Gluing process for manufacturing cool fabric

Abstract

The invention relates to the technical field of functional fabrics, in particular to a gluing process for manufacturing a cool fabric. According to the gluing process, the problems that the cooling effect of the fabric is reduced after the fabric is washed with water and the moisture absorption performance of the fabric is poor are solved. The surface energy of the fabric is improved by combining the processes of preparation of a cool gluing solution, fabric pretreatment, gradient gluing treatment, hydrophilic finishing, sectional curing and drying and antistatic treatment, the prepared cool gluing solution contains surface modified inorganic nanoparticles, eutectic system phase change microcapsules and other components, and the surface of the fabric is improved through gradient gluing treatment. Enabling functional components to permeate into gaps of the yarns and controlling surface film formation; finally, the cool fabric is obtained according to six gluing processes, and the fabric still has a cool effect after being washed with water, has good hygroscopicity and is comfortable to wear.

Description

Technical Field

[0001] The invention relates to the technical field of functional fabrics, in particular to a gluing process for making cool fabrics. Background Art

[0002] In hot weather or during strenuous exercise, the human body secretes a lot of sweat. If the sweat cannot be discharged or absorbed, it will cause discomfort. Therefore, the quality of the fabrics worn is crucial. Cool fabrics are popular as a kind of fabric that has a cooling effect, enhances the refreshing feeling of the human body, and is light in weight. The existing preparation process of cool fabrics mainly focuses on the selection of fiber materials, the innovation of fabric structure, and the improvement of finishing process. By selecting fibers with good moisture absorption and breathability, or using special weaving structures to increase air circulation, a certain cooling effect can be achieved. In addition, some chemical finishing agents are also used to give fabrics a cool feeling, but these methods often have problems such as insufficient durability, high cost, or being unfriendly to the environment.

[0003] The main purpose of the traditional sizing process is to improve the stiffness, wrinkle resistance and wear resistance of the fabric, and to give the fabric certain functionality, such as waterproof and anti-fouling properties. However, few studies have combined the sizing process with giving the fabric a cool feeling. Existing cool fabrics mostly use menthol finishing agents or metal oxide coatings to increase the coolness of the fabric, but the volatility of menthol leads to insufficient durability of the cool feeling, and the performance decreases after washing; metal oxides affect the air permeability of the fabric; and the traditional padding process leads to uneven distribution of functional materials. Therefore, the development of a new sizing process that can improve the performance of the fabric while giving the fabric a lasting and comfortable cool feeling has important practical significance and market value.

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

[0005] The purpose of the present invention is to provide a gluing process for making cool fabrics. The surface energy of the fabric is improved by combining the preparation of a cool gluing solution, fabric pretreatment, gradient gluing treatment, hydrophilic finishing, segmented curing and drying, and antistatic treatment processes. The prepared cool gluing solution contains components such as surface-modified inorganic nanoparticles and eutectic system phase change microcapsules. After the gradient gluing treatment, the functional components penetrate into the yarn gaps and control the surface film formation. Finally, the cool fabric is obtained according to the six-step gluing process. The fabric still has a cool effect after washing, has good hygroscopicity, and is comfortable to wear.

[0006] To achieve the above object, the present invention provides the following technical solutions: The present invention provides a gluing process for making cool fabrics, and the gluing process is as follows: S1: preparing a cool glue solution: dispersing surface-modified inorganic nanoparticles, eutectic phase-change microcapsules, film-forming polymers, crosslinking agents, dispersants and p-toluenesulfonic acid in deionized water, mixing and ultrasonicating to obtain a cool glue solution; S2 fabric pretreatment: the fabric is subjected to plasma treatment to obtain a surface treated fabric; The fabric contains cotton fiber and modal. Modal is made from natural wood pulp through a spinning process. The fiber is soft and smooth, has excellent hygroscopicity, and can quickly absorb sweat and moisture from the skin surface to keep the skin dry. Modal has high strength and can maintain good performance even in a wet state and is not easy to deform. Cotton fiber is a fiber developed from the epidermal hair cells of the seeds of cotton plants of the Malvaceae family. It is a natural plant fiber that can quickly absorb sweat from the skin surface when worn, making people feel comfortable without feeling stuffy. It is soft, comfortable and breathable.

[0007] S3 gradient sizing treatment: immersing in a cool sizing solution, first padding at -90 to -65 kPa, and second padding at normal pressure to obtain a cool fabric precursor; S4 hydrophilic finishing: impregnated with hydrophilic finishing agent to obtain cool fabric to be cured; S5 segmented curing and drying: after pre-baking, cure at 115-130℃ for 1-3min to obtain a cool fabric intermediate; S6 antistatic treatment: impregnated with antistatic raw materials to obtain cool fabrics; The eutectic system phase change microcapsules are prepared from chitosan solution, sodium alginate solution, alkane and calcium chloride solution.

[0008] Preferably, the mass volume ratio of surface modified inorganic nanoparticles to deionized water in S1 is 1.5-3:100; the mass volume ratio of eutectic system phase change microcapsules to deionized water is 4-7:100; the mass ratio of film-forming polymer to deionized water is 8:100; the mass ratio of crosslinking agent to deionized water is 0.3-0.7:100; and the mass ratio of dispersant to deionized water is 0.1-0.2:100.

[0009] 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 react with magnetic stirring at 50-65°C for 3.5-5.5 hours; wash and dry after centrifugation to obtain amino inorganic nanoparticles; add polylactic acid and ethylene-vinyl acetate copolymer for reflux reaction to obtain surface-modified inorganic nanoparticles; the ratio of the added amounts of silane coupling agent, polylactic acid and ethylene-vinyl acetate copolymer is 0.2-0.5:4.5-7.5:2.5-5.5.

[0010] Preferably, the inorganic nanoparticles are one of nano-silicon dioxide, nano-zinc oxide, nano-titanium oxide, nano-montmorillonite and nano-boron nitride.

[0011] 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 a core material raw material; drip the chitosan solution into the core material raw material, and then drip the sodium alginate solution to obtain a composite wall material; drip the calcium chloride solution into the composite wall material, react at 400-800r / min for 1-1.5h, centrifuge and wash, and then vacuum dry at 25-30°C to obtain a eutectic system phase change microcapsule.

[0012] Preferably, the ratio of the chitosan in the chitosan solution, the sodium alginate in the sodium alginate solution and the alkane is 2-3:3-4:8-15; the alkane is obtained by mixing alkane 1 and alkane 2 in a mass ratio of 2:3; alkane 1 is one of octadecane, hexadecane, heptadecane and butyl stearate; and alkane 2 is one of octadecane and nonadecane.

[0013] Preferably, the crosslinking agent in S1 is butanetetracarboxylic acid, hexamethylenediamine, chromium sulfate and borax mixed in a mass ratio of 1:1:1:1; the total immersion time in the S3 gradient gluing treatment is 10-25min; the immersion mass ratio of the surface treated fabric to the cool gluing solution is 1:20-30; the liquid carrying rate after the first immersion and rolling is controlled to be 85%, and the rolling rate is 120%; the liquid carrying rate after the second immersion and rolling is 60%, and the rolling rate is 75%.

[0014] Liquid carrying rate refers to the percentage of the weight of liquid carried by the fabric after the padding treatment to the dry weight of the fabric, reflecting the amount of treatment liquid absorbed by the fabric during the padding process; Rolling rate: refers to the percentage of the weight of liquid remaining on the fabric after the fabric is rolled to the weight of liquid carried by the fabric before rolling. The rolling rate reflects the degree of squeezing of the liquid on the fabric during the rolling process; Preferably, the immersion time of S4 hydrophilic finishing is 10-15 minutes; the pre-baking temperature in S5 segmented curing and drying is 65-80°C.

[0015] Compared with the prior art, the present invention has the following beneficial effects: 1. In terms of raw material processing, inorganic nanoparticles are surface modified to enable them to be closely combined with the fabric and assist in heat dissipation; eutectic system phase change microcapsules are prepared, and the phase change characteristics of alkanes in the core material are used to absorb heat. The preparation process of the shell material and the core material is controlled to obtain microcapsules with stable performance; in terms of process, the fabric is pretreated to increase the surface energy, and a gradient glue treatment is used to evenly distribute the functional components. The segmented curing and drying method is used to enhance the stability of the adhesive film. The fabric has a good cooling effect and can effectively absorb human body heat, allowing the wearer to stay cool and comfortable in a hot environment.

[0016] 2. By optimizing the dosage of cross-linking agent, adjusting the impregnation process parameters, controlling the dosage of polylactic acid and ethylene-vinyl acetate copolymer modified with inorganic nanoparticles, and performing gradient gluing treatment in S3, the first negative pressure impregnation and the second normal pressure impregnation are performed to enhance the connection strength between the gluing liquid component and the fabric; the hydrophilic finishing makes the fabric have good hygroscopicity, which can quickly absorb sweat and diffuse; the segmented curing and drying ensures sufficient cross-linking reaction and improves the stability of the film; and the particle size of the eutectic phase change microcapsules in S12 is controlled; the synergistic effect of the above processes makes the fabric still have good cooling performance after washing, and key components such as eutectic phase change microcapsules and surface modified inorganic nanoparticles are not easy to fall off, and good hygroscopicity is maintained. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 The gluing process diagram for making cool fabrics according to the present invention. DETAILED DESCRIPTION

[0018] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0019] See also Figure 1 The present invention provides a gluing process for making cool fabrics, and the technical solution is as follows: The substance information involved in the present invention is as follows: 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, brand Engage™ 8100; polylactic acid was purchased from Sigma-Aldrich, Mw 18000-24000.

[0020] Example 1 S1 Preparation of cool glue solution: 2g surface modified inorganic nanoparticles, 6g eutectic phase change microcapsules, 8g film-forming polymer, 0.5g crosslinking agent, 0.1g dispersant and 0.1g p-toluenesulfonic acid were dispersed in 100mL water, stirred at room temperature for 30min, and ultrasonically dispersed at a power of 500W for 15min to obtain a uniform and stable cool glue solution; the film-forming polymer is polyvinyl alcohol (PVA), sodium carboxymethyl cellulose (CMC) and acrylic acid-acrylate copolymer mixed in a mass ratio of 1:1:1; the dispersant is sodium polyacrylate and sodium tripolyphosphate mixed in a mass ratio of 1:1; S2 fabric pretreatment: the fabric was washed and dried; then the surface was treated with plasma, the argon gas flow rate was 0.1 LPM, the pulse frequency was set to 10 Hz, and the treatment time was 150 s, so that the surface energy of the fabric was increased to 65 mN / m, and the surface treated fabric was obtained; the cotton fiber content in the fabric was 60%, and the modal content was 40%; S3 gradient sizing treatment: the pre-treated surface treated fabric is immersed in the prepared cool sizing solution, the total immersion time is 20 minutes, and the immersion mass ratio of the fabric to the cool sizing solution is 1:20; the first impregnation: vacuum negative pressure impregnation (-85kPa) ensures that the microcapsules penetrate into the yarn gaps, the liquid carrying rate is controlled at 85%, and the rolling rate is 120%; the second impregnation: the surface film thickness is controlled at normal pressure to be 20µm, the liquid carrying rate is 60%, and the rolling rate is 75%, and the cool fabric precursor is obtained; the impregnation time in the first impregnation is 15 minutes, and the impregnation time in the second impregnation is 5 minutes; in the absence of special instructions, the ratio of the impregnation time in the first impregnation to the impregnation time in the second impregnation is 3:1; S4 hydrophilic finishing: the impregnated fabric is immersed in a hydrophilic finishing agent polyethylene glycol aqueous solution with a concentration of 5 g / L, an impregnation ratio of 1:20, and an impregnation time of 13 min, and then rolled, with the rolling ratio controlled at 60%, to obtain a cool fabric to be cured; S5 segmented curing and drying: pre-dry the impregnated fabric at 75°C for 5 minutes, then heat it to 130°C at a heating rate of 5°C / min, cure it for 1 minute, and then dry it at 80°C to constant weight to obtain a cool fabric intermediate; S6 Antistatic Treatment: The cool fabric intermediate is immersed in the antistatic raw material, and then dried to obtain the cool fabric; the antistatic raw material is a non-ionic antistatic agent aqueous solution with a mass concentration of 5%; the material-liquid mass ratio of the immersion is 1:15, and the immersion time is 20 minutes. Figure 1 shown.

[0021] The preparation process of S11 surface modified inorganic nanoparticles is as follows: 10g of inorganic nanoparticles were dispersed in 80mL of ethanol and 20mL of deionized water, and ultrasonically treated for 30min (power 300W) to form a uniform suspension; 0.3g of silane coupling agent KH-550 was added thereto, and magnetic stirring was carried out at 60℃ for 4h; centrifuged (5000 rpm, 15min) and washed with ethanol 3 times to remove the unreacted coupling agent, and then dried to obtain amino inorganic nanoparticles; 5g of polylactic acid and 5g of ethylene-vinyl acetate copolymer were dissolved in 200mL of dichloromethane, and stirred at 60℃ until completely dissolved to obtain a modified material solution; the amino inorganic nanoparticles were added to the modified material solution, and 0.1g of dicyclohexylcarbodiimide (DCC) and 0.1g of 4-dimethylaminopyridine (DMAP) were added, and refluxed at 75℃ for 6h under nitrogen protection; centrifuged (6000 rpm, 20 min) and washed with dichloromethane three times, and dried in vacuum (60 °C, 12 h) to obtain inorganic nanoparticles grafted with polylactic acid / ethylene-vinyl acetate copolymer, i.e., surface-modified inorganic nanoparticles.

[0022] The preparation process of S12 eutectic system phase change microcapsules is as follows: Preparation of wall material raw materials: 3 g of chitosan (deacetylation degree 85%) was slowly added to 300 mL of 2% mass fraction glacial acetic acid aqueous solution, and stirred at a speed of 300 r / min using a magnetic stirrer for 40 min until the chitosan was completely dissolved to obtain a chitosan solution with a mass fraction of 1%; 3 g of sodium alginate was added to 150 mL of deionized water, and an electric stirrer was turned on and stirred at a speed of 200 r / min for 90 min to completely dissolve the sodium alginate to prepare a sodium alginate solution with a mass fraction of 2%; Preparation of core material raw materials: 10g of eutectic system of alkane mixture is heated to a molten state, and the temperature is controlled at 50-60°C; then, it is slowly poured into 100mL of 5% Tween 80 aqueous solution at the same temperature, and stirred at a speed of 1500r / min for 45min using a high-speed stirrer to form a core material emulsion; the alkane is obtained by mixing alkane 1 and alkane 2 in a mass ratio of 2:3; alkane 1 is tetradecane, and alkane 2 is nonadecane.

[0023] The prepared chitosan solution was slowly added to the emulsion at a rate of 1 drop / s, and stirring was continued during the dropping process, and the stirring speed was maintained at 300r / min; after the dropping was completed, stirring was continued for 20min to fully mix the chitosan and the emulsion; the sodium alginate solution was added dropwise at the same dropping speed, and stirring was continued for 1.5h after the addition was completed; during this period, chitosan and sodium alginate gradually formed a composite wall material on the surface of the emulsion droplets through ionic crosslinking; The mixed solution was slowly poured into a calcium chloride solution containing 10 g of calcium chloride dissolved in 200 mL of deionized water, and stirring was started at the same time. The stirring speed was 800 r / min and the reaction was carried out for 1 hour to promote further solidification and molding of the wall material. During the solidification process, calcium ions reacted with carboxyl groups in sodium alginate to cross-link and enhance the structural strength of the wall material. After the reaction, the microcapsules were separated by centrifugation at 4000 r / min for 10 min. Then, the microcapsules were washed with deionized water for 5 times, and centrifuged after each washing to completely remove the residual reagents on the surface. Finally, the washed microcapsules were dried in a vacuum drying oven at 25°C until the moisture content was less than 0.3%, thereby obtaining eutectic phase change microcapsules.

[0024] Embodiment 2-4 Different from Example 1, the preparation process of the eutectic system phase change microcapsules is changed, as shown in Table 1.

[0025] Table 1 Preparation process of eutectic phase change microcapsules

[0026] Comparative Example 1 The difference from Example 1 is that the dosage of alkane in S12 is 4 g.

[0027] Comparative Example 2 is different from Example 1 in that only one alkane is used in S12, and only tetradecane is used as the core material of the eutectic system phase change microcapsules.

[0028] Comparative Example 3 is different from Example 1 in that only one type of alkane is used in S12, and only nonadecane is used as the core material of the eutectic system phase change microcapsules.

[0029] Comparative Example 4 Different from Example 1, no eutectic phase change microcapsules were added to the cool glue solution prepared in S1.

[0030] Comparative Example 5 The difference from Example 1 is that the dosage of chitosan in S12 is 0.5 g, and the dosage of sodium alginate is 1 g.

[0031] Experimental Example 1 According to the test standard GB∕T 35263-2017 “Testing and evaluating the instantaneous coolness of textiles upon contact”, the cooling performance of the cooling fabric was tested, and the test results are shown in Table 2.

[0032] Table 2 Test results of fabric cooling performance of Examples 1-4 and Comparative Examples 1-5

[0033] The cool fabric prepared by the gluing process of the present invention has a contact coolness coefficient of 0.19-0.24 J / cm after testing under the gluing process of Examples 1-4. 2 ·s. The preparation process of eutectic phase change microcapsules is adjusted and the dosage of eutectic phase change microcapsules in the glue solution is changed, so that the fabric has good cooling properties; the alkane is melted and then treated to obtain a core material emulsion, and the chitosan solution is added dropwise to the core material emulsion, and then the sodium alginate solution is added dropwise. During this process, the amino groups in the chitosan molecules and the carboxyl groups in the sodium alginate molecules undergo ionic crosslinking reactions 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 are combined through ionic bonds to form a composite wall material, which tightly wraps the alkane eutectic system to form the basic structure of the microcapsule; after adding the calcium chloride solution, the carboxyl groups in the sodium alginate can undergo a crosslinking reaction with the calcium ions to form a more stable three-dimensional network structure; the calcium ions react with multiple sodium alginate molecules ...eutectic system and forms the basic structure of the microcapsule; after adding the calcium chloride solution, the carboxyl groups in the sodium alginate can undergo a crosslinking reaction with the calcium ions to form a more stable three-dimensional network structure; the calcium ions react with multiple sodium alginate molecules to form a composite wall material, which tightly wraps the eutectic system and forms the basic structure of the microcapsule; after adding the calcium chloride solution, the carboxyl groups in the sodium alginate can undergo a crosslinking reaction with the calcium ions to form a more stable three-dimensional network structure; the calcium ions react with multiple sodium The carboxyl group combination in the sodium alginate molecule enhances the structural strength of the wall material, improves the stability of the microcapsule, makes it less likely to break during subsequent processing and application in the fabric, and improves its cooling performance; different alkane combinations and dosages are used, and the phase change temperature and phase change enthalpy 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 the melt combination, it is included in the shell material, melts and absorbs heat at a temperature higher than the melting point of the mixed alkane, and then solidifies again after the temperature is lowered, thereby achieving the temperature regulating effect of the microcapsule, and utilizing the differences in the phase change characteristics of different alkanes to make the microcapsule absorb heat more effectively when worn by the human body and enhance the cool feeling. In Comparative Example 1, the dosage of alkane is too low, and the heat value absorbed during the molten phase change is low, so the contact cooling 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 microcapsule, and the contact cooling coefficient is significantly reduced. Under the same alkane dosage and the same experimental conditions, it is always in a molten state, and the cooling effect of the fabric is deteriorated; in Comparative Example 3, only nonadecane is used as the core material of the eutectic system phase change microcapsule, and the contact cooling coefficient is reduced; in Comparative Example 4, no eutectic system phase change microcapsule is added, and the fabric has poor control effect on high temperature conditions, and a cool wearing effect cannot be achieved; in Comparative Example 5, the shell thickness of the eutectic system phase change microcapsule obtained is relatively reduced, but it does not affect the contact cooling coefficient.

[0034] Embodiment 5-8 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 shown in Table 3. The nano silicon dioxide particle size used in Table 3 is 20 nm; the nano zinc oxide particle size is 50 nm; the nano titanium oxide particle size is 30 nm; the nano montmorillonite particle size is 1 nm; and the nano boron nitride particle size is 40 nm.

[0035] Table 3 Preparation process and dosage of surface modified inorganic nanoparticles in S11

[0036] Comparative Example 6 is different from Example 8 in that no surface-modified inorganic nanoparticles are added.

[0037] Comparative Example 7 is different from Example 1 in that the inorganic nanoparticles are not modified.

[0038] Comparative Example 8 The difference from Example 1 is that the dosage of the surface-modified inorganic nanoparticles is 10 g.

[0039] Experimental Example 2 The cooling performance of the cooling fabrics obtained in the above embodiments and comparative examples was tested, and the test results are shown in Table 4.

[0040] Table 4 Test results of fabric cooling performance of Examples 1, 5-8 and Comparative Examples 6-8

[0041] The cool fabric prepared by the gluing process of the present invention has a contact coolness coefficient of 0.20-0.26 J / cm under the conditions of Example 1 and Examples 5-8. 2 ·s. Through surface modification of inorganic nanoparticles, nano-silicon dioxide, nano-zinc oxide, nano-titanium oxide, nano-montmorillonite and nano-boron nitride inorganic nanoparticles are selected, and surface modification is firstly carried out by using KH-550 modification treatment, silane hydrolysis and condensation with the surface hydroxyl groups of nanoparticles to form Si-O-Si bonds, and amino groups are grafted, which can react with the hydroxyl groups on the surface of the fabric, the active groups in polylactic acid and ethylene-vinyl acetate copolymer, and the carboxyl and amino groups of the cross-linking agent to enhance the bonding force with the fabric; these nanoparticles have good thermal conductivity or photocatalytic performance, which is conducive to the conduction and dissipation of heat, thereby enhancing the coolness of the fabric; at the same time, after modification, the improved process is controlled, and the bonding force between the surface-modified inorganic nanoparticles and the fabric is increased, thereby making the fabric have a cool effect. Surface-modified inorganic nanoparticles play an important role in heat conduction and dissipation. If they are not added, this heat dissipation pathway is lacking, resulting in a significant decrease in the coolness of the fabric. Therefore, in Comparative Example 6, surface-modified inorganic nanoparticles are not added, and the performance of the fabric is reduced. The surface-modified inorganic nanoparticles cannot cooperate with the eutectic system phase change microcapsules to increase the coolness of the fabric. In Comparative Example 7, the inorganic nanoparticles are not modified, and their ability to bind to the fabric is reduced, so the contact coolness coefficient is reduced. In Comparative Example 8, the amount of surface-modified inorganic nanoparticles added is increased. Although the contact coolness coefficient is improved, the particle size of the fabric surface is increased and the flatness is reduced.

[0042] Examples 9-11 Different from Example 8, the process conditions of S1 preparation of cool glue solution, S3 gradient glue treatment and S11 surface modification of inorganic nanoparticles are changed, which are specifically shown in Table 5.

[0043] Table 5 Process conditions of S1, S3 and S11

[0044] Comparative Example 9 is different from Example 8 in that S1 only adds butanetetracarboxylic acid as a crosslinking agent.

[0045] Comparative Example 10 Different from Example 8, no cross-linking agent was added to S1.

[0046] Comparative Example 11 is different from Example 8 in that vacuum negative pressure impregnation is not performed in the first padding stage S3.

[0047] Comparative Example 12 is different from Example 8 in that S3 only performs the first padding stage without performing the second padding stage.

[0048] Comparative Example 13 Different from Example 8, the inorganic nanoparticles were only modified with KH-550, and no copolymerization grafting of polylactic acid and ethylene-vinyl acetate copolymer was performed. The prepared aminated inorganic nanoparticles were used as surface-modified inorganic nanoparticles.

[0049] Experimental Example 3 The coolness and hygroscopicity tests were conducted. The coolness test was conducted according to the method of Experimental Example 1, and the coolness test was conducted after washing for 30 times. The hygroscopicity test results were expressed as the diffusion diameter of water after 60 seconds (close-fitting surface / cm), which refers to the diameter of the water diffusion formed after 60 seconds when a drop of water is dropped on the close-fitting surface. It reflects the water absorption and diffusion speed of the close-fitting surface of the fabric. The larger the diffusion diameter, the faster the fabric can absorb sweat and diffuse it, which helps to improve the dryness and comfort of wearing. The final test results are shown in Table 6.

[0050] Table 6 Cooling and hygroscopic properties of Examples 8-11, Comparative Examples 2, 5 and 8-13

[0051] The cool fabric obtained by the gluing process of the present invention has a contact coolness coefficient of 0.21-0.26 J / cm under the conditions of Examples 8-11. 2 ·s, the contact coolness coefficient after washing is 0.16-0.22J / cm 2·s, and the diffusion diameter after 60s is 2.24-2.42cm. By adjusting the process conditions of S1, S3 and S11, and adjusting the dosage of S1 crosslinker, the groups in the crosslinker can react with the active groups contained in the surface-modified inorganic nanoparticles and eutectic phase change microcapsules, as well as with the hydroxyl groups on the surface of the fabric after pretreatment, so that the above substances are stably connected to the fabric through chemical bonds, thereby exerting a stable cooling effect. In addition, the connection strength between the components in the glue solution and the fabric is increased, and the water washing effect is good. After washing, the key material components can still be connected to the fabric, and the coolness of the fabric is improved. The performance is good; in S3, the immersion time and immersion ratio are adjusted so that the glue solution can fully contact and immerse the fabric; by adjusting the negative vacuum pressure of the first impregnation in S3, and then performing the second impregnation at normal pressure, the surface-modified inorganic nanoparticles and eutectic phase change microcapsules are easier to fill into the fiber gaps during the fabric gluing process, increasing the number and connectivity of pores between fibers, providing more channels for the diffusion and rise of water, thereby improving the water absorption performance of the fabric and increasing the dryness and comfort of the fabric; by adjusting the polylactic acid and ethylene- The dosage of vinyl acetate copolymer is adjusted, polylactic acid and ethylene-vinyl acetate copolymer are evenly distributed on the surface of inorganic nanoparticles through chemical bonds, polylactic acid has good hygroscopicity, and ethylene-vinyl acetate copolymer can play a buffering role in the process of washing the fabric. Both are used to modify inorganic nanoparticles, and the added DCC dehydrating agent promotes the amidation / esterification reaction between the carboxylic acid group of polylactic acid and the acetate group of ethylene-vinyl acetate copolymer and the amino group on the surface of the nanoparticles, and the access of DMAP increases the reaction rate; the reaction is carried out under nitrogen protection, 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 inorganic nanoparticles to form polylactic acid / ethylene-vinyl acetate copolymer grafted inorganic nanoparticles; then in the S5 segmented curing and drying process, under the action of p-toluenesulfonic acid catalyst, the amino groups on the surface of the nanoparticles can undergo dehydration condensation reaction with the hydroxyl groups on the surface of the fabric to form -NH-CO- chemical bonds; p-toluenesulfonic acid provides protons in the reaction system, and the protons combine with the hydroxyl groups on the surface of the fabric to form -OH 2 + , -OH 2 + Leave, thereby promoting the reaction between the amino or ester group and the hydroxyl group of the fabric, thereby improving the bonding effect between the glue component and the fabric.

[0052] In Comparative Example 2, only tetradecane is used as the core material of the eutectic phase change microcapsule. Due to its low melting point, it is difficult to maintain a solid state during the fabric washing process, and it cannot provide a lasting cooling effect on the fabric. The contact cooling coefficient is significantly reduced after washing, and the diffusion diameter after 60 seconds is also reduced compared with Example 8; in Comparative Example 5, the dosage of chitosan and sodium alginate is too low, the shell layer of the eutectic phase change microcapsule is thin, the stability decreases after washing, rupture occurs, the effective component is lost, and the cooling performance and water absorption effect are reduced; in Comparative Example 8, the dosage of surface modified inorganic nanoparticles is too high. When the number of cross-linking agents and effective active sites is constant, the binding performance of the effective components in the glue solution with the fabric is reduced, and a large number of effective components are only physically loaded on the fabric surface and removed after washing. Therefore, the contact cooling coefficient after washing is significantly reduced compared with before washing, and the water absorption performance is reduced; in Comparative Example 9, only butanetetracarboxylic acid is added as a cross-linking agent, the cross-linking performance is reduced, and the cooling and water absorption performance of the fabric are reduced; in Comparative Example 10, no cross-linking agent is added, and the fabric performance is further reduced. In the first impregnation stage S3 of comparative example 11, vacuum negative pressure impregnation is not performed, and the effective components cannot be filled in the gaps of the fabric and solidified, thereby failing to improve the washability of the fabric, and the water transfer effect of the water transfer channel is reduced, thereby reducing the water absorption performance of the fabric. In Comparative Example 12, only the first impregnation stage is performed without the second impregnation stage, and the performance of the fabric is reduced. In the first negative pressure impregnation stage, although the surface-modified inorganic nanoparticles and eutectic system phase change microcapsules are more easily filled into the fiber gaps, increasing the number and connectivity of the pores between the fibers, the distribution of these particles between the fibers is not uniform; when the second normal pressure impregnation is performed, the distribution of the particles is adjusted and compacted to make them more evenly and stably distributed in the fabric; in the absence of the second impregnation, the unevenly distributed and loosely fixed microcapsules and nanoparticles are easily fallen off the fabric during the washing process. The eutectic system phase change microcapsules are the key component for providing a cool feeling. Their falling off will greatly reduce the ability of the fabric to regulate temperature through phase change after washing, thereby causing a significant decrease in the contact coolness coefficient; and through the second normal pressure impregnation, the film-forming polymer can form a continuous, uniform, and thick film on the surface of the fabric. This layer of film can not only protect the microcapsules and nanoparticles, making them not easy to fall off, but also enhance the overall stability of the fabric; if only the first impregnation is performed, the film cannot be completely formed, and when washed with water, water easily penetrates between the fibers and the particles, destroying the combination of the particles and the fabric, further reducing the cooling performance; during the washing process of the fabric of Comparative Example 12, the fibers swell and shrink, and the unstable pore structure is easily destroyed, resulting in the narrowing or clogging of the water diffusion channel. The water cannot diffuse as quickly as the normally treated fabric, so the diffusion diameter is significantly reduced. Comparative Example 13 uses aminated inorganic nanoparticles as surface-modified inorganic nanoparticles, and the functions of polylactic acid and ethylene-vinyl acetate copolymer cannot be exerted, and the cross-linking performance with the fabric is reduced, and finally the cooling and water absorption performance of the fabric are reduced.

[0053] Examples 12-13 Different from Example 10, the process conditions of S1 preparation of cool glue solution, S12 preparation process of eutectic system phase change microcapsules, S2 fabric pretreatment, S4 hydrophilic finishing and S5 segmented curing and drying are changed, as shown in Table 7. The S12 stirring speed and S12 reaction time in Table 7 are the reaction process conditions after adding calcium chloride solution in the preparation process of S12 eutectic system phase change microcapsules.

[0054] Table 7 Process conditions of S1-S6

[0055] Comparative Example 14 is different from Example 10 in that no dispersant is added.

[0056] Comparative Example 15 The difference from Example 10 is that no S2 fabric pretreatment is performed.

[0057] Comparative Example 16 is different from Example 10 in that S4 hydrophilic finishing is not performed.

[0058] Comparative Example 17 is different from Example 10 in that S5 does not perform segmented curing and drying, but is cured at 130° C. for 2.5 min to obtain the fabric.

[0059] Comparative Example 18 is different from Example 10 in that the heating temperature in S5 is 160°C.

[0060] Comparative Example 19 is different from Example 10 in that the stirring speed in S12 is 2000 r / min.

[0061] Comparative Example 20 is different from Example 10 in that the stirring speed in S12 is 200 r / min.

[0062] Experimental Example 4 The eutectic phase change microcapsules obtained by the S12 preparation process were tested for particle size. At the same time, the cooling fabrics obtained in the above embodiments and comparative examples were tested for cooling performance and water absorption performance. The final results are shown in Table 8.

[0063] Table 8 Performance test results of Examples 10, 12, 13 and Comparative Examples 14-20

[0064] In the gluing 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 coolness coefficient is 0.23-0.26 J / cm 2 ·s, the contact coolness coefficient after washing is 0.19-0.23J / cm 2·s, diffusion diameter after 60s, 2.28-2.42cm on the skin-friendly surface. In S1, the amount of dispersant is adjusted to improve the dispersion performance of the substances in the glue solution. In S2, plasma treatment is carried out in an argon atmosphere, and high-energy particles are generated by pulse discharge to impact the surface of the fabric to improve the bonding force between the fabric and the glue solution. In S4, hydrophilic finishing allows the hydrophilic finishing agent to adhere appropriately and improves the water absorption performance of the fabric. In S5, segmented curing and drying: pre-baking removes part of the moisture, and the temperature is raised to 115-130℃ at a fixed heating rate to cure, so that the cross-linking agent undergoes a cross-linking reaction to form a stable network structure and enhance the stability of the film. Finally, it is dried at 80℃ to a constant weight to ensure that the fabric is dry and has stable performance. In addition, the centrifugation conditions in the preparation step S12 are limited, and the particle size of the microcapsules is within a reasonable range, so as to achieve temperature regulation by utilizing the alkane phase change. In comparative example 14, the contact coolness coefficient and the contact coolness coefficient after washing are significantly lower than those in example 10, and the diffusion diameter does not change much after 60 seconds. There is no dispersant, and the components are unevenly dispersed, which affects the cross-linking reaction and the formation of the adhesive film, resulting in unreasonable distribution of microcapsules and nanoparticles, reducing the cooling performance and washability, but having relatively little effect on water diffusion; in comparative example 15, no fabric pretreatment is performed, the surface energy of the fabric is low, and the adsorption and binding ability of the adhesive liquid is poor, so that the amount of cooling functional components attached is small, and it is easy to fall off during washing, which seriously affects the cooling and water absorption performance; in comparative example 16, no hydrophilic finishing is performed, the fabric has poor hydrophilicity, and the water diffusion is slow Although the cooling feeling is less affected, the overall wearing comfort is reduced due to the decreased water absorption performance; in Comparative Example 17, no segmented curing and drying is performed, resulting in insufficient cross-linking reaction, poor film stability, easy detachment of microcapsules and nanoparticles, reduced cooling performance and washability, 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, which destroys the fabric structure and component performance, resulting in excessive cross-linking or component decomposition, reduced cooling performance and washability, and decreased fabric water absorption capacity; in Comparative Examples 19 and 20, the obtained eutectic system phase change microcapsules have a particle size that is too large or too small, which is not conducive to improving fabric performance.

[0065] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A gluing process for making cool fabrics, characterized in that: The gluing process is as follows: S1: preparing a cool glue solution: dispersing surface-modified inorganic nanoparticles, eutectic phase-change microcapsules, film-forming polymers, crosslinking agents, dispersants and p-toluenesulfonic acid in deionized water, mixing and ultrasonicating to obtain the cool glue solution; S2 fabric pretreatment: the fabric is subjected to plasma treatment to obtain a surface treated fabric; S3 gradient sizing treatment: immersing in the cool sizing solution, first padding at -90 to -65 kPa, and second padding at normal pressure to obtain a cool fabric precursor; S4 hydrophilic finishing: impregnated with hydrophilic finishing agent to obtain cool fabric to be cured; S5 segmented curing and drying: after pre-baking, cure at 115-130℃ for 1-3min to obtain a cool fabric intermediate; S6 antistatic treatment: dipping in antistatic raw materials to obtain the cool fabric; The eutectic system phase change microcapsule is prepared from chitosan solution, sodium alginate solution, alkane and calcium chloride solution.

2. The gluing process for making cool fabrics according to claim 1, characterized in that: The mass volume ratio of the surface modified inorganic nanoparticles to the deionized water in S1 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; and the mass ratio of the dispersant to the deionized water is 0.1-0.2:

100.

3. The gluing process for making cool fabric according to claim 1, characterized in that: The preparation process of the surface modified inorganic nanoparticles described in S1 is as follows: add a silane coupling agent to a suspension containing ethanol, the deionized water and the inorganic nanoparticles, and react with magnetic stirring at 50-65°C for 3.5-5.5 hours; wash and dry after centrifugation to obtain amino inorganic nanoparticles; add polylactic acid and ethylene-vinyl acetate copolymer for reflux reaction to obtain the surface modified inorganic nanoparticles; the ratio of the added amount 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.

4. The gluing process for making cool fabrics according to claim 3 is characterized in that: The inorganic nanoparticles are one of nano silicon dioxide, nano zinc oxide, nano titanium oxide, nano montmorillonite and nano boron nitride.

5. The gluing process for making cool fabric according to claim 1, characterized in that: The preparation process of the eutectic system phase change microcapsules described in S1 is as follows: the alkane is melted at 50-60°C, and poured into a solution containing the deionized water and Tween 80 to obtain a core material raw material; the chitosan solution is dripped into the core material raw material, and then the sodium alginate solution is dripped to obtain a composite wall material; the calcium chloride solution is dripped into the composite wall material, reacted at 400-800r / min for 1-1.5h, centrifuged and washed, and then vacuum dried at 25-30°C to obtain the eutectic system phase change microcapsules.

6. The gluing process for making cool fabrics according to claim 5, characterized in that: The ratio of the chitosan in the chitosan solution, the sodium alginate in the sodium alginate solution and the alkane is 2-3:3-4:8-15; the alkane is obtained by mixing alkane 1 and alkane 2 in a mass ratio of 2:3; the alkane 1 is one of octadecane, hexadecane, heptadecane and butyl stearate; the alkane 2 is one of octadecane and nonadecane.

7. The gluing process for making cool fabric according to claim 1, characterized in that: The cross-linking agent in S1 is butanetetracarboxylic acid, hexamethylenediamine, chromium sulfate and borax mixed in a mass ratio of 1:1:1:1; the total immersion time in the gradient gluing treatment in S3 is 10-25min; the immersion mass ratio of the surface treated fabric to the cool gluing solution is 1:20-30; the liquid carrying rate after the first dipping and rolling is controlled to be 85%, and the rolling rate is 120%; the liquid carrying rate after the second dipping and rolling is 60%, and the rolling rate is 75%.

8. The gluing process for making cool fabric according to claim 1, characterized in that: The immersion time of the hydrophilic finishing in S4 is 10-15 minutes; the pre-baking temperature in the segmented curing and drying in S5 is 65-80°C.

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