A nylon bio-based composite double-layer fabric, its preparation method, and a waterproof and moisture-permeable fabric

Abstract

The present invention provides a nylon bio-based composite double-layer fabric, a preparation method thereof, and a waterproof and moisture-permeable fabric. The raw materials of the nylon bio-based composite double-layer fabric include the following components in parts by weight: 80-100 parts of nylon bio-based polyurethane liquefied resin, 2-5 parts of cross-linking agent, 1.5-3 parts of accelerator, 0.5-2 parts of leveling agent, 1-3 parts of isocyanate wash-fastness synergist, and 5-20 parts of composite glue. The present invention provides a nylon bio-based composite double-layer fabric with excellent weather resistance, high extensibility and stretchability, comfortable skin feel and higher breathability. It has good waterproof and moisture-permeable performance, and can therefore be subjected to at least 10 or more times of washing, machine washing and drying treatments.

Description

Technical Field

[0001] The present invention belongs to the technical field of fabric materials, and particularly relates to a nylon bio-based composite double-layer fabric, a preparation method thereof, and a waterproof and moisture-permeable fabric. Background Art

[0002] A waterproof and moisture-permeable membrane is a composite membrane material with excellent waterproof and moisture-permeable properties. It can effectively protect clothes from moisture damage while maintaining a good user experience. Thermoplastic polyurethane elastomer (TPU) film is made of TPU pellets through a special process. It has the advantages of high hydrostatic pressure resistance, high moisture permeability, good hand feeling, good processing performance, and resistance to washing and dry cleaning, so its application range is extremely wide. In the past two years, in order to meet the industrialization and green application requirements of TPU waterproof and moisture-permeable membrane products, researchers have vigorously developed many bio-based degradable materials to achieve the above purposes.

[0003] Currently, most of the commercial functional membrane materials disclosed in the prior art are non-degradable materials, which mainly come from components such as polyurethane, thermoplastic polyurethane elastomer, or polyvinyl chloride in petroleum components. Therefore, when these materials are disposed of after clothing is discarded, they can only be destroyed by incineration, unable to meet the requirements of low-carbon green recycling. It can be seen that it is necessary to modify the above materials or develop alternative materials so that they can be recycled by means of low-carbon emission treatment. For example, after recycled, waste clothes can be quickly degraded into water and carbon dioxide under composting conditions, avoiding the adverse impact on the environment caused by a large number of non-degradable clothes.

[0004] In addition, the uses of the bio-based films disclosed in the prior art mostly stay in the aspects of using for crops or packaging bags, unable to meet various application scenarios such as waterproof, moisture-permeable and breathable, and high elastic stretch. At the same time, the bio-based films disclosed in the prior art still need to overcome the technical problems of low strength and low durability for machine washing, and inability to be mass-produced.

[0005] Therefore, in this field, there is an urgent need to develop a bio-based waterproof and moisture-permeable membrane to solve the above problems. Summary of the Invention

[0006] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a nylon bio-based composite double-layer fabric, a preparation method thereof, and a waterproof and moisture-permeable fabric. The present invention provides a nylon bio-based composite double-layer fabric with excellent weather resistance, high extensibility and stretchability, comfortable skin feel, and higher breathability. It has good waterproof and moisture-permeable properties, and therefore can be subjected to at least more than 10 times of washing, machine washing, and drying treatments.

[0007] To achieve the purpose of this invention, the present invention adopts the following technical solutions:

[0008] In the first aspect, the present invention provides a nylon bio-based composite double-layer fabric. The raw materials of the nylon bio-based composite double-layer fabric include the following components by weight: 80-100 parts of nylon bio-based polyurethane liquefied resin, 2-5 parts of cross-linking agent, 1.5-3 parts of accelerator, 0.5-2 parts of leveling agent, 1-3 parts of isocyanate wash-fastness synergist, and 5-20 parts of composite glue.

[0009] On the one hand, the bio-based content in the nylon bio-based composite double-layer fabric provided by the present invention is >99%, and it has strong hydrolysis resistance. This is mainly because when the bio-based nylon 510 masterbatch in the preparation raw materials of the nylon bio-based polyurethane liquefied resin is processed into a film through melt liquefaction, after the bio-based nylon and related materials are organically combined, the fabric has excellent weather resistance, high extensibility and elasticity, comfortable skin feel and good air permeability, and can be subjected to at least 10 times of water washing, machine washing and drying treatments. Therefore, it has excellent waterproof and moisture-permeable performance. On the other hand, when the human body wears the above-mentioned nylon bio-based composite double-layer fabric during exercise, sweat vapor will quickly diffuse and discharge along with the hydrophilic moisture-conducting membrane material, and the weather resistance life of the membrane material is longer, and it is more comfortable and durable to wear.

[0010] By regulating the weight parts of the above-mentioned various components, the present invention not only facilitates leveling and increases the dryness of the film surface, but also can prevent adhesion during storage; in particular, the isocyanate wash-fastness synergist grafts and crosslinks with the polyurethane chain segment and the polymer chain of the composite glue to play a synergistic role, significantly increasing the peel fastness and hydrostatic pressure resistance of the fabric. If the number of parts is too low, the membrane material is prone to swelling and damage during repeated household water washing when wearing the clothing, and the water pressure is more likely to drop severely. On the contrary, it is not easy to process.

[0011] Preferably, the raw materials of the nylon bio-based composite double-layer fabric include the following components by weight: 100 parts of nylon bio-based polyurethane liquefied resin, 3-4 parts of cross-linking agent, 2-3 parts of accelerator, 0.5-1 part of leveling agent, 1-2 parts of isocyanate wash-fastness synergist, and 10-20 parts of composite glue.

[0012] Preferably, the preparation raw materials of the nylon bio-based polyurethane liquefied resin include bio-based nylon 510.

[0013] Preferably, the cross-linking agent includes isocyanate compounds.

[0014] In the present invention, the above-mentioned cross-linking agent is a general-purpose, non-yellowing cross-linking agent and has high-activity cyanate groups.

[0015] Preferably, the isocyanate compounds include any one or a combination of at least two of high-activity isocyanate, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), or bio-based 1,5-pentane diisocyanate (PDI).

[0016] Preferably, the accelerator includes any one of a melamine compound, a polyol chain extender or a diamine chain extender, or a combination of at least two thereof.

[0017] Preferably, the leveling agent includes any one of polyether-modified polydimethylsiloxane (BYK), acrylate polymer (VOK) or fluorocarbon-modified polyacrylate leveling agent (CANFAIR) or a combination of at least two thereof.

[0018] Preferably, the isocyanate wash fastness enhancer includes any one of blocked isocyanate modified silicone wax, trimethylammonium chloride or acrylate emulsion, or a combination of at least two of them, so as to increase the wash fastness of the material.

[0019] Preferably, the composite adhesive comprises a moisture-curing reactive hot melt adhesive.

[0020] Preferably, the moisture-curing reactive hot melt adhesive includes any one of polyester hot melt adhesive and polyether hot melt adhesive, or a combination of at least two of them.

[0021] Preferably, the raw materials of the nylon bio-based composite double-layer fabric also include 20-50 parts of bio-based fluorine-free waterproofing agent by weight, preferably 25-40 parts, for example, 20 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 45 parts, 50 parts, etc.

[0022] In the present invention, the bio-based fluorine-free waterproofing agent is selected from bio-based fluorine-free waterproofing agent FK-9H (ECO-BARRIER X-9H), which is an acrylic fluorine-free waterproofing agent using natural palm oil and its derivatives as raw materials, wherein 70% of the raw materials are derived from renewable plants (industrial corn starch, etc.), and is a polyurethane fluorine-free waterproofing agent. The bio-based fluorine-free waterproofing agent provided by the present invention has the advantages of better versatility, excellent waterproof performance, better washability, and slight hand scratches, and does not affect the peeling fastness of the coating composite.

[0023] In a second aspect, the present invention provides a method for preparing the nylon bio-based composite double-layer fabric according to the first aspect, the method comprising the following steps:

[0024] A nylon bio-based polyurethane liquefied resin, a bridging agent, an accelerator, a leveling agent and an isocyanate wash durability enhancer are prepared to obtain a green embryo, and then the green embryo is extruded to obtain a micro-shaped base tape;

[0025] The micro-shaped base tape is pretreated and peeled off to obtain a nylon bio-based polyurethane waterproof and breathable membrane; the nylon bio-based polyurethane waterproof and breathable membrane, bio-based fabric and composite adhesive are composited and cured to obtain the nylon bio-based composite double-layer fabric.

[0026] Preferably, the pretreatment sequentially includes a transfer coating, a casting, and a baking process.

[0027] Preferably, the composite adhesive needs to be heat-melted before the composite.

[0028] Preferably, the temperature for curing is 40 - 60°C, the humidity is 60 - 90%, and the time is 12 - 48 h. The temperature can be, for example, 40°C, 45°C, 50°C, 55°C, 60°C, etc.; the humidity can be, for example, 60%, 70%, 80%, 90%, etc.; the time can be, for example, 12 h, 18 h, 20 h, 25 h, 30 h, 35 h, 40 h, 45 h, 48 h, etc.

[0029] In a third aspect, the present invention provides a waterproof and moisture-permeable fabric, and the waterproof and moisture-permeable fabric includes the nylon bio-based composite double-layer fabric according to the first aspect.

[0030] Preferably, the moisture permeability of the waterproof and moisture-permeable fabric after 10 times of machine washing is 3000 - 20000 g / m 2 , for example, it can be 3000 g / m 2 , 4000 g / m 2 , 5000 g / m 2 , 6000 g / m 2 , 8000 g / m 2 , 10000 g / m 2 , 12000 g / m 2 , 15000 g / m 2 , 18000 g / m 2 , 20000 g / m 2 etc.

[0031] In the present invention, the moisture permeability of the waterproof and moisture-permeable fabric after 10 times of machine washing is tested under the standard of JISL1099.B1, and the time is 24 h.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] The present invention provides a nylon bio-based composite double-layer fabric. On the one hand, the content of bio-based materials in the nylon bio-based composite double-layer fabric provided by the present invention is > 99%, and it has strong hydrolysis resistance. This is mainly because when the bio-based nylon 510 masterbatch in the raw materials for preparing the nylon bio-based polyurethane liquefied resin is processed into a film through melt liquefaction, after the organic combination of the bio-based nylon and related materials, the fabric has excellent weather resistance, high stretchability, comfortable skin feel and good air permeability, and can be washed, machine-washed and dried at least 10 times or more, so it has excellent waterproof and moisture-permeable performance. On the other hand, when the human body wears the above-mentioned nylon bio-based composite double-layer fabric during exercise, sweat vapor will quickly diffuse and discharge along with the hydrophilic moisture-conducting membrane material, the weather resistance life of the membrane material is longer, and it is more comfortable and durable to wear. Detailed Embodiments

[0034] The technical solution of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0035] Embodiment 1

[0036] This embodiment provides a nylon bio-based composite double-layer fabric. The raw materials of the nylon bio-based composite double-layer fabric include the following components by weight: 100 parts of nylon bio-based polyurethane liquefied resin, 3 parts of a high-activity isocyanate (purchased from Gaoding Company) cross-linking agent, 2 parts of melamine accelerator, 0.5 part of polyether-modified polydimethylsiloxane leveling agent, 1 part of blocked isocyanate-modified silicone wax, 10 parts of Jianyang 628 glue, and 35 parts of bio-based fluorine-free waterproof agent FK-9H (ECO-BARRIER X-9H) (brand Rudolf Bio NPE).

[0037] This embodiment provides a method for the above-mentioned nylon bio-based composite double-layer fabric, and the method includes the following steps:

[0038] Mix and stir the nylon bio-based polyurethane liquefied resin, cross-linking agent, accelerator, leveling agent and isocyanate wash resistance synergist at 25°C at a rotation speed of 600 rpm for 7 minutes, and make a green embryo after mixing evenly at a constant temperature of 40°C and let it stand. Then put the green embryo into a co-extrusion machine and extrude it at 40°C. The compression ratio of the co-extrusion machine is 20 to obtain a micro-shaped base belt;

[0039] The micro-shaped baseband is subjected to transfer coating, casting and baking treatments respectively and then dried. The drying temperature is 150°C and the time is 3 minutes. After peeling, a nylon bio-based polyurethane waterproof and moisture-permeable film is obtained. The Jianyang 628 glue is melted at 85°C and then conveyed to the engraving roller groove through a glue pump. Then, the nylon bio-based polyurethane waterproof and moisture-permeable film and the bio-based fabric are respectively introduced into a hot melt adhesive laminating machine. After checking that the safety and the front and back sides are correct, the hot melt adhesive laminating machine is started. The parameters of the hot melt adhesive laminating machine are as follows: pressure 0.5 pa, temperature 86°C, speed 12 m / min, and the roller is 1500 dots. The nylon bio-based polyurethane moisture-permeable film and the bio-based fabric are subjected to dot-shaped automatic lamination. The two layers of the nylon bio-based polyurethane moisture-permeable film and the bio-based fabric after lamination are automatically cured for more than 24 hours in a constant aging workshop with 85% humidity and 50°C to obtain the nylon bio-based composite double-layer fabric.

[0040] Example 2

[0041] The difference between this example and Example 1 is that the raw materials of the nylon bio-based composite double-layer fabric include the following components by weight: 100 parts of nylon bio-based polyurethane liquefied resin, 4 parts of a high-activity isocyanate (purchased from Gaoding Company) cross-linking agent, 2 parts of melamine accelerator, 0.5 part of polyether-modified polydimethylsiloxane leveling agent, 2 parts of blocked isocyanate-modified silicone wax, 12 parts of Jianyang 628 glue, and 25 parts of bio-based fluorine-free waterproof agent FK-9H (ECO-BARRIER X-9H) (brand RudolfBio NPE). And the compression ratio of the co-extruder is 23, the drying temperature is 160°C, the time is 2.5 minutes, the parameters of the hot melt adhesive laminating machine are: pressure 0.5 pa, temperature 88°C, speed 15 m / min, and the roller is 1200 dots. Others are the same as in Example 1.

[0042] Example 3

[0043] The difference between this example and Example 1 is that the raw materials of the nylon bio-based composite double-layer fabric include the following components by weight: 100 parts of nylon bio-based polyurethane liquefied resin, 4 parts of a high-activity isocyanate (purchased from Gaoding Company) cross-linking agent, 3 parts of melamine accelerator, 1 part of polyether-modified polydimethylsiloxane leveling agent, 2 parts of blocked isocyanate-modified silicone wax, 20 parts of Jianyang 628 glue, and 40 parts of bio-based fluorine-free waterproof agent FK-9H (ECO-BARRIER X-9H) (brand Rudolf BioNPE). Others are the same as in Example 1.

[0044] Example 4

[0045] The difference between this example and Example 1 is that the blocked isocyanate-modified silicone wax is replaced with an equal weight of trimethylammonium chloride. Others are the same as in Example 1.

[0046] Example 5

[0047] The difference between this embodiment and embodiment 1 is that no bio-based waterproofing agent is added to the raw materials of the nylon bio-based composite double-layer fabric, and the rest is the same as embodiment 1.

[0048] Example 6

[0049] The difference between this embodiment and embodiment 1 is that Daikin ordinary C6 waterproofing agent (model TG-4875) is used instead of the bio-based fluorine-free waterproofing agent FK-9H (ECO-BARRIER X-9H) (brand name Rudolf Bio NPE), and the rest is the same as embodiment 1.

[0050] Comparative Example 1

[0051] The difference between this comparative example and Example 1 is that the nylon bio-based polyurethane liquefied resin is replaced with an equal weight portion of nylon 66 resin, and the rest is the same as Example 1.

[0052] Comparative Example 2

[0053] The difference between this comparative example and Example 1 is that the nylon bio-based polyurethane liquefied resin is replaced with an equal weight portion of polyurethane resin, and the rest is the same as Example 1.

[0054] Comparative Example 3

[0055] The difference between this comparative example and Example 1 is that the raw materials of the nylon bio-based composite double-layer fabric include the following components in parts by weight: 70 parts of nylon bio-based polyurethane liquefied resin, 1 part of high-activity isocyanate (purchased from Gaoding Company) bridging agent, 0.5 parts of melamine accelerator, 0.5 parts of polyether modified polydimethylsiloxane leveling agent, 0.5 parts of blocked isocyanate modified silicone wax, 1 part of Jianyang 628 glue and 10 parts of bio-based fluorine-free waterproofing agent FK-9H (ECO-BARRIER X-9H) (brand name Rudolf Bio NPE), and the rest are the same as Example 1.

[0056] Comparative Example 4

[0057] The difference between this comparative example and Example 1 is that the raw materials of the nylon bio-based composite double-layer fabric include the following components in parts by weight: 110 parts of nylon bio-based polyurethane liquefied resin, 8 parts of high-activity isocyanate (purchased from Gaoding Company) bridging agent, 6 parts of melamine accelerator, 3 parts of polyether modified polydimethylsiloxane leveling agent, 5 parts of blocked isocyanate modified silicone wax, 25 parts of Jianyang 628 glue and 60 parts of bio-based fluorine-free waterproofing agent FK-9H (ECO-BARRIER X-9H) (brand name Rudolf BioNPE), and the rest are the same as Example 1.

[0058] Comparative Example 5

[0059] The difference between this comparative example and Example 1 is that no isocyanate wash-fastness enhancer is added, and the others are the same as in Example 1.

[0060] Test conditions

[0061] The nylon bio-based composite double-layer fabrics provided in Examples 1 to 6 and Comparative Examples 1 to 5 were tested, and the test methods are as follows:

[0062] (1) Hydrostatic pressure: Take fabric samples with an area of 20 cm² at 3 - 5 different positions, with the film side facing up, and test according to the ISO811 standard. Start reading when three continuous small water droplets appear; 2 The fabric samples, with the film side facing up, are tested according to the ISO811 standard until three continuous small water droplets appear and then start reading;

[0063] (2) Moisture permeability: Test according to the JISL1099.B1 potassium acetate standard solution;

[0064] (3) Hydrostatic pressure after 10 washes: Test according to the ISO6330.4N standard, and then evaluate at a rate of 60 cm / min according to ISO811;

[0065] (4) Moisture permeability after 10 washes: After washing according to the ISO6330.4N standard, dry at 60 °C for testing;

[0066] (5) Peel strength: Press the adhesive tape at 460 °C × 10 m / min × 0.8 Mpa × 2 cm, and test according to the FZ / T01010 standard.

[0067] The test results are shown in Table 1:

[0068] Table 1

[0069]

[0070] As can be seen from Table 1, Examples 1 - 4 in the present invention provide a nylon bio-based composite double-layer fabric with excellent weather resistance, high stretchability, comfortable skin feel and higher breathability. It has good waterproof and moisture-permeable properties, and can therefore be washed, machine-washed and dried at least 10 times or more. In particular, the nylon bio-based composite double-layer fabric provided in Example 2 has the best comprehensive performance.

[0071] Comparing Example 1 with Examples 5 - 6, it can be seen that in Example 5, without using a waterproof agent, the adhesive will penetrate into the fabric surface, resulting in a large coating amount, lower moisture permeability and a harder hand feeling. Not using a bio-based fluorine-free waterproof agent or using a common waterproof agent cannot achieve all the technical effects of the present invention and causes environmental pollution. In addition, the more the amount of the bio-based fluorine-free waterproof agent added, the stronger the peelability and the skin feel of the film material, but it will affect the wash-fastness effect.

[0072] Comparing Example 1 with Comparative Examples 1-2, it can be seen that replacing the type of nylon bio-based polyurethane liquefied resin will result in the lack of bio-based environmental protection elements and is easily affected by the modulus of the relevant adhesive solution itself, affecting the water resistance and moisture permeability of the film material.

[0073] Comparing Example 1 with Comparative Examples 3-4, it can be seen that the film-forming adhesion of the raw materials of the nylon bio-based composite double-layer fabric provided in Comparative Examples 3-4 is poor and does not have practical operability. The present invention regulates the weight parts of each component to enable the prepared fabric to have good comprehensive performance.

[0074] Comparing Example 1 with Comparative Example 5, it can be seen that the lack of isocyanate wash-fastness synergist will make the moisture permeability and water resistance of the fabric worse.

[0075] The applicant declares that the present invention uses the above examples to illustrate the process method of the present invention, but the present invention is not limited to the above process steps, that is, it does not mean that the present invention must rely on the above process steps to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent replacement of the raw materials selected for the present invention, the addition of auxiliary components, the selection of specific methods, etc. all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A waterproof and breathable fabric, characterized in that: The waterproof and breathable fabric includes a nylon bio-based composite double-layer fabric; The raw materials of the nylon bio-based composite double-layer fabric include the following components by weight: 80-100 parts of nylon bio-based polyurethane liquefied resin, 2-5 parts of bridging agent, 1.5-3 parts of accelerator, 0.5-2 parts of leveling agent, 1-2 parts of washing durability enhancer, 5-20 parts of composite glue and 20-50 parts of bio-based fluorine-free waterproofing agent; The washing durability enhancer includes any one or a combination of at least two of blocked isocyanate modified silicone wax, trimethylammonium chloride or acrylate emulsion; The raw materials for preparing the nylon bio-based polyurethane liquefied resin include bio-based nylon 510; The moisture permeability of the waterproof and breathable fabric after 10 machine washings is 15000-20000g / m 2 .

2. The waterproof and breathable fabric according to claim 1, characterized in that: The raw materials of the nylon bio-based composite double-layer fabric include the following components by weight: 100 parts of nylon bio-based polyurethane liquefied resin, 3-4 parts of bridging agent, 2-3 parts of accelerator, 0.5-1 part of leveling agent, 1-2 parts of washing durability enhancer, 10-20 parts of composite glue and 25-40 parts of bio-based fluorine-free waterproofing agent.

3. The waterproof and breathable fabric according to claim 1, characterized in that: The bridging agent includes isocyanate compounds.

4. The waterproof and breathable fabric according to claim 3, characterized in that: The isocyanate compound includes any one of highly active isocyanate, toluene diisocyanate, diphenylmethane diisocyanate or bio-based 1,5-pentane diisocyanate, or a combination of at least two thereof.

5. The waterproof and breathable fabric according to claim 1, characterized in that: The accelerator includes any one of melamine compounds, polyol chain extenders or diamine chain extenders, or a combination of at least two of them.

6. The waterproof and breathable fabric according to claim 1, characterized in that: The leveling agent includes any one of polyether-modified polydimethylsiloxane, acrylate polymer or fluorocarbon-modified polyacrylate leveling agent or a combination of at least two thereof.

7. The waterproof and breathable fabric according to claim 1, characterized in that: The composite adhesive includes a moisture-curing reactive hot melt adhesive.

8. The waterproof and breathable fabric according to claim 7, characterized in that: The moisture-curing reactive hot melt adhesive includes any one of polyester hot melt adhesive and polyether hot melt adhesive, or a combination of at least two of them.

9. The waterproof and breathable fabric according to claim 1, characterized in that: The preparation method of the nylon bio-based composite double-layer fabric comprises the following steps: A nylon bio-based polyurethane liquefied resin, a bridging agent, an accelerator, a leveling agent and a washing durability enhancer are prepared to obtain a green embryo, and then the green embryo is extruded to obtain a micro-shaped base tape; The micro-shaped base tape is pretreated and peeled off to obtain a nylon bio-based polyurethane waterproof and breathable membrane; the nylon bio-based polyurethane waterproof and breathable membrane, bio-based fabric and composite adhesive are composited and cured to obtain the nylon bio-based composite double-layer fabric.

10. The waterproof and breathable fabric according to claim 9, characterized in that: The pretreatment includes transfer coating, casting and baking processes in sequence.

11. The waterproof and breathable fabric according to claim 9, characterized in that: The composite adhesive needs to be subjected to a hot-melt treatment before the composite.

12. The waterproof and breathable fabric according to claim 9, characterized in that: The curing temperature is 40-60° C., the humidity is 60-90%, and the curing time is 12-48 hours.

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