Manufacturing process of fluoride-free oil-proof elastic fabric

Abstract

The invention discloses a manufacturing process of a fluoride-free oil-proof elastic fabric, and relates to the technical field of elastic fabrics, and the manufacturing process comprises a pretreatment part, a dyeing part and an after-treatment part; wherein the pretreatment part comprises the steps of taking gray cloth and sequentially carrying out cold batch, desizing twice, refining and pre-shaping to obtain pre-finished gray cloth; the dyeing part comprises the following steps: putting the pre-finished gray cloth into a dye solution containing dye for dyeing treatment, and then sequentially carrying out water washing, soaping, acid washing and water washing to obtain dyed gray cloth; the after-finishing part comprises the following steps: putting the dyed gray cloth into a fluorine-free oil-proof finishing agent working solution for padding treatment, and sequentially drying, sizing, tentering and preshrinking to obtain a finished product elastic fabric; the fluoride-free oil-proof finishing agent is a POSS (Polyhedral Oligomeric Silsesquioxane)-nano silicon dioxide and organic silicon fluoride-free oil-proof finishing agent. The oil-proof antifouling paint has efficient oil-proof and antifouling effects.

Description

Technical Field

[0001] This application relates to the field of elastic fabric technology, and in particular to a manufacturing process for a fluorine-free oil-resistant elastic fabric. Background Technology

[0002] Fluorine-free oil-resistant elastic fabric is a textile fabric that does not contain fluorine compounds and has oil-resistant and elastic recovery properties. It achieves its oil-resistant effect through non-fluorine oil-resistant finishing technology, such as finishing with fluorine-free waterproofing agents, while adding elastic fibers such as spandex to ensure the fabric's stretch and resilience.

[0003] However, the waterproofing effect of fluorine-free waterproofing agents is not ideal. The core issue is their high surface tension, which prevents them from achieving oil-repellent properties like fluorine-containing waterproofing agents by reducing the surface tension to below that of oil. Specifically, the surface tension of fluorine-free waterproofing agents is typically higher than that of oils, thus failing to effectively prevent oil from penetrating the fabric and resulting in poor oil repellency. Furthermore, fluorine-free waterproofing agents cannot form a comb-like structure identical or similar to that of fluorine-containing agents, hindering their ability to effectively reduce surface tension and achieve superior oil repellency.

[0004] Therefore, conventional fluorine-free waterproofing agents can only provide waterproofing and cannot simultaneously achieve oil and stain resistance. They also cannot effectively prevent oil penetration and adhesion, and therefore need improvement. Summary of the Invention

[0005] In view of this, the purpose of this application is to provide a manufacturing process for fluorine-free oil-resistant elastic fabric to achieve efficient oil and stain resistance. The specific solution is as follows:

[0006] A manufacturing process for a fluorine-free, oil-resistant elastic fabric includes a pretreatment section, a dyeing section, and a finishing section; wherein:

[0007] The pretreatment section includes taking the fabric and sequentially performing cold stacking, desizing twice, refining and pre-forming to obtain the pre-finished fabric;

[0008] The dyeing process includes immersing the pre-finished fabric in a dye solution containing dye for dyeing treatment, and then sequentially washing with water, soaping, acid washing and washing with water to obtain the dyed fabric.

[0009] The finishing process includes immersing the dyed fabric in a fluorine-free oil-resistant finishing agent working solution for padding, and then sequentially drying, setting, stretching, and pre-shrinking to obtain the finished elastic fabric.

[0010] The fluorine-free oil-resistant finishing agent is a POSS-nano silica@organosilicon-based fluorine-free oil-resistant finishing agent.

[0011] Preferably, in the pretreatment section, the cold pile uses liquid alkali with a concentration of 20-30 g / L, controls the temperature at 75-85℃, the pH at 11-13, and treats for 24-48 hours; the desizing uses liquid alkali with a concentration of 2-5 g / L, controls the temperature at 50-60℃, the pH at 11-13, and treats for 30-60 minutes; the refining uses a nonionic surfactant with a concentration of 3-8 g / L, controls the temperature at 90-100℃, and treats for 30-60 minutes; the pre-setting uses a temperature of 160-180℃ and a setting speed of 20-30 m / min.

[0012] Preferably, in the dyeing section, the dyeing treatment involves immersing the pre-finished fabric in a dye solution composed of 1-5 owf% dye, 0.5-2 g / L leveling agent, and pH adjuster, controlling the liquor ratio at 1:15-20, the temperature of the dye solution at 90-95℃, and maintaining the temperature for 30-60 minutes; the soaping involves using 2-5 g / L soaping agent and controlling the temperature at 80-90℃ for 15-30 minutes; the acid washing involves using 1-2 g / L acetic acid and controlling the pH at 4-5 for 10-15 minutes.

[0013] Preferably, the dye is a siloxane-grafted modified dye, and the preparation method of the siloxane-grafted modified dye includes: Step ① mixing and stirring the base dye and DMF at a ratio of 1g:4.8-5mL, and controlling the mixing temperature at 60-65℃ to obtain a pre-mixed dye solution after the base dye is completely dissolved; Step ② adding a modified monomer and DBTDL at a mass ratio of 100:15-20:0.5-1 to the base dye to the pre-mixed dye solution, stirring and mixing evenly, raising the temperature to 80-90℃, and holding under inert gas protection for 2-3 hours to obtain a modified reaction mixture; Step ③ lowering the temperature of the modified reaction mixture to 40-50℃ and adding triethylamine while stirring, controlling the ratio of triethylamine to base dye at 2-3mL:100g, then adding excess deionized water and stirring to precipitate and obtain the siloxane-grafted modified dye; and adding 0.3-0.8g / L of polyether-modified polysiloxane compatibilizer to the dye solution and stirring evenly.

[0014] Preferably, the modified monomer is γ-aminopropyltriethoxysilane-modified polydimethylsiloxane with a molecular weight of 800-1200 and an amino value of 0.3-0.5 mmol / g.

[0015] Preferably, in the finishing section, the slurry rate of the padding treatment is 60-80%; the drying is carried out at a controlled temperature of 80-100℃ for 30 seconds to 1 minute; the setting is carried out at a controlled temperature of 160-180℃ for 1-1.5 minutes; the stretching is carried out at a controlled temperature of 160-180℃ and a speed of 25-35 m / min; the pre-shrinking is carried out using wet heat pre-shrinking, and the wet heat pre-shrinking temperature is controlled at 130-150℃ and the humidity is controlled at 80-90%, the pre-shrinking speed is 5 m / min, and the fabric is entered and exited without tension.

[0016] Preferably, the POSS-nano silica@organosilicon-based fluorine-free oil-resistant finishing agent contains 3-12 wt% nano silica and 1-5 wt% POSS.

[0017] Preferably, the preparation method of the POSS-nano silica@organosilicon-based fluorine-free oil-resistant finishing agent includes the following steps: Step ① Dissolving 5-8 parts by weight of polycarboxylate dispersant in 800-1000 parts of deionized water, stirring evenly, then adding 25-40 parts of hydrophobic modified nano silica and 10-15 parts of POSS, stirring evenly to obtain a pre-dispersion; Step ② Performing ultrasonic dispersion treatment on the dispersion, controlling the ultrasonic power at 300-500W and the ultrasonic time at 10-15min, to obtain an ultrasonic dispersion with D50≤150nm; Step ③ Adding the ultrasonic dispersion to 500 parts of basic finishing agent and stirring for 30-40min, then heating to 40-50℃ and adding 2.5-5 parts of HDI trimer crosslinking agent, and stirring for 30-40min to obtain the finished POSS-nano silica@organosilicon-based fluorine-free oil-resistant finishing agent.

[0018] Preferably, the base finishing agent is a polysiloxane-type organosilicon-based fluorine-free oil-resistant finishing agent or a paraffin-acrylate copolymer-type hydrocarbon-based fluorine-free oil-resistant finishing agent.

[0019] Preferably, in step ③, the finished POSS-nano silica@organosilicon-based fluorine-free oil-resistant finishing agent is obtained by adding deionized water and adjusting the viscosity at 25°C to 50-100 mPa·s.

[0020] As can be seen from the above solutions, this application provides a manufacturing process for fluorine-free oil-resistant elastic fabric, which has the following beneficial effects:

[0021] 1. By combining nano-silica with POSS and a base finishing agent, a composite protective layer with a micro-nano rough structure and a low surface energy organosilicon layer is formed on the surface of the dyed fabric. The micron-level protrusions of nano-silica and the cage-like structure of POSS are used to construct a nano-level texture. By superimposing the low surface energy characteristics of organosilicon, the oil contact angle is significantly improved to reduce oil adhesion. The three-dimensional structure is also used to enhance the wear resistance of the composite protective layer, thereby extending the duration of the anti-fouling effect.

[0022] 2. By using siloxane-grafted modified dyes in synergy with fluorine-free oil-resistant finishing agents, the siloxane fragments in the dyes grafted with γ-aminopropyltriethoxysilane-modified polydimethylsiloxane are improved to enhance their compatibility with the fluorine-free oil-resistant finishing agents. Furthermore, the addition of polyether-modified polysiloxane compatibilizers further promotes the interfacial bonding effect between the siloxane-grafted modified dyes and the fluorine-free oil-resistant finishing agents, forming a double-layer protective layer structure that combines dye transition and finishing agent function. This avoids mutual interference between the dyeing and finishing processes and allows the siloxane-grafted modified dyes to provide anchoring points for the fluorine-free oil-resistant finishing agents, improving the adhesion of the fluorine-free oil-resistant finishing agents, effectively increasing the difficulty of removal after washing, and achieving enhanced stain resistance and durability.

[0023] 3. By controlling the padding rate, the adhesion of the fluorine-free oil-repellent finishing agent is improved, and the setting temperature and setting time are effectively controlled to promote the reaction of the HDI trimer crosslinking agent, so that the fluorine-free oil-repellent finishing agent forms a three-dimensional network structure. At the same time, by controlling the temperature, time and concentration, the various parameters are effectively coordinated to improve the uniformity and stability of the surface layer structure of the finished elastic fabric, thereby effectively exerting the oil and stain repellency effect. Detailed Implementation

[0024] The technical solutions described below in conjunction with the embodiments of this application will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of the embodiments. Based on the embodiments of this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0025] It should be mentioned that the fabric used in this embodiment is a fabric made of spandex and nylon that has undergone high-temperature setting. The base dye is Acid Red G. Of course, nylon can be replaced with polyester or other chemical fiber materials, and the base dye and processing temperature can be adjusted accordingly, which will not be elaborated here. In addition, the DMF used in this embodiment is N,N-dimethylformamide, DBTDL is dibutyltin dilaurate, and POSS is octaphenyl POSS. Meanwhile, the base finishing agent used in this embodiment is a polysiloxane-type organosilicon fluorine-free oil-resistant finishing agent with a solid content of 30%, purchased from Shanghai Huzheng Industrial Co., Ltd., with the brand name SIF-FS30. The hydrophobically modified nano-silica was purchased from Wuhu Jikang New Material Technology Co., Ltd., with the brand name SS-S50K. The γ-aminopropyltriethoxysilane modified polydimethylsiloxane was purchased from Hubei Xinlantian New Material Co., Ltd.

[0026] The following is a detailed description of the manufacturing process of a fluorine-free oil-resistant elastic fabric according to this application.

[0027] A manufacturing process for a fluorine-free, oil-resistant elastic fabric includes a pretreatment section, a dyeing section, and a finishing section. Among them:

[0028] The pretreatment process includes sequentially subjecting the grey fabric to cold stacking, two desizing cycles, refining, and pre-setting to obtain the pre-finished grey fabric. It should be noted that in the pretreatment process, cold stacking uses a 20-30 g / L liquid alkali solution, controlled at 75-85℃ and pH 11-13, for 24-48 hours. Desizing uses a 2-5 g / L liquid alkali solution, controlled at 50-60℃ and pH 11-13, for 30-60 minutes. Refining uses a 3-8 g / L nonionic surfactant solution, controlled at 90-100℃, for 30-60 minutes. Pre-setting is performed at a controlled temperature of 160-180℃ and a setting speed of 20-30 m / min.

[0029] The dyeing process involves immersing the pre-finished fabric in a dye solution containing dye for dyeing treatment, followed by sequential washing, soaping, acid washing, and washing to obtain the dyed fabric. It should be noted that in the dyeing process, the dyeing treatment involves immersing the pre-finished fabric in a dye solution composed of 1-5 owf% dye, 0.5-2 g / L leveling agent, and pH adjuster, controlling the liquor ratio at 1:15-20, the dye solution temperature at 90-95℃, and holding for 30-60 minutes. Soaping is performed using 2-5 g / L soaping agent at 80-90℃ for 15-30 minutes. Acid washing is performed using 1-2 g / L acetic acid at a pH of 4-5 for 10-15 minutes.

[0030] It should be mentioned that, in this embodiment, in order to improve the bonding effect between the dye and the finishing part, the dye used is a siloxane-grafted modified dye. The preparation method of the siloxane-grafted modified dye includes step ① mixing and stirring the base dye and DMF at a ratio of 1g:4.8-5mL, and controlling the mixing temperature at 60-65℃ to obtain a pre-mixed dye solution after the base dye is completely dissolved; step ② adding a modified monomer and DBTDL to the pre-mixed dye solution at a mass ratio of 100:15-20:0.5-1 to the base dye, and in this embodiment, the modified monomer is γ-aminopropyltriethoxy with a molecular weight of 800-1200 and an amino value of 0.3-0.5mmol / g. Silane-modified polydimethylsiloxane is mixed evenly by stirring, and then the temperature is raised to 80-90℃ and kept at this temperature for 2-3 hours under inert gas protection to obtain a modified reaction mixture. In step ③, the temperature of the modified reaction mixture is lowered to 40-50℃ and triethylamine is added and stirred. The ratio of the amount of triethylamine added to the base dye is controlled to be 2-3 mL: 100 g. After adding excess deionized water, the mixture is stirred to precipitate and obtain siloxane-grafted modified dye. 0.3-0.8 g / L of polyether-modified polysiloxane compatibilizer is added to the dye solution and stirred evenly.

[0031] The finishing process includes immersing the dyed greige fabric in a fluorine-free oil-repellent finishing agent working solution for padding. After sequential drying, setting, stretching, and pre-shrinking, the finished elastic fabric is obtained. It should be noted that in the finishing process, the padding liquid ratio is 60-80%. Drying is carried out at a controlled temperature of 80-100℃ for 30-60 seconds. Setting is carried out at a controlled temperature of 160-180℃ for 1-1.5 minutes. Stretching is carried out at a controlled temperature of 160-180℃ and a speed of 25-35 m / min. Pre-shrinking is performed using wet heat pre-shrinking, with the temperature controlled at 130-150℃ and the humidity at 80-90%, the pre-shrinking speed at 5 m / min, and the fabric entering and exiting without tension.

[0032] Meanwhile, in the embodiments of this application, the fluorine-free oil-repellent finishing agent is POSS-nano silica@organosilicon-based fluorine-free oil-repellent finishing agent. The POSS-nano silica@organosilicon-based fluorine-free oil-repellent finishing agent contains 3-12 wt% nano silica and 1-5 wt% POSS. The preparation method of POSS-nano silica@organosilicon-based fluorine-free oil-resistant finishing agent includes the following steps: Step ① Dissolve 5-8 parts by weight of polycarboxylate dispersant in 800-1000 parts of deionized water, stir evenly, add 25-40 parts of hydrophobic modified nano silica and 10-15 parts of POSS, stir evenly to obtain a pre-dispersion liquid; Step ② Perform ultrasonic dispersion treatment on the dispersion liquid, control the ultrasonic power to be 300-500W and the ultrasonic time to be 10-15min, and obtain an ultrasonic dispersion liquid with D50≤150nm; Step ③ Add the ultrasonic dispersion liquid to 500 parts of basic finishing agent and stir for 30-40min, then heat to 40-50℃ and add 2.5-5 parts of HDI trimer crosslinking agent, stir for 30-40min, and after adding deionized water and adjusting the viscosity at 25℃ to 50-100mPa·s, obtain the finished product POSS-nano silica@organosilicon-based fluorine-free oil-resistant finishing agent.

[0033] The base finishing agent is either a polysiloxane-type organosilicon-based fluorine-free oil-resistant finishing agent or a paraffin-acrylate copolymer-type hydrocarbon-based fluorine-free oil-resistant finishing agent.

[0034] Example 1

[0035] A manufacturing process for a fluorine-free, oil-resistant elastic fabric includes a pretreatment section, a dyeing section, and a finishing section. Among them:

[0036] The pretreatment process includes sequentially subjecting the greige fabric to cold stacking, two desizing cycles, refining, and pre-setting to obtain the pre-finished greige fabric. It should be noted that in the pretreatment process, cold stacking uses a 20 g / L liquid alkali solution, controlled at 75°C and pH 11, for 24 hours. Desizing uses a 2 g / L liquid alkali solution, controlled at 50°C and pH 11, for 60 minutes. Refining uses a 3 g / L nonionic surfactant solution, controlled at 90°C, for 60 minutes. Pre-setting is performed at a controlled temperature of 160°C and a setting speed of 20 m / min.

[0037] The dyeing process involves immersing the pre-finished fabric in a dye solution containing dye for dyeing treatment, followed by sequential washing, soaping, acid washing, and washing to obtain the dyed fabric. It should be noted that in the dyeing process, the pre-finished fabric is immersed in a dye solution consisting of 1 owf% dye, 0.5 g / L leveling agent, and pH adjuster, with a liquor ratio controlled at 1:15 and the dye solution temperature at 90℃ for 60 minutes. Soaping is performed using 2 g / L soaping agent at 80℃ for 30 minutes. Acid washing is performed using 1 g / L acetic acid at pH 4 for 10 minutes.

[0038] It should be mentioned that, in the embodiments of this application, in order to improve the bonding effect between the dye and the finishing part, the dye used is a siloxane grafted modified dye. The preparation method of siloxane-grafted modified dye includes step ① mixing and stirring a base dye with DMF at a ratio of 1g:4.8mL, and controlling the mixing temperature at 60℃ to obtain a pre-mixed dye solution after the base dye is completely dissolved; step ② adding a modified monomer and DBTDL at a mass ratio of 100:15:0.5 to the base dye to the pre-mixed dye solution, wherein the modified monomer in this embodiment is γ-aminopropyltriethoxysilane-modified polydimethylsiloxane, and after stirring and mixing evenly, raising the temperature to 80℃ and holding it at this temperature for 3 hours under inert gas protection to obtain a modified reaction mixture; step ③ lowering the temperature of the modified reaction mixture to 40℃ and adding triethylamine while stirring, controlling the ratio of triethylamine to base dye at 2mL:100g, and then adding excess deionized water and stirring to precipitate and obtain the siloxane-grafted modified dye; and adding 0.3g / L of polyether-modified polysiloxane compatibilizer to the dye solution and stirring evenly.

[0039] The finishing process involves immersing the dyed greige fabric in a fluorine-free oil-repellent finishing agent working solution for padding. After sequential drying, setting, stretching, and pre-shrinking, the finished elastic fabric is obtained. It should be noted that the padding liquid ratio in the finishing process is 73%. Drying is performed at a controlled temperature of 80℃ for 45 seconds. Setting is performed at a controlled temperature of 180℃ for 1 minute. Stretching is performed at a controlled temperature of 180℃ and a speed of 25 m / min. Pre-shrinking is performed using wet heat pre-shrinking, with the temperature controlled at 150℃ and humidity at 80%, a pre-shrinking speed of 5 m / min, and tension-free fabric entry and exit.

[0040] Meanwhile, in the embodiments of this application, the fluorine-free oil-resistant finishing agent is POSS-nano silica@organosilicon-based fluorine-free oil-resistant finishing agent. The preparation method of POSS-nano silica@organosilicon-based fluorine-free oil-resistant finishing agent includes the following steps: Step ① Dissolve 5 parts by weight of polycarboxylate dispersant in 800 parts of deionized water, stir evenly, add 25 parts of hydrophobic modified nano silica and 10 parts of POSS, stir evenly to obtain a pre-dispersion liquid; Step ② Perform ultrasonic dispersion treatment on the dispersion liquid, control the ultrasonic power to be 300W and the ultrasonic time to be 10min, and obtain an ultrasonic dispersion liquid with D50≤150nm; Step ③ Add the ultrasonic dispersion liquid to 500 parts of polysiloxane-type organosilicon-based fluorine-free oil-resistant finishing agent and stir for 30min, then heat to 40℃ and add 2.5 parts of HDI trimer crosslinking agent, stir for 30min, and after adding deionized water and adjusting the viscosity to 55mPa·s at 25℃, obtain the finished product POSS-nano silica@organosilicon-based fluorine-free oil-resistant finishing agent.

[0041] Example 2

[0042] A manufacturing process for a fluorine-free, oil-resistant elastic fabric includes a pretreatment section, a dyeing section, and a finishing section. Among them:

[0043] The pretreatment process includes sequentially subjecting the greige fabric to cold stacking, two desizing cycles, refining, and pre-setting to obtain the pre-finished greige fabric. It should be noted that in the pretreatment process, cold stacking uses a 20 g / L liquid alkali solution, controlled at 80°C and pH 11.5, for 48 hours. Desizing uses a 3 g / L liquid alkali solution, controlled at 55°C and pH 11.5, for 40 minutes. Refining uses a 5 g / L nonionic surfactant solution, controlled at 95°C, for 50 minutes. Pre-setting is performed at a controlled temperature of 180°C and a setting speed of 25 m / min.

[0044] The dyeing process involves immersing the pre-finished fabric in a dye solution containing dye for dyeing treatment, followed by sequential washing, soaping, acid washing, and washing to obtain the dyed fabric. It should be noted that in the dyeing process, the pre-finished fabric is immersed in a dye solution consisting of 3 owf% dye, 1 g / L leveling agent, and a pH adjuster, with a liquor ratio controlled at 1:18 and the dye solution temperature at 92℃ for 45 minutes. Soaping is performed using a 3 g / L soaping agent at 85℃ for 22 minutes. Acid washing is performed using 1.5 g / L acetic acid at a pH of 4.5 for 13 minutes.

[0045] It should be mentioned that, in this embodiment, in order to improve the bonding effect between the dye and the finishing part, the dye used is a siloxane-grafted modified dye. The preparation method of the siloxane-grafted modified dye includes step ① mixing the base dye and DMF at a ratio of 1g:4.9mL and stirring, and controlling the mixing temperature at 63℃ to obtain a pre-mixed dye solution after the base dye is completely dissolved; step ② adding a modified monomer and DBTDL at a mass ratio of 100:18:0.7 to the base dye to the pre-mixed dye solution, and the modified monomer in this embodiment is γ-aminopropyltriethoxysilane-modified polydimethylsiloxane. After stirring and mixing evenly, the temperature is raised to 85℃ and kept at this temperature for 2.5h under inert gas protection to obtain a modified reaction mixture; step ③ lowering the temperature of the modified reaction mixture to 45℃ and adding triethylamine while stirring, controlling the ratio of the amount of triethylamine added to the base dye to 2.5mL:100g, and then adding excess deionized water and stirring to precipitate and obtain the siloxane-grafted modified dye. Add 0.5 g / L of polyether-modified polysiloxane compatibilizer to the dye solution and stir until homogeneous.

[0046] The finishing process includes immersing the dyed greige fabric in a fluorine-free oil-repellent finishing agent working solution for padding. After sequential drying, setting, stretching, and pre-shrinking, the finished elastic fabric is obtained. It should be noted that in the finishing process, the padding liquid ratio is 78%. Drying is performed at a controlled temperature of 90℃ for 45 seconds. Setting is performed at a controlled temperature of 170℃ for 1.2 minutes; stretching is performed at a controlled temperature of 170℃ and a speed of 30 m / min. Pre-shrinking is performed using wet heat pre-shrinking, with the temperature controlled at 135℃ and humidity at 85%, a pre-shrinking speed of 5 m / min, and tension-free fabric entry and exit.

[0047] Meanwhile, in the embodiments of this application, the fluorine-free oil-resistant finishing agent is POSS-nano silica@organosilicon-based fluorine-free oil-resistant finishing agent. The preparation method of POSS-nano silica@organosilicon-based fluorine-free oil-resistant finishing agent includes the following steps: Step ① Dissolve 7 parts by weight of polycarboxylate dispersant in 900 parts of deionized water, stir evenly, add 30 parts of hydrophobic modified nano silica and 12 parts of POSS, stir evenly to obtain a pre-dispersion liquid; Step ② Perform ultrasonic dispersion treatment on the dispersion liquid, control the ultrasonic power to be 400W and the ultrasonic time to be 12min, and obtain an ultrasonic dispersion liquid with D50≤150nm; Step ③ Add the ultrasonic dispersion liquid to 500 parts of polysiloxane-type organosilicon-based fluorine-free oil-resistant finishing agent and stir for 35min, then raise the temperature to 45℃ and add 4 parts of HDI trimer crosslinking agent, stir for 35min, and after adding deionized water and adjusting the viscosity to 70mPa·s at 25℃, obtain the finished product POSS-nano silica@organosilicon-based fluorine-free oil-resistant finishing agent.

[0048] Example 3

[0049] A manufacturing process for a fluorine-free, oil-resistant elastic fabric includes a pretreatment section, a dyeing section, and a finishing section. Among them:

[0050] The pretreatment process includes sequentially subjecting the greige fabric to cold stacking, two desizing cycles, refining, and pre-setting to obtain the pre-finished greige fabric. It should be noted that in the pretreatment process, cold stacking uses a 30 g / L liquid alkali solution, controlled at 85°C and pH 13, for 48 hours. Desizing uses a 5 g / L liquid alkali solution, controlled at 60°C and pH 13, for 30 minutes. Refining uses an 8 g / L nonionic surfactant solution, controlled at 100°C, for 30 minutes. Pre-setting is performed at a controlled temperature of 180°C and a setting speed of 30 m / min.

[0051] The dyeing process involves immersing the pre-finished fabric in a dye solution containing dye for dyeing treatment, followed by sequential washing with water, soaping, acid washing, and washing with water to obtain the dyed fabric. It should be noted that in the dyeing process, the dyeing treatment involves immersing the pre-finished fabric in a dye solution composed of 5 owf% dye, 2 g / L leveling agent, and pH adjuster, controlling the liquor ratio at 1:20, the dye solution temperature at 95℃, and holding for 30 minutes. Soaping is performed using 5 g / L soaping agent at 90℃ for 15 minutes. Acid washing is performed using 2 g / L acetic acid at pH 5 for 10 minutes.

[0052] It should be mentioned that, in the embodiments of this application, in order to improve the bonding effect between the dye and the finishing part, the dye used is a siloxane grafted modified dye. The preparation method of siloxane-grafted modified dye includes the following steps: Step ① Mixing and stirring the base dye and DMF at a ratio of 1g:5mL, and controlling the mixing temperature at 65℃ to obtain a pre-mixed dye solution after the base dye is completely dissolved; Step ② Adding a modified monomer and DBTDL at a mass ratio of 100:20:1 to the base dye to the pre-mixed dye solution, wherein the modified monomer in this embodiment is γ-aminopropyltriethoxysilane-modified polydimethylsiloxane, and after stirring and mixing evenly, raising the temperature to 90℃ and holding it at this temperature for 2 hours under inert gas protection to obtain a modified reaction mixture; Step ③ Lowering the temperature of the modified reaction mixture to 50℃ and adding triethylamine while stirring, controlling the ratio of triethylamine to base dye at 3mL:100g, and then adding excess deionized water and stirring to precipitate and obtain the siloxane-grafted modified dye; and adding 0.8g / L of polyether-modified polysiloxane compatibilizer to the dye solution and stirring evenly.

[0053] The finishing process involves immersing the dyed greige fabric in a fluorine-free oil-repellent finishing agent working solution for padding. After sequential drying, setting, stretching, and pre-shrinking, the finished elastic fabric is obtained. It should be noted that in the finishing process, the padding liquid ratio is 65%. Drying is performed at a controlled temperature of 100℃ for 1 minute. Setting is performed at a controlled temperature of 180℃ for 1 minute. Stretching is performed at a controlled temperature of 180℃ and a speed of 35 m / min. Pre-shrinking is performed using wet heat pre-shrinking, with the temperature controlled at 130℃ and humidity at 90%, a pre-shrinking speed of 5 m / min, and tension-free fabric entry and exit.

[0054] Meanwhile, in the embodiments of this application, the fluorine-free oil-resistant finishing agent is POSS-nano silica@organosilicon-based fluorine-free oil-resistant finishing agent. The preparation method of POSS-nano silica@organosilicon-based fluorine-free oil-resistant finishing agent includes the following steps: Step ① Dissolve 8 parts by weight of polycarboxylate dispersant in 1000 parts of deionized water, stir evenly, add 40 parts of hydrophobic modified nano silica and 15 parts of POSS, stir evenly to obtain a pre-dispersion liquid; Step ② Perform ultrasonic dispersion treatment on the dispersion liquid, control the ultrasonic power to be 500W and the ultrasonic time to be 15min, and obtain an ultrasonic dispersion liquid with D50≤150nm; Step ③ Add the ultrasonic dispersion liquid to 500 parts of polysiloxane-type organosilicon-based fluorine-free oil-resistant finishing agent and stir for 40min, then heat to 50℃ and add 5 parts of HDI trimer crosslinking agent, stir for 40min, and after adding deionized water and adjusting the viscosity to 90mPa·s at 25℃, obtain the finished product POSS-nano silica@organosilicon-based fluorine-free oil-resistant finishing agent.

[0055] Comparative Example 1

[0056] The difference between Comparative Example 1 and Example 3 is that the fluorine-free oil-resistant finishing agent in Comparative Example 1 is a polysiloxane-type organosilicon fluorine-free oil-resistant finishing agent.

[0057] Comparative Example 2

[0058] The difference between Comparative Example 2 and Example 3 is that the dye in Comparative Example 2 is Acid Red G that has not been modified by siloxane grafting.

[0059] Comparative Example 3

[0060] The difference between Comparative Example 3 and Example 3 is that no 0.8 g / L of polyether-modified polysiloxane compatibilizer was added to the dye solution in Comparative Example 3.

[0061] Performance testing:

[0062] 1. Oil resistance rating: According to GB / T 30159.1-2013 Liquid contamination method, pressed peanut oil is used, and the penetration is observed after 30 seconds. The rating is divided into 1-5 levels, with level 5 being the best.

[0063] 2. Stain resistance rating: According to FZ / T 01118-2012 "Test and evaluation of stain resistance performance of textiles" "wiping method / 30 wipings", the fabric is coated with high-salt dilute fermented soy sauce and wiped 30 times according to the standard procedure. The stain residue level is evaluated by gray scale card. The level is divided into 1-5, with level 5 being the best.

[0064] 3. Oil resistance rating after washing: According to GB / T 8629-2017, the product is washed 5 times at 40℃, tumbled and dried, and then the oil resistance rating is tested. The rating is divided into 1-5, with 5 being the best.

[0065] 4. Colorfastness: According to GB / T 3921-2008 "Textiles - Tests for colorfastness to washing", after washing at 40℃, the fading and staining grades of the fabric are assessed using a gray scale, with grades ranging from 1 to 5, and grade 5 being the best.

[0066] 5. Elastic recovery rate: According to GB / T 3923.1-2013 "Textiles - Tensile properties of fabrics - Part 1: Determination of breaking strength and elongation at break", the fabric is stretched to 120% elongation and then recovered for 30 minutes. The difference between the stretched length and the residual length after recovery is calculated as a percentage of the stretched length.

[0067] The performance test results are shown in Table 1 below.

[0068] Table 1 Performance Test Results

[0069] As shown in Table 1 above, Example 1 of this application forms a basic micro-nano rough structure using POSS-nano silica@organosilicon finishing agent. The siloxane-modified dye and 0.3 g / L of polyether-modified polysiloxane compatibilizer synergistically reduce the surface energy of the fabric, achieving an oil repellency level of 4. After washing, the oil repellency level reaches 3, demonstrating a significant improvement in oil repellency durability. However, compared to Examples 2 and 3, Example 1 has a lower amount of finishing agent adhesion and cross-linking degree, resulting in lower oil repellency and wash retention rates compared to Examples 2 and 3.

[0070] Meanwhile, in Comparative Example 1, the use of only a polysiloxane-type silicone-based fluorine-free oil-repellent finishing agent resulted in a higher surface energy of the fabric due to the lack of a micro-nano rough structure, making it easier for oil stains to penetrate. This reduced the oil repellency level from level 4 in Example 3 to level 1. Furthermore, the lack of nanoparticle anchoring in the fluorine-free oil-repellent finishing agent led to reduced adhesion, making it prone to peeling off after washing. In Comparative Example 2, the use of Acid Red G dye without siloxane fragments resulted in poor compatibility with the polysiloxane-type silicone-based fluorine-free oil-repellent finishing agent. This caused the polysiloxane-type silicone-based fluorine-free oil-repellent finishing agent to easily form island-like adhesions on the surface of the dyed fabric, leading to insufficient oil repellency continuity and a reduction in the oil repellency level from level 4 in Example 3 to level 1. Additionally, the weak bonding between Acid Red G and the fibers of the pre-treated fabric resulted in decreased dyeing wash fastness. In Comparative Example 3, the lack of a polyether-modified polysiloxane compatibilizer as a bridge for intermolecular connections reduces the interfacial bonding force between the siloxane fragments of the siloxane-grafted modified dye and the fluorine-free oil-resistant finishing agent, resulting in the local detachment of the fluorine-free oil-resistant finishing agent and a reduction in the oil resistance level to Grade 1.

[0071] In summary, this application provides a manufacturing process for a fluorine-free oil-resistant elastic fabric. This process involves combining nano-silica and POSS with a base finishing agent to form a composite protective layer on the surface of the dyed fabric, consisting of a micro-nano rough structure and a low surface energy organosilicon layer. The process utilizes the micron-level protrusions of nano-silica and the cage-like structure of POSS to construct a nano-level texture. By combining the low surface energy characteristics of organosilicon, the process significantly improves the oil contact angle, thereby reducing accidental adhesion. Furthermore, the three-dimensional structure enhances the abrasion resistance of the composite protective layer, thus extending the duration of the anti-fouling effect. Meanwhile, by using siloxane-grafted modified dyes in synergy with fluorine-free oil-resistant finishing agents, the siloxane fragments in the dyes grafted with γ-aminopropyltriethoxysilane-modified polydimethylsiloxane are improved to enhance their compatibility with the fluorine-free oil-resistant finishing agents. Furthermore, the addition of polyether-modified polysiloxane compatibilizers further promotes the interfacial bonding effect between the siloxane-grafted modified dyes and the fluorine-free oil-resistant finishing agents, forming a dual-layer protective structure that combines dye transition and finishing agent function. This avoids mutual interference between the dyeing and finishing processes and allows the siloxane-grafted modified dyes to provide anchoring points for the fluorine-free oil-resistant finishing agents, improving the adhesion of the fluorine-free oil-resistant finishing agents, effectively increasing the difficulty of removal after washing, and achieving enhanced stain resistance and durability. In the overall manufacturing process, the adhesion effect of the fluorine-free oil-repellent finishing agent is improved by controlling the padding and rolling rate, and the setting temperature and setting time are effectively controlled to promote the reaction of the HDI trimer crosslinking agent, so that the fluorine-free oil-repellent finishing agent forms a three-dimensional network structure. At the same time, the control of temperature, time and concentration are coordinated to effectively improve the uniformity and stability of the surface layer structure of the finished elastic fabric, thereby effectively exerting the oil and stain repellency effect.

[0072] The terms “first,” “second,” “third,” “fourth,” etc., used in this application (if applicable) are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence. It should be understood that such data can be interchanged where appropriate so that the embodiments described herein can be implemented in orders other than those described herein. Furthermore, the terms “comprising” and “having,” and any variations thereof, are intended to cover non-exclusive inclusion; for example, a process, method, or apparatus that includes a series of steps or units is not necessarily limited to those explicitly listed, but may include other steps or units not explicitly listed or inherent to such processes, methods, or apparatus.

[0073] It should be noted that the use of terms such as "first" and "second" in this application is for descriptive purposes only and should not be construed as indicating or implying their relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include at least one of those features. Furthermore, the technical solutions of the various embodiments can be combined with each other, but this must be based on the ability of those skilled in the art to implement them. If the combination of technical solutions is contradictory or impossible to implement, such a combination of technical solutions should be considered non-existent and not within the scope of protection claimed in this application.

[0074] This document uses specific examples to illustrate the principles and implementation methods of this application. The descriptions of the above embodiments are only for the purpose of helping to understand the methods and core ideas of this application. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this application. Therefore, the content of this specification should not be construed as a limitation of this application.

Claims

1. A process for making a fluorine-free oil repellent elastic fabric, characterized in that, It includes pretreatment, staining, and finishing processes; among which: The pretreatment section includes taking the fabric and sequentially performing cold stacking, desizing twice, refining and pre-forming to obtain the pre-finished fabric; The dyeing process includes immersing the pre-finished fabric in a dye solution containing dye for dyeing treatment, and then sequentially washing with water, soaping, acid washing and washing with water to obtain the dyed fabric. The finishing process includes immersing the dyed fabric in a fluorine-free oil-resistant finishing agent working solution for padding, and then sequentially drying, setting, stretching, and pre-shrinking to obtain the finished elastic fabric. The fluorine-free oil-resistant finishing agent is a POSS-nano silica@organosilicon-based fluorine-free oil-resistant finishing agent.

2. The manufacturing process of a fluorine-free oil-resistant elastic fabric according to claim 1, characterized in that: In the pretreatment section, the cold pile uses liquid alkali with a concentration of 20-30 g / L, controls the temperature at 75-85℃, the pH at 11-13, and treats for 24-48 hours; the desizing uses liquid alkali with a concentration of 2-5 g / L, controls the temperature at 50-60℃, the pH at 11-13, and treats for 30-60 minutes; the refining uses nonionic surfactant with a concentration of 3-8 g / L, controls the temperature at 90-100℃, and treats for 30-60 minutes; the pre-setting uses a temperature of 160-180℃ and a setting speed of 20-30 m / min.

3. The manufacturing process of a fluorine-free oil-resistant elastic fabric according to claim 1, characterized in that: In the dyeing section, the dyeing treatment involves immersing the pre-finished fabric in a dye solution composed of 1-5 owf% dye, 0.5-2 g / L leveling agent, and pH adjuster, controlling the liquor ratio at 1:15-20, the temperature of the dye solution at 90-95℃, and maintaining the temperature for 30-60 minutes; the soaping involves using 2-5 g / L soaping agent and controlling the temperature at 80-90℃ for 15-30 minutes; the acid washing involves using 1-2 g / L acetic acid and controlling the pH at 4-5 for 10-15 minutes.

4. The manufacturing process of a fluorine-free oil-resistant elastic fabric according to claim 1 or 3, characterized in that: The dye is a siloxane-grafted modified dye. The preparation method of the siloxane-grafted modified dye includes the following steps: Step ① Mixing and stirring the base dye and DMF at a ratio of 1g:4.8-5mL, and controlling the mixing temperature at 60-65℃ to obtain a pre-mixed dye solution after the base dye is completely dissolved; Step ② Adding a modified monomer and DBTDL at a mass ratio of 100:15-20:0.5-1 to the pre-mixed dye solution, stirring and mixing evenly, raising the temperature to 80-90℃, and holding under inert gas protection for 2-3 hours to obtain a modified reaction mixture; Step ③ Lowering the temperature of the modified reaction mixture to 40-50℃ and adding triethylamine while stirring, controlling the ratio of triethylamine to base dye at 2-3mL:100g, then adding excess deionized water and stirring to precipitate and obtain the siloxane-grafted modified dye; and adding 0.3-0.8g / L of polyether-modified polysiloxane compatibilizer to the dye solution and stirring evenly.

5. The manufacturing process of a fluorine-free oil-resistant elastic fabric according to claim 4, characterized in that: The modified monomer is γ-aminopropyltriethoxysilane-modified polydimethylsiloxane with a molecular weight of 800-1200 and an amino value of 0.3-0.5 mmol / g.

6. The manufacturing process of a fluorine-free oil-resistant elastic fabric according to claim 1, characterized in that: In the finishing process, the slurry rate of the padding treatment is 60-80%; the drying is carried out at a controlled temperature of 80-100℃ for 30 seconds to 1 minute; the setting is carried out at a controlled temperature of 160-180℃ for 1-1.5 minutes; the stretching is carried out at a controlled temperature of 160-180℃ and a speed of 25-35 m / min; the pre-shrinking is carried out using wet heat pre-shrinking, with the temperature controlled at 130-150℃ and the humidity at 80-90%, the pre-shrinking speed at 5 m / min, and the fabric is fed in and out without tension.

7. The manufacturing process of a fluorine-free oil-resistant elastic fabric according to claim 1, characterized in that: The POSS-nano silica@organosilicon-based fluorine-free oil-resistant finishing agent contains 3-12 wt% nano silica and 1-5 wt% POSS.

8. The manufacturing process of a fluorine-free oil-resistant elastic fabric according to claim 7, characterized in that: The preparation method of the POSS-nano silica@organosilicon-based fluorine-free oil-resistant finishing agent includes the following steps: Step ① Dissolve 5-8 parts by weight of polycarboxylate dispersant in 800-1000 parts of deionized water, stir evenly, add 25-40 parts of hydrophobic modified nano silica and 10-15 parts of POSS, stir evenly to obtain a pre-dispersion; Step ② Perform ultrasonic dispersion treatment on the dispersion, control the ultrasonic power to be 300-500W and the ultrasonic time to be 10-15min, and obtain an ultrasonic dispersion with D50≤150nm; Step ③ Add the ultrasonic dispersion to 500 parts of basic finishing agent and stir for 30-40min, then heat to 40-50℃ and add 2.5-5 parts of HDI trimer crosslinking agent, and stir for 30-40min to obtain the finished POSS-nano silica@organosilicon-based fluorine-free oil-resistant finishing agent.

9. The manufacturing process of a fluorine-free oil-resistant elastic fabric according to claim 8, characterized in that: The base finishing agent is a polysiloxane-type organosilicon-based fluorine-free oil-resistant finishing agent or a paraffin-acrylate copolymer-type hydrocarbon-based fluorine-free oil-resistant finishing agent.

10. The manufacturing process of a fluorine-free oil-resistant elastic fabric according to claim 7, characterized in that: In step ③, the finished POSS-nano silica@organosilicon-based fluorine-free oil-resistant finishing agent is obtained by adding deionized water and adjusting the viscosity at 25℃ to 50-100 mPa·s.

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