A sizing process for making cool fabrics

Abstract

The present invention relates to the technical field of functional fabrics, and specifically to a sizing process for making cool fabrics. The sizing process of the present invention overcomes the problems that the cool effect of fabric materials decreases after being washed with water and the moisture absorption performance of the materials themselves is poor. By combining processes such as preparing a cool sizing solution, fabric pretreatment, gradient sizing treatment, hydrophilic finishing, segmented curing and drying, and antistatic treatment, the surface energy of the fabric is improved. The prepared cool sizing solution contains components such as surface-modified inorganic nanoparticles and eutectic system phase change microcapsules. Through gradient sizing treatment, the functional components penetrate into the yarn gaps and control the surface film formation. Finally, a cool fabric is obtained according to the six sizing processes. The fabric still has a cool effect after being washed with water, has good moisture absorption, and is comfortable to wear.

Description

Technical Field

[0001] The present invention relates to the technical field of functional fabrics, and specifically to a sizing process for making cool fabrics. Background Art

[0002] In hot weather or during strenuous exercise, the human body secretes a large amount of sweat. If the sweat cannot be discharged or absorbed, discomfort will occur. Therefore, the quality of the fabric worn is crucial. Cool fabrics, which have characteristics such as a cool effect, enhance the refreshing feeling of human wearing, and are light in weight, are very popular. The existing preparation processes of cool fabrics mainly focus on the selection of fiber materials, the innovation of fabric structures, and the improvement of post-finishing processes, etc. By selecting fibers with good hygroscopicity and air permeability, or adopting special weaving structures to increase air circulation, a certain cool effect can be achieved. In addition, some chemical post-finishing agents are also applied to endow the fabric with a cool feeling, but these methods often have problems such as insufficient durability, high cost, or being not environmentally friendly enough.

[0003] The main purpose of traditional sizing processes is to improve the stiffness, wrinkle resistance, and abrasion resistance of fabrics, and endow fabrics with certain functions, such as waterproof and stain-resistant properties, etc. However, there is little research on combining the sizing process with endowing fabrics with a cool feeling; most existing cool fabrics use menthol finishing agents or metal oxide coatings to increase the coolness of the fabric, but the volatility of menthol results in insufficient durability of the cool feeling, and the performance deteriorates after washing; metal oxides affect the air permeability of the fabric; the traditional padding process leads to uneven distribution of functional materials. Therefore, developing a new type of sizing process, which can endow fabrics with a long-lasting and comfortable cool feeling while improving the fabric performance, has important practical significance and market value.

[0004] Therefore, a sizing process for making cool fabrics is proposed. Summary of the Invention

[0005] The purpose of the present invention is to provide a sizing process for making cool fabrics. By combining processes such as preparing a cool sizing solution, fabric pretreatment, gradient sizing treatment, hydrophilic finishing, segmented curing and drying, and antistatic treatment, the surface energy of the fabric is enhanced. The prepared cool sizing solution contains components such as surface-modified inorganic nanoparticles and eutectic system phase change microcapsules. Through gradient sizing treatment, the functional components penetrate into the yarn gaps and control the surface film formation; finally, a cool fabric is obtained according to six sizing processes. The fabric still has a cool effect after being washed with water, and has good hygroscopicity and is comfortable to wear.

[0006] To achieve the above purpose, the present invention provides the following technical solutions:

[0007] The present invention provides a sizing process for making cool fabrics, and the sizing process is as follows:

[0008] S1 Preparation of a cool sizing solution: Dispersed surface-modified inorganic nanoparticles, eutectic system phase change microcapsules, film-forming polymers, cross-linking agents, dispersants, and p-toluenesulfonic acid in deionized water. After mixing, ultrasonic treatment was carried out to obtain a cool sizing solution;

[0009] S2 Fabric pretreatment: The fabric was subjected to plasma treatment to obtain a surface-treated fabric;

[0010] The fabric contains cotton fibers and modal. Modal is made from natural wood pulp through a spinning process. The fiber is soft and smooth, has excellent hygroscopicity, can quickly absorb sweat and moisture on the skin surface, and keep the skin dry. Modal has relatively high strength and can maintain good performance even in the wet state and is not easily deformed. Cotton fibers are fibers developed from the epidermal hair cells of the seeds of plants in the genus Gossypium of the Malvaceae family. They are a natural plant fiber. When worn, they can quickly absorb sweat on the skin surface, making people feel comfortable and not generating a stuffy feeling. They are soft and comfortable with good breathability.

[0011] S3 Gradient sizing treatment: Immersed in the cool sizing solution, the first padding was carried out at -90 to -65 kPa, and the second padding was carried out at atmospheric pressure to obtain a precursor of the cool fabric;

[0012] S4 Hydrophilic finishing: Immersed in a hydrophilic finishing agent to obtain a cool fabric to be cured;

[0013] S5 Step-by-step curing and drying: After pre-drying, it was cured at 115 - 130 °C for 1 - 3 min and dried to obtain an intermediate of the cool fabric;

[0014] S6 Antistatic treatment: Immersed in antistatic raw materials to obtain a cool fabric;

[0015] The eutectic system phase change microcapsules were prepared from chitosan solution, sodium alginate solution, alkane, and calcium chloride solution.

[0016] Preferably, in S1, the mass-volume ratio of the surface-modified inorganic nanoparticles to deionized water is 1.5 - 3:100; the mass-volume ratio of the eutectic system phase change microcapsules to deionized water is 4 - 7:100; the mass ratio of the film-forming polymer to deionized water is 8:100; the mass ratio of the cross-linking agent to deionized water is 0.3 - 0.7:100; the mass ratio of the dispersant to deionized water is 0.1 - 0.2:100.

[0017] Preferably, the preparation process of the surface-modified inorganic nanoparticles in S1 is as follows: Add a silane coupling agent to a suspension containing ethanol, deionized water, and inorganic nanoparticles, and magnetically stir and react at 50 - 65°C for 3.5 - 5.5 h; after centrifugation, wash and dry to obtain amino-functionalized inorganic nanoparticles; add polylactic acid and ethylene-vinyl acetate copolymer and reflux to obtain surface-modified inorganic nanoparticles; the dosage ratio of the silane coupling agent, polylactic acid, and ethylene-vinyl acetate copolymer is 0.2 - 0.5:4.5 - 7.5:2.5 - 5.5.

[0018] Preferably, the inorganic nanoparticles are one of nano-silica, nano-zinc oxide, nano-titanium oxide, nano-montmorillonite, and nano-boron nitride.

[0019] Preferably, the preparation process of the eutectic system phase change microcapsules in S1 is as follows: Melt the alkane at 50 - 60°C and pour it into a solution containing deionized water and Tween 80 to obtain the core material raw material; drop the chitosan solution into the core material raw material, and then drop the sodium alginate solution to obtain the composite wall material; drop the calcium chloride solution into the composite wall material, react at 400 - 800 r / min for 1 - 1.5 h, wash by centrifugation, and then vacuum dry at 25 - 30°C to obtain the eutectic system phase change microcapsules.

[0020] Preferably, the dosage ratio of chitosan in the chitosan solution, sodium alginate in the sodium alginate solution, and alkane is 2 - 3:3 - 4:8 - 15; the alkane is obtained by mixing alkane one and alkane two in a mass ratio of 2:3; alkane one is one of octadecane, hexadecane, heptadecane, and butyl stearate; alkane two is one of octadecane and nonadecane.

[0021] Preferably, the cross-linking agent in S1 is obtained by mixing butanetetracarboxylic acid, hexamethylenediamine, chromium sulfate, and borax in a mass ratio of 1:1:1:1; the total impregnation time in the S3 gradient sizing treatment is 10 - 25 min; the impregnation mass ratio of the surface-treated fabric to the cool sizing solution is 1:20 - 30; the liquor pickup rate after the first padding is controlled at 85%, and the expression rate is 120%; the liquor pickup rate after the second padding is 60%, and the expression rate is 75%.

[0022] The liquor pickup rate refers to the percentage of the weight of the liquid carried by the fabric after padding treatment to the dry weight of the fabric, which reflects the amount of treatment liquid absorbed by the fabric during the padding process; the expression rate: is the percentage of the weight of the liquid remaining on the fabric after rolling to the weight of the liquid carried by the fabric before rolling, and the expression rate reflects the degree of extrusion of the liquid on the fabric during the rolling process;

[0023] Preferably, the impregnation time for the hydrophilic finishing in S4 is 10 - 15 min; the pre-drying temperature in the S5 staged curing and drying is 65 - 80°C.

[0024] Compared with the prior art, the beneficial effects of the present invention are:

[0025] 1. In terms of raw material treatment, by surface-modifying inorganic nanoparticles, they can be closely combined with the fabric and assist in heat dissipation; preparing eutectic system phase change microcapsules, using the phase change characteristics of alkanes in the core material to absorb heat, and controlling the preparation processes of the shell material and the core material to obtain microcapsules with stable performance; in terms of process, pre-treating the fabric to enhance the surface energy, using gradient sizing treatment to evenly distribute the functional components, and segmented curing and drying to enhance the stability of the glue film; enabling the fabric to have a good cooling effect, effectively absorbing the heat of the human body, and keeping the wearer cool and comfortable in a hot environment.

[0026] 2. By optimizing the dosage of the crosslinking agent, adjusting the impregnation process parameters, controlling the dosages of polylactic acid and ethylene-vinyl acetate copolymer with surface-modified inorganic nanoparticles, and performing gradient sizing treatment in S3, carrying out negative-pressure first padding and atmospheric-pressure second padding, the connection strength between the sizing liquid components and the fabric is enhanced; hydrophilic finishing makes the fabric have good hygroscopicity, can quickly absorb sweat and diffuse it; segmented curing and drying ensures sufficient crosslinking reaction and improves the stability of the glue film; and controlling the particle size of the eutectic system phase change microcapsules in S12; the above processes act synergistically, so that the fabric still has good cooling performance after washing, and key components such as eutectic system phase change microcapsules and surface-modified inorganic nanoparticles are not easily detached, and good hygroscopicity is maintained. Description of the Drawings

[0027] Figure 1 It is a sizing process diagram for making a cool fabric according to the present invention. Detailed Embodiments

[0028] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0029] Please refer to Figure 1 , the present invention provides a sizing process for making a cool fabric, and the technical solution is as follows:

[0030] The substance information involved in the present invention is as follows:

[0031] Sodium carboxymethyl cellulose CAS: 9004-32-4; p-Toluenesulfonic acid CAS: 104-15-4; Acrylic acid-acrylate copolymer CAS: 25133-97-5; Sodium polyacrylate CAS: 9003-04-7; Sodium tripolyphosphate CAS: 7758-29-4; Tetradecane CAS: 629-59-4; Hexadecane CAS: 15716-08-2; Heptadecane CAS: 629-78-7; Butyl stearate CAS: 123-95-5; Octadecane CAS: 593-45-3; Nonadecane CAS: 629-92-5; KH-550 CAS: 919-30-2; Tween 80 CAS: 9005-65-6; Polyvinyl alcohol and polyethylene glycol were purchased from Nanjing Chemical Reagent Co., Ltd.; Ethylene-vinyl acetate copolymer was purchased from Dow Chemical, grade Engage™ 8100; Polylactic acid was purchased from Sigma-Aldrich, Mw 18000 - 24000.

[0032] Example 1

[0033] S1 Preparation of the cool sizing solution: Disperse 2 g of surface-modified inorganic nanoparticles, 6 g of eutectic system phase change microcapsules, 8 g of film-forming polymer, 0.5 g of cross-linking agent, 0.1 g of dispersant and 0.1 g of p-toluenesulfonic acid in 100 mL of water, stir at room temperature for 30 min, and perform ultrasonic dispersion at a power of 500 W for 15 min to obtain a uniform and stable cool sizing solution; The film-forming polymer is a mixture of polyvinyl alcohol (PVA), sodium carboxymethyl cellulose (CMC) and acrylic acid-acrylate copolymer in a mass ratio of 1:1:1; The dispersant is a mixture of sodium polyacrylate and sodium tripolyphosphate in a mass ratio of 1:1;

[0034] S2 Fabric pretreatment: Wash and dry the fabric; then perform plasma treatment on its surface, with an argon gas flow rate of 0.1 LPM, a pulse frequency set at 10 Hz, and a treatment time of 150 s to increase the surface energy of the fabric to 65 mN / m, obtaining a surface-treated fabric; The fabric contains 60% cotton fiber and 40% modal.

[0035] S3 Gradient sizing treatment: Immerse the surface-treated fabric after pretreatment in the prepared cool sizing solution. The total immersion time is 20 min, and the immersion mass ratio of the fabric to the cool sizing solution is 1:20. First padding: Vacuum negative pressure immersion (-85 kPa) ensures that the microcapsules penetrate into the yarn gaps, with the liquor pickup rate controlled at 85% and the expression rate 120%. Second padding: Under normal pressure, control the surface film thickness to be 20 µm, with the liquor pickup rate 60% and the expression rate 75% to obtain the precursor of the cool fabric. The immersion time in the first padding is 15 min, and the immersion time in the second padding is 5 min. Subsequently, without special instructions, the ratio of the immersion time in the first padding to the immersion time in the second padding is 3:1.

[0036] S4 Hydrophilic finishing: Immerse the impregnated fabric in an aqueous solution of polyethylene glycol as a hydrophilic finishing agent with a concentration of 5 g / L, an immersion ratio of 1:20, and an immersion time of 13 min, and then carry out rolling, with the expression rate controlled at 60% to obtain the cool fabric to be cured.

[0037] S5 Segmented curing and drying: Pre-dry the impregnated fabric at 75 °C for 5 min, then increase the temperature to 130 °C at a heating rate of 5 °C / min and cure for 1 min, and then dry at 80 °C to constant weight to obtain the intermediate of the cool fabric.

[0038] S6 Antistatic treatment: Immerse the intermediate of the cool fabric in the antistatic raw material and dry after immersion to obtain the cool fabric; the antistatic raw material is an aqueous solution of a non-ionic antistatic agent with a mass concentration of 5%; the mass ratio of the impregnated material liquid is 1:15, and the immersion time is 20 min. The above sizing process is specifically as Figure 1 shown.

[0039] The preparation process of the surface-modified inorganic nanoparticles in S11 is as follows:

[0040] Disperse 10 g of inorganic nanoparticles in 80 mL of ethanol and 20 mL of deionized water, and ultrasonically treat for 30 min (power 300 W) to form a homogeneous suspension; add 0.3 g of silane coupling agent KH-550 thereto, and magnetically stir and react at 60 °C for 4 h; centrifuge (5000 rpm, 15 min) and wash with ethanol three times to remove the unreacted coupling agent, and then dry to obtain amino-functionalized inorganic nanoparticles; dissolve 5 g of polylactic acid and 5 g of ethylene-vinyl acetate copolymer in 200 mL of dichloromethane, and stir at 60 °C until completely dissolved to obtain a modified material solution; add the amino-functionalized inorganic nanoparticles to the modified material solution, add 0.1 g of dicyclohexylcarbodiimide (DCC) and 0.1 g of 4-dimethylaminopyridine (DMAP), and reflux and react at 75 °C for 6 h under nitrogen protection; centrifuge (6000 rpm, 20 min) and wash with dichloromethane three times, and vacuum dry (60 °C, 12 h) to obtain inorganic nanoparticles grafted with polylactic acid / ethylene-vinyl acetate copolymer, that is, surface-modified inorganic nanoparticles.

[0041] The preparation process of the S12 eutectic system phase change microcapsules is as follows:

[0042] Preparation of wall material raw materials: Slowly add 3 g of chitosan (degree of deacetylation 85%) to 300 mL of 2% (mass fraction) aqueous acetic acid solution, and at the same time use a magnetic stirrer to stir at a speed of 300 r / min for 40 min until the chitosan is completely dissolved to obtain a 1% (mass fraction) chitosan solution; add 3 g of sodium alginate to 150 mL of deionized water, turn on the electric stirrer, and stir at a speed of 200 r / min for 90 min to completely dissolve the sodium alginate to prepare a 2% (mass fraction) sodium alginate solution;

[0043] Preparation of core material raw materials: Heat 10 g of the eutectic system mixed with alkanes to the molten state, and control the temperature at 50 - 60 °C; then, slowly pour it into 100 mL of 5% (mass fraction) aqueous Tween 80 solution at the same temperature, and use a high-speed stirrer to stir at a speed of 1500 r / min for 45 min to form a core material emulsion; the alkanes are obtained by mixing alkane one and alkane two in a mass ratio of 2:3; alkane one is tetradecane, and alkane two is nonadecane.

[0044] Slowly drop the prepared chitosan solution into the emulsion at a rate of 1 drop / s, and continuously stir during the dropping process, and maintain the stirring speed at 300 r / min; after the dropping is completed, continue to stir for 20 min to fully mix the chitosan and the emulsion; dropwise add the sodium alginate solution at the same dropping speed, and after the addition is completed, continuously stir for 1.5 h; during this period, chitosan and sodium alginate gradually form a composite wall material on the surface of the emulsion droplets through ionic crosslinking.

[0045] Slowly pour the above-mentioned mixed solution into a calcium chloride solution prepared by dissolving 10 g of calcium chloride in 200 mL of deionized water. Meanwhile, start stirring at a speed of 800 r / min and react for 1 h to promote further solidification and shaping of the wall material. During the solidification process, cross-linking reactions occur between calcium ions and carboxyl groups in sodium alginate, enhancing the structural strength of the wall material.

[0046] After the reaction, centrifuge at a speed of 4000 r / min for 10 min to separate the microcapsules. Then, wash the microcapsules 5 times with deionized water, and centrifuge and separate after each washing to thoroughly remove the residual reagents on the surface. Finally, place the washed microcapsules in a vacuum drying oven at 25 °C and dry until the water content is lower than 0.3% to obtain the eutectic system phase change microcapsules.

[0047] Examples 2 - 4

[0048] Different from Example 1, the preparation process of the eutectic system phase change microcapsules is changed, as shown in Table 1 specifically.

[0049] Table 1 Preparation process of the eutectic system phase change microcapsules

[0050]

[0051] Comparative Example 1 Different from Example 1, the dosage of alkane in S12 is 4 g.

[0052] Comparative Example 2 Different from Example 1, only one kind of alkane is used in S12, and only tetradecane is used as the core material of the eutectic system phase change microcapsules.

[0053] Comparative Example 3 Different from Example 1, only one kind of alkane is used in S12, and only nonadecane is used as the core material of the eutectic system phase change microcapsules.

[0054] Comparative Example 4 Different from Example 1, no eutectic system phase change microcapsules are added to the cool sizing solution prepared in S1.

[0055] Comparative Example 5 Different from Example 1, the dosage of chitosan in S12 is 0.5 g, and the dosage of sodium alginate is 1 g.

[0056] Experimental Example 1

[0057] According to the test standard of GB∕T 35263 - 2017 "Textiles - Detection and evaluation of the instantaneous cool feeling performance in contact", the cool performance of the cool fabric is tested, and the test results are shown in Table 2.

[0058] Table 2 Test results of the cool performance of the fabrics in Examples 1 - 4 and Comparative Examples 1 - 5

[0059]

[0060] The cool fabric prepared by the sizing process of the present invention, after testing, has a contact cool feeling coefficient of 0.19 - 0.24 J / cm 2 ·s under the sizing processes of Examples 1 - 4. By adjusting the preparation process of the eutectic system phase change microcapsules and changing the dosage of the eutectic system phase change microcapsules added to the sizing solution, the coolness of the fabric is improved; the alkane is treated after melting to obtain a core material emulsion, the chitosan solution is dropped into the core material emulsion, and then the sodium alginate solution is dropped. During this process, the amino group in the chitosan molecule and the carboxyl group in the sodium alginate molecule undergo an ionic cross-linking reaction on the surface of the emulsion droplets. Chitosan carries a positive charge under acidic conditions, and sodium alginate carries a negative charge. The positive and negative charges attract each other and combine through ionic bonds to form a composite wall material, tightly wrapping the alkane eutectic system to form the basic structure of the microcapsules; after adding calcium chloride solution, the carboxyl group in sodium alginate can cross-link with calcium ions to form a more stable three-dimensional network structure; calcium ions combine with the carboxyl groups in multiple sodium alginate molecules, enhancing the structural strength of the wall material and improving the stability of the microcapsules, making them not easily broken during subsequent processing and application in the fabric, and improving their cool performance; by using different alkane combinations and dosages, the phase change temperatures and phase change enthalpies of different alkane combinations are different. The melting point of tetradecane is 5.5 °C, the melting point of nonadecane is 32 °C, the melting point of hexadecane is 18 °C, the melting point of octadecane is 28 °C, the melting point of heptadecane is 22 °C, and the melting point of butyl stearate is 25 °C. After melting and combining, they are included in the shell material, melting and absorbing heat at a temperature higher than the melting point of the mixed alkane, and then solidifying again when the temperature decreases, thereby achieving the temperature regulation effect of the microcapsules, and using the differences in the phase change characteristics of different alkanes to make the microcapsules more effectively absorb heat when worn by the human body and enhance the cool feeling. In Comparative Example 1, the dosage of the alkane is too low, and the heat absorption value during melting phase change is low, so the contact cool feeling coefficient is lower than that of Example 1; in Comparative Example 2, only tetradecane is used as the core material of the eutectic system phase change microcapsules, and the contact cool feeling coefficient decreases significantly. Under the same alkane dosage and the same experimental conditions, it is always in a molten state, and the cool effect of the fabric becomes worse; in Comparative Example 3, only nonadecane is used as the core material of the eutectic system phase change microcapsules, and the contact cool feeling coefficient decreases somewhat; in Comparative Example 4, no eutectic system phase change microcapsules are added, and the fabric has a poor regulation effect on high-temperature conditions and cannot achieve a cool wearing effect; in Comparative Example 5, the shell layer thickness of the obtained eutectic system phase change microcapsules is relatively reduced, but it does not affect the contact cool feeling coefficient.

[0061] Examples 5 - 8

[0062] Different from Example 1, the preparation process of the surface-modified inorganic nanoparticles in S11 and the dosage of the surface-modified inorganic nanoparticles in S1 are changed, as specifically shown in Table 3. The particle sizes of the nano-silica, nano-zinc oxide, nano-titanium oxide, nano-montmorillonite, and nano-boron nitride used in Table 3 are 20 nm, 50 nm, 30 nm, 1 nm, and 40 nm, respectively.

[0063] Table 3 Preparation Process and Dosage of Surface-Modified Inorganic Nanoparticles in S11

[0064]

[0065] Comparative Example 6 Different from Example 8, no surface-modified inorganic nanoparticles were added.

[0066] Comparative Example 7 Different from Example 1, the inorganic nanoparticles were not modified.

[0067] Comparative Example 8 Different from Example 1, the dosage of the surface-modified inorganic nanoparticles was 10 g.

[0068] Experimental Example 2

[0069] The cool fabrics obtained from the above examples and comparative examples were tested for their cool performance, and the test results are shown in Table 4.

[0070] Table 4 Test Results of the Cool Performance of the Fabrics in Examples 1, 5 - 8 and Comparative Examples 6 - 8

[0071]

[0072] For the cool fabrics prepared according to the sizing process of the present invention, under the conditions of Example 1 and Examples 5 - 8, the contact cool feeling coefficient is 0.20 - 0.26 J / cm 2·s. By surface modification of inorganic nanoparticles, inorganic nanoparticles such as nano-silica, nano-zinc oxide, nano-titanium oxide, nano-montmorillonite, and nano-boron nitride are selected. After surface modification, first, KH-550 is used for modification. The silane hydrolyzes and condenses with the hydroxyl groups on the surface of the nanoparticles to form Si-O-Si bonds, grafting amino groups, which can react with the hydroxyl groups on the fabric surface, the active groups in polylactic acid and ethylene-vinyl acetate copolymer, as well as the carboxyl and amino groups of the crosslinking agent, enhancing the binding force with the fabric; these nanoparticles have good thermal conductivity or photocatalytic performance, which helps in the conduction and dissipation of heat, thereby enhancing the cool feeling of the fabric; at the same time, after modification, by controlling the improved process, the binding force between the surface-modified inorganic nanoparticles and the fabric increases, and then the fabric has a cool effect. Surface-modified inorganic nanoparticles play an important role in heat conduction and dissipation. Without addition, this heat dissipation pathway is lacking, resulting in a significant decline in the cool performance of the fabric. Therefore, in Comparative Example 6, surface-modified inorganic nanoparticles are not added, and the performance of the fabric decreases. The surface-modified inorganic nanoparticles cannot cooperate with the eutectic system phase change microcapsules to enhance the coolness of the fabric. In Comparative Example 7, the inorganic nanoparticles are not surface-modified, and the binding ability with the fabric decreases, so the contact coolness coefficient decreases. In Comparative Example 8, the dosage of surface-modified inorganic nanoparticles increases. Although the contact coolness coefficient increases to some extent, the particle size on the fabric surface increases, and the flatness decreases.

[0073] Examples 9 - 11

[0074] Different from Example 8, the process conditions of S1 for preparing the cool sizing solution, S3 for gradient sizing treatment, and S11 for surface-modified inorganic nanoparticles are changed, as specifically shown in Table 5.

[0075] Table 5 Process conditions of S1, S3, and S11

[0076]

[0077] Comparative Example 9 Different from Example 8, only butane tetracarboxylic acid is added as the crosslinking agent in S1.

[0078] Comparative Example 10 Different from Example 8, no crosslinking agent is added in S1.

[0079] Comparative Example 11 Different from Example 8, no vacuum negative pressure impregnation is carried out in the first padding stage of S3.

[0080] Comparative Example 12 Different from Example 8, only the first padding stage is carried out in S3, and the second padding is not carried out.

[0081] Comparative Example 13 is different from Example 8 in that the inorganic nanoparticles are only treated with KH-550 modification and not subjected to copolymer grafting of polylactic acid and ethylene-vinyl acetate copolymer. That is, the prepared amino-functionalized inorganic nanoparticles are used as surface-modified inorganic nanoparticles.

[0082] Experimental Example 3

[0083] The coolness and moisture absorption properties were tested. The coolness test was carried out according to the method of Experimental Example 1, and the coolness test was carried out after 30 washes; the moisture absorption test results were expressed as the diffusion diameter (next to the skin surface / cm) after 60 s of water, which means a drop of water was dropped on the next to the skin surface, and the diameter formed by the diffusion of water after 60 s; it reflects the water absorption and diffusion speed of the fabric on the next to the skin surface. The larger the diffusion diameter, the faster the fabric can absorb sweat and make it diffuse, which helps to improve the dryness and comfort of wearing. The final test results are shown in Table 6.

[0084] Table 6 Coolness and moisture absorption properties of Examples 8-11, Comparative Examples 2, 5 and 8-13

[0085]

[0086] For the cool fabric obtained by the sizing process of the present invention, under the conditions of Examples 8-11, the contact coolness coefficient is 0.21-0.26 J / cm 2 ·s, and the contact coolness coefficient after washing is 0.16-0.22 J / cm 2·s, the diffusion diameter is 2.24 - 2.42 cm after 60 s. By adjusting the process conditions of S1, S3, and S11, and adjusting the dosage of the cross-linking agent in S1, the groups in the cross-linking agent can react with the active groups contained in the surface-modified inorganic nanoparticles and the eutectic system phase change microcapsules, and react with the hydroxyl groups on the surface of the fabric after pretreatment, so as to stably connect the above substances to the fabric through chemical bonds, thereby exerting a stable cooling effect. In addition, the connection strength between the components in the sizing solution and the fabric increases, and the washing resistance effect is good. After washing, the key substance components can still be connected to the fabric, and the fabric has good cooling performance; in S3, by adjusting the impregnation time and impregnation ratio, the sizing solution can fully contact and impregnate the fabric; by adjusting the negative vacuum pressure of the first padding in S3 and then performing the second padding under normal pressure, the surface-modified inorganic nanoparticles and the eutectic system phase change microcapsules are more likely to fill into the fiber gaps during the fabric sizing process, increasing the number and connectivity of the pores between the fibers, providing more channels for the diffusion and rise of moisture, thereby improving the water absorption performance of the fabric and increasing the dry and comfortable feeling of the fabric; by adjusting the dosages of polylactic acid and ethylene-vinyl acetate copolymer in the S11 process, polylactic acid and ethylene-vinyl acetate copolymer are uniformly distributed on the surface of the inorganic nanoparticles through chemical bonds. Polylactic acid has good hygroscopicity, and ethylene-vinyl acetate copolymer can play a buffering role during the washing process of the fabric. Both are used to modify the inorganic nanoparticles. The added DCC dehydrating agent promotes the amidation / esterification reaction between the carboxylic acid group of polylactic acid and the acetic acid group of ethylene-vinyl acetate copolymer and the amino group on the surface of the nanoparticles. The access of DMAP increases the reaction rate; the reaction is carried out under nitrogen protection to prevent impurities such as oxygen in the air from interfering with the reaction and ensure the smooth progress of the reaction; through this reaction, polylactic acid and ethylene-vinyl acetate copolymer are grafted onto the surface of the inorganic nanoparticles to form inorganic nanoparticles grafted with polylactic acid / ethylene-vinyl acetate copolymer; then in the S5 segmented curing and drying process, under the action of p-toluenesulfonic acid catalyst, the amino group on the surface of the nanoparticles can undergo dehydration condensation reaction with the hydroxyl group on the surface of the fabric to form -NH-CO- chemical bond; p-toluenesulfonic acid provides protons in the reaction system, and the protons combine with the hydroxyl group on the surface of the fabric to form -OH2 + , -OH2 + leave, thereby promoting the reaction between the amino or ester group and the fabric hydroxyl group, and further improving the binding effect between the sizing solution components and the fabric.

[0087] In Comparative Example 2, only tetradecane was used as the core material of the eutectic system phase change microcapsules. Due to its low melting point, it was difficult to maintain a solid state during the fabric washing process, and it could not provide a lasting cooling effect for the fabric. After washing, the contact coolness coefficient decreased significantly, and the diffusion diameter after 60 s was also lower than that of Example 8; in Comparative Example 5, the dosages of chitosan and sodium alginate were too low, and the shell layer of the eutectic system phase change microcapsules was relatively thin. After washing, the stability decreased, resulting in cracking, loss of effective components, and reduction of cooling performance and water absorption effect; in Comparative Example 8, the dosage of surface-modified inorganic nanoparticles was too high. With a certain amount of cross-linking agent and effective active sites, the binding performance between the effective components in the sizing solution and the fabric decreased, and a large amount of effective components were only physically loaded on the fabric surface and removed after washing. Therefore, the contact coolness coefficient after washing decreased significantly compared with that before washing, and the water absorption performance decreased; in Comparative Example 9, only butanetetracarboxylic acid was added as the cross-linking agent, resulting in reduced cross-linking performance and decreased cooling and water absorption properties of the fabric; in Comparative Example 10, no cross-linking agent was added, further deteriorating the fabric performance. In the first padding stage of S3 in Comparative Example 11, vacuum negative pressure impregnation was not carried out, and the effective components could not be filled into the voids of the fabric and cured, thus unable to improve the wash resistance of the fabric, and the water conveyance effect of the water conveyance channels decreased, and the water absorption performance of the fabric decreased. In Comparative Example 12, only the first padding stage was carried out without the second padding, resulting in decreased fabric performance. In the negative pressure first padding stage, although the surface-modified inorganic nanoparticles and the eutectic system phase change microcapsules were more likely to fill into the fiber gaps, increasing the number and connectivity of the pores between the fibers, the distribution of these particles between the fibers was not uniform; during the normal pressure second padding, the distribution of the particles was adjusted and compacted to make them more uniform and stable in the fabric; without the second padding, during the washing process, the unevenly distributed and loosely fixed microcapsules and nanoparticles were likely to fall off from the fabric. The eutectic system phase change microcapsules are the key components for providing a cooling sensation, and their shedding will significantly reduce the fabric's ability to regulate temperature through phase change after washing, thereby leading to a significant decrease in the contact coolness coefficient; and through the normal pressure second padding, the film-forming polymer can form a continuous, uniform and film with a certain thickness on the fabric surface. This film can not only protect the microcapsules and nanoparticles from falling off, but also enhance the overall stability of the fabric; only the first padding is carried out, and the film cannot be formed completely. During washing, water is likely to invade between the fibers and the particles, destroying the binding between the particles and the fabric, further reducing the cooling performance; during the washing process of the fabric in Comparative Example 12, the fibers swell and shrink, and the unstable pore structure is easily damaged, resulting in the narrowing or blocking of the water diffusion channels, and the water cannot diffuse as quickly as the normally treated fabric, so the diffusion diameter decreases significantly. In Comparative Example 13, the amino-functionalized inorganic nanoparticles were used as the surface-modified inorganic nanoparticles, and the functions of polylactic acid and ethylene-vinyl acetate copolymer could not be exerted, and the cross-linking performance with the fabric decreased, ultimately reducing the cooling and water absorption properties of the fabric.

[0088] Examples 12 - 13

[0089] Different from Example 10, the process conditions of S1 for preparing the cool sizing solution, S12 for preparing the eutectic system phase change microcapsules, S2 for fabric pretreatment, S4 for hydrophilic finishing, and S5 for segmented curing and drying are changed, as shown in Table 7 specifically. The stirring speed and reaction time in S12 in Table 7 are both the reaction process conditions after adding calcium chloride solution in the preparation process of the eutectic system phase change microcapsules in S12.

[0090] Table 7 Process conditions of S1 - S6

[0091]

[0092] Comparative Example 14 Different from Example 10, no dispersant is added.

[0093] Comparative Example 15 Different from Example 10, S2 fabric pretreatment is not carried out.

[0094] Comparative Example 16 Different from Example 10, S4 hydrophilic finishing is not carried out.

[0095] Comparative Example 17 Different from Example 10, in S5, segmented curing and drying is not carried out, but the fabric is cured at 130°C for 2.5 min to obtain the fabric.

[0096] Comparative Example 18 Different from Example 10, the heating temperature in S5 is 160°C.

[0097] Comparative Example 19 Different from Example 10, the stirring speed in S12 is 2000 r / min.

[0098] Comparative Example 20 Different from Example 10, the stirring speed in S12 is 200 r / min.

[0099] Experimental Example 4

[0100] The particle size of the eutectic system phase change microcapsules obtained by the S12 preparation process is tested, and at the same time, the cool performance and water absorption performance of the cool fabrics obtained from the above examples and comparative examples are tested. The final results are shown in Table 8.

[0101] Table 8 Performance test results of Examples 10, 12, 13 and Comparative Examples 14 - 20

[0102]

[0103] For the sizing process of the present invention, under the conditions of Examples 10, 12 and 13, the eutectic system phase change microcapsules are 0.8 - 1.2 μm, and the contact cool feeling coefficient is 0.23 - 0.26 J / cm 2·s, the contact cool feeling coefficient after washing is 0.19 - 0.23 J / cm 2 ·s. After 60 s, the diffusion diameter on the skin-contact side is 2.28 - 2.42 cm. In S1, the dosage of the dispersant is adjusted to improve the dispersion performance of the substances in the sizing solution. In S2, plasma treatment is carried out in an argon atmosphere, and high-energy particles are generated by pulsed discharge to impact the fabric surface, improving the bonding strength between the fabric and the sizing solution. In S4, hydrophilic finishing is carried out to moderately attach the hydrophilic finishing agent to improve the water absorption performance of the fabric. In S5, segmented curing and drying: pre-drying removes part of the moisture, and then it is heated to 115 - 130 °C for curing at a fixed heating rate to cause the cross-linking agent to undergo a cross-linking reaction, forming a stable network structure, enhancing the stability of the glue film. Finally, it is dried at 80 °C to constant weight to ensure that the fabric is dry and its performance is stable. And the centrifugation conditions in the preparation step of S12 are limited, and the microcapsule particle size is within a reasonable range, so as to achieve temperature regulation by using the phase change of alkanes. In Comparative Example 14, the contact cool feeling coefficient and the contact cool feeling coefficient after washing are significantly lower than those in Example 10. After 60 s, the diffusion diameter changes little. Without a dispersant, the components are unevenly dispersed, affecting the cross-linking reaction and the formation of the glue film, resulting in an unreasonable distribution of microcapsules and nanoparticles, reducing the cool feeling performance and wash resistance, but having a relatively small impact on water diffusion. In Comparative Example 15, no fabric pretreatment is carried out, the surface energy of the fabric is low, the adsorption and bonding ability to the sizing solution is poor, the attachment amount of the cool functional components is small, and it is easy to fall off during washing, seriously affecting the cool feeling and water absorption performance. In Comparative Example 16, no hydrophilic finishing is carried out, the fabric has poor hydrophilicity, and the water diffusion is slow. Although the impact on the cool feeling is small, the overall wearing comfort is reduced due to the decrease in water absorption performance. In Comparative Example 17, no segmented curing and drying is carried out, resulting in insufficient cross-linking reaction, poor stability of the glue film, easy shedding of microcapsules and nanoparticles, reducing the cool feeling performance and wash resistance, and at the same time affecting the fabric structure and hindering water diffusion and absorption. In Comparative Example 18, the heating temperature is too high, damaging the fabric structure and component performance, resulting in excessive cross-linking or component decomposition, reducing the cool feeling performance and wash resistance, and the water absorption capacity of the fabric decreases. In Comparative Examples 19 and 20, the eutectic system phase change microcapsules obtained have too large or too small particle sizes, which are not conducive to the improvement of the fabric performance.

[0104] Although the embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions and variations can be made therein without departing from the principles and spirit of the present invention, and the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A sizing process for making cool fabrics, characterized in that: The sizing process is as follows: S1 Prepare the cool sizing solution: Disperse surface-modified inorganic nanoparticles, eutectic system phase change microcapsules, film-forming polymers, cross-linking agents, dispersants, and p-toluenesulfonic acid in deionized water, and obtain the cool sizing solution by ultrasonic mixing after mixing; the cross-linking agent is obtained by mixing butanetetracarboxylic acid, hexamethylenediamine, chromium sulfate, and borax in a mass ratio of 1:1:1:1; the dispersant is obtained by mixing sodium polyacrylate and sodium tripolyphosphate in a mass ratio of 1:1; S2 Fabric pretreatment: The fabric is subjected to plasma treatment to obtain a surface-treated fabric; S3 Gradient sizing treatment: Immerse in the cool sizing solution, perform the first padding under -90 to -65 kPa, and perform the second padding at normal pressure to obtain a precursor of the cool fabric; S4 Hydrophilic finishing: Immerse in a hydrophilic finishing agent to obtain a cool fabric to be cured; S5 Segmented curing and drying: After pre-drying, cure at 115 - 130 °C for 1 - 3 min, and dry to obtain an intermediate of the cool fabric; S6 Antistatic treatment: Immerse in antistatic raw materials to obtain the cool fabric; The preparation process of the surface-modified inorganic nanoparticles is as follows; Add a silane coupling agent to a suspension containing ethanol, the deionized water, and inorganic nanoparticles, and magnetically stir and react at 50 - 65 °C for 3.5 - 5.5 h; After centrifugation, wash and dry to obtain amino-functionalized inorganic nanoparticles; Add polylactic acid and ethylene-vinyl acetate copolymer and reflux to react to obtain the surface-modified inorganic nanoparticles; The dosage ratio of the silane coupling agent, the polylactic acid, and the ethylene-vinyl acetate copolymer is 0.2 - 0.5:4.5 - 7.5:2.5 - 5.5; The inorganic nanoparticles are one of nano-silica, nano-zinc oxide, nano-titanium oxide, nano-montmorillonite, and nano-boron nitride; The eutectic system phase change microcapsules are prepared from a chitosan solution, a sodium alginate solution, an alkane, and a calcium chloride solution; The alkane is obtained by mixing alkane one and alkane two in a mass ratio of 2:3; Alkane one is one of octadecane, hexadecane, and heptadecane; Alkane two is one of octadecane and nonadecane; Alkane one and alkane two are selected from different alkanes; Melt the alkane at 50 - 60 °C and pour it into a solution containing the deionized water and Tween 80 to obtain a core material raw material; Drop the chitosan solution into the core material raw material, and then drop the sodium alginate solution to obtain a composite wall material; Drop the calcium chloride solution into the composite wall material, react at 400 - 800 r / min for 1 - 1.5 h, and after centrifugation and washing, vacuum dry at 25 - 30 °C to obtain the eutectic system phase change microcapsules.

2. The sizing process for making a cool fabric according to claim 1, characterized in that: In S1, the mass-volume ratio of the surface-modified inorganic nanoparticles to the deionized water is 1.5 - 3:100; the mass-volume ratio of the eutectic system phase change microcapsules to the deionized water is 4 - 7:100; the mass ratio of the film-forming polymer to the deionized water is 8:100; the mass ratio of the cross-linking agent to the deionized water is 0.3 - 0.7:100; the mass ratio of the dispersant to the deionized water is 0.1 - 0.2:

100.

3. The sizing process for making a cool fabric according to claim 1, characterized in that: The dosage ratio of chitosan in the chitosan solution, sodium alginate in the sodium alginate solution, and the alkane is 2-3:3-4:8-15.

4. The sizing process for making a cool fabric according to claim 1, characterized in that: In the gradient sizing treatment in S3, the total impregnation time is 10-25 min; the impregnation mass ratio of the surface-treated fabric to the cool sizing solution is 1:20-30; the liquor pickup rate after the first padding is controlled at 85%, and the expression rate is 120%; the liquor pickup rate after the second padding is 60%, and the expression rate is 75%.

5. The sizing process for making a cool fabric according to claim 1, characterized in that: In S4, the impregnation time for the hydrophilic finishing is 10-15 min; in S5, the pre-drying temperature in the segmented curing and drying is 65-80 °C.

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