CN121065961A - Fluorine-free waterproof composite fabric and preparation method thereof - Google Patents
Fluorine-free waterproof composite fabric and preparation method thereofInfo
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- CN121065961A CN121065961A CN202511630450.3A CN202511630450A CN121065961A CN 121065961 A CN121065961 A CN 121065961A CN 202511630450 A CN202511630450 A CN 202511630450A CN 121065961 A CN121065961 A CN 121065961A
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Abstract
The invention relates to the technical field of functional textile fabrics, in particular to a fluorine-free waterproof composite fabric and a preparation method thereof, comprising the following steps of S1, preprocessing, cleaning and drying a basic fabric; S2, preparing stable dispersion liquid, S3, preparing a waterproof layer, S4, preparing double-component reactive coating slurry, S5, coating the reactive coating slurry prepared in the step S4, S6, performing hot pressing treatment to prepare a surface protection layer, and S7, obtaining the fluorine-free waterproof composite fabric. The invention realizes excellent waterproof performance, maintains air permeability, water resistance, soft texture of the fabric and wearing comfort.
Description
Technical Field
The invention relates to the technical field of functional textile fabrics, in particular to a fluorine-free waterproof composite fabric and a preparation method thereof.
Background
The traditional high-end waterproof fabric has the long-term three-core dilemma that firstly, the excellent waterproof performance of the fabric highly depends on fluorine-containing compounds (such as PFOS and PFOA) as a durable waterproof finishing agent (DWR), but the perfluoro/polyfluoroalkyl substances (PFAS) are difficult to degrade naturally, can continuously accumulate in the environment, can enter a human body through a biological chain, and is hidden with huge ecological and health risks, so that a global regulatory organization continuously tightens the use banning of the fabric, secondly, although some fluorine-free alternatives appear on the market, the fabric realizes the waterproof effect only by means of physical adsorption or surface wrapping, has weak binding force and poor durability, and can not meet the actual use requirement after being subjected to water washing or friction for a plurality of times, thirdly, the thick coating applied for achieving the waterproof purpose often causes stiff fabric and rapid air permeability drop, and can easily generate obvious noise during activities, and seriously sacrifices the soft feel and wearing comfort of clothing. These pain points together form a key bottleneck for the technical upgrading and market development of the current waterproof fabric.
In the prior art, CN 115816961B is a terylene waterproof composite fabric, which comprises a fabric substrate, a waterproof layer applied to the surface of the fabric substrate and a functional film compounded on the bottom surface of the fabric substrate through an adhesive layer, wherein the waterproof layer consists of nano SiO 2 modified polyurethane emulsion, acrylic ester emulsion and amino silicone oil emulsion, and after the surface of the fabric substrate is subjected to waterproof finishing, the bottom surface of the fabric substrate is coated with hot melt adhesive, and then the functional film is compounded, so that the terylene waterproof composite fabric is obtained. The processing method comprises the steps of slowly adding nano SiO 2 modified polyurethane emulsion into acrylic ester emulsion under ① stirring, adding amino silicone oil emulsion, dispersing uniformly to obtain waterproof finishing liquid, padding the dyed polyester fabric with the waterproof finishing liquid of ②, drying ③, baking, coating hot melt adhesive on the back of the polyester substrate fabric with ④, and laminating and compounding with a functional film to obtain the polyester waterproof composite fabric. According to the scheme, the nano SiO 2 modified polyurethane emulsion can be used for preparing the composite fabric with a good waterproof effect, but the air permeability of the composite fabric is slightly lost, and the water resistance of the fabric still has room for improvement.
Disclosure of Invention
In order to overcome the defects, the invention provides the fluorine-free waterproof composite fabric and the preparation method thereof, and the polyisocyanate curing agent is utilized to simultaneously carry out covalent bonding reaction with the hydroxyl-terminated polyurethane resin and the functional groups on the surfaces of the nano particles, so that excellent waterproof performance is realized, and the air permeability, the water resistance, the soft texture of the fabric and the wearing comfort are maintained.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the fluorine-free waterproof composite fabric comprises the following steps:
s1, preprocessing, cleaning and drying a basic fabric;
S2, dispersing 1-10 parts by mass of hydrophobic nano silicon dioxide in 100 parts by mass of organic solvent to prepare stable dispersion liquid, and adopting ultrasonic treatment to ensure uniform dispersion, wherein the organic solvent is one or a mixture of two of ethanol and isopropanol;
S3, dividing the base fabric treated in the step S1 into a surface A and a surface B, uniformly spraying the dispersion liquid on the surface A of the base fabric treated in the step S1 by using spraying equipment, and then preheating and drying the surface B for 3-5min under the vacuum condition of 60-80 ℃ to enable hydrophobic nano silicon dioxide particles to be attached to the surface of the fiber and completely volatilize an organic solvent, so as to prepare a waterproof layer, wherein the loading amount of the hydrophobic nano silicon dioxide particles on the base fabric after drying is 3-5g/m 2, namely the unit area mass of the waterproof layer is 3-5g/m 2;
s4, preparing a bi-component reactive coating slurry;
The component A is prepared by dissolving 100 parts of hydroxyl end-capped polyurethane resin in 20-50 parts of organic solvent according to parts by mass;
the component B is a polyisocyanate curing agent which is an HDI trimer or an IPDI trimer;
The preparation method of the double-component reactive coating slurry comprises the steps of firstly preparing an A component into a mixture with the solid content of 20% -40% by using an organic diluent, then mixing the diluted A component with a B component according to the mass ratio of 3-5:1, and simultaneously adding a wetting leveling agent with the total mass of 0.5% -2% of the system, an antifoaming agent with the total mass of 0.5% -2% and a plasticizer with the total mass of 1% -5%, wherein the organic solvent in the A component and the diluent used for preparing the slurry are one or more of ethyl acetate, acetone and methyl ethyl ketone, the plasticizer is a benzoate plasticizer or a citrate plasticizer, and the wetting leveling agent is a polyether modified polysiloxane leveling agent, and the antifoaming agent is an organosilicon antifoaming agent so as to prepare the reactive coating slurry;
S5, coating the reactive coating slurry prepared in the step S4 on the surface A of the fabric treated in the step S3 by adopting a knife coating or roller coating mode, and controlling the thickness of a wet film to be 100-200 mu m;
S6, placing the fabric coated in the step S5 in hot-pressing equipment, carrying out hot-pressing treatment for 2-8min under the temperature range of 120-150 ℃ and the pressure condition of 0.5-2MPa, enabling the polyisocyanate curing agent to chemically react with the hydroxyl-terminated polyurethane resin and the functional groups on the surfaces of the hydrophobic nano silicon dioxide particles to form covalent bond, and realizing crosslinking and curing to obtain a surface protection layer;
s7, naturally cooling the fabric treated in the step S6 to room temperature to obtain the fluorine-free waterproof composite fabric.
In the scheme, pretreatment cleaning and drying of the basic fabric are the basic premise of the whole preparation process, the cleanliness and dryness of the surface of the fabric are required to be focused, because oil stains, slurry or moisture remained on the surface of the fabric can directly obstruct effective adhesion of subsequent hydrophobic nano silicon dioxide particles, shrinkage cavities, bubbles or uneven solidification can be caused during coating of the reactive coating slurry, a continuous stable waterproof structure can not be formed, the interface combination basis of each subsequent functional layer and fabric fibers can be ensured by thoroughly cleaning and drying to remove impurities and eliminate moisture, in the preparation of the hydrophobic nano silicon dioxide dispersion liquid, the ethanol and isopropanol are selected due to the compatibility of the polarity of the ethanol and the hydrophobic nano silicon dioxide dispersion liquid and the hydrophobic modification groups on the surface of the nano particles, the stable dispersion of the particles can be realized, the characteristics of easy volatilization and no residue can be realized, if other solvents are selected to possibly cause particle agglomeration or residual impurities to influence the waterproof performance, the ultrasonic treatment is a key means for breaking the agglomeration of the nano particles, if the agglomeration particles are omitted or insufficient, the hydrophobic microstructure of the surface of the sprayed fabric A is incomplete, local failure is caused, and the uniform waterproof surface can be realized only by realizing uniform dispersion of the particles, and the continuous hydrophobic surface layer can be laid. Spraying the dispersion liquid on the surface A, and then carrying out vacuum preheating drying on the surface B, wherein the vacuum environment and the cooperation of mild temperature are required to be focused, the vacuum condition can accelerate the volatilization of the organic solvent, the secondary aggregation of particles caused by slow volatilization of the solvent during normal pressure drying is avoided, the mild temperature can prevent the high temperature from damaging the fiber structure of the fabric, if the temperature is too high, the physical property of the fabric is damaged, the subsequent hand feeling is influenced, the combination of the reactive coating and the nano particles is interfered by the solvent residue if the temperature is too low, the core of the step is that the nano particles are primarily and firmly attached to the surface of the surface A fiber through Van der Waals force to form an initial hydrophobic layer, and meanwhile, the original structural integrity of the fabric is considered.
The preparation of the dual-component reactive coating slurry needs to pay attention to the coordination of functions and dosage of all components, hydroxyl-terminated polyurethane resin in the component A is taken as a core matrix, nanoparticles and fabric fibers can be tightly adhered, hydroxyl contained in the hydroxyl-terminated polyurethane resin can provide sites for crosslinking reaction, an organic solvent is used for adjusting the solubility of the resin to adapt to a knife coating or roller coating process, too little solvent dosage can lead to slurry viscosity and difficult coating uniformity, too much solvent dosage can easily cause sagging of a wet film to lead to uneven coating thickness, the component B is reacted with hydroxyl to form a urea bond crosslinking structure, the mass ratio of the component A, B needs to be precisely controlled, if the ratio of the component B is too high, the crosslinking density can be too high, the coating stiffness is increased, the fabric handfeel is poor, if the ratio is too low, the crosslinking reaction is insufficient, the coating adhesion is weakened, the coating is easy to fall off, the addition of a wetting leveling agent is used for improving the spreadability of the slurry on the surface of a hydrophobic nano layer, the surface, the hydrophilic leveling agent is not easy to cause sagging of the slurry, the slurry is easy to occur, the water-proof component is difficult to cause sagging, the coating is difficult to cause uneven, the coating thickness, the effect of the coating is reduced, the overall coating can be caused by the excessive consumption of the hydrophilic leveling agent is difficult to cause the problem, the problem of the coating is caused by the problem of poor coating, the overall coating performance is reduced, the overall coating performance can be caused by the problem of poor coating, and the coating performance is caused by the problem of poor coating, and the interface strength is caused by the problem of poor coating, and the coating can be caused by poor quality. When the sizing agent is coated by adopting a knife coating or roller coating mode, the thickness of a wet film needs to be controlled to balance the waterproof performance and the hand feeling of the fabric, the too thick wet film can cause the too thick coating and the increase of stiffness after drying, the soft hand feeling requirement is violated, and the too thin film can not completely wrap the nano particles to form a continuous waterproof film, so that waterproof holes are easy to occur. The hot-pressing treatment is a core link for realizing the stabilization of a waterproof structure, the cooperative adaptation of temperature, pressure and time is required to be ensured, the temperature is required to reach the threshold value of the crosslinking reaction of hydroxyl and polyisocyanate curing agents, meanwhile, hydroxyl-terminated polyurethane and nano silicon dioxide surface functional groups are pushed to form covalent bonds, the reaction is incomplete due to the fact that the temperature is too low, firm bonding cannot be realized, the fabric is deformed or the coating is excessively crosslinked and becomes brittle, the pressure is used for promoting the close contact of the coating with the fabric and nano particles, interface gaps are eliminated, the interface bonding is loose due to the fact that the pressure is insufficient, layering is easy after washing, the fabric fiber is possibly crushed due to the fact that the interface gaps are eliminated, the time is required to meet the complete process of the crosslinking reaction and covalent bond bonding, the reaction is not complete due to the fact that the reaction is too short, the coating aging is possibly caused due to the fact that the coating is too long is long, the firm bonding of a nano hydrophobic layer, a polyurethane coating and the fabric fiber can be realized due to the cooperation of the fact that the three is ensured, and the soft hand feeling is simultaneously realized. And finally, quenching is avoided by natural cooling, internal stress is generated between the fabric and the coating due to quenching, the fabric is deformed, the coating is cracked, the integrity of the waterproof structure is destroyed, the fabric and the coating can be slowly contracted by natural cooling, the structure is stable, and finally, a composite fabric structure which is free of fluorine, stable in waterproof performance and soft in hand feeling is constructed through the cooperation of process control and component functions of each step, so that the preset technical aim is fulfilled.
Preferably, in the step S1, the base fabric is a nylon woven fabric or a polyester woven fabric, and the unit area mass of the base fabric is 80-150g/m 2.
Preferably, in step S1, the pretreatment includes washing the base fabric with a neutral detergent to remove spin finish and weaving slurry.
Preferably, in step S2, the hydrophobic nano silica is obtained by surface modification treatment of gas phase nano silica with an original particle size of 10-40nm with a silane coupling agent.
Preferably, the silane coupling agent is hexamethyldisilazane or dodecyl trimethoxy silane.
Preferably, in step S2, the power of the ultrasonic treatment is 300-500W, and the treatment time is 15-30min.
Preferably, in the step S3, the diameter of a nozzle of the spraying device is 0.3-0.5mm, the spraying air pressure is 0.2-0.4MPa, and the spraying distance is 15-25cm.
Preferably, in step S3, the absolute pressure of the vacuum condition is 10 to 70kPa.
The scheme also provides the fluorine-free waterproof composite fabric prepared by the method, which comprises a basic fabric layer, a waterproof layer and a surface protection layer.
Compared with the prior art, the advantage of this scheme lies in:
1. Through the compatibility of the hydrophobic nano silicon dioxide and the hydroxyl-terminated polyurethane resin system, the polyisocyanate curing agent is utilized to simultaneously generate covalent bonding reaction with the hydroxyl-terminated polyurethane resin and the functional groups on the surfaces of the nano particles, so that a firm nano anchoring-polymer crosslinked somatic network structure is formed at the interface, the chemical stability and physical durability of the waterproof layer are ensured, and the defect that the traditional physical coating is easy to peel is avoided.
2. In the whole process chain, the vacuum dispersion of the nano particles is adhered to the low-temperature hot-press solidification of the reactive slurry, and parameters of the steps are coupled with each other and progressive layer by layer, so that the uniform distribution and complete coating of the functional components on the surface of the fiber are ensured, the damage of high temperature and high pressure to the hand feeling of the fabric is effectively avoided, and the excellent waterproof performance is finally realized, and meanwhile, the air permeability, the soft texture of the fabric and the wearing comfort are maintained.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the present embodiment and comparative example:
Adding 100 parts of deionized water into a reaction kettle with stirring according to parts by weight, starting to slowly heat to 45 ℃, adding 4 parts of sodium citrate, stirring until the sodium citrate is completely dissolved, sequentially adding 12 parts of fatty alcohol polyoxyethylene ether AEO-9 and 7 parts of dodecyl dimethyl betaine BS-12, slowly stirring to avoid excessive foam generation until the solution becomes even and clear, finally adding 4 parts of propylene glycol, continuously stirring for 15-20 minutes, ensuring that all components are uniformly mixed, cooling to room temperature, and detecting and adjusting the pH value to 7;
the hydroxyl end-capped polyurethane resin (TPU) is selected from Libo 5703;
The defoaming agent is an organosilicon defoaming agent CL-266;
The polyether modified polysiloxane flatting agent is Anjikang 7333.
Example 1
The preparation method of the fluorine-free waterproof composite fabric comprises the following steps:
s1, preprocessing, cleaning and drying a basic fabric, wherein the basic fabric is nylon woven fabric, and the unit area mass of the basic fabric is 115g/m 2;
S2, dispersing 5 parts by mass of hydrophobic nano silicon dioxide in 100 parts by mass of organic solvent to prepare stable dispersion liquid, and performing ultrasonic treatment with the power of 400W for 22min to ensure uniform dispersion, wherein the organic solvent is ethanol;
S3, uniformly spraying the dispersion liquid on the surface A of the base fabric treated in the step S1 by using spraying equipment, wherein the diameter of a nozzle of the spraying equipment is 0.4mm, the spraying air pressure is 0.3MPa, the spraying distance is 20cm, and then preheating and drying are carried out on the surface B at the temperature of 70 ℃ under the absolute pressure of 40kPa for 4 minutes to obtain a waterproof layer, wherein the loading amount of the hydrophobic nano silicon dioxide particles is 4g/m 2;
s4, preparing a bi-component reactive coating slurry;
The two-component reactive coating slurry comprises 100 parts by mass of hydroxyl-terminated polyurethane resin and 35 parts by mass of organic solvent;
the component B is a polyisocyanate curing agent, wherein the polyisocyanate curing agent is an HDI trimer;
Preparing a bi-component reactive coating slurry, namely firstly preparing an A component with an organic diluent to obtain a solid content of 30%, then mixing the diluted A component with a B component according to a mass ratio of 4:1, and simultaneously adding a wetting and leveling agent accounting for 1.2% of the total mass of the system, a defoaming agent accounting for 1.2% and a plasticizer accounting for 3%, wherein the organic solvent in the A component and the diluent used for preparing the slurry are ethyl acetate, and the plasticizer is a benzoate plasticizer B50 to prepare the reactive coating slurry;
S5, coating the reactive coating slurry prepared in the step S4 on the surface A of the fabric treated in the step S3 in a blade coating mode, and controlling the thickness of a wet film to be 150 mu m;
s6, placing the fabric coated in the step S5 in hot-pressing equipment, and performing hot-pressing treatment for 5min under the pressure condition of 1.2MPa at the temperature range of 135 ℃ to obtain a surface protection layer;
s7, naturally cooling the fabric treated in the step S6 to room temperature to obtain the fluorine-free waterproof composite fabric.
Example 2
The preparation method of the fluorine-free waterproof composite fabric comprises the following steps:
s1, preprocessing, cleaning and drying a basic fabric, wherein the basic fabric is a terylene woven fabric, and the unit area mass of the basic fabric is 80g/m 2;
s2, dispersing 1 part by mass of hydrophobic nano silicon dioxide in 100 parts by mass of organic solvent to prepare stable dispersion liquid, and carrying out ultrasonic treatment with the power of 300W for 30min to ensure uniform dispersion, wherein the organic solvent is isopropanol;
S3, uniformly spraying the dispersion liquid on the surface A of the base fabric treated in the step S1 by using spraying equipment, wherein the diameter of a nozzle of the spraying equipment is 0.3mm, the spraying air pressure is 0.2MPa, the spraying distance is 25cm, and then preheating and drying are carried out on the surface B at the temperature of 60 ℃ under the absolute pressure of 70kPa for 5min to obtain a waterproof layer, wherein the loading amount of the hydrophobic nano silicon dioxide particles is 3g/m 2;
s4, preparing a bi-component reactive coating slurry;
The two-component reactive coating slurry comprises 100 parts by mass of hydroxyl-terminated polyurethane resin and 20 parts by mass of organic solvent;
The component B is a polyisocyanate curing agent which is an IPDI trimer;
Preparing a bi-component reactive coating slurry, namely firstly preparing an A component with an organic diluent to obtain a solid content of 20%, then mixing the diluted A component with a B component according to a mass ratio of 3:1, and simultaneously adding a wetting and leveling agent accounting for 0.5% of the total mass of the system, an antifoaming agent accounting for 0.5% and a plasticizer accounting for 1%, wherein the organic solvent in the A component and the diluent used for preparing the slurry are acetone, and the plasticizer is triethyl citrate to prepare the reactive coating slurry;
S5, coating the reactive coating slurry prepared in the step S4 on the surface A of the fabric treated in the step S3 in a roller coating mode, and controlling the thickness of a wet film to be 100 mu m;
S6, placing the fabric coated in the step S5 in hot-pressing equipment, and performing hot-pressing treatment for 8min under the temperature range of 120 ℃ and the pressure condition of 0.5MPa to obtain a surface protection layer;
s7, naturally cooling the fabric treated in the step S6 to room temperature to obtain the fluorine-free waterproof composite fabric.
Example 3
The preparation method of the fluorine-free waterproof composite fabric comprises the following steps:
S1, preprocessing, cleaning and drying a basic fabric, wherein the basic fabric is nylon woven fabric, and the unit area mass of the basic fabric is 150g/m 2;
S2, dispersing 10 parts by mass of hydrophobic nano silicon dioxide in 100 parts by mass of organic solvent to prepare stable dispersion liquid, and carrying out ultrasonic treatment with the power of 500W for 15min to ensure uniform dispersion, wherein the organic solvent is a mixture of ethanol and isopropanol;
S3, uniformly spraying the dispersion liquid on the surface A of the base fabric treated in the step S1 by using spraying equipment, wherein the diameter of a nozzle of the spraying equipment is 0.5mm, the spraying air pressure is 0.4MPa, the spraying distance is 15cm, and then preheating and drying are carried out on the surface B at 80 ℃ for 3min under the absolute pressure of 10kPa to obtain a waterproof layer, wherein the loading amount of the hydrophobic nano silicon dioxide particles is 5g/m 2;
s4, preparing a bi-component reactive coating slurry;
the two-component reactive coating slurry comprises 100 parts by mass of hydroxyl-terminated polyurethane resin and 50 parts by mass of organic solvent;
the component B is a polyisocyanate curing agent, wherein the polyisocyanate curing agent is an HDI trimer;
preparing a bi-component reactive coating slurry, namely firstly preparing an A component with an organic diluent to obtain a solid content of 40%, then mixing the diluted A component with a B component according to a mass ratio of 5:1, and simultaneously adding a wetting leveling agent accounting for 2% of the total mass of the system, a defoaming agent accounting for 2% and a plasticizer accounting for 5%, wherein the organic solvent in the A component and the diluent used for preparing the slurry are methyl ethyl ketone, and the plasticizer is a benzoate plasticizer B50 to prepare the reactive coating slurry;
s5, coating the reactive coating slurry prepared in the step S4 on the surface A of the fabric treated in the step S3 in a blade coating mode, and controlling the thickness of a wet film to be 200 mu m;
S6, placing the fabric coated in the step S5 in hot-pressing equipment, and performing hot-pressing treatment for 2min under the pressure condition of 2MPa at the temperature range of 150 ℃ to obtain a surface protection layer;
s7, naturally cooling the fabric treated in the step S6 to room temperature to obtain the fluorine-free waterproof composite fabric.
Example 4
The preparation method of the fluorine-free waterproof composite fabric comprises the following steps:
S1, preprocessing, cleaning and drying a basic fabric, wherein the basic fabric is a terylene woven fabric, and the unit area mass of the basic fabric is 100g/m 2;
S2, dispersing 3 parts by mass of hydrophobic nano silicon dioxide in 100 parts by mass of organic solvent to prepare stable dispersion liquid, and carrying out ultrasonic treatment with the power of 350W for 25min to ensure uniform dispersion, wherein the organic solvent is isopropanol;
S3, uniformly spraying the dispersion liquid on the surface A of the base fabric treated in the step S1 by using spraying equipment, wherein the diameter of a nozzle of the spraying equipment is 0.35mm, the spraying air pressure is 0.25MPa, the spraying distance is 22cm, and then preheating and drying are carried out on the surface B at 65 ℃ for 4.5min under the absolute pressure of 50kPa to obtain a waterproof layer, wherein the loading amount of the hydrophobic nano silicon dioxide particles is 3.5g/m 2;
s4, preparing a bi-component reactive coating slurry;
the two-component reactive coating slurry comprises 100 parts by mass of hydroxyl-terminated polyurethane resin and 25 parts by mass of organic solvent;
The component B is a polyisocyanate curing agent which is an IPDI trimer;
Preparing a bi-component reactive coating slurry, namely firstly preparing an A component into a mixture with the solid content of 25% by using an organic diluent, then mixing the diluted A component with a B component according to the mass ratio of 3.5:1, and simultaneously adding a wetting and leveling agent with the total mass of 1% of the system, a defoaming agent with the mass of 1.5% and a plasticizer with the mass ratio of 1:1 by using an organic solvent in the A component and the diluent used for preparing the slurry as a mixture of ethyl acetate and acetone, wherein the plasticizer is triethyl citrate, so as to prepare the reactive coating slurry;
s5, coating the reactive coating slurry prepared in the step S4 on the surface A of the fabric treated in the step S3 in a roller coating mode, and controlling the thickness of a wet film to be 120 mu m;
S6, placing the fabric coated in the step S5 in hot-pressing equipment, and performing hot-pressing treatment for 6min under the temperature range of 125 ℃ and the pressure condition of 1MPa to obtain a surface protection layer;
s7, naturally cooling the fabric treated in the step S6 to room temperature to obtain the fluorine-free waterproof composite fabric.
Example 5
The preparation method of the fluorine-free waterproof composite fabric comprises the following steps:
s1, preprocessing, cleaning and drying a basic fabric, wherein the basic fabric is nylon woven fabric, and the unit area mass of the basic fabric is 130g/m 2;
s2, dispersing 8 parts by mass of hydrophobic nano silicon dioxide in 100 parts by mass of organic solvent to prepare stable dispersion liquid, and carrying out ultrasonic treatment with the power of 450W for 18min to ensure uniform dispersion, wherein the organic solvent is a mixture of ethanol and isopropanol;
S3, uniformly spraying the dispersion liquid on the surface A of the base fabric treated in the step S1 by using spraying equipment, wherein the diameter of a nozzle of the spraying equipment is 0.45mm, the spraying air pressure is 0.35MPa, the spraying distance is 18cm, and then preheating and drying are carried out on the surface B at the temperature of 75 ℃ under the absolute pressure of 25kPa for 3.5min to obtain a waterproof layer, wherein the loading amount of the hydrophobic nano silicon dioxide particles is 4.5g/m 2;
s4, preparing a bi-component reactive coating slurry;
the two-component reactive coating slurry comprises 100 parts by mass of hydroxyl-terminated polyurethane resin and 45 parts by mass of organic solvent;
the component B is a polyisocyanate curing agent, wherein the polyisocyanate curing agent is an HDI trimer;
Preparing a bi-component reactive coating slurry, namely firstly preparing an A component into a mixture with the solid content of 35% by using an organic diluent, then mixing the diluted A component with a B component according to the mass ratio of 4.5:1, and simultaneously adding a wetting leveling agent with the total mass of 1.8% of the system, a defoaming agent with the mass of 0.8% and a plasticizer with the mass ratio of 4%, wherein the organic solvent in the A component and the diluent used for preparing the slurry are a mixture with the mass ratio of methyl ethyl ketone to acetone of 1:1, and the plasticizer is a benzoate plasticizer B50 to prepare the reactive coating slurry;
S5, coating the reactive coating slurry prepared in the step S4 on the surface A of the fabric treated in the step S3 in a blade coating mode, and controlling the thickness of a wet film to be 180 mu m;
S6, placing the fabric coated in the step S5 in hot-pressing equipment, and performing hot-pressing treatment for 3min under the temperature range of 145 ℃ and the pressure condition of 1.8MPa to obtain a surface protection layer;
s7, naturally cooling the fabric treated in the step S6 to room temperature to obtain the fluorine-free waterproof composite fabric.
Comparative example 1
The only difference from example 1 is that the fumed silica is not surface modified.
Comparative example 2
The only difference from example 1 is that there is no surface protection layer. The method comprises the following specific steps:
s1, preprocessing, cleaning and drying a basic fabric, wherein the basic fabric is nylon woven fabric, and the unit area mass of the basic fabric is 115g/m 2;
S2, dispersing 5 parts by mass of hydrophobic nano silicon dioxide in 100 parts by mass of organic solvent to prepare stable dispersion liquid, and performing ultrasonic treatment with the power of 400W for 22min to ensure uniform dispersion, wherein the organic solvent is ethanol;
S3, uniformly spraying the dispersion liquid on the surface A of the base fabric treated in the step S1 by using spraying equipment, wherein the diameter of a nozzle of the spraying equipment is 0.4mm, the spraying air pressure is 0.3MPa, the spraying distance is 20cm, and then preheating and drying are carried out on the surface B at the temperature of 70 ℃ under the absolute pressure of 40kPa for 4 minutes to obtain a waterproof layer, wherein the loading amount of the hydrophobic nano silicon dioxide particles is 4g/m 2;
s4, naturally cooling the fabric treated in the step S3 to room temperature to obtain the fluorine-free waterproof composite fabric.
Comparative example 3
The only difference from example 1 is that no waterproof layer was present. The method comprises the following specific steps:
the preparation method of the fluorine-free waterproof composite fabric comprises the following steps:
s1, preprocessing, cleaning and drying a basic fabric, wherein the basic fabric is nylon woven fabric, and the unit area mass of the basic fabric is 115g/m 2;
s2, dividing the base fabric processed in the step S1 into a surface A and a surface B, uniformly spraying ethanol on the surface A of the base fabric processed in the step S1 by using spraying equipment, wherein the diameter of a nozzle of the spraying equipment is 0.4mm, the spraying air pressure is 0.3MPa, the spraying distance is 20cm, and then preheating and drying are carried out for 4min under the conditions that the surface B faces upwards, the temperature is 70 ℃ and the absolute pressure is 40 kPa;
S3, preparing a bi-component reactive coating slurry;
The two-component reactive coating slurry comprises 100 parts by mass of hydroxyl-terminated polyurethane resin and 35 parts by mass of organic solvent;
the component B is a polyisocyanate curing agent, wherein the polyisocyanate curing agent is an HDI trimer;
Preparing a bi-component reactive coating slurry, namely firstly preparing an A component with an organic diluent to obtain a solid content of 30%, then mixing the diluted A component with a B component according to a mass ratio of 4:1, and simultaneously adding a wetting and leveling agent accounting for 1.2% of the total mass of the system, a defoaming agent accounting for 1.2% and a plasticizer accounting for 3%, wherein the organic solvent in the A component and the diluent used for preparing the slurry are ethyl acetate, and the plasticizer is a benzoate plasticizer B50 to prepare the reactive coating slurry;
s4, coating the reactive coating slurry prepared in the step S3 on the surface A of the fabric treated in the step S3 in a blade coating mode, and controlling the thickness of a wet film to be 150 mu m;
S5, placing the fabric coated in the step S4 in hot-pressing equipment, and performing hot-pressing treatment for 5min under the pressure condition of 1.2MPa at the temperature range of 135 ℃ to obtain a surface protection layer;
S6, naturally cooling the fabric treated in the step S5 to room temperature to obtain the fluorine-free waterproof composite fabric.
Comparative example 4
The only difference from example 1 is that the fumed silica is surface-modified with KH 550.
Comparative example 5
The only difference from example 1 is that in S3, the drying process a is facing upwards.
Comparative example 6
The only difference from example 1 is that in S3, the drying process is carried out at normal pressure.
Comparative example 7
The only difference from example 1 is that the hydrophobic nano-silica particle loading is 6g/m 2.
Comparative example 8
The only difference from example 1 is that the hydrophobic nano-silica particle loading is 2.5g/m 2.
Comparative example 9
The difference from example 1 is only that in S4, the A component and the B component are mixed in a mass ratio of 2.5:1.
Comparative example 10
The difference from example 1 is only that in S4, the A component and the B component are mixed in a mass ratio of 5.5:1.
Comparative example 11
The only difference from example 1 is that the base fabric is a cotton fabric.
Comparative example 12
The difference from example 1 is only that the autoclave treatment was carried out for 5min at 160℃and a pressure of 1.2 MPa.
Comparative example 13
The only difference from example 1 is that S5 controls the wet film thickness to 80 μm.
Comparative example 14
The only difference from example 1 is that S5 controls the wet film thickness to 210 μm.
The detection method comprises the following steps:
1. Static waterproof Property (hydrostatic pressure): reference GB/T4744-2013 "method for detecting and evaluating Water resistance of textiles" hydrostatic pressure;
the method comprises the steps of applying gradually rising water pressure to one side of the fabric, and recording a pressure value (unit: kPa) when water is permeated for the first time;
The qualification requirement is that the pressure is generally more than or equal to 30kPa (which corresponds to the daily waterproof requirement, such as a wind and rain environment).
2. The dynamic waterproof performance (spraying method) refers to GB/T4745-2012, the fabric is inclined for 45 degrees, water with a specified flow rate is sprayed, and the fabric is scored according to the surface water wetting area and the penetration condition (1-5 grades, 5 grades are optimal);
And the qualification requirement is that the initial spray grade is more than or equal to 4 grades, so that the surface water drops are ensured not to fall off and infiltrate.
3. The durability of water resistance after water washing is that standard water washing (simulating daily use) is carried out for 10/20 times according to GB/T8629-2017 household washing and drying program for textile test, and the hydrostatic pressure and the spray grade are retested after water washing.
4. Tear strength reference GB/T3917.2-2009 section 2 of textile fabric tear properties determination of trouser sample (single slit) tear strength;
The method comprises testing maximum force (N) of the trouser sample during tearing;
the requirement is that the longitudinal and latitudinal tearing strength is not less than 15N (the conventional requirement of nylon/terylene fabrics).
5. Friction (dry/wet friction) the surface of the facing was rubbed with a rubbing cloth (dry/wet) at a specified pressure, followed by retesting "hydrostatic pressure" and "spray rating".
6. Hand feeling evaluation, namely scoring the softness and smoothness by 5 professionals (grade 1-5, grade 5 is optimal) according to GB/T18888-2002 "hand feeling method for textile hand feeling evaluation", and taking an average value;
Objective evaluation, namely testing bending stiffness (unit: mN, m) by a fabric style instrument, wherein the smaller the stiffness value is, the softer the stiffness value is;
the subjective hand feeling score is more than or equal to 4 grades, the bending rigidity is less than or equal to 50mN and m is equal to the hand feeling of untreated fabric.
7. And (3) detecting fluorine content, namely detecting fluorine ions or organic fluorine residues in the fabric by adopting an Ion Chromatography (IC) or a gas chromatography-mass spectrometry (GC-MS), wherein the fluorine content meets the limit value of fluorine-free in national standard GB/T3066-2014 (less than or equal to 50 mg/kg).
8. Air permeability detection, namely, measuring the air flow (unit: mm/s or L/m 2, s) passing through the unit area of the fabric in unit time under the pressure difference of 100Pa by referring to GB/T5453-1997 determination of air permeability of textile fabrics, wherein the larger the air flow, the better the air permeability.
The test results are shown in tables 1-3, wherein the blank group is the basic fabric used in example 1, and the control group is the performance index of the sample prepared by referring to CN 115816961B.
Table 1 results of performance tests for examples, blank, and control
TABLE 2 comparative examples 1-7 Performance test results
TABLE 3 comparative examples 8-14 Performance test results
The blank group has no hydrophobic structure and protective coating on the surface of the fabric because no waterproof finishing is performed, the static waterproof performance and the dynamic waterproof performance are at extremely low level, only the physical performance of the basic fabric is provided, the air permeability is at a higher value because no extra coating is used for blocking, and the essence of the untreated fabric lacking a waterproof function is intuitively embodied. As a comparison group as a prior art scheme, although a certain waterproof effect is realized by means of nano SiO 2 modified polyurethane, a covalent bond bonding system of nano particles and resin is not constructed, the waterproof performance after washing is obviously attenuated compared with that of examples 1-5, and the coating structure is relatively thick, so that the coating structure not only has hard hand feeling and higher bending stiffness, but also blocks part of fiber pores, so that the air permeability is greatly lower than that of the examples.
The embodiment can realize excellent waterproof performance, durability, soft hand feeling and high air permeability at the same time, and is characterized in that the technical scheme is cooperatively designed, wherein the surface of the gas-phase nano silicon dioxide modified by a hydrophobic silane coupling agent such as hexamethyldisilazane or dodecyl trimethoxysilane is provided with sufficient hydrophobic groups, the uniform dispersion is realized through ultrasonic treatment, the vacuum drying of the surface facing upwards is matched with the surface B, so that particle agglomeration is avoided, pores are prevented, stable adhesion of the particles on the surface of the fiber is ensured to form a continuous hydrophobic layer, and in the bi-component reactive coating, a covalent bond crosslinking network is formed by a polyisocyanate curing agent, hydroxyl-terminated polyurethane resin and functional groups on the surface of the nano particles, the chemical combination strengthens the adhesive force between all layers, effectively resists performance attenuation caused by water washing and friction, and simultaneously reserves an air permeable channel between the fibers by precisely controlling A, B component mass ratio, wet film thickness and hot pressing parameters on the premise of ensuring the integrity of the coating, and gives consideration to the soft texture of the fabric.
The reason for the performance difference between each comparative example and the examples is the deviation of a single technical link, namely, in the comparative example 1, the nano silicon dioxide is not subjected to hydrophobic modification, the surface lacks hydrophobic groups, an effective hydrophobic layer cannot be formed on the surface of the fiber, and the waterproof performance is obviously reduced; in comparative example 2, the surface protection layer is not prepared, and only the nano hydrophobic layer is used, so that nano particles are easy to fall off in the water washing process, and the waterproof durability is suddenly reduced; in comparative example 3, the waterproof function is directly lost due to the fact that a waterproof layer is not built, the performance is close to a blank group, in comparative example 4, KH550 aminosilane coupling agent is adopted to modify nano silicon dioxide, the surface of particles is hydrophilic, a hydrophobic surface layer cannot be built, the waterproof effect is poor, in comparative example 5, A faces upwards, the nano particles are easily accumulated or fall off under the action of gravity, the hydrophobic layer is unevenly distributed, both waterproof and air permeability are reduced, in comparative example 6, normal-pressure drying is adopted, the volatilization speed of a solvent is slow, secondary agglomeration of the nano particles is initiated, fiber pores are blocked, the air permeability is reduced, the integrity of the hydrophobic layer is damaged, the waterproof performance is weakened, the hydrophobic nano silicon dioxide particles in comparative example 7 are excessively loaded, excessive particles fill the fiber gaps, the waterproof performance is slightly improved, but seriously block the air permeability channels, the fabric feel is hardened, the load of comparative example 8 is excessively low, the hydrophobic layer is discontinuous, a complete waterproof barrier cannot be formed, the waterproof performance is insufficient, in comparative example 9, the A component and the B component are mixed according to a mass ratio of 2.5:1, the polyisocyanate curing agent is excessively mixed, the crosslinking density is excessively high, the coating is hard and the coating is blocked, the air permeability is poor, the air permeability is excessively contracted, the crosslinking ratio of the coating is not fully mixed according to a ratio of the air permeability ratio of 5:10, the coating has weak adhesive force, is easy to crack and fall off after washing, has poor waterproof durability, the comparative example 11 adopts cotton cloth as a basic fabric, cotton cloth fibers have hydrophilicity and loose structure, has weak bonding force with a hydrophobic coating, has insufficient waterproof performance and lower self strength, so that the tear strength is reduced, the hot pressing temperature of the comparative example 12 is 160 ℃, the hot pressing temperature exceeds the tolerance range of the fabric and the coating, the fiber structure is damaged, the coating ages and embrittles, the tear strength is reduced, the hand feeling is hardened, the coating is excessively contracted and plugs pores at high temperature, the air permeability is reduced, the wet film thickness of the comparative example 13 is excessively thin, the coating cannot completely cover the surfaces of nano particles and the fiber to form a discontinuous protective layer, the waterproof performance is poor, the wet film thickness of the comparative example 14 is excessively thick, the coating excessively covers the fiber pores, the waterproof performance is excellent, the air permeability is greatly reduced, and the thick coating causes the hand feeling of the fabric to be hardened.
It should be noted that the foregoing description is only a preferred embodiment of the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood that modifications, equivalents, improvements and modifications to the technical solution described in the foregoing embodiments may occur to those skilled in the art, and all modifications, equivalents, and improvements are intended to be included within the spirit and principle of the present invention.
Claims (10)
1. The preparation method of the fluorine-free waterproof composite fabric is characterized by comprising the following steps of:
s1, preprocessing, cleaning and drying a basic fabric;
s2, dispersing 1-10 parts by mass of hydrophobic nano silicon dioxide in 100 parts by mass of organic solvent to prepare stable dispersion liquid;
S3, dividing the base fabric processed in the step S1 into a surface A and a surface B, uniformly spraying a dispersion liquid on the surface A, and then preheating and drying for 3-5min at 60-80 ℃ under vacuum condition on the surface B to obtain a waterproof layer;
s4, preparing a bi-component reactive coating slurry;
The component A is prepared by dissolving 100 parts of hydroxyl end-capped polyurethane resin in 20-50 parts of organic solvent according to parts by mass;
the component B is polyisocyanate curing agent;
preparing a double-component reactive coating slurry, namely preparing an A component into a mixture with the solid content of 20% -40% by using an organic diluent, then mixing the diluted A component with a B component according to the mass ratio of 3-5:1, and simultaneously adding a wetting leveling agent with the total mass of 0.5% -2% of the system, a defoaming agent with the total mass of 0.5% -2% and a plasticizer with the total mass of 1% -5% to prepare the reactive coating slurry;
s5, coating the reactive coating slurry prepared in the step S4 on the surface A of the fabric treated in the step S3, and controlling the wet film thickness to be 100-200 mu m;
s6, carrying out hot pressing treatment on the fabric coated in the step S5 to obtain a surface protection layer;
s7, naturally cooling the fabric treated in the step S6 to room temperature to obtain the fluorine-free waterproof composite fabric.
2. The method for producing a fluorine-free waterproof composite fabric according to claim 1, wherein in the step S1, the base fabric is a nylon woven fabric or a polyester woven fabric, and the mass per unit area is 80-150g/m 2.
3. The method for producing a fluorine-free waterproof composite fabric according to claim 1, wherein in step S1, the pretreatment comprises washing the base fabric with a neutral detergent.
4. The preparation method of the fluorine-free waterproof composite fabric as claimed in claim 1, wherein in the step S2, the hydrophobic nano silicon dioxide is obtained by carrying out surface modification treatment on gas-phase nano silicon dioxide with the original particle size of 10-40nm by a silane coupling agent, wherein the silane coupling agent is hexamethyldisilazane or dodecyl trimethoxysilane, and the organic solvent is one or a mixture of two of ethanol and isopropanol.
5. The preparation method of the fluorine-free waterproof composite fabric as claimed in claim 1, wherein the organic solvent in the component A and the diluent used in the preparation of slurry are one or more of ethyl acetate, acetone and methyl ethyl ketone, the plasticizer is a benzoate plasticizer or a citrate plasticizer, the wetting leveling agent is a polyether modified polysiloxane leveling agent, the defoaming agent is an organosilicon defoaming agent, and the polyisocyanate curing agent is an HDI trimer or an IPDI trimer.
6. The method for preparing the fluorine-free waterproof composite fabric according to claim 1, wherein the hot pressing treatment condition is 120-150 ℃ and the hot pressing treatment is carried out for 2-8min under the pressure condition of 0.5-2 MPa.
7. The method for producing fluorine-free waterproof composite fabric according to claim 1, wherein in step S3, the absolute pressure of the vacuum condition is 10 to 70kPa.
8. The method for preparing fluorine-free waterproof composite fabric according to claim 1, wherein in step S5, the reactive coating slurry prepared in step S4 is coated on the a surface of the fabric treated in step S3 by a doctor blade or roll coating method.
9. The method for preparing fluorine-free waterproof composite fabric according to claim 1, wherein in the step S3, the hydrophobic nano silica particles have a loading capacity of 3-5g/m 2 after drying.
10. A fluorine-free waterproof composite fabric manufactured by the manufacturing method of the fluorine-free waterproof composite fabric according to any one of claims 1 to 9.
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| CN120384421A (en) * | 2025-04-22 | 2025-07-29 | 明仁精细化工（嘉兴）有限公司 | Preparation method of fluorine-free waterproofing agent based on polyurethane-nanosilica composite |
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| JP2000017581A (en) * | 1998-06-30 | 2000-01-18 | Kuraray Co Ltd | Method for producing leather-like sheet material |
| CN102317338A (en) * | 2009-03-27 | 2012-01-11 | 卡尔·弗罗伊登伯格公司 | Method for formulating a reactive polyurethane emulsion |
| CN106480724A (en) * | 2016-11-16 | 2017-03-08 | 丹东优耐特纺织品有限公司 | Anti-aging, cold-resistant, antibacterial, the processing method of high moisture-inhibiting raincoat fabric |
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