CN117227297A - Manufacturing process of washable durable waterproof outdoor environment-friendly fabric - Google Patents

Abstract

The invention provides a manufacturing process for washable, long-lasting waterproof outdoor environmentally friendly fabrics, and belongs to the technical field of textile fabrics. In the present invention, the warp and weft yarns are firstly twisted, warped, and woven to obtain a gray cloth. The gray cloth is then degreased, washed, and dried with a degreasing agent, and then surface-finished with a water-repellent finishing agent and hot melt adhesive. The polyurethane microporous film is bonded and cured to the surface of the fabric, and then the warp-knitted nylon mesh fabric is compounded on the surface of the film to produce an outdoor environmentally friendly fabric. The fabric has long-lasting waterproofness, anti-aging, good wear resistance, excellent washing resistance, does not contain fluorine-based waterproofing agents, and is environmentally friendly.

Description

A manufacturing process for washable, long-lasting waterproof outdoor environmentally friendly fabrics

Technical field

The invention belongs to the technical field of textile fabrics, and specifically relates to a production process of a washable, long-lasting waterproof outdoor environmentally friendly fabric.

Background technique

With the improvement of people's living standards, outdoor sports are becoming more and more popular among young people, so the research and development of outdoor protective fabrics is also attracting more and more attention. In addition to meeting the requirements of ordinary fabrics, outdoor fabrics must also have long-lasting washability, long-lasting waterproofing and other functions.

Waterproof fabrics are generally surface-finished with waterproofing agents to obtain waterproof properties. Waterproofing agent is one of the indispensable functional additives in the textile industry. At present, the waterproofing agent with the largest market share is usually fluorine-containing waterproofing agent. Fluorine-containing waterproofing agents are usually composed of a large number of oligomers or polymers containing fluorine groups, which can give fiber materials good waterproof and oil-proof properties. However, fluorine-containing compounds can cause environmental and ecological problems. For example, PFOA stands for perfluorooctanoic acid and its ammonium-containing main salt, or "C8". It is an important raw material for textile "three-proof finishing agents". Perfluorooctanoic acid and its salts are organic pollutants that are difficult to degrade and have high persistence in the environment. The full name of PFOS is perfluorooctane sulfonyl compound (C8F17SO2X). It is extremely persistent and is one of the most difficult organic pollutants to decompose. Currently, many countries have banned the use of PFOS in products; APEO is an alkyl compound. Phenol polyoxyethylene ether has poor biodegradability and strong acute toxicity. In addition, it will decompose to produce alkylphenol. Alkylphenol is a banned environmental hormone and is currently used in many countries. Use is prohibited.

Patent CN113276533A discloses a waterproofing agent. The preparation method includes: emulsifier sodium dodecyl sulfate, OS-15, TX-30 and deionized water to form an emulsifier solution; BA, MMA, St and n-hexadecane Stir and mix evenly to form mixed monomers; mix the mixed monomers and emulsifier solution to obtain an emulsion; mix part of the emulsion with surface-modified nano- _SiO2 , add the initiator for reaction, and drop the remaining emulsion and initiator aqueous solution. Add n-hexadecane, MMA, BA, GMA (glycidyl methacrylate) and organic silicon monomer mixture to obtain a nano-modified acrylate emulsion. When the temperature of the reaction system drops below 40°C, add aminopolysiloxane Alkane emulsion, stir to obtain waterproofing agent emulsion.

Patent CN116463846A discloses a water-repellent woven knitted fabric and its preparation method, which includes: combining the woven fabric and the base fabric based on acupuncture technology to obtain the woven knitted fabric; impregnating the woven knitted fabric In the water-repellent finishing agent, the water-repellent finishing agent is made of fluorine-free water-repellent agent, triethylene diethylene It is obtained by stirring and mixing amine, isomeric ten-alcohol polyoxyethylene ether, oleic acid polyethylene glycol diester and water.

Although the current research on waterproof outdoor fabrics has made some progress, its waterproof effect is far from meeting the requirements of protective clothing. Water will penetrate into the fabric if it stays on the surface for a long time, and its water resistance is poor. After washing, it will cause Water resistance becomes worse.

Contents of the invention

The object of the present invention is to address the shortcomings of the existing technology and provide a manufacturing process for a washable and long-lasting waterproof outdoor environmentally friendly fabric. The fabric has long-lasting waterproofness, anti-aging properties, good wear resistance, excellent washability, and does not contain Fluorine waterproofing agent, environmentally friendly.

In order to achieve the above objects, the technical solutions adopted by the present invention are as follows:

A method for preparing a washable and durable waterproof outdoor environmentally friendly fabric, including the following steps:

(1) Twist the warp and weft yarns, warp them, and weave the cloth to obtain gray cloth;

(2) Use degreaser to remove oil from the gray fabric, wash and dry it;

(3) Then use the water-repellent finishing agent gray fabric to perform water-repellent finishing;

(4) The surface of the gray cloth is composited with a polyurethane microporous film;

(5) Polyurethane microporous film surface composite warp knitted nylon mesh cloth; among which,

The water-repellent finishing agent includes: fluorine-free waterproofing agent, cross-linking agent, penetrating agent, nonylphenol polyoxyethylene ether, coconut oil fatty acid diethanolamide and water.

Further, in step (1), the warp yarn and weft yarn are both made of 50D DTY polypropylene yarn and/or 75D DTY polypropylene yarn. The biggest advantage of polypropylene fiber is its light texture, with a density of only 0.91g/ ^cm3 . It is the lightest variety among common chemical fibers, so polypropylene fiber of the same weight can obtain a higher coverage area than other fibers. Secondly, polypropylene has very little hygroscopicity and almost no moisture absorption. The moisture regain rate under general atmospheric conditions is close to zero.

Further, in step (1), in the double-twisting treatment, the 50D yarn material is doubled to 600 twists, and the 75D yarn material is doubled to 450 twists. Control the number of twists to further improve the processability of polypropylene yarn and improve the resistance to pilling and snagging.

Further, in step (1), the warping speed is 300-450m/min.

Further, in step (1), the weaving step is: at a rotation speed of 400-500m/min, through the forward and backward movement of the reed and the up and down movement of the heald frame, the warp and weft yarns are interlaced with each other to weave into a plain weave gray cloth.

Further, in step (1), the density of the gray cloth is:

When the warp and weft are 50D DTY polypropylene yarn, the warp density is 180 threads/inch, the weft density is 120 threads/inch, and the total density is 300 threads/inch;

When the warp and weft are made of 75D DTY polypropylene yarn, the warp density is 110 threads/inch, the weft density is 80 threads/inch, and the total density is 190 threads/inch.

Further, in step (2), the concentration of the degreasing agent is 0.3-1g/L, and the bath ratio during the degreasing process is 1:15-20.

Further, in step (2), the washing refers to washing with water or cleaning agent at least 2 times, washing temperature: 60-80°C, washing time 15-30 minutes; the cleaning agent is a neutral cleaning agent or ion cleaning agent, the concentration is 1.5-3.0g/L. Preferably, in step (2), the washing step is: first washing with a cleaning agent at least once, and then washing with water at least once. The present invention preferably uses a cleaning agent to clean the gray fabric first, and then cleans it with water. Controlling the cleaning conditions can achieve full cleaning of the gray fabric, which is conducive to the full penetration of the subsequent anti-repellent finishing agent and lays a better foundation for the durable waterproofing of the fabric. Foundation.

Further, in step (2), the drying step is: put the washed gray fabric into a setting machine, and heat set it at a temperature of 120-135°C at a speed of 20-30m/min for 1-2 minutes.

Further, in step (3), the water-repellent finishing agent includes: fluorine-free waterproofing agent 60-90g/L, cross-linking agent 8-15g/L, penetrating agent 0.5-1.2g/L, nonylphenol polyoxygen Vinyl ether 1-3g/L, coconut oil fatty acid diethanolamide 2-5g/L, and the balance is water.

Preferably, in step (3), the water-repellent finishing agent includes: 80g/L fluorine-free waterproofing agent, 10g/L cross-linking agent, 1g/L penetrant, and 2.5g/L nonylphenol polyoxyethylene ether. , Coconut oil fatty acid diethanolamide 4g/L, the balance is water.

The fluorine-free waterproofing agent selected in this invention is RUCO-DRY ECO, J-XR88 or R-ACE, which has the characteristics of safety, sustainability, and environmental protection, is made into a water-repellent finishing agent with other components. After the fabric is treated with the water-repellent finishing agent, a uniform film can be quickly formed on the surface and has good waterproof properties. In the present invention, a certain amount of nonylphenol polyoxyethylene ether and coconut oil fatty acid diethanolamide are added to the water-repellent finishing agent, and combined with other components, it can not only promote the full penetration of the water-repellent finishing agent on the surface of the fabric, but also increase the interaction with the fabric. The composite fastness is improved, so that the fabric can prevent water penetration even if it is in contact with water for a long time, and it still has good waterproof performance after washing; in addition, fluorine-free waterproofing agent and cross-linking agent are padded on the surface of the fabric , after baking to form a film, the feel of the fabric will become slightly harder, while the introduction of nonylphenol polyoxyethylene ether and coconut oil fatty acid diethanolamide can improve the feel of the fabric.

In the present invention, the cross-linking agent is selected from the group consisting of N-methylol melamine, isocyanate, isomer alcohol polyoxyethylene ether sulfated castor oil, sodium alkyl sulfonate, sodium alkyl benzene sulfonate, and sodium alkyl sulfate. , sodium secondary alkyl sulfonate, sodium secondary alkyl sulfate, sodium alkyl naphthalene sulfonate, sodium alkyl succinate sulfonate, sodium sulfamate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether , at least one of phosphate ester compounds; the penetrating agent is AEP, OEP-70, JFC-1, JFC-2, JFC-E, JFC-M, OP-4, polyoxyethylene alkylamine or At least one of the sorbitan esters.

Further, in step (3), the water-repellent finishing adopts two-immersion and two-rolling method, the pressure is 3-4kg/cm ² , the rolling residue rate is 85-120%, pre-baking at 100-110°C for 1-5min, 160- Bake at 175°C for 3-5 minutes.

Preferably, in step (3), the water-repellent finishing adopts two-immersion and two-padding methods, with a pressure of 4kg/cm ² , a rolling residue rate of 100%, pre-baking at 105°C for 3 minutes, and baking at 170°C for 5 minutes.

In the present invention, the polyurethane microporous membrane is prepared by the following method: polyether polyurethane resin and polyester resin are mixed according to a mass ratio of 10:2-3.5, and 3-4 mass times of dimethylformamide are added , stir and dissolve at 50-65°C, coat on the transfer body, then transfer to a dimethylformamide aqueous solution with a mass concentration of 15-20% to solidify into a film, wash with water, and dry to obtain a polyurethane microporous film, gram weight is 10-20g/m ² .

Further, during the preparation process of the polyurethane microporous membrane, the weight average molecular weight of the polyether polyurethane resin is 2-4×10 ⁵ .

Further, during the preparation process of the polyurethane microporous membrane, the polyester resin raw materials include: terephthalic acid, propylene glycol, triethylene glycol, 4,4'-diaminodiphenylmethane, and a catalyst; the terephthalic acid, The molar ratio of propylene glycol, triethylene glycol, and 4,4'-diaminodiphenylmethane is 10:8-10:2-4:0.5-1. Preferably, the molar ratio of terephthalic acid, propylene glycol, triethylene glycol, and 4,4'-diaminodiphenylmethane is 10:10:3:0.7.

Further, during the preparation process of the polyurethane microporous membrane, the catalyst is a phthalate ester catalyst or an organic tin catalyst, and the amount of the catalyst is 2-5% of the mass of terephthalic acid.

Further, during the preparation process of the polyurethane microporous membrane, the polyester resin is prepared by the following method: terephthalic acid, propylene glycol, and triethylene glycol are mixed, heated to 180-200°C under nitrogen protection, and reacted for 1.5-2 hours. Raise the temperature to 230-250°C, add a catalyst, and continue the reaction at 180-200 Pa for 2-4 hours to obtain polyester resin.

Polyurethane microporous membrane has the advantages of waterproof, breathable, windproof, warm, and the membrane surface does not swell when exposed to water. It can effectively prevent water molecules of different sizes from entering. The diameter of the micropores is much larger than that of water vapor molecules, so water vapor molecules can freely pass through the microporous membrane. The pores are quickly discharged from the body, so that sweat will not condense on the skin surface to form moisture, stickiness, and dullness, and the water vapor balance in the body can be maintained at all times. The present invention composites the polyurethane microporous film with the fabric, and the hydrostatic pressure of the composite fabric is significantly increased. , the moisture permeability becomes better. After a long period of simulated rain spray, the polypropylene cloth will not have wrinkles, swelling and other appearance changes on the cloth surface, and the waterproofness has been improved. The applicant also found that adding a certain amount of polyester resin to the polyurethane microporous membrane reduces the amount of polyurethane, and introduces a certain proportion of triethylene glycol and 4,4'-diaminodiphenylmethane into the polyester resin molecular chain, which has a certain effect. The synergistic effect not only does not affect the moisture permeability of the polyurethane microporous film, but also helps to further improve the wear resistance, and can improve the moisture and heat aging resistance of the polyurethane microporous film, thereby improving the fabric's resistance to moisture and heat aging. Poor resistance to moisture and heat for a long time It can still maintain high strength after treatment.

Further, the step (4) of compounding the polyurethane microporous film is: apply hot melt glue on the surface of the fabric with a dispensing amount of 6-8g/m ² and stick the polyurethane microporous film to the fabric at 80-90°C. Put it together and place it in a constant temperature and humidity environment for more than 24 hours to fully solidify the hot melt adhesive.

Further, the step (5) of composite warp-knitted nylon mesh cloth is: apply hot melt glue on the surface of the polyurethane microporous film, the amount of glue dispensed is 6-8g/m ² , and the temperature is 80-90°C with 20D Warp knitted nylon mesh fabric is composite, with a weight of 60-90g/m ² .

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

1. The outdoor environmentally friendly fabric proposed by the present invention has properties such as water resistance, long-lasting and efficient waterproofing, good moisture permeability, wear resistance, and aging resistance, and can meet the safety and comfort needs of outdoor campers.

2. The present invention uses a fluorine-free waterproofing agent, which is safe, sustainable and environmentally friendly. Nonylphenol polyoxyethylene ether and coconut oil fatty acid diethanolamide are added to the water-repellent finishing agent to cooperate with the fluorine-free waterproofing agent to promote water-repelling finishing. The agent can fully penetrate into the surface of the fabric, increase the composite fastness with the fabric, improve the waterproofness and washability, in addition, it can avoid the hardening of the hand feeling caused by the film formation of the water-repellent finishing agent on the surface of the fabric, improve the hand feel of the fabric, and increase comfort. sex.

3. In the present invention, the polyurethane microporous film is compounded on the surface of the fabric, which can improve the waterproof and moisture permeability of the fabric. Adding polyester to the polyurethane microporous film will not only not affect the moisture permeability of the polyurethane microporous film, but also help to further improve the wear resistance. It can improve the resistance of polyurethane microporous film to moisture and heat aging, thereby improving the fabric's poor resistance to moisture and heat aging, and it can still maintain high strength after long-term moisture and heat treatment.

Description of drawings

Figure 1 is an infrared spectrum of polyester resin in Example 1 of the present invention;

Figure 2 is a schematic diagram of the aging resistance test results (strength reduction rate) of the outdoor environmentally friendly fabric of the present invention.

Detailed ways

The following non-limiting examples can enable those of ordinary skill in the art to understand the present invention more comprehensively, but do not limit the present invention in any way. The following content is only an illustrative description of the scope of protection of the present invention. Those skilled in the art can make various changes and modifications to the invention of the present invention based on the disclosed content, and they should also fall within the scope of protection of the present invention. .

The present invention will be further described below in the form of specific examples. Various chemical reagents used in the examples of the present invention were obtained through conventional commercial channels unless otherwise specified.

Example 1

The preparation method of washable and durable waterproof outdoor environmentally friendly fabrics includes the following steps:

(1) Twist the 50D DTY polypropylene yarn to 600 times and twist it into a whole shaft through the warping machine at a speed of 300m/min, and then use the forward and backward movement of the reed and the heald frame at a speed of 400m/min. Up and down movement, the warp and weft yarns are intertwined with each other to form a plain weave gray cloth. The density of the gray cloth is: the warp yarn density is 180 yarns/inch, the weft yarn density is 120 yarns/inch, and the total density is 300 yarns/inch.

(2) Dissolve the degreaser DO-1173 in water to make a 1g/L degreaser aqueous solution. According to the liquor ratio of the gray cloth and the degreaser aqueous solution is 1:15, put the gray cloth into the degreaser aqueous solution and soak it for 20 minutes. , and then wash it once with cleaning agent (ionic cleaning agent-418A from Xiamen Guanhuida Chemical Co., Ltd., concentration: 1.5g/L) and water. Washing temperature: 60°C, washing time 30 minutes; put the washed gray fabric into In the setting machine, heat set at 120°C for 2 minutes at a speed of 20m/min.

(3) Dip and roll the gray fabric twice in the water-repellent finishing agent, the pressure is 3kg/cm ² , the rolling residue rate is 85%, pre-bake at 100°C for 5 minutes, and bake at 160°C for 5 minutes; the water-repellent finishing agent contains: None Fluorine waterproofing agent RUCO-DRYECO 60g/L, isomer alcohol polyoxyethylene ether sulfated castor oil 15g/L, penetrating agent JFC-11.2g/L, nonylphenol polyoxyethylene ether 3g/L, coconut oil fatty acid diethanol Amide 5g/L, the balance is water.

(4) Mix polyether polyurethane resin (weight average molecular weight: 2×10 ⁵ ) and polyester resin at a mass ratio of 10:2, add to 4 mass times of dimethylformamide, stir and dissolve at 50°C , coated on the transfer body with a coating thickness of 15 μm, then transferred to a dimethylformamide aqueous solution with a mass concentration of 15% to solidify into a film, washed with water, and dried to obtain a polyurethane microporous film. Apply hot melt glue on the surface of the fabric at a dosage of 6g/m ² , attach the polyurethane microporous film to the fabric at 80°C, and place it in a constant temperature and humidity environment for more than 24 hours to fully solidify the hot melt glue.

(5) Dot-coat hot melt glue on the surface of the polyurethane microporous film, with a dispensing amount of 6g/m ² , and compound it with 20D warp-knitted nylon mesh fabric at 80°C, with a weight of 600g/m ² .

In this embodiment, the polyester resin is prepared by the following method: terephthalic acid, propylene glycol, triethylene glycol, and 4,4'-diaminodiphenylmethane in a molar ratio of 10:8:2:0.5 Mix, heat to 200°C for 1.5 hours under nitrogen protection, raise the temperature to 240°C, add a catalyst, and continue the reaction at 200 Pa for 4 hours to obtain a polyester resin with a weight average molecular weight of approximately 3×10 ⁴ .

Example 2

The preparation method of washable and durable waterproof outdoor environmentally friendly fabrics includes the following steps:

(1) Twist the 75D DTY polypropylene yarn to 450 times and twist it into a whole shaft through the warping machine at a speed of 400m/min, and then use the forward and backward movement of the reed and the heald frame at a speed of 450m/min. The up and down movement, the warp and weft yarns are intertwined with each other to form a plain weave gray cloth. The density of the gray cloth is: the warp yarn density is 110 yarns, the weft yarn density is 80 yarns/inch, and the total density is 190 yarns/inch.

(2) Dissolve the degreaser DO-1173 in water to make a 1g/L degreaser aqueous solution. According to the bath ratio of the gray cloth and the degreaser aqueous solution is 1:20, put the gray cloth into the degreaser aqueous solution and soak it for 20 minutes. , and then wash it once with cleaning agent (ionic cleaning agent-418A from Xiamen Guanhuida Chemical Co., Ltd., concentration: 2.0g/L) and water. Washing temperature: 70°C, washing time 30 minutes; put the washed gray fabric into In the setting machine, heat set at a temperature of 130°C for 2 minutes at a speed of 30m/min.

(3) Dip and roll the gray fabric twice in the water-repellent finishing agent, the pressure is 4kg/cm ² , the rolling residue rate is 120%, pre-bake at 110°C for 3 minutes, and bake at 170°C for 4 minutes; the water-repellent finishing agent contains: None Fluorine waterproofing agent R-ACE 80g/L, sodium alkyl succinate sulfonate 10g/L, penetrating agent JFC-11.0g/L, nonylphenol polyoxyethylene ether 2.5g/L, coconut oil fatty acid diethanolamide 4g/L, The remainder is water.

(4) Mix polyether polyurethane resin (weight average molecular weight: 3×10 ⁵ ) and polyester resin at a mass ratio of 10:2.8, add it to 4 times the mass of dimethylformamide, stir and dissolve at 60°C , coated on the transfer body with a coating thickness of 18 μm, then transferred to a dimethylformamide aqueous solution with a mass concentration of 20% to solidify into a film, washed with water, and dried to obtain a polyurethane microporous film. Apply hot melt glue on the surface of the fabric at a dispensing amount of 7g/m ² , laminate the polyurethane microporous film to the fabric at 85°C, and place it in a constant temperature and humidity environment for more than 24 hours to fully solidify the hot melt glue.

(5) Dot-coat hot melt glue on the surface of the polyurethane microporous film, with a dispensing amount of 7g/m ² , and compound it with 20D warp-knitted nylon mesh fabric at 85°C, with a weight of 600g/m ² .

In this embodiment, the polyester resin is prepared by the following method: terephthalic acid, propylene glycol, triethylene glycol, and 4,4'-diaminodiphenylmethane in a molar ratio of 10:10:3:0.7 Mix, heat to 200°C for 2 hours under nitrogen protection, raise the temperature to 250°C, add a catalyst, and continue the reaction at 180 Pa for 3 hours to obtain a polyester resin with a weight average molecular weight of approximately 2.8×10 ⁴ .

Example 3

The preparation method of washable and durable waterproof outdoor environmentally friendly fabrics includes the following steps:

(1) Twist the 75D DTY polypropylene yarn to 450 times and twist it into a whole shaft through the warping machine at a speed of 450m/min, and then use the forward and backward movement of the reed and the heald frame at a speed of 500m/min. The up and down movement, the warp and weft yarns are intertwined with each other to form a plain weave gray cloth. The density of the gray cloth is: the warp yarn density is 110 yarns, the weft yarn density is 80 yarns/inch, and the total density is 190 yarns/inch.

(2) Dissolve the degreaser DO-1173 in water to make a 1g/L degreaser aqueous solution. According to the bath ratio of the gray cloth and the degreaser aqueous solution is 1:20, put the gray cloth into the degreaser aqueous solution and soak it for 20 minutes. , and then wash it once with cleaning agent (ionic cleaning agent-418A from Xiamen Guanhuida Chemical Co., Ltd., concentration: 3.0g/L) and water. Washing temperature: 80°C, washing time 30 minutes; put the washed gray fabric into In the setting machine, heat set at a temperature of 130°C for 2 minutes at a speed of 30m/min.

(3) Dip and roll the gray fabric twice in the water-repellent finishing agent, the pressure is 4kg/cm ² , the rolling residue rate is 120%, pre-bake at 120°C for 3 minutes, and bake at 175°C for 4 minutes; the water-repellent finishing agent contains: None Fluorine waterproofing agent J-XR8890g/L, sodium alkyl succinate sulfonate 8g/L, penetrating agent JFC-10.5g/L, nonylphenol polyoxyethylene ether 1g/L, coconut oil fatty acid diethanolamide 2g/L , the balance is water.

(4) Mix polyether polyurethane resin (weight average molecular weight: 4×10 ⁵ ) and polyester resin at a mass ratio of 10:3.5, add to 4 mass times of dimethylformamide, stir and dissolve at 60°C , coated on the transfer body with a coating thickness of 20 μm, then transferred to a dimethylformamide aqueous solution with a mass concentration of 20% to solidify into a film, washed with water, and dried to obtain a polyurethane microporous film. Apply hot melt glue on the surface of the fabric at a dosage of 8g/m ² , attach the polyurethane microporous film to the fabric at 90°C, and place it in a constant temperature and humidity environment for more than 24 hours to fully solidify the hot melt glue.

(5) Apply hot melt glue on the surface of the polyurethane microporous film at a dosage of 8g/m ² and compound it with 20D warp-knitted nylon mesh fabric at 90°C with a weight of 600g/m ² .

In this embodiment, the polyester resin is prepared by the following method: terephthalic acid, propylene glycol, triethylene glycol, and 4,4'-diaminodiphenylmethane in a molar ratio of 10:10:4:1 Mix, heat to 200°C for 2 hours under nitrogen protection, raise the temperature to 250°C, add a catalyst, and continue the reaction at 180 Pa for 3 hours to obtain a polyester resin with a weight average molecular weight of approximately 3.5×10 ⁴ .

Comparative example 1

The difference from Example 2 is that the water-repellent finishing agent includes: fluorine-free waterproofing agent RUCO-DRYECO 80g/L, sodium alkyl succinate sulfonate 10g/L, penetrating agent JFC-11.0g/L, coconut oil fatty acid diethanol Amide 4g/L, the balance is water.

Comparative example 2

The difference from Example 2 is that the water-repellent finishing agent includes: fluorine-free waterproofing agent RUCO-DRYECO 80g/L, sodium alkyl succinate sulfonate 10g/L, penetrating agent JFC-11.0g/L, nonylphenol Polyoxyethylene ether 2.5g/L, the balance is water.

Comparative example 3

The difference from Example 2 is that the water-repellent finishing agent includes: fluorine-free waterproofing agent RUCO-DRYECO 80g/L, sodium alkyl succinate sulfonate 10g/L, and penetrating agent JFC-11.0g/ L. The balance is water.

Comparative example 4

The difference from Example 2 is that the polyester resin is prepared by the following method: terephthalic acid, propylene glycol, triethylene glycol, and 4,4'-diaminodiphenylmethane in a molar ratio of 10:10: Mix 1:0.3, under nitrogen protection, heat to 200°C and react for 2 hours, raise the temperature to 250°C, add the catalyst, continue the reaction at 180 Pa for 3 hours to obtain polyester resin.

Comparative example 5

The difference from Example 2 is that the polyester resin is prepared by the following method: terephthalic acid, propylene glycol, triethylene glycol, and 4,4'-diaminodiphenylmethane in a molar ratio of 10:10: Mix 5:1.5, heat to 200°C for 2 hours under nitrogen protection, raise the temperature to 250°C, add the catalyst, continue the reaction at 180 Pa for 3 hours to obtain polyester resin.

Comparative example 6

The difference from Example 2 is that an equal molar amount of propylene glycol is used to replace 4,4'-diaminodiphenylmethane; the polyester resin is prepared by the following method: terephthalic acid, propylene glycol, and triethylene glycol are prepared according to Mix at a molar ratio of 10:10.7:3, heat to 200°C for 2 hours under nitrogen protection, raise the temperature to 250°C, add a catalyst, and continue the reaction at 180 Pa for 3 hours to obtain polyester resin.

Comparative example 7

The difference from Example 2 is that an equal molar amount of propylene glycol is used to replace triethylene glycol; the polyester resin is prepared by the following method: terephthalic acid, propylene glycol, 4,4'-diaminodiphenylmethane according to Mix at a molar ratio of 10:13:0.7, heat to 200°C for 2 hours under nitrogen protection, raise the temperature to 250°C, add a catalyst, and continue the reaction at 180 Pa for 3 hours to obtain polyester resin.

Comparative example 8

The difference from Example 2 is that an equal molar amount of propylene glycol is used to replace triethylene glycol and 4,4'-diaminodiphenylmethane; the polyester resin is prepared by the following method: terephthalic acid, propylene glycol are molar Mix at a ratio of 10:13.7, heat to 200°C for 2 hours under nitrogen protection, raise the temperature to 250°C, add a catalyst, and continue the reaction at 180 Pa for 3 hours to obtain polyester resin.

Comparative example 9

The difference from Example 2 is that the polyurethane microporous membrane is only made of polyether polyurethane resin and does not contain polyester resin.

Test example 1

The polyester resin obtained in Example 1 was subjected to nuclear magnetic resonance analysis and testing, using deuterated chloroform as the solvent and a resonance frequency of 400 MHz. The results are as follows: In ¹ H-NMR, the characteristic peaks at δ=1.97 and 4.15ppm belong to the methylene group in propylene glycol, δ=8.20-8.25 corresponds to the chemical shift of the proton peak of the benzene ring, and δ=4.17 is triethylene glycol. The chemical shift of the methylene group, δ=7.84, corresponds to the chemical shift of NH in the amide group, indicating that 4,4'-diaminodiphenylmethane reacts with terephthalic acid to form an amide group.

The polyester resin obtained in Example 1 was subjected to an infrared spectrum test with a scanning range of 4000-500 cm ^-1 and the results are shown in Figure 1.

The results in Figure 1 show that the curve has an absorption peak of -OH near 3538cm ^-1 , a strong absorption peak of ester carbonyl -C=O near 1725cm ^-1 , and an ester C(=O)-OC group near 1155cm ^-1 The strong absorption peak indicates the formation of ester groups. The area around 738 cm ^-1 is due to the out-of-plane bending vibration absorption of the para-disubstituted benzene ring, which is a characteristic peak of the terephthalic acid group. The above results indicate that terephthalic acid and polyols The reaction produces polyester; the curve near 1085cm ^-1 is the absorption peak of the ether group COC, which is the characteristic peak of the ether bond in triethylene glycol, and the curve near 1535cm ^-1 and 1270cm ^-1 is the characteristic peak of the amide group, which is It is caused by the reaction between the amino group and the carboxyl group in 4,4'-diaminodiphenylmethane to form an amide group. It can be seen that triethylene glycol and 4,4'-diaminodiphenylmethane are successfully reacted and introduced into the molecular chain of polyester.

Test example 2

Use the fabrics obtained in Examples 1-3 and Comparative Examples 1-9 as samples to test their hydrostatic pressure (refer to ISO811-2018, 60cm/min, hydrostatic pressure plus mesh lining test) and wear resistance (refer to ISO12947-2016) , moisture permeability (refer to JIS-L1099A1, straight cup method), the results are shown in Table 1 below.

Table 1

Group Hydrostatic pressure/(mmH ₂ O) Wear resistance Moisture permeability (g/m ² ·day) Example 1 10120 ≥50000 times 6113 Example 2 10870 ≥50000 times 6280 Example 3 10655 ≥50000 times 6225 Comparative example 1 9074 ≥50000 times 6230 Comparative example 2 9255 ≥50000 times 6185 Comparative example 3 8864 ≥50000 times 6207 Comparative example 4 9856 ≥50000 times 6065 Comparative example 5 10250 ≥50000 times 6022 Comparative example 6 10080 ≥50000 times 5950 Comparative example 7 10822 ≥40000 times 5838 Comparative example 8 10630 ≥40000 times 5920 Comparative example 9 10286 ≥30000 times 6160

The results show that the hydrostatic pressure of the fabrics obtained in Examples 1-3 of the present invention reaches more than 10000mmH ₂ O, the abrasion resistance reaches more than 50000 times, the water repellent performance reaches level 5, and the moisture permeability is >6000g/m ² ·day, indicating that the present invention The resulting fabric has excellent waterproof, moisture permeability and abrasion resistance. It can also be seen that the hydrostatic pressure of the fabrics obtained in Comparative Examples 1-3 is slightly lower than that of the Examples. It can be seen that adding a certain amount of nonylphenol polyoxyethylene ether and coconut oil fatty acid diethanolamide to the water-repellent finishing agent can further improve the The waterproof properties of the fabric. The abrasion resistance of the fabrics obtained in Comparative Examples 4-9 is lower than that of the Examples, and the moisture permeability is slightly lower than that of the Examples. It can be seen that part of the polyurethane microporous film is replaced by polyurethane, and triethylene glycol and 4,4'-diethylene glycol are used in the polyester. The presence of aminodiphenylmethane helps to improve the moisture permeability and wear resistance of the polyurethane microporous film, thereby helping to improve the wear resistance of the fabric.

Test example 3

Using the fabrics obtained in Examples 1-3 and Comparative Examples 1-3 as samples, the water-repellent and water-repellent properties of the fabrics were tested according to the Bondisman rain method of ISO4920-2012 and GB/T14577-1993 respectively; and then according to ISO6330 : In 2012, the water-repellent and water-repellent properties after washing were tested using a type A washing machine, 4N program, 40°C for 10 times, and dried in the shade.

The results are shown in Table 2 below.

Table 2

The results show that the water repellency of the fabric obtained by the present invention before washing is level 5, and it can still maintain level 4-5 after being washed 10 times; the water repellency measured by the Bondis door rain method before washing is ≥ level 4, and the water repellency after washing is ≥ level 4. The final water repellency is level 4; and the fabric will not appear to have wrinkles, swelling or other appearance changes after a long period of simulated rain spray. It shows that the fabric obtained by the present invention has superior water-repellent and water-repellent properties. The water-repellent and water-repellent properties of the fabrics obtained in Comparative Examples 1-3 before washing reached level 4 and above. However, after being washed 10 times, the water-repellent and water-repellent properties dropped significantly, which is quite different from Example 2. It can be seen that A certain amount of nonylphenol polyoxyethylene ether and coconut oil fatty acid diethanolamide are added to the water-repellent finishing agent of the present invention, which has a certain synergistic effect and can improve the maintenance of waterproofness of the fabric after washing, that is, improve the durability of the fabric. Waterproof performance.

Test example 4

The initial strength (GB/T19976-2005) of the fabrics obtained in Example 2 and Comparative Examples 4-9 were tested respectively. After being placed for 7 days at a temperature of 70°C and a relative humidity of 95%, the strength of the fabric was tested. The strength reduction rate was calculated. The results are as follows As shown in Figure 2.

The results show that the strength of the fabric obtained in the preferred embodiment 2 of the present invention only decreases by 5.6% after being placed for 7 days at a temperature of 70°C and a relative humidity of 95%. The strength change rate is small and the aging resistance is excellent. The strength reduction rate of the fabric obtained in Comparative Examples 4-9 after being placed for 7 days at a temperature of 70°C and a relative humidity of 95% is significantly different from that of Example 2. It can be seen that the composition of the polyester in the polyurethane microporous film affects the aging resistance of the film. It has a greater impact on performance, thus affecting the aging resistance of the fabric. When a certain amount of triethylene glycol and 4,4'-diaminodiphenylmethane are added to the polyester chain segment, it will help improve the aging resistance of the fabric.

The above description of the embodiments is to facilitate those of ordinary skill in the technical field to understand and use the invention. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without inventive efforts. Therefore, the present invention is not limited to the above embodiments. Based on the disclosure of the present invention, improvements and modifications made by those skilled in the art without departing from the scope of the present invention should be within the protection scope of the present invention.

Claims (10)

1. A method for preparing washable and durable waterproof outdoor environmentally friendly fabrics, which is characterized by comprising the following steps: (1) Twist the warp and weft yarns, warp them, and weave the cloth to obtain gray cloth; (2) Use degreaser to remove oil from the gray fabric, wash and dry it; (3) Then use the water-repellent finishing agent gray fabric to perform water-repellent finishing; (4) The surface of the gray cloth is composited with a polyurethane microporous film; (5) Polyurethane microporous film surface composite warp knitted nylon mesh cloth; among which, The water-repellent finishing agent includes: fluorine-free waterproofing agent, cross-linking agent, penetrating agent, nonylphenol polyoxyethylene ether, coconut oil fatty acid diethanolamide and water. 2. The preparation method according to claim 1, characterized in that, in step (1), the warp yarn and weft yarn adopt 50D DTY polypropylene yarn material and/or 75D DTY polypropylene yarn material; The density of the gray cloth is: When the warp and weft are 50D DTY polypropylene yarn, the warp density is 180 threads/inch, the weft density is 120 threads/inch, and the total density is 300 threads/inch; When the warp and weft are made of 75D DTY polypropylene yarn, the warp density is 110 threads/inch, the weft density is 80 threads/inch, and the total density is 190 threads/inch. 3. The preparation method according to claim 1, characterized in that the water-repellent finishing agent includes: fluorine-free waterproofing agent 60-90g/L, cross-linking agent 8-15g/L, penetrating agent 0.5-1.2g/L. L, nonylphenol polyoxyethylene ether 1-3g/L, coconut oil fatty acid diethanolamide 2-5g/L, and the balance is water. 4. The preparation method according to claim 3, characterized in that the water-repellent finishing agent contains: 80g/L fluorine-free waterproofing agent, 10g/L cross-linking agent, 1g/L penetrating agent, nonylphenol polymer Oxyethylene ether 2.5g/L, coconut oil fatty acid diethanolamide 4g/L, and the balance is water. 5. The preparation method according to claim 1, characterized in that the fluorine-free waterproofing agent is selected from the group consisting of RUCO-DRYECO, J-XR88, At least one of R-ACE. 6. The preparation method according to claim 1, characterized in that the water-repellent finishing adopts two dipping and two rolling methods, the pressure is 3-4kg/cm ² , the rolling residue rate is 85-120%, and it is prepared at 100-110°C. Bake for 1-5 minutes, bake at 160-175℃ for 3-5 minutes. 7. The preparation method according to claim 1, characterized in that, in step (4), the polyurethane microporous membrane is prepared by the following method: polyether polyurethane resin, polyester resin according to 10:2-3.5 Mix at a mass ratio, add to dimethylformamide, stir and dissolve at 50-65°C, coat on the transfer body, then transfer to dimethylformamide aqueous solution to solidify into a film, wash with water, and dry to obtain polyurethane microporous membrane. 8. The preparation method according to claim 7, wherein the polyester resin raw material includes: terephthalic acid, propylene glycol, triethylene glycol, 4,4'-diaminodiphenylmethane, and catalyst; The molar ratio of terephthalic acid, propylene glycol, triethylene glycol, and 4,4'-diaminodiphenylmethane is 10:8-10:2-4:0.5-1. 9. The preparation method according to claim 8, characterized in that the molar ratio of terephthalic acid, propylene glycol, triethylene glycol, and 4,4'-diaminodiphenylmethane is 10:10:3:0.7 . 10. The preparation method according to claim 7 or 8, characterized in that the polyester resin is prepared by the following method: mixing terephthalic acid, propylene glycol, and triethylene glycol, and heating to 180-180°C under nitrogen protection. React at 200°C for 1.5-2h, raise the temperature to 230-250°C, add a catalyst, and continue the reaction at 180-200Pa for 2-4h to obtain polyester resin.