Textile size with high degree of combination and method for preparing the same

Abstract

The application relates to a high-bonding textile sizing agent, which comprises the following components in parts by weight: a starch component 20-50 parts by weight, an acrylate 5-10 parts by weight, a water-based polyurethane 2-3 parts by weight, sodium carbonate 0.5-2 parts by weight, styrene 6-12 parts by weight, an emulsifier 5-8 parts by weight, an initiator 1-1.5 parts by weight, sodium polyphosphate 1-2 parts by weight, algin 5-10 parts by weight, blue-green algae extract 1-1.5 parts by weight, a softener 5-8 parts by weight, triethylamine 5-8 parts by weight, and deionized water 70-100 parts by weight. The application selects an acrylic emulsion, a water-based polyurethane and algin as auxiliary sizing agent components of the textile sizing, and the auxiliary sizing agent components are mixed with the starch sizing agent, and the synergistic effect among the substances can effectively improve the stability of the sizing agent and effectively improve the application adhesion and bonding degree of the sizing agent to the yarn.

Description

Technical Field

[0001] This application relates to the field of textile sizing technology, and in particular to high-adhesion textile sizing and its preparation method. Background Technology

[0002] In the textile weaving process, warp yarns are prone to breakage and weaving defects due to repeated friction from loom parts and between yarns. Unsized warp yarns also tend to have more surface hairs, causing yarn entanglement and unclear weaving. These problems can easily affect the smooth progress of weaving and reduce efficiency. Therefore, most short-fiber and filament warp yarns used in textile fabrics require sizing before weaving. Sizing involves preparing a water-dispersible sizing agent for warp yarns, applying it to the warp yarns, and allowing some of the sizing to penetrate the yarn while some is applied to the surface. After drying, the internal sizing causes the fibers to bond together, while the surface sizing forms a film.

[0003] The main components of textile sizing agents are adhesives and auxiliaries. After sizing warp yarns, adhesives effectively improve their weaveability, reduce yarn breaks, and ensure weaving efficiency and fabric quality. Auxiliaries, on the other hand, can compensate for some shortcomings of adhesives, thereby improving the quality of sized yarns. Currently, there are four main types of textile sizing agents widely used: modified starch, polyvinyl alcohol, polyester, and polyacrylate sizing agents, all of which are natural or synthetic polymers with thickening properties. However, existing textile sizing agents formulated from multiple agents suffer from low adhesion and insufficient bonding between the sizing agent and the yarn. Therefore, improving the adhesion and bonding of textile sizing agents remains a challenge. Summary of the Invention

[0004] To improve the adhesion and bonding strength of textile sizing agents, this application provides a textile sizing agent with high bonding strength and a method for preparing the same.

[0005] In the first aspect, this application provides a textile sizing agent with high bonding strength, using the following technical solution: The high-binding textile sizing agent comprises the following components in parts by weight: 20-50 parts starch, 5-10 parts acrylate, 2-3 parts waterborne polyurethane, 0.5-2 parts sodium carbonate, 6-12 parts styrene, 5-8 parts emulsifier, 1-1.5 parts initiator, 1-2 parts sodium polyphosphate, 5-10 parts alginate, 1-1.5 parts cyanobacterial extract, 5-8 parts softener, 5-15 parts triethylamine, and 70-100 parts deionized water.

[0006] By adopting the above technical solution, starch is selected as the main sizing component for textile sizing because starch is a natural polysaccharide polymer with good film-forming properties and high adhesion to both natural and regenerated cellulose fibers, making it easy to desizing. Acrylic esters, styrene, waterborne polyurethane, and alginate are selected as auxiliary sizing components for textile sizing. By mixing these auxiliary sizing components with starch sizing, the adhesion of the sizing to the yarn can be effectively improved, the film-forming effect of the sizing can be enhanced, and the bonding between the textile sizing and the yarn can be increased. Triethylamine is selected as a neutralizing agent to adjust the pH value of the solution. Softeners are selected to improve the smoothness and softness of the fabric. Blue-green algae extract containing pectin and cellulose is selected to improve the adhesion performance of the sizing to the yarn in textile sizing. Sodium carbonate and sodium polyphosphate can promote yarn swelling and improve the adhesion and bonding effect of the sizing on the yarn.

[0007] In one specific implementation, the starch component is a mixture of carboxymethyl starch, acid-hydrolyzed starch, and acetate starch.

[0008] By adopting the above technical solution, native starch exhibits good adhesion to hydrophilic fibers, but extremely poor adhesion to hydrophobic synthetic fibers, making it unsuitable for sizing synthetic fibers such as polyester. Sizing can easily affect yarn quality and weaving efficiency. By modifying native starch, the adhesion of modified starch to synthetic fibers can be improved, especially to polyester-cotton blended yarns, enhancing the flexibility of the sizing film and improving the thermal stability of the sizing agent.

[0009] In one specific implementation, the mass ratio of carboxymethyl starch, acid-hydrolyzed starch, and acetate starch is (0.5-0.8):(0.3-0.5):(0.5-0.8).

[0010] By employing the above technical solutions, carboxymethyl starch is obtained by etherification of the hydroxyl groups in native starch. This starch forms a slurry film with high flexibility and stable viscosity, while also exhibiting good miscibility. Adding inorganic acids to the starch solution at temperatures below the gelatinization temperature catalyzes the hydrolysis of starch, generating acid-hydrolyzed starch, thereby reducing the degree of polymerization of starch macromolecules and improving its sizing performance. The hydroxyl groups in native starch undergo esterification with acids, resulting in partial replacement of hydroxyl groups with ester groups, thus yielding acetate starch, which is used to improve adhesion to hydrophobic synthetic fibers. By compounding these three types of starch, a main sizing system for textile sizing is formed, thereby improving the chemical properties of the sizing agent and giving it better adhesion and film-forming properties.

[0011] In one specific embodiment, the carboxymethyl starch is grafted with acrylamide, and the acrylamide-grafted carboxymethyl starch is prepared as follows: Distilled water was added to carboxymethyl starch and heated and stirred to obtain a starch slurry solution; then distilled water was added to acrylamide monomer and stirred evenly; the acrylamide solution was added to the starch slurry solution and stirred while adjusting the pH to remove oxygen; then potassium persulfate aqueous solution was added, heated and reacted, and then removed; the reactants were precipitated and dried to obtain carboxymethyl starch grafted with acrylamide.

[0012] By adopting the above technical solution, acrylamide oligomer branches are grafted onto carboxymethyl starch, so that acrylamide combines with starch chains in the form of side chains to form polymers. By grafting high-performance polymers, the thermal stability of the graft copolymer is improved, thereby giving it excellent sizing properties and biodegradability, and also improving its compatibility with other sizing agents.

[0013] In one specific implementation, the acrylates include one or more of methyl acrylate, ethyl acrylate, butyl acrylate, and methyl methacrylate.

[0014] In one specific implementation, the waterborne polyurethane is prepared as follows: polyether polyol and polyester polyol are mixed and heated, and dehydrated under vacuum for 1-3 hours. Then, isophorone diisocyanate, dibutyltin dilaurate and hexamethylene diisocyanate are added. After heating, 1,6-hexanediol and dimethylolpropionic acid are added. After heating and holding at the temperature, an acid-base adjuster is added to adjust the pH. After stirring, the mixture is vacuum filtered and discharged.

[0015] By adopting the above technical solution, the soft segment of waterborne polyurethane is composed of polyol, and the hard segment is composed of isocyanate and chain extender. The soft segment can affect the flexibility of the molecular chain, and the flexibility can affect the dispersion effect of the molecular chain in the system. The ether bonds in polyether polyol can rotate freely, which increases the flexibility of the molecular chain and is conducive to the extension of the molecular chain and dispersion in the system. The ester groups in polyester polyol have higher polarity than ether bonds and better affinity with water, which can improve the dispersibility of the emulsion. Therefore, choosing to compound polyether polyol and polyester polyol to prepare waterborne polyurethane can improve the hydrophilicity and solution dispersion stability of waterborne polyurethane. Furthermore, because waterborne polyurethane has excellent film-forming ability and abrasion resistance, and strong adhesion to fibers, the bonding between the sizing agent and the yarn is strengthened. By adding waterborne polyurethane as one of the auxiliary main sizing components, the bonding and application adhesion between starch sizing agent and yarn can be improved, while giving the yarn strong abrasion resistance.

[0016] In one specific feasible embodiment, the preservative is further comprising 5-8 parts by weight of a preservative composed of iodopropynyl n-butylcarbamate, octylisothiazolinone, and methyl benzimidazole carbamate in a mass ratio of (0.8-1):(0.8-1):(0.5-0.8).

[0017] By adopting the above technical solution, three preservatives with high anti-mildew efficacy and high compatibility with sizing agents are selected and applied to yarn through compounding, so that the yarn can obtain significant anti-mildew and antibacterial ability. At the same time, since the main sizing system of this application is starch sizing agent, starch sizing agent is prone to mold growth. Therefore, adding preservatives can play a certain role in inhibiting this phenomenon.

[0018] In one specific implementation, the initiator includes one or more of ammonium persulfate, sodium persulfate, and potassium persulfate.

[0019] By adopting the above technical solution, ammonium persulfate, sodium persulfate, and potassium persulfate are all water-soluble persulfates, suitable for emulsion or aqueous solution polymerization reaction systems; water-soluble persulfates are used as initiators to promote the polymerization reaction of acrylate monomers, so as to generate homopolymers or copolymers, thereby forming an auxiliary sizing system for textile sizing.

[0020] Secondly, this application provides a method for preparing a textile sizing agent with high binding strength, using the following technical solution: A method for preparing a textile sizing agent with high binding strength includes the following steps: S1. Divide the deionized water into two parts, take one part and mix it with the emulsifier, heat it to 80-90℃, and obtain solution A; S2. Take acrylate and styrene, mix them well to obtain solution B; S3. Take another portion of deionized water and initiator to prepare an initiator aqueous solution. First, add part of the initiator aqueous solution to solution A, stir, then add solution B and the remaining initiator aqueous solution dropwise, mix well, and react. S4. Cool to 40-50℃, add triethylamine to adjust the pH, then add starch components, waterborne polyurethane, sodium carbonate, sodium polyphosphate, alginate, blue algae extract, preservatives and softeners, and mix well to obtain the final product.

[0021] In summary, this application includes at least one of the following beneficial technical effects: 1. This application selects acrylic emulsion, waterborne polyurethane, and alginate as auxiliary sizing components for textile sizing. Among them, acrylic ester has strong adhesion and film-forming properties; waterborne polyurethane has excellent film-forming ability and very good adhesion to both hydrophilic and hydrophobic fibers, thereby effectively improving the bonding between textile sizing agent and yarn; alginate also has strong adhesion and film-forming properties. By mixing these auxiliary sizing components with starch sizing agent, the synergistic effect between the substances can effectively improve the stability of the sizing agent and effectively improve the adhesion and bonding of the sizing agent to the yarn.

[0022] 2. This application improves the characteristics of starch sizing film made from native starch, such as "brittle and hard" and poor thermal stability, by modifying starch. It also combines three modified starches to form the main sizing system for textile sizing, thereby improving the chemical properties of the sizing. Since the starch sizing in the main sizing system is prone to mold growth, a preservative composed of iodopropynyl n-butylcarbamate, octylisothiazolinone, and benzimidazole carbamate is added to reduce the mold growth of the starch sizing, which also helps to improve the anti-mold and antibacterial effect of the yarn. Detailed Implementation

[0023] In this application, the alginate was purchased from Merck Electronic Materials, model number 180947; the softener was purchased from Dongguan Taiyang New Material Technology, model number TYW-129; the polyether polyols were specifically graded N-220 and GEP-330N; the polyester polyol was purchased from Chengdu Kelong Chemical, model number PBA2000; the carboxymethyl starch was purchased from Shanghai Yuanye Biotechnology, model number S30572; the acetate starch was purchased from Shanghai Yingxin Laboratory Equipment, model number TX2287; the acid-hydrolyzed starch was purchased from Chengdu Hongbo; and all other raw materials were commercially available.

[0024] Preparation Example Preparation Example 1 Distilled water and carboxymethyl starch were mixed at a mass ratio of 30:1 and heated to 50°C to dissolve, yielding a starch slurry solution. Acrylamide was weighed at a mass ratio of 1:1 with carboxymethyl starch, and then distilled water at a mass ratio of 1:1 with acrylamide was added and stirred until homogeneous to obtain an acrylamide solution. The acrylamide solution was added to the starch slurry solution and stirred continuously. The pH was adjusted to 7.5 using sodium hydroxide and glacial acetic acid, and then nitrogen gas was introduced into the container containing the solution. Potassium persulfate and distilled water were weighed, with a mass ratio of potassium persulfate to acrylamide of 0.005:1. Potassium persulfate was dissolved in water to prepare a 0.5% potassium persulfate solution, which was then added to the starch slurry solution and heated at 50°C for 3 hours. Finally, the solution was precipitated using 95% ethanol, and the precipitate was dried at 50°C for 22 hours. After pulverization, carboxymethyl starch grafted with acrylamide was obtained.

[0025] Preparation Example 2 Distilled water and carboxymethyl starch were mixed at a mass ratio of 30:1 and heated to 60°C to dissolve, yielding a starch slurry solution. Acrylamide was weighed at a mass ratio of 1:1 with carboxymethyl starch, and then distilled water at a mass ratio of 1:1 with acrylamide was added and stirred until homogeneous to obtain an acrylamide solution. The acrylamide solution was added to the starch slurry solution and stirred continuously. The pH was adjusted to 10 using sodium hydroxide and glacial acetic acid, and then nitrogen gas was introduced into the container containing the solution. Potassium persulfate and distilled water were weighed, with a mass ratio of potassium persulfate to acrylamide of 0.005:1. Potassium persulfate was dissolved in water to prepare a 1% potassium persulfate solution, which was then added to the starch slurry solution and heated at 70°C for 5 hours. Finally, the solution was precipitated using 95% ethanol, and the precipitate was dried at 60°C for 26 hours. After pulverization, carboxymethyl starch grafted with acrylamide was obtained.

[0026] Preparation Example 3 Polyether N-220, polyether GEP-330N, and polyester polyol were mixed in a mass ratio of 1:1:2 and heated to 90°C. The mixture was then dehydrated under a vacuum of 0.6 MPa for 1 hour. After cooling to 60°C, a mixture of isophorone diisocyanate, dibutyltin dilaurate, and hexamethylene diisocyanate in a mass ratio of 1:1 (to the polyester polyol) was added, with the mass ratio of isophorone diisocyanate, dibutyltin dilaurate, and hexamethylene diisocyanate being 1:0.5:1. The mixture was stirred and heated to 75°C for 1 hour. Finally, a mass fraction of [missing information - likely a specific ingredient or ingredient] was added. 6% dimethylolpropionic acid, wherein the mass ratio of isophorone diisocyanate to dimethylolpropionic acid is 5:1, is heated to 90°C and held for 2 hours. During the reaction, acetone with a mass ratio of 1:1 to dimethylolpropionic acid is added. After the reaction is completed, the temperature is lowered to 35°C, and triethylamine is added to adjust the pH to 7.5. Then, deionized water and ethylenediamine are added sequentially, wherein the mass ratio of deionized water to isophorone diisocyanate is 4:1, and the mass ratio of ethylenediamine to isophorone diisocyanate is 0.1:1. After stirring, acetone is removed and the product is filtered to obtain waterborne polyurethane.

[0027] Preparation Example 4 Polyether N-220, polyether GEP-330N, and polyester polyol were mixed in a mass ratio of 1:1:2 and heated to 120°C. The mixture was then dehydrated under a vacuum of 1.0 MPa for 3 hours. After cooling to 60°C, a mixture of isophorone diisocyanate, dibutyltin dilaurate, and hexamethylene diisocyanate in a mass ratio of 1:1 (to the polyester polyol) was added, with the mass ratio of isophorone diisocyanate, dibutyltin dilaurate, and hexamethylene diisocyanate being 1:0.5:1. The mixture was stirred and heated to 75°C for 3 hours. Finally, a mass fraction of [missing information - likely a specific ingredient or ingredient] was added. 6% dimethylolpropionic acid, wherein the mass ratio of isophorone diisocyanate to dimethylolpropionic acid is 5:1, is heated to 100℃ and held for 4 hours. During the reaction, acetone with a mass ratio of 1:1 to dimethylolpropionic acid is added. After the reaction is completed, the temperature is lowered to 45℃, and triethylamine is added to adjust the pH to 7.5. Then, deionized water and ethylenediamine are added sequentially, wherein the mass ratio of deionized water to isophorone diisocyanate is 4:1, and the mass ratio of ethylenediamine to isophorone diisocyanate is 0.1:1. After stirring, acetone is removed and the product is filtered to obtain waterborne polyurethane. Example

[0028] Example 1 The high-binding textile sizing agent is prepared from the following raw materials: 20g starch component, 5g methyl acrylate, 2g waterborne polyurethane, 0.5g sodium carbonate, 6g styrene, 5g emulsifier, 1g initiator, 1g sodium polyphosphate, 5g alginate, 1g blue algae extract, 5g softener, 5g triethylamine, and 70g deionized water. The starch component was prepared from raw materials including carboxymethyl starch, acid-hydrolyzed starch, and acetate starch in a mass ratio of 0.5:0.3:0.5; the waterborne polyurethane was prepared from Preparation Example 3.

[0029] The preparation method is as follows: S1. Divide the deionized water into two equal parts, take one part and mix it with the emulsifier, heat it to 80°C, and obtain solution A. S2. Take acrylate and styrene, mix them well to obtain solution B; S3. Take another portion of deionized water and initiator to prepare an initiator aqueous solution. First, add half of the initiator aqueous solution to solution A, stir, then add solution B and the remaining initiator aqueous solution dropwise, mix well, and continue the reaction for 2 hours. S4. Cool to 40℃, add triethylamine to adjust the pH, then add starch components, waterborne polyurethane, sodium carbonate, sodium polyphosphate, alginate, blue algae extract and softener, mix well to obtain the final product.

[0030] Example 2 The high-binding textile sizing agent is prepared from the following raw materials: 35g starch component, 8g methyl acrylate, 2.5g waterborne polyurethane, 1g sodium carbonate, 9g styrene, 6.5g emulsifier, 1.2g initiator, 1.5g sodium polyphosphate, 8g alginate, 1.2g cyanobacterial extract, 6.5g softener, 10g triethylamine, and 85g deionized water. The starch component was prepared from raw materials including carboxymethyl starch, acid-hydrolyzed starch, and acetate starch in a mass ratio of 0.5:0.3:0.5; the waterborne polyurethane was prepared from Preparation Example 3.

[0031] The preparation method is as follows: S1. Divide the deionized water into two equal parts, take one part and mix it with the emulsifier, heat it to 85°C, and obtain solution A. S2. Take acrylate and styrene, mix them well to obtain solution B; S3. Take another portion of deionized water and initiator to prepare an initiator aqueous solution. First, add half of the initiator aqueous solution to solution A, stir, then add solution B and the remaining initiator aqueous solution dropwise, mix well, and continue the reaction for 2 hours. S4. Cool to 45℃, add triethylamine to adjust the pH, then add starch components, waterborne polyurethane, sodium carbonate, sodium polyphosphate, alginate, blue algae extract and softener, and mix well to obtain the final product.

[0032] Example 3 The high-binding textile sizing agent is prepared from the following raw materials: 50g starch component, 10g methyl acrylate, 3g waterborne polyurethane, 2g sodium carbonate, 12g styrene, 8g emulsifier, 1.5g initiator, 2g sodium polyphosphate, 10g alginate, 1.5g cyanobacterial extract, 8g softener, 15g triethylamine, and 100g deionized water. The starch component was prepared from raw materials including carboxymethyl starch, acid-hydrolyzed starch, and acetate starch in a mass ratio of 0.5:0.3:0.5; the waterborne polyurethane was prepared from Preparation Example 3.

[0033] The preparation method is as follows: S1. Divide the deionized water into two equal parts by mass, take one part and mix it with the emulsifier, heat it to 90°C, and obtain solution A. S2. Take acrylate and styrene, mix them well to obtain solution B; S3. Take another portion of deionized water and initiator to prepare an initiator aqueous solution. First, add half of the initiator aqueous solution to solution A, stir, then add solution B and the remaining initiator aqueous solution dropwise, mix well, and continue the reaction for 2 hours. S4. Cool to 50℃, add triethylamine to adjust the pH, then add starch components, waterborne polyurethane, sodium carbonate, sodium polyphosphate, alginate, blue algae extract and softener, mix well to obtain the final product.

[0034] Example 4 The only difference between this embodiment and Example 1 is that the raw materials for preparing the starch component include carboxymethyl starch, acid-hydrolyzed starch, and acetate starch in a mass ratio of 0.65:0.45:0.65.

[0035] Example 5 The only difference between this embodiment and Example 1 is that the raw materials for preparing the starch component include carboxymethyl starch, acid-hydrolyzed starch, and acetate starch in a mass ratio of 0.8:0.5:0.8.

[0036] Example 6 The only difference between this embodiment and Example 1 is that the raw materials for preparing the starch component include carboxymethyl starch and acid-hydrolyzed starch in a mass ratio of 0.5:0.8.

[0037] Example 7 The only difference between this embodiment and Example 1 is that the raw materials for preparing the starch component include carboxymethyl starch and acetate starch in a mass ratio of 0.5:0.8.

[0038] Example 8 The only difference between this embodiment and Embodiment 1 is that the raw materials for preparing the starch component include acid-hydrolyzed starch and acetate starch in a mass ratio of 0.8:0.5.

[0039] Example 9 The only difference between this embodiment and Example 1 is that the raw materials for preparing the starch component include carboxymethyl starch, acid-hydrolyzed starch, and acetate starch in a mass ratio of 0.2:0.2:1.

[0040] Example 10 The only difference between this embodiment and Example 1 is that the carboxymethyl starch in the starch component is grafted with acrylamide, specifically obtained from Preparation Example 1.

[0041] Example 11 The only difference between this embodiment and Example 1 is that the carboxymethyl starch in the starch component is grafted with acrylamide, specifically obtained from Preparation Example 2.

[0042] Example 12 The only difference between this embodiment and Example 1 is that the waterborne polyurethane was prepared in Example 4.

[0043] Example 13 The high-binding textile sizing agent is prepared from the following raw materials: 20g starch component, 5g methyl acrylate, 2g waterborne polyurethane, 0.5g sodium carbonate, 6g styrene, 5g emulsifier, 1g initiator, 1g sodium polyphosphate, 5g alginate, 5g preservative, 1g blue algae extract, 5g softener, and 70g deionized water. The starch component was prepared from carboxymethyl starch, acid-hydrolyzed starch, and acetate starch in a mass ratio of 0.5:0.3:0.5. The preservative was prepared from 1.9 g of iodopropynyl n-butylcarbamate, 1.9 g of octylisothiazolinone, and 1.2 g of benzimidazole methyl carbamate. The waterborne polyurethane was prepared from Preparation Example 3.

[0044] The preparation method is as follows: S1. Divide the deionized water into two equal parts, take one part and mix it with the emulsifier, heat it to 80°C, and obtain solution A. S2. Take acrylate, styrene and dodecyl mercaptan, mix them well to obtain solution B; S3. Take another portion of deionized water and initiator to prepare an initiator aqueous solution. First, add half of the initiator aqueous solution to solution A, stir, then add solution B and the remaining initiator aqueous solution dropwise, mix well, and continue the reaction for 2 hours. S4. Cool to 40℃, add triethylamine to adjust the pH, then add starch components, waterborne polyurethane, sodium carbonate, sodium polyphosphate, alginate, preservative, cyanobacterial extract and softener, mix well to obtain the final product.

[0045] Example 14 The high-binding textile sizing agent is prepared from the following raw materials: 20g starch component, 5g methyl acrylate, 2g waterborne polyurethane, 0.5g sodium carbonate, 6g styrene, 5g emulsifier, 1g initiator, 1g sodium polyphosphate, 5g alginate, 8g preservative, 1g blue algae extract, 5g softener, and 70g deionized water. The starch component was prepared from carboxymethyl starch, acid-hydrolyzed starch, and acetate starch in a mass ratio of 0.5:0.3:0.5. The preservative was prepared from 3.05 g of iodopropynyl n-butylcarbamate, 3.05 g of octylisothiazolinone, and 1.9 g of benzimidazole methyl carbamate. The waterborne polyurethane was prepared from Preparation Example 3.

[0046] The preparation method is as follows: S1. Divide the deionized water into two equal parts, take one part and mix it with the emulsifier, heat it to 80°C, and obtain solution A. S2. Take acrylate, styrene and dodecyl mercaptan, mix them well to obtain solution B; S3. Take another portion of deionized water and initiator to prepare an initiator aqueous solution. First, add half of the initiator aqueous solution to solution A, stir, then add solution B and the remaining initiator aqueous solution dropwise, mix well, and continue the reaction for 2 hours. S4. Cool to 40℃, add triethylamine to adjust the pH, then add starch components, waterborne polyurethane, sodium carbonate, sodium polyphosphate, alginate, preservative, cyanobacterial extract and softener, mix well to obtain the final product.

[0047] Example 15 The only difference between this embodiment and Example 13 is that the raw materials for preparing the preservative include: 1.79g of iodopropynyl n-butylcarbamate, 1.79g of octylisothiazolinone, and 1.42g of benzimidazole carbamate.

[0048] Example 16 The only difference between this embodiment and Example 13 is that the raw materials for preparing the preservative include: 1.9g of iodopropynyl n-butylcarbamate and 3.1g of octylisothiazolinone.

[0049] Example 17 The only difference between this embodiment and Example 13 is that the raw materials for preparing the preservative include: 1.9g of iodopropynyl n-butylcarbamate and 3.1g of benzimidazole carbamate.

[0050] Example 18 The only difference between this embodiment and Example 13 is that the raw materials for preparing the preservative include: 1.9g of octylisothiazolinone and 3.1g of benzimidazole carbamate.

[0051] Comparative Example 1 The high-binding textile sizing agent is prepared from the following raw materials: 5g methyl acrylate, 2g waterborne polyurethane, 0.5g sodium carbonate, 6g styrene, 5g emulsifier, 1g initiator, 1g sodium polyphosphate, 5g alginate, 1g blue algae extract, 5g softener, 5g triethylamine, and 70g deionized water. The waterborne polyurethane was prepared in Preparation Example 3.

[0052] The preparation method is as follows: S1. Divide the deionized water into two equal parts, take one part and mix it with the emulsifier, heat it to 80°C, and obtain solution A. S2. Take acrylate and styrene, mix them well to obtain solution B; S3. Take another portion of deionized water and initiator to prepare an initiator aqueous solution. First, add half of the initiator aqueous solution to solution A, stir, then add solution B and the remaining initiator aqueous solution dropwise, mix well, and continue the reaction for 2 hours. S4. Cool to 40℃, add triethylamine to adjust the pH to 6.5, then add water-based polyurethane, sodium carbonate, sodium polyphosphate, alginate, blue algae extract and softener, and mix well to obtain the final product.

[0053] Comparative Example 2 The only difference between this comparative example and Example 1 is that the acrylate, styrene, initiator, emulsifier, and triethylamine are replaced with an equal amount of starch component; The preparation method is as follows: S1. During preparation, deionized water is added to the starch component, followed by sodium carbonate, sodium polyphosphate, and alginate. The mixture is stirred and thoroughly mixed to obtain solution A. S2. Add cyanobacterial extract and softener to solution A obtained in S1, heat and stir at 35°C until homogeneous.

[0054] Comparative Example 3 The only difference between this comparative example and Example 1 is that the waterborne polyurethane is replaced with an equal amount of starch component.

[0055] Comparative Example 4 The only difference between this comparative example and Example 1 is that the alginate is replaced with an equal amount of starch component.

[0056] Comparative Example 5 The only difference between this comparative example and Example 1 is that sodium carbonate and sodium polyphosphate are replaced with equal amounts of starch components.

[0057] Performance testing Viscosity thermal stability determination: First, the slurry was dissolved in water to prepare a slurry concentration of 6%. The slurry was boiled at 95℃, and the viscosity values ​​were measured at 60 min, 90 min, 120 min, 150 min, and 180 min, and the viscosity thermal stability was calculated. Viscosity thermal stability (%) = 100 - viscosity fluctuation rate; Viscosity fluctuation rate (%) = (max|η - η'| / η) × 100. Where η is the slurry viscosity value measured at 95℃ for 1 h; max|η - η'| / η is the range of viscosity values ​​measured at 95℃ for 1 h and every 30 min thereafter.

[0058] Emulsion stability test: According to the national standard GB / T6753.3-1986, the room temperature storage stability refers to the appearance observed after standing at room temperature for 3 months; the 50℃ storage stability refers to the appearance observed after standing in a 50℃ oven for 1 month; the centrifugal stability test speed: 4000 r / min, test time: 10 min; the freezing cycle test is to place the emulsion in a -10℃ freezer and then take it out to thaw naturally, repeat 3 times and observe the appearance.

[0059] Breaking strength test: The sized yarn was tested for breaking strength on a YG068C yarn strength tester, with each type of yarn tested 30 times.

[0060] Table 1. Results of viscosity measurement, emulsion stability and tensile strength measurement Referring to Table 1, compared with Comparative Examples 1-5, the textile sizing agents in Examples 1-3 all exhibited stronger viscosity thermal stability, emulsion stability, and breaking strength. This indicates that the present application selected starch component as the main sizing agent component for textile sizing, and simultaneously selected acrylic emulsion, waterborne polyurethane, and alginate as auxiliary sizing agents. Through the synergistic effect between these substances, the adhesion and stability of the sizing agent to the yarn were effectively improved, thereby increasing the bonding degree between the textile sizing agent and the yarn and improving the film-forming effect of the sizing agent.

[0061] The starch component is a natural polysaccharide polymer with good film-forming properties. It has high adhesion to both natural and regenerated cellulose fibers and is easy to desizing. Meanwhile, acrylates, waterborne polyurethane, and alginate have strong adhesion and film-forming properties. By mixing these auxiliary slurry components with starch slurry, a complete slurry system can be formed with excellent slurry performance.

[0062] The acrylate monomers are copolymerized by using an initiator to promote the polymerization reaction of the acrylate monomers, so as to generate homopolymers or copolymers, thereby forming an auxiliary sizing system for textile sizing. This is beneficial to improve the adhesion of the sizing agent to the yarn, improve the film-forming effect of the adhesive, so that the yarn obtains a film layer with better flexibility, and improves the abrasion resistance of the yarn during the weaving process.

[0063] Referring to Table 1, compared with Comparative Example 1, Examples 1 and 4-9 were compounded with starch components, all of which were composed of modified starch. This is because the original starch molecular chain is composed of glucose residue structural units. Because there are many primary hydroxyl groups in the molecule, the intermolecular forces between adjacent molecules are strong, resulting in poor chain flexibility of starch molecules and brittle and hard film. At the same time, the glucose residues contain many polar groups, which leads to poor adhesion of original starch to non-polar molecules in synthetic fibers. Therefore, by modifying the original starch, the defects of original starch can be improved.

[0064] Carboxymethyl starch is obtained by etherifying the hydroxyl groups in native starch. The starch forms a slurry film with high flexibility and relatively stable viscosity, and also has good miscibility. Meanwhile, inorganic acids are added to the starch solution at a temperature below the gelatinization temperature to catalyze a reaction, causing the starch to hydrolyze and generate acid-hydrolyzed starch, thereby reducing the degree of polymerization of starch macromolecules and improving its sizing performance. Furthermore, the hydroxyl groups in native starch undergo esterification with acids, causing some of the hydroxyl groups on the starch molecules to be replaced by ester groups, thereby obtaining acetate starch, which is used to improve the adhesion to hydrophobic synthetic fibers.

[0065] Combining Examples 1, 4-5, and 9, by adjusting the mass ratio of the three types of starch, the modified starches were able to exert a synergistic effect. The optimal slurry system was achieved when the mass ratio of the starch components was 0.8:0.5:0.8, resulting in higher adhesiveness and film-forming properties. Examples 6-8 involved blending two types of starch, and the test data showed that the results of Examples 6-8 were inferior to those of Examples 1 and 4-5. Example 9 involved blending carboxymethyl starch, acid-hydrolyzed starch, and acetate starch in a mass ratio of 0.2:0.2:1. The test results showed that when the mass ratio of the starch components exceeded (0.5-0.8):(0.3-0.5):(0.5-0.8), the test results were poor.

[0066] Referring to Table 1, and in conjunction with Example 1, Examples 10-11 involve grafting carboxymethyl starch, which allows acrylamide to combine with the starch chain in a side chain manner to form a polymer. By grafting with a high-performance polymer, the thermal stability of the graft copolymer and the thermal stability of the emulsion are improved, thereby giving it excellent sizing properties and biodegradability, and also improving its compatibility with other sizing agents.

[0067] Referring to Table 1, based on Examples 1 and 12, it can be concluded that waterborne polyurethane is added as an auxiliary sizing component in this application, and two methods for preparing waterborne polyurethane are provided. This is because waterborne polyurethane has excellent film-forming ability and wear resistance, and strong adhesion to fibers, thereby strengthening the bond between the sizing and the yarn. When added to the main sizing system, it can improve the bonding and application adhesion of the starch sizing, while also giving the yarn strong wear resistance.

[0068] Referring to Table 1, based on Example 1 and Comparative Example 5, it can be seen that when sodium carbonate and sodium polyphosphate are added to the textile sizing agent simultaneously, it can effectively swell the fibers, thereby improving the yarn's absorption of the sizing agent, and improving adhesion performance and the breaking strength of the sized yarn.

[0069] Antibacterial performance determination: Preservatives were added to the slurry and stirred until evenly dispersed. Blank circular filter paper discs with a diameter of 6.0 mm were punched out, and 20 μL of 0.2 wt% preservative was added to each disc. The discs were then air-dried in a sterile environment, with three replicates per group. Approximately 20 mL of sterilized sugar-containing inorganic salt culture medium was poured into a 9 cm diameter petri dish. After the culture medium had solidified horizontally, 100 μL of mold spore suspension was inoculated and spread evenly. The air-dried filter paper discs were then affixed to the surface of the culture medium and incubated at 28°C and 95% humidity for 7 days. After the experiment, the diameter of the inhibition zone was measured with calipers and photographed. The control sample was a blank sample.

[0070] Anti-corrosion performance testing: The anti-mildew test method refers to the petri dish method in GB / T 24346-2009 "Evaluation of Anti-mildew Performance of Textiles". The anti-mildew grade is divided into three levels: Grade 1: No obvious mildew growth under a magnifying glass; Grade 2: Sparse or localized mildew growth; Grade 3: Large area of ​​mildew coverage.

[0071] Table 2 Results of Antibacterial and Antiseptic Properties Referring to Table 2, compared with Example 1, the textile sizing agents in Examples 13-18 all contained preservatives. Using iodopropynyl n-butylcarbamate, octylisothiazolinone, and methyl benzimidazole carbamate as research subjects, and Penicillium chrysogenum and Aspergillus versicolor as model fungi, a highly effective antifungal and antimicrobial agent with good compatibility with the sizing agent was formulated, resulting in significant antifungal and antimicrobial capabilities for the yarn. The test results showed that the optimal antifungal and antimicrobial ability was achieved when the mass ratio of iodopropynyl n-butylcarbamate, octylisothiazolinone, and methyl benzimidazole carbamate was 0.8:0.5:0.8. Furthermore, multiple experiments indicated that iodopropynyl n-butylcarbamate and octylisothiazolinone had good binding properties with the sizing agent, and starch sizing agents could enhance the antimicrobial effects of iodopropynyl n-butylcarbamate and octylisothiazolinone. Since starch slurry is prone to mold growth, adding preservatives can help inhibit this phenomenon.

[0072] The above are all preferred embodiments of this application, and are not intended to limit the scope of protection of this application. Therefore, all equivalent changes made in accordance with the structure, shape and principle of this application should be covered within the scope of protection of this application.

Claims

1. A textile sizing agent with high binding strength, characterized in that, The product comprises the following components by weight: 20-50 parts starch, 5-10 parts acrylate, 2-3 parts waterborne polyurethane, 0.5-2 parts sodium carbonate, 6-12 parts styrene, 5-8 parts emulsifier, 1-1.5 parts initiator, 1-2 parts sodium polyphosphate, 5-10 parts alginate, 1-1.5 parts cyanobacterial extract, 5-8 parts softener, 5-15 parts triethylamine, 70-100 parts deionized water, and 5-8 parts preservative; the preservative is composed of iodopropynyl n-butylcarbamate, octylisothiazolinone, and benzimidazole methyl carbamate in a mass ratio of (0.8-1):(0.8-1):(0.5-0.8). The starch component is a mixture of carboxymethyl starch, acid-hydrolyzed starch, and acetate starch; the mass ratio of carboxymethyl starch, acid-hydrolyzed starch, and acetate starch is (0.5-0.8):(0.3-0.5):(0.5-0.8). The carboxymethyl starch is grafted with acrylamide, and the preparation of the acrylamide-grafted carboxymethyl starch is as follows: Distilled water and carboxymethyl starch are mixed at a mass ratio of 30:1 and heated to 60°C to dissolve, resulting in a starch slurry solution; acrylamide at a mass ratio of 1:1 with carboxymethyl starch is weighed, and then distilled water at a mass ratio of 1:1 with acrylamide is added, and the mixture is stirred evenly to obtain an acrylamide solution; the acrylamide solution is added to the starch slurry solution and stirred continuously, and the pH is adjusted to 10 using sodium hydroxide and glacial acetic acid, and then nitrogen gas is introduced into the container containing the solution; potassium persulfate and distilled water are weighed, with a mass ratio of potassium persulfate to acrylamide of 0.005:1, and potassium persulfate is dissolved in water to prepare a 1% potassium persulfate solution, which is then added to the starch slurry solution and heated at 70°C for 5 hours; finally, the solution is precipitated using 95% ethanol, and after precipitation, it is dried at 60°C for 26 hours, pulverized, and the acrylamide-grafted carboxymethyl starch is obtained; The waterborne polyurethane is prepared as follows: polyether polyol and polyester polyol are mixed and heated, and dehydrated under vacuum for 1-3 hours. Then, isophorone diisocyanate, dibutyltin dilaurate and hexamethylene diisocyanate are added. After heating, 1,6-hexanediol and dimethylolpropionic acid are added. After heating and keeping warm, an acid-base adjuster is added to adjust the pH. After stirring, vacuum filtration is performed and the material is discharged.

2. The high-adhesion textile sizing agent according to claim 1, characterized in that: The acrylates include one or more of methyl acrylate, ethyl acrylate, butyl acrylate, and methyl methacrylate.

3. The high-adhesion textile sizing agent according to claim 1, characterized in that: The initiator includes one or more of ammonium persulfate, sodium persulfate, and potassium persulfate.

4. The method for preparing the high-adhesion textile sizing agent according to any one of claims 1-3, characterized in that: Includes the following steps: S1. Divide the deionized water into two parts. Take one part and mix it with the emulsifier. Heat the mixture to 80-90℃ to obtain solution A. S2. Take acrylate and styrene and mix them to obtain solution B. S3. Take the other part of the deionized water and mix it with the initiator to prepare an initiator aqueous solution. First, add part of the initiator aqueous solution to solution A and stir. Then, add solution B and the remaining initiator aqueous solution dropwise, mix well, and react. S4. Cool the mixture to 40-50℃, add triethylamine to adjust the pH, and then add starch components, waterborne polyurethane, sodium carbonate, sodium polyphosphate, alginate, cyanobacterial extract, preservative, and softener. Mix well to obtain the final solution.

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