic acid, and react at constant temperature for 30min; S8, cool to room temperature, slowly add water, and emulsify and disperse for 1 hour to obtain an anti-fibrillation agent.

[0024] Fabric treatment Anti-fibrillation auxiliaries finishing: fabric sample → padding (3% owf. auxiliaries, first immersion for 30s, then immersion and padding, padding rate: 70-80%) → 185℃*2.5min shaping and drying → cooling → comparison of wet friction fastness grade, anti-pilling grade, and fibrillation of washed fabrics.

[0025] The present invention is directed to a method for determining the fibrillation degree of lyocell knitted fabrics, which is to test the anti-pilling grade of the lyocell fabrics and the white frost phenomenon on the surface of the fabrics before and after washing, and then to perform auxiliary evaluation by means of a wet friction test on cotton textiles dyed with reactive dyes, wherein the blank sample is a control sample. The finished fabrics are tested for wet friction fastness performance according to GB / T 3920-2008, the anti-pilling grade is tested according to GB / T 4802.2-2008, and the lyocell knitted fabrics are washed according to the AATCC 2A standard, with 45 minutes being counted as one wash. The test results are shown in Table 1 below. A comparison of the white frost on the surface of lyocell fabrics before and after finishing is shown in Table 1 below. Figure 1 shown.

[0026] Table 1 Comparison of fabric properties after finishing

[0027] As can be seen from Table 1, the wet friction effect of fabrics not treated with anti-fibrillating auxiliaries is poor, while the wet friction fastness of fabrics treated with anti-fibrillating auxiliaries is improved, showing excellent wet friction resistance; the unfinished Lyocell knitted fabric has a large amount of hairiness and some small pills after 125 frictions, and a large area of ​​small pills appear on the surface of the fabric after 500 frictions, while the pilling performance of the fabric treated with anti-fibrillating auxiliaries is suppressed, showing better anti-pilling performance.

[0028] The untreated and anti-fibrillation auxiliaries treated fabrics were washed and compared before and after washing. Figure 1 It can be found that white frost appears on the surface of the untreated lyocell fabric after 5 washings, while a small amount or trace amount of white frost appears on the treated lyocell fabric after washing; a large amount of white frost appears on the surface of the untreated lyocell fabric after 10 washings, while the rate of increase of white frost on the treated lyocell fabric after washing is significantly slowed down. The anti-fibrillation additive with added nanoparticles is significantly better than the anti-fibrillation additive without added nanoparticles in avoiding fiber anti-fibrillation.

[0029] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A wet-friction-resistant anti-fibrillation auxiliary agent, characterized in that: The invention is prepared from the following raw materials: 1-25% of polyol, 8-10% of diisocyanate, 0.8-1% of carbon nanotube nanoparticles, 0.01-0.1% of catalyst, 0-4% of solvent, 1-2% of chain extender, 0-2% of end-capping agent, 1-2% of salt-forming agent and 60-70% of water.

2. A wet-friction-resistant anti-fibrillation auxiliary agent according to claim 1, characterized in that: The general formula of the prepared anti-fibrillation agent is shown in Formula 1: 。 3. The wet-friction-resistant anti-fibrillation auxiliary agent according to claim 1, characterized in that: The polyol is at least one of polyethylene glycol 400, polyethylene glycol 1000, polyethylene glycol 1500 and polyethylene glycol 2000.

4. The wet-friction-resistant anti-fibrillation auxiliary agent according to claim 1, characterized in that: The solvent is at least one of propylene glycol methyl ether acetate, acetone, methyl ethyl ketone, dioxane, N-methyl pyrrolidone and N,N-dimethylformamide.

5. The wet-friction-resistant anti-fibrillation auxiliary agent according to claim 1, characterized in that: The chain extender is a small molecule polyol containing tertiary amino groups, selected from at least one of N-methyldiethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, 3-dimethylamino-1,2-propylene glycol, and N,N-dimethyl-2-(dihydroxymethyl)butylamine.

6. The wet-friction-resistant anti-fibrillation auxiliary agent according to claim 1, characterized in that: The end-capping agent is at least one of acetanilide, butanone oxime, sodium bisulfite and phenol.

7. The wet-friction-resistant anti-fibrillation auxiliary agent according to claim 1, characterized in that: The salt-forming agent is at least one of glacial acetic acid, hydrochloric acid, epichlorohydrin, oxalic acid and methyl iodide.

8. The method for preparing the anti-fibrillation auxiliary agent according to claim 1, characterized in that: The following steps are involved: S1. Add a certain amount of polyol into a reaction vessel and perform a decompression dehydration treatment at 120°C for 3 hours; S2, cool down to 50-60℃, add catalyst, and stir evenly for 5-15min; S3, add diisocyanate dropwise, raise the temperature to 70-80°C after the addition is completed, and react at a constant temperature for 1-3 hours to make NCO reach the theoretical value to obtain a polyurethane prepolymer; S4, cool down to 60-65℃, add solvent, and stir evenly for 5-15min; S5, add chain extender dropwise, raise the temperature to 70-80°C, and react at constant temperature for 0.5-2h; S6. Add a certain amount of end-capping agent to cap the residual NCO, and react at a constant temperature for 0.5-1h; S7, the temperature is controlled at 50-70°C, a salt-forming agent is added, and the reaction is carried out at a constant temperature for 5-30 minutes; S8. Control the temperature at 30-70°C, slowly add water, and emulsify and disperse for 1 hour to obtain an anti-fibrillation agent with a content of 30-40%.

9. The method for preparing the anti-fibrillation auxiliary agent according to claim 8, characterized in that: The diisocyanate is isophorone diisocyanate IPDI, and the molar ratio of the diisocyanate -NCO to the polyol -OH is 1.6-2.2:1; The amount of the solvent is 0-4%, the amount of the chain extender is 2%-6%, the molar ratio of the end-capping agent to the residual NCO is 0-1.5:1, and the molar ratio of the salt-forming agent to the chain extender is 0.5-1:1.

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