Manufacturing process of wear-resistant and crease-resistant embroidery cloth

Abstract

The invention discloses a manufacturing process of wear-resistant and crease-resistant embroidery cloth, which comprises the following steps: S1, preparing modified silicon nitride wear-resistant particles, S2, preparing a wear-resistant and crease-resistant finishing liquid, and S3, carrying out two-dipping and two-rolling treatment on the embroidery cloth in the wear-resistant and crease-resistant finishing liquid, and then washing and drying to obtain the wear-resistant and crease-resistant embroidery cloth. The wear resistance and the wrinkle resistance of the embroidery cloth are improved through the dual effects of chemical grafting and esterification crosslinking, epoxy groups are grafted on the surface of nano silicon nitride by adopting epoxypropyl silane, the nano silicon nitride reacts with closed amino isocyanate group terminated polyethylene glycol to obtain modified silicon nitride wear-resistant particles, and the wear resistance and the wrinkle resistance of the embroidery cloth are improved when the modified silicon nitride wear-resistant particles are padded and dried. According to the present invention, the high temperature deblocking isocyanate group reacts with the hydroxyl group or the amino group of the cotton and linen fiber of the embroidery cloth to achieve the stable fixation of the particles, and the anti-wrinkle system uses the synergistic effect of the mixed polybasic acid and the polybasic acid to jointly react with the fiber hydroxyl group to form the three-dimensional cross-linked network fixed fiber structure so as to effectively improve the anti-wrinkle performance of the embroidery cloth.

Description

Technical Field

[0001] The present invention relates to the technical field of fabric treatment, and particularly relates to a manufacturing process of wear-resistant and wrinkle-resistant embroidered fabric. Background Art

[0002] Traditional embroidered fabrics are mostly made of cotton and linen materials, etc. Although they have good moisture absorption and breathability, they have problems such as easy wrinkling and poor wear resistance, which to a certain extent limit the durability and application scenarios of embroidered products. To solve this problem, there are already technologies in the market to improve performance through fiber blending, structure enhancement or post-treatment processes. For example, polyester-cotton blended fabrics combine the wear resistance of polyester and the comfort of cotton, and Cordura fabrics, nylon fibers, etc. are also used to enhance wear resistance. In terms of anti-wrinkle technology, processes such as resin finishing, liquid ammonia finishing, and bi-enzyme finishing are widely used. These technologies improve the anti-wrinkle performance by changing the fiber structure or reducing surface friction.

[0003] Based on the above situation, in the prior art, the patent with the patent number CN201810959304.9 discloses a wear-resistant and color-protecting embroidered fabric and its manufacturing method, belonging to the field of embroidery. The manufacturing method includes the following steps: applying a wear-resistant agent on the surface of the dyed fabric for the first time to obtain a primary material with a first wear-resistant layer, embroidering the primary material with the wax-coated embroidery thread, and then applying the wear-resistant agent on the surface of the embroidered primary material for the second time to obtain an embroidered fabric with a second wear-resistant layer. The wear-resistant agent is obtained by mixing potassium hexatitanate, polytetrafluoroethylene, molybdenum disulfide, boron carbide, silicon carbide micropowder, epoxy resin and water. This manufacturing method is simple and easy to operate, can maintain the wear resistance of the embroidered fabric for a long time, reduce the quality loss after friction of the embroidered fabric, and the obtained wear-resistant and color-protecting embroidered fabric has strong wear resistance and small quality loss after long-term use.

[0004] Although the above patent improves the wear resistance of the embroidered fabric to a certain extent by applying a wear-resistant agent containing composite materials such as potassium hexatitanate and polytetrafluoroethylene in stages on the fabric surface and combining the application of wax-coated embroidery thread, in combination with the actual use scenario requirements, this technology still has the problem of insufficient synergistic optimization of wear resistance persistence and anti-wrinkle performance. Specifically, on the one hand, although the high proportion of epoxy resin in the wear-resistant agent can fix the wear-resistant particles, it will cause the flexibility of the fabric to decrease, and local peeling is likely to occur due to the brittleness of the coating after repeated friction, accelerating the loss of wear-resistant components; on the other hand, this method does not carry out anti-wrinkle modification for the fiber characteristics of substrates such as cotton, linen and silk. The permanent wrinkles generated during the use of the fabric due to bending and folding not only affect the beauty but also increase the risk of fiber breakage. Summary of the Invention

[0005] In view of the technical defects in the background art, the present invention proposes a manufacturing process of wear-resistant and wrinkle-resistant embroidered fabric, which solves the above technical problems and meets the actual needs. The specific technical solutions are as follows: A manufacturing process for a wear-resistant and wrinkle-resistant embroidered fabric, comprising the following steps: S1. Prepare modified silicon nitride wear-resistant particles; S11. Prepare 15-30% acetone solutions of a blocking agent and amino isocyanate group-terminated polyethylene glycol respectively to obtain a blocking agent-acetone solution and an amino isocyanate group-terminated polyethylene glycol-acetone solution. Add the amino isocyanate group-terminated polyethylene glycol-acetone solution to a three-necked flask, slowly dropwise add the blocking agent-acetone solution, and under nitrogen protection, reflux and react at 60-80 °C for 4-6 hours. Distill off the solvent under reduced pressure to obtain blocked amino isocyanate group-terminated polyethylene glycol; S12. Mix absolute ethanol, 3-(2,3-epoxypropoxy)propyltrimethoxysilane and deionized water, then add nano-silicon nitride particles, and react under stirring conditions for 6 h. After the reaction, filter, wash, and place the product in a vacuum drying oven at 80 °C for drying for 8 h to obtain modified silicon nitride; S13. Ultrasonically disperse modified silicon nitride and blocked amino isocyanate group-terminated polyethylene glycol in a DMF solvent, and then keep stirring and reacting at 90-105 °C for 6 h. Centrifuge, wash, and vacuum dry to obtain modified silicon nitride wear-resistant particles; S2. Prepare a wear-resistant and wrinkle-resistant finishing solution; Stir polybasic acid, mixed polybasic acid, penetrant, sodium hypophosphite, and modified silicon nitride wear-resistant particles evenly in deionized water to obtain a wear-resistant and wrinkle-resistant finishing solution. The concentrations of each raw material component in the wear-resistant and wrinkle-resistant finishing solution are: 10-30 g / L polybasic acid, 60-80 g / L mixed polybasic acid, 1-5 g / L penetrant, 1-5 g / L modified silicon nitride wear-resistant particles, and 30-35 g / L sodium hypophosphite; S3. Perform two-dip and two-roll treatment on the embroidered fabric in the wear-resistant and wrinkle-resistant finishing. First, immerse it for 10 min at room temperature, with a liquor pick-up of 90%, immerse it for 5 min at room temperature for the second time, with a liquor pick-up of 90%, pre-dry it at 80 °C for 5 min, cure it at 110-160 °C for 10 min, then wash it with water and dry it to obtain the wear-resistant and wrinkle-resistant embroidered fabric.

[0006] As a further technical solution of the present invention, in step S11, prepare 15% acetone solutions of the blocking agent and amino isocyanate group-terminated polyethylene glycol respectively to obtain a 15% blocking agent-acetone solution and a 15% amino isocyanate group-terminated polyethylene glycol-acetone solution. The molar ratio of isocyanate groups to the blocking agent in the reaction system of the amino isocyanate group-terminated polyethylene glycol-acetone solution and the blocking agent-acetone solution is 1:1.

[0007] As a further technical solution of the present invention, in step S11, the sealing agent is any one of diethylene glycol monobutyl ether and methyl ethyl ketoxime, and the structural formula of the amino isocyanate group-terminated polyethylene glycol is: NH2-(CH2CH2)n-CH2CH2-NCO, where n is 4-8.

[0008] As a further technical solution of the present invention, in step S12, anhydrous ethanol, deionized water, and 3-(2,3-epoxypropoxy)propyltrimethoxysilane are mixed evenly at a mass ratio of 20:1:1.5, and then 1.5 wt% of nano silicon nitride particles are added to the feed liquid and ultrasonically dispersed evenly to obtain a nano silicon nitride suspension. The reaction is carried out for 6 h under stirring conditions. After the reaction is completed, filtration and washing are carried out, and the product is placed in a vacuum drying oven at 80°C for 8 h to obtain modified silicon nitride.

[0009] As a further technical solution of the present invention, in step S13, the mass percentages of the modified silicon nitride, the blocked amino isocyanate group-terminated polyethylene glycol, and the DMF solvent are: 2.5% modified silicon nitride, 10% blocked amino isocyanate group-terminated polyethylene glycol, and 87.5% DMF solvent.

[0010] As a further technical solution of the present invention, in step S12, the particle size of the nano silicon nitride particles is 20-60 nm, and the specific surface area is 45-60 m 2 / g.

[0011] As a further technical solution of the present invention, in step S2, the penetrant is selected from any one of JFC, APEO, AEO, and AS.

[0012] As a further technical solution of the present invention, in step S2, the polybasic acid is selected from any one of polymaleic acid and polyacrylic acid. The molecular weight of the polymaleic acid is 1110-1480, and the molecular weight of the polyacrylic acid is 1080-1440.

[0013] As a further technical solution of the present invention, in step S2, the mixed polybasic acid is composed of citric acid and malic acid, and the mass ratio of citric acid to malic acid is (1-2):1.

[0014] The beneficial effects of the present invention are as follows: Improve the wear resistance and wrinkle resistance of embroidered fabrics through the dual effects of chemical grafting and esterification crosslinking. In terms of wear-resistant modification, epoxypropylsilane is used to graft epoxy groups onto the surface of nano-silicon nitride, and then it reacts with polyethylene glycol capped with blocked amino isocyanate groups to introduce blocked isocyanate groups. When passing through padding and drying, the isocyanate groups released at high temperature react with the hydroxyl or amino groups of the cotton and linen fibers of the embroidered fabric to achieve stable fixation of wear-resistant particles. The wrinkle-resistant system utilizes the synergistic effect of mixed polyacids and polybasic acids. Some carboxyl groups of the polybasic acid are esterified and crosslinked with the hydroxyl groups of the organic acid, and the remaining carboxyl groups, together with the carboxyl groups of the mixed polyacid, react with the fiber hydroxyl groups to form a three-dimensional crosslinked network to fix the fiber structure, thereby effectively improving the wrinkle resistance of the embroidered fabric. Specific implementation mode

[0015] The following combines relevant embodiments to illustrate the implementation mode of the present invention. The implementation mode of the present invention is not limited to the following embodiments, and the relevant necessary components involved in the present invention should be regarded as well-known technologies in the technical field, which can be known and mastered by those skilled in the technical field.

[0016] A manufacturing process for wear-resistant and wrinkle-resistant embroidered fabrics includes the following steps: S1. Prepare modified silicon nitride wear-resistant particles; S11. Prepare 15 - 30% acetone solutions of the blocking agent and polyethylene glycol capped with amino isocyanate groups respectively to obtain the blocking agent - acetone solution and polyethylene glycol capped with amino isocyanate groups - acetone solution. Add the polyethylene glycol capped with amino isocyanate groups - acetone solution to a three-necked flask, slowly drop the blocking agent - acetone solution, and under nitrogen protection, reflux and react at 60 - 80 °C for 4 - 6 hours, and remove the solvent by vacuum distillation to obtain polyethylene glycol capped with blocked amino isocyanate groups; S12. Mix absolute ethanol, 3-(2,3-epoxypropoxy)propyltrimethoxysilane and deionized water, then add nano-silicon nitride particles, react under stirring conditions for 6 h, after the reaction, filter, wash, and place the product in a vacuum drying oven at 80 °C for 8 h to obtain modified silicon nitride; S13. Ultrasonically disperse the modified silicon nitride and polyethylene glycol capped with blocked amino isocyanate groups in DMF solvent, and then keep stirring and reacting at 90 - 105 °C for 6 h, centrifuge, wash, and vacuum dry to obtain modified silicon nitride wear-resistant particles; S2. Prepare a wear-resistant and wrinkle-resistant finishing solution; The polyacid, the mixed polyacid, the penetrant, the sodium hypophosphite, and the modified silicon nitride wear-resistant particles are uniformly stirred in deionized water to obtain a wear-resistant and wrinkle-resistant finishing liquid, wherein the concentrations of the raw material components in the wear-resistant and wrinkle-resistant finishing liquid are: 10-30 g / L polyacid, 60-80 g / L mixed polyacid, 1-5 g / L penetrant, 1-5 g / L modified silicon nitride wear-resistant particles, and 30-35 g / L sodium hypophosphite; S3. The embroidery fabric is subjected to two-immersion and two-rolling treatments in the wear-resistant and wrinkle-resistant finishing, firstly immersed in the first immersion at room temperature for 10 min, with a rolling rate of 90%, then immersed in the second immersion at room temperature for 5 min, with a rolling rate of 90%, pre-baked at 80°C for 5 min, baked at 110-160°C for 10 min, then washed and dried to obtain the wear-resistant and wrinkle-resistant embroidery fabric.

[0017] It should be noted that in the above-mentioned production process, the embroidery fabric used is made of cotton and linen.

[0018] The present invention uses 3-(2,3-epoxypropoxy)propyltrimethoxysilane to modify the surface of nano silicon nitride particles to introduce epoxy groups, thereby providing reaction sites for subsequent reactions with the amino groups of blocked aminoisocyanate-terminated polyethylene glycol, and facilitating the introduction of blocked isocyanate groups into the surface of nano silicon nitride particles.

[0019] The isocyanate group is blocked by the reaction of the blocking agent with the aminoisocyanate-terminated polyethylene glycol. The epoxypropyl group of the modified silicon nitride reacts with the amino group of the aminoisocyanate-terminated polyethylene glycol in the DMF solvent to introduce the blocked isocyanate group into the surface of the nano silicon nitride particles. During the padding and drying process, the high temperature unblocks the blocked isocyanate group and releases the isocyanate group again. The isocyanate group can react with the hydroxyl and amino groups on the surface of the cotton and linen embroidery fabric fibers, thereby fixing the nano silicon nitride particles on the cotton and linen fibers of the embroidery fabric, effectively improving the wear resistance of the embroidery fabric.

[0020] The invention enhances the wrinkle resistance of embroidery cloth through the synergistic effect of polyacids, selects polyacids (polymaleic acid, polyacrylic acid) and mixed polyacids (mixture of citric acid and malic acid), both of which contain hydroxyl groups and carboxyl groups, part of the carboxyl groups of the polyacids undergo esterification reaction with the hydroxyl groups contained in both the citric acid and the malic acid, part of the carboxyl groups of the polyacids undergo esterification reaction with the hydroxyl groups on the surface of the cotton and linen fibers of the embroidery cloth, carboxyl groups of the citric acid and malic acid undergo esterification reaction with the hydroxyl groups on the surface of the cotton and linen fibers of the embroidery cloth, and multiple esterification cross-linking reactions are used to fix the position of the cotton and linen fibers of the embroidery cloth, thereby effectively enhancing the wrinkle resistance of the embroidery cloth.

[0021] As one of the preferred embodiments of the present invention, in step S11, the blocking agent and the amino isocyanate group-terminated polyethylene glycol are respectively formulated into 15% acetone solutions to obtain a 15% blocking agent-acetone solution and a 15% amino isocyanate group-terminated polyethylene glycol-acetone solution. The molar ratio of the isocyanate group to the blocking agent in the reaction system of the amino isocyanate group-terminated polyethylene glycol-acetone solution and the blocking agent-acetone solution is 1:1.

[0022] Further, in step S11, the blocking agent is any one of diethylene glycol monobutyl ether and methyl ethyl ketoxime, and the structural formula of the amino isocyanate group-terminated polyethylene glycol is: NH2-(CH2CH2)n-CH2CH2-NCO, where n is 4-8.

[0023] Specifically, the blocking agent is preferably methyl ethyl ketoxime. Methyl ethyl ketoxime has a high reaction activity and can quickly undergo a blocking reaction with the isocyanate group to form a more stable blocking structure. And during the subsequent high-temperature deblocking process, it can quickly release the isocyanate group, thereby better achieving the purpose of fixing the nano-silicon nitride particles on the embroidery fabric fibers and further improving the wear resistance of the embroidery fabric.

[0024] The isocyanate group (-NCO) in the amino isocyanate group-terminated polyethylene glycol (structural formula: NH2-(CH2CH2)n-CH2CH2-NCO, n is 4 - 8) has a high reaction activity. The active hydrogen atoms (such as hydroxyl hydrogen and oxime hydrogen) in the blocking agent (such as diethylene glycol monobutyl ether and methyl ethyl ketoxime) can undergo a nucleophilic addition reaction with the isocyanate group to generate a stable blocking product. In this process, the isocyanate group is blocked and its reaction activity is temporarily inhibited.

[0025] During the subsequent padding and drying process, high temperature will deblock the blocked isocyanate groups and release the isocyanate groups again. The deblocked isocyanate groups can react with the hydroxyl and amino groups on the surface of the cotton and linen embroidery fabric fibers, and with the hydroxyl groups of the mixed polyacid, and thus participate in the esterification crosslinking system formed by the polybasic acid, the mixed acid and the hydroxyl groups of the cotton and linen embroidery fabric fibers. The reaction of the isocyanate group with the hydroxyl group on the fiber surface will generate a urethane bond, and the reaction with the amino group will generate a urea bond, thereby fixing the nano-silicon nitride particles on the cotton and linen fibers of the embroidery fabric, and thus improving the wear resistance of the embroidery fabric.

[0026] As a further technical solution of the present invention, in step S12, absolute ethanol, deionized water, and 3-(2,3-epoxypropoxy)propyltrimethoxysilane are mixed evenly at a mass ratio of 20:1:1.5. Then, 1.5 wt% of nano-silicon nitride particles are added to the feed liquid, and ultrasonic dispersion is carried out evenly to obtain a nano-silicon nitride suspension. The reaction is carried out for 6 h under stirring conditions. After the reaction is completed, filtration and washing are carried out, and the product is placed in a vacuum drying oven at 80 °C for drying for 8 h to obtain modified silicon nitride.

[0027] Further, in step S12, the particle size of the nano-silicon nitride particles is 20-60 nm, and the specific surface area is 45-60 m 2 / g.

[0028] Specifically, the particle size of the nano-silicon nitride particles is preferably 20 nm, and the specific surface area is 60 m 2 / g. The smaller particle size and larger specific surface area enable the nano-silicon nitride particles to have higher surface energy, an increase in the number of surface atoms, and enhanced reaction activity. This is beneficial to the reaction between 3-(2,3-epoxypropoxy)propyltrimethoxysilane and the surface of the nano-silicon nitride particles, improving the modification efficiency. In addition, the larger specific surface area can provide more reaction sites, enabling the epoxy groups on the surface of the modified silicon nitride particles to fully react with the amino groups of the blocked amino-isocyanate-terminated polyethylene glycol in the subsequent steps, thereby enhancing the binding effect between the modified silicon nitride wear-resistant particles and the embroidery fabric fibers and improving the wear resistance of the embroidery fabric.

[0029] Under stirring conditions, the trimethoxysilyl group of 3-(2,3-epoxypropoxy)propyltrimethoxysilane (which contains epoxy groups and trimethoxysilyl groups in its structure) will undergo a hydrolysis reaction, and the hydrolyzed silanol groups ((HO)3Si -) will undergo a condensation reaction with the hydroxyl groups (≡Si - OH) on the surface of the nano-silicon nitride particles to form Si - O - Si bonds, thereby grafting 3-(2,3-epoxypropoxy)propyltrimethoxysilane onto the surface of the nano-silicon nitride particles. In this way, epoxy groups are introduced onto the surface of the nano-silicon nitride particles.

[0030] After the reaction is completed, filtration and washing can remove unreacted 3-(2,3-epoxypropoxy)propyltrimethoxysilane and other impurities. Placing the product in a vacuum drying oven at 80 °C for drying for 8 h can further remove residual solvents and moisture to obtain pure modified silicon nitride particles.

[0031] As one of the preferred embodiments of the present invention, in step S13, the mass percentages of the modified silicon nitride, blocked amino-isocyanate-terminated polyethylene glycol, and DMF solvent are respectively: 2.5% modified silicon nitride, 10% blocked amino-isocyanate-terminated polyethylene glycol, and 87.5% DMF solvent.

[0032] The reaction principle of step S13 is mainly based on the ring-opening addition reaction between the epoxy group on the surface of the modified silicon nitride and the amino group of the blocked aminoisocyanate-terminated polyethylene glycol. In step S12, epoxy groups are introduced into the surface of the nano silicon nitride particles by modification with 3-(2,3-epoxypropoxy)propyltrimethoxysilane. The epoxy groups have high reactivity and can undergo a ring-opening reaction. The blocked aminoisocyanate-terminated polyethylene glycol contains an amino group (-NH2) in its structure. The amino group has nucleophilicity and can attack the carbon atom in the epoxy group to induce a ring-opening reaction.

[0033] Through the above-mentioned ring-opening addition reaction, the blocked amino isocyanate-terminated polyethylene glycol is grafted onto the surface of the modified silicon nitride particles. In this way, the isocyanate groups in a blocked state are introduced onto the surface of the nano silicon nitride particles. In the subsequent padding and drying process, the high temperature will unblock the isocyanate groups in the blocked state and release the isocyanate groups again. These unblocked isocyanate groups can react with the hydroxyl and amino groups on the surface of the cotton and linen embroidery fabric fibers, thereby firmly fixing the nano silicon nitride particles on the cotton and linen fibers of the embroidery fabric, thereby achieving the purpose of improving the wear resistance of the embroidery fabric.

[0034] As a further technical solution of the present invention, in step S2, the penetrant is selected from any one of JFC, APEO, AEO and AS.

[0035] Specifically, the penetrant is preferably JFC, which has good penetrating ability and can quickly reduce the surface tension of the finishing liquid, making it easier to penetrate into the fibers of the embroidery cloth. Compared with other penetrants, JFC can make the finishing liquid enter the interior of the cloth faster under the same conditions, thereby improving the penetration efficiency. For example, under the same treatment time and temperature, the finishing liquid using JFC as a penetrant can penetrate into the fibers of the deeper layers of the cloth, making the finishing effect more significant.

[0036] JFC has good compatibility with other ingredients in wear-resistant and anti-wrinkle finishing liquid, such as polyacid, mixed polyacid, modified silicon nitride wear-resistant particles, etc. It will not chemically react with these ingredients, nor will it affect their stability and performance. This ensures the quality of the finishing liquid is stable during storage and use, and can achieve the best finishing effect.

[0037] During the finishing process, the generation of foam may interfere with the uniform application and treatment effect of the finishing liquid. JFC has low foaming performance and will not produce excessive foam during the stirring and impregnation process, which is conducive to the uniform distribution and penetration of the finishing liquid. In contrast, some other penetrants may produce a lot of foam, causing the finishing liquid to overflow or fail to evenly cover the fabric, affecting the finishing quality.

[0038] As one of the preferred embodiments of the present invention, in step S2, the polybasic acid is selected from any one of polymaleic acid and polyacrylic acid. The molecular weight of the polymaleic acid is 1110-1480, and the molecular weight of the polyacrylic acid is 1080-1440.

[0039] In step S2, the mixed polybasic acid is composed of citric acid and malic acid, and the mass ratio of citric acid to malic acid is (1-2):1.

[0040] Specifically, the polybasic acid is preferably polymaleic acid, and the molecular chain of polymaleic acid contains multiple carboxyl groups (-COOH). When polymaleic acid is selected as the polybasic acid, these carboxyl groups can undergo esterification reactions with the hydroxyl groups (-OH) in the mixed polybasic acid (citric acid and malic acid) and the hydroxyl groups on the surface of the cotton and linen fibers of the embroidery fabric. In the final embroidery fabric product, the esterification cross-linked structure formed by polymaleic acid, the mixed polybasic acid, and the fiber surface can enhance the binding force between the fibers, thereby restricting the relative sliding of the fibers. When the embroidery fabric is subjected to an external force, the fibers are not easily displaced and deformed, thus improving the wrinkle resistance of the embroidery fabric.

[0041] In step S3, the mixed polybasic acid is composed of citric acid and malic acid. Both citric acid and malic acid contain multiple hydroxyl groups and carboxyl groups. Under the catalytic action of sodium hypophosphite, the hydroxyl groups of citric acid and malic acid can undergo esterification reactions with the carboxyl groups of polymaleic acid, and the carboxyl groups of citric acid and malic acid can undergo esterification reactions with the hydroxyl groups of the embroidery fabric fibers, thereby tightly connecting the polybasic acid, the mixed polybasic acid, and the embroidery fabric fibers together to form a more complex esterification cross-linked system. The esterification cross-linked system can more effectively restrict the relative movement of the fibers and improve the wrinkle resistance of the embroidery fabric.

[0042] The polybasic acid and the mixed polybasic acid have a synergistic effect in increasing the wrinkle resistance of the embroidery fabric. The polybasic acid first reacts with the hydroxyl groups on the fiber surface to form a preliminary cross-linked structure. Then, after the mixed polybasic acid is added, on the one hand, it further reacts with the polybasic acid to enhance the complexity and stability of the cross-linked structure; on the other hand, the mixed polybasic acid directly reacts with the hydroxyl groups on the fiber surface to expand the cross-linking range. This synergistic effect makes the binding between the fibers tighter and the cross-linked structure more perfect, thereby effectively improving the wrinkle resistance of the embroidery fabric.

[0043] Example 1 S1: Prepare modified silicon nitride wear-resistant particles Methyl ethyl ketoxime and amino isocyanate group-terminated polyethylene glycol (structural formula: NH2-(CH2CH2)n-CH2CH2-NCO, n = 8) were respectively prepared into 15% acetone solutions. Under nitrogen protection, the amino isocyanate group-terminated polyethylene glycol-acetone solution was slowly added dropwise to the blocking agent-acetone solution, and refluxed at 60-80 °C for 4-6 hours. The molar ratio of isocyanate group to blocking agent was 1:1. After the reaction, the solvent was removed by distillation under reduced pressure to obtain blocked amino isocyanate group-terminated polyethylene glycol.

[0044] Absolute ethanol, deionized water, and 3-(2,3-epoxypropoxy)propyltrimethoxysilane were mixed at a mass ratio of 20:1:1.5, and 1.5 wt% of nano silicon nitride particles (particle size 20 nm, specific surface area 60 m 2 / g) were added. After ultrasonic dispersion, the mixture was stirred and reacted for 6 hours. The reaction product was filtered, washed, and vacuum dried at 80 °C for 8 hours to obtain modified silicon nitride with epoxy groups grafted on the surface.

[0045] The modified silicon nitride (2.5 wt%) and blocked amino isocyanate group-terminated polyethylene glycol (10 wt%) were dispersed in DMF solvent (87.5 wt%). The mixture was stirred and reacted at 90-105 °C for 6 hours. After centrifugation, washing, and vacuum drying, modified silicon nitride wear-resistant particles with blocked amino isocyanate group-terminated polyethylene glycol grafted on the surface were obtained.

[0046] S2: Preparation of wear-resistant and wrinkle-resistant finishing liquid Polymeric polyacid (polymaleic acid, molecular weight 1480), mixed polyacid (citric acid: malic acid = 2:1), penetrant (JFC), sodium hypophosphite, and modified silicon nitride wear-resistant particles were prepared at the following concentrations: polymeric polyacid: 30 g / L, mixed polyacid: 80 g / L, penetrant (JFC): 2.5 g / L, modified silicon nitride wear-resistant particles: 5 g / L, sodium hypophosphite: 35 g / L.

[0047] S3: Padding treatment of embroidered fabric S3. The embroidered fabric was subjected to two-padding and two-rolling treatments in the wear-resistant and wrinkle-resistant finishing. First, it was padded at room temperature for 10 min with a liquor pick-up of 90%, padded at room temperature for 5 min with a liquor pick-up of 90%, pre-dried at 80 °C for 5 min, cured at 120 °C for 10 min, then washed with water and dried to obtain wear-resistant and wrinkle-resistant embroidered fabric.

[0048] Comparative Example 1 The difference between Comparative Example 1 and Example 1 was that in step S1, the blocking agent was changed to diethylene glycol monobutyl ether, and the curing temperature in step S3 was 155 °C, and the rest was the same as in Example 1.

[0049] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that in step S1, the particle size of nano-silicon nitride is 60 nm and the specific surface area is 45 m 2 / g, and the rest is the same as in Example 1.

[0050] Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that in step S2, the penetrant is changed to APEO, and the rest is the same as in Example 1.

[0051] Comparative Example 4 The difference between Comparative Example 4 and Example 1 is that in step S2, the polybasic acid is polyacrylic acid (molecular weight 1080), and the mixed polybasic acid: citric acid: malic acid = 1:1 (mass ratio), and the rest is the same as in Example 1.

[0052] Comparative Example 5 The difference between Comparative Example 5 and Example 1 is that in step S2, the mixed polybasic acid is not used, and only polymaleic acid (molecular weight 1480) is used, and the rest is the same as in Example 1.

[0053] The abrasion resistance, wrinkle resistance of the above Example 1 and Comparative Examples 1-5 were tested. The test method for wrinkle resistance: GB / T 3819-1997 "Textiles - Determination of fabric crease recovery - Recovery angle method", the test method for abrasion resistance: GB / T 21196.2-2007 "Textiles - Determination of Martindale fabric abrasion resistance - Part 2: Determination of specimen damage", and the test results are shown in the following table:

[0054] In the above test data, in Comparative Example 1, the blocking agent was changed to diethylene glycol monobutyl ether, and its number of friction times (7500 times) was lower than that of Example 1 (8250 times), and the wrinkle recovery angle (270°) was also slightly lower than that of Example 1 (280°). Using methyl ethyl ketoxime as the blocking agent, due to its high reactivity, it can react with the isocyanate group more quickly to form a more stable blocked structure, and better release the isocyanate group during the subsequent high-temperature deblocking process, fixing the nano-silicon nitride particles on the embroidery fabric fibers, thereby improving the wear resistance of the embroidery fabric and also contributing to the improvement of the wrinkle resistance.

[0055] In the above test data, in Comparative Example 2, the particle size of nano-silicon nitride is 60 nm and the specific surface area is 45 m 2 / g, and its number of friction cycles (6,500 times) is significantly lower than that of Example 1 (8,250 times), indicating that the smaller particle size and larger specific surface area endow the nano-silicon nitride particles with higher surface energy, an increased number of surface atoms, enhanced reactivity, which is conducive to the reaction between 3-(2,3-epoxypropoxy)propyltrimethoxysilane and the surface of the nano-silicon nitride particles, improving the modification efficiency, enhancing the bonding effect between the modified silicon nitride wear-resistant particles and the embroidery fabric fibers, and thus improving the wear resistance and wrinkle resistance of the embroidery fabric.

[0056] Among the above test data, in Comparative Example 3, the penetrant was changed to APEO, and its number of friction cycles (7,000 times) was lower than that of Example 1 (8,250 times), which indicates that the JFC penetrant has good penetration ability, can rapidly reduce the surface tension of the finishing liquid, make the finishing liquid easier to penetrate into the fibers of the embroidery fabric, improve the penetration efficiency, contribute to the better performance of the finishing liquid, and thus enhance the wear resistance and wrinkle resistance of the embroidery fabric.

[0057] Among the above test data, in Comparative Example 4, the polybasic acid was polyacrylic acid (molecular weight 1,080), and in the mixed polybasic acid, citric acid: malic acid = 1:1 (mass ratio), and its wrinkle recovery angle (250°) was significantly lower than that of Example 1 (280°). This shows that the number of carboxyl groups in the polybasic acid and the mixed polybasic acid can significantly affect the wrinkle resistance of the embroidery fabric. The number of carboxyl groups provided by Comparative Example 4 decreased, weakening the esterification crosslinking system formed between the polybasic acid and the mixed polybasic acid and the hydroxyl groups on the embroidery fabric fibers, and also weakening the esterification crosslinking system formed between the hydroxyl groups of the mixed polybasic acid and the carboxyl groups of the polybasic acid. The weakening of the above two esterification crosslinking systems makes the fibers of the embroidery fabric more likely to undergo relative sliding and displacement when subjected to external forces, resulting in a decrease in the wrinkle recovery angle and a decline in the wrinkle resistance.

[0058] Among the above test data, in Comparative Example 5, the mixed polybasic acid was omitted (only polymaleic acid was used), and its wrinkle recovery angle (200°) was significantly lower than that of Example 1 (280°), indicating that there is a synergistic effect between the mixed polybasic acid (citric acid and malic acid) and the polybasic acid in increasing the wrinkle resistance of the embroidery fabric. The addition of the mixed polybasic acid can expand the crosslinking range, the crosslinking structure is more perfect, and the fibers are not easy to undergo relative sliding and displacement, thus effectively improving the wrinkle resistance of the embroidery fabric.

[0059] In summary, the choice and ratio of the blocking agent, the characteristics of the nano-silicon nitride particles, the penetrant, and the polybasic acid and the mixed polybasic acid all have a significant impact on the wear resistance and wrinkle resistance of the embroidery fabric. The raw material selection and ratio in the examples of the present invention can effectively improve the comprehensive performance of the embroidery fabric.

[0060] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can still be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A manufacturing process for wear-resistant and wrinkle-resistant embroidered fabric, characterized in that, It includes the following steps: S1. Prepare modified silicon nitride wear-resistant particles; S11. Prepare 15-30% acetone solutions of the blocking agent and amino isocyanate-terminated polyethylene glycol respectively to obtain a blocking agent-acetone solution and an amino isocyanate-terminated polyethylene glycol-acetone solution. Add the amino isocyanate-terminated polyethylene glycol-acetone solution to a three-necked flask, slowly dropwise add the blocking agent-acetone solution, and under nitrogen protection, reflux and react at 60-80 °C for 4-6 hours. Remove the solvent by vacuum distillation to obtain blocked amino isocyanate-terminated polyethylene glycol; S12. Mix anhydrous ethanol, 3-(2,3-epoxypropoxy)propyltrimethoxysilane and deionized water, then add nano-silicon nitride particles, react under stirring conditions for 6 h, after the reaction is completed, filter, wash, and place the product in a vacuum drying oven at 80 °C for 8 h to obtain modified silicon nitride; S13. Ultrasonically disperse the modified silicon nitride and blocked amino isocyanate-terminated polyethylene glycol in a DMF solvent, then keep stirring and reacting at 90-105 °C for 6 h, centrifuge, wash, and vacuum dry to obtain modified silicon nitride wear-resistant particles; S2. Prepare a wear-resistant and wrinkle-resistant finishing solution; Stir polybasic acid, mixed polybasic acid, penetrant, sodium hypophosphite, and modified silicon nitride wear-resistant particles evenly in deionized water to obtain a wear-resistant and wrinkle-resistant finishing solution. The concentrations of each raw material component in the wear-resistant and wrinkle-resistant finishing solution are: 10-30 g / L of polybasic acid, 60-80 g / L of mixed polybasic acid, 1-5 g / L of penetrant, 1-5 g / L of modified silicon nitride wear-resistant particles, and 30-35 g / L of sodium hypophosphite; S3. Perform two-dip and two-roll treatment on the embroidered fabric in the wear-resistant and wrinkle-resistant finishing. First, immerse it at room temperature for 10 min with a liquor pickup of 90%, immerse it at room temperature for 5 min for the second time with a liquor pickup of 90%, pre-dry it at 80 °C for 5 min, cure it at 110-160 °C for 10 min, then wash it with water and dry it to obtain a wear-resistant and wrinkle-resistant embroidered fabric.

2. The manufacturing process of a wear-resistant and wrinkle-resistant embroidered fabric according to claim 1, characterized in that, In step S11, prepare 15% acetone solutions of the blocking agent and amino isocyanate-terminated polyethylene glycol respectively to obtain a 15% blocking agent-acetone solution and a 15% amino isocyanate-terminated polyethylene glycol-acetone solution. The molar ratio of isocyanate groups to the blocking agent in the reaction system of the amino isocyanate-terminated polyethylene glycol-acetone solution and the blocking agent-acetone solution is 1:

1.

3. The manufacturing process of a wear-resistant and wrinkle-resistant embroidered fabric according to claim 1, characterized in that, In step S11, the blocking agent is any one of diethylene glycol monobutyl ether and methyl ethyl ketoxime, and the structural formula of the amino isocyanate-terminated polyethylene glycol is: NH2-(CH2CH2)n-CH2CH2-NCO, where n is 4-8.

4. The manufacturing process of a wear-resistant and wrinkle-resistant embroidered fabric according to claim 1, characterized in that, In step S12, mix anhydrous ethanol, deionized water, and 3-(2,3-epoxypropoxy)propyltrimethoxysilane evenly according to a mass ratio of 20:1:1.5, then add 1.5 wt% of nano-silicon nitride particles to the feed liquid, ultrasonically disperse it evenly to obtain a nano-silicon nitride suspension, react under stirring conditions for 6 h, after the reaction is completed, filter, wash, and place the product in a vacuum drying oven at 80 °C for 8 h to obtain modified silicon nitride.

5. The manufacturing process of a wear-resistant and wrinkle-resistant embroidered fabric according to claim 1, characterized in that, In step S13, the mass percentages of the modified silicon nitride, the blocked amino isocyanate group-terminated polyethylene glycol, and the DMF solvent are respectively: 2.5% modified silicon nitride, 10% blocked amino isocyanate group-terminated polyethylene glycol, and 87.5% DMF solvent.

6. The manufacturing process of a wear-resistant and wrinkle-resistant embroidered fabric according to claim 1, characterized in that, In step S12, the particle size of the nano silicon nitride particles is 20 - 60 nm, and the specific surface area is 45 - 60 m 2 / g.

7. The manufacturing process of a wear-resistant and wrinkle-resistant embroidered fabric according to claim 1, characterized in that, In step S2, the penetrant is selected from any one of JFC, APEO, AEO, and AS.

8. The manufacturing process of a wear-resistant and wrinkle-resistant embroidered fabric according to claim 1, characterized in that, In step S2, the polybasic acid is selected from any one of polymaleic acid and polyacrylic acid. The molecular weight of the polymaleic acid is 1110 - 1480, and the molecular weight of the polyacrylic acid is 1080 - 1440.

9. The manufacturing process of a wear-resistant and wrinkle-resistant embroidered fabric according to claim 1, characterized in that, In step S2, the mixed polybasic acid is composed of citric acid and malic acid, and the mass ratio of citric acid to malic acid is (1 - 2):1.

Images