阅读说明：本技术 一种疏水阻燃高阻隔生化防护复合面料的制备方法 (Preparation method of hydrophobic flame-retardant high-barrier biochemical protection composite fabric ) 是由 刘其霞 顾玉培 季涛 葛建龙 单浩如 胡世棋 冯康义 于 2021-06-07 设计创作，主要内容包括：本发明公开了一种疏水阻燃高阻隔生化防护复合面料的制备方法,具体为在聚合物阻隔膜双侧粘合高强尼龙织物和轻薄型尼龙织物,得到复合样品；然后将复合样品室温固化,得到多层复合面料；再采用溶剂型疏水阻燃涂料,在多层复合面料双侧进行表面涂层整理；最后将表面涂层整理后的多层复合面料进行烘干,得到疏水阻燃高阻隔生化防护复合面料。本发明的高阻隔防护复合面料以聚合物薄膜作为阻隔材料,在保障阻隔性能和力学性能的同时,可大大降低复合面料的面密度,应用于隔绝式化学防护装备,能够提供稳定的化学防护能力,避免橡胶基防护面料存在的面密度大,生产工艺复杂等问题。(The invention discloses a preparation method of a hydrophobic flame-retardant high-barrier biochemical protection composite fabric, which is characterized in that high-strength nylon fabrics and light and thin nylon fabrics are bonded on both sides of a polymer barrier film to obtain a composite sample; then curing the composite sample at room temperature to obtain a multilayer composite fabric; then adopting solvent type hydrophobic flame retardant coating to perform surface coating finishing on both sides of the multilayer composite fabric; and finally, drying the multilayer composite fabric with the finished surface coating to obtain the hydrophobic flame-retardant high-barrier biochemical protection composite fabric. The high-barrier protective composite fabric provided by the invention takes the polymer film as the barrier material, can greatly reduce the surface density of the composite fabric while keeping the barrier property and the mechanical property, is applied to the isolated chemical protective equipment, can provide stable chemical protective capability, and avoids the problems of large surface density, complex production process and the like of the rubber-based protective fabric.)

1. A preparation method of a hydrophobic flame-retardant high-barrier biochemical protective composite fabric is characterized by comprising the following steps:

step 1, bonding a high-strength nylon fabric and a light and thin nylon fabric on two sides of a polymer barrier film to obtain a composite sample;

step 2, curing the composite sample at room temperature to obtain a multilayer composite fabric;

step 3, adopting solvent type hydrophobic flame retardant coating to perform surface coating finishing on both sides of the multilayer composite fabric;

and 4, drying the multilayer composite fabric with the finished surface coating to obtain the hydrophobic flame-retardant high-barrier biochemical protection composite fabric.

2. The preparation method of the hydrophobic flame-retardant high-barrier biochemical protective composite fabric according to claim 1, wherein the polymer barrier film in the step 1 is any one of EVOH, PVDC or PA.

3. The preparation method of the hydrophobic flame-retardant high-barrier biochemical protective composite fabric according to claim 1, wherein the high-strength nylon fabric in the step 1 is a nylon fabric with a yarn fineness of 70-250D, a warp-wise strength of more than 800N and a weft-wise strength of more than 500N.

4. The preparation method of the hydrophobic, flame-retardant and high-barrier biochemical protective composite fabric according to claim 1, wherein the light and thin nylon fabric in the step 1 is a nylon fabric with a yarn fineness of 15-40D.

5. The preparation method of the hydrophobic flame-retardant high-barrier biochemical protective composite fabric according to claim 1, wherein the adhesive used for bonding in the step 1 is a TPU hot melt adhesive film with a thickness of 6 to 10 filaments.

6. The method for preparing the hydrophobic flame-retardant high-barrier biochemical protective composite fabric as claimed in claim 1, wherein the high-strength nylon fabric and the light and thin nylon fabric are bonded to both sides of the polymer barrier film in step 1 by hot pressing, wherein the hot pressing temperature is 110-.

7. The preparation method of the hydrophobic flame-retardant high-barrier biochemical protective composite fabric according to claim 1, wherein the room-temperature curing time in the step 2 is 8-24 hours.

8. The preparation method of the hydrophobic flame-retardant high-barrier biochemical protective composite fabric according to claim 1, wherein the solvent-based hydrophobic flame-retardant coating in the step 3 is a hydrophobic flame-retardant polyurethane coating.

9. The preparation method of the hydrophobic flame-retardant high-barrier biochemical protective composite fabric according to claim 1, wherein the drying process in the step 4 comprises two stages, wherein the first stage drying temperature is 50-80 ℃ and the drying time is 20-40 min, and the second stage drying temperature is 90-160 ℃ and the drying time is 2-6 min.

Technical Field

The invention relates to the technical field of biochemical protective materials, in particular to a preparation method of a light high-barrier protective composite fabric.

Background

With the rapid development of industry and the variety of modern war, chemical leakage accidents frequently occur and cause certain casualties. For example, in 2004, a certain general chemical plant in Chongqing has explosion and chlorine leakage accidents, resulting in 9 deaths, 3 injuries and nearly 15 million evacuated people; in 2017 india dangerous chemical leakage events occurred, causing injury to at least 487 people, etc. Therefore, it is of great significance to provide reliable and effective protection for personnel in the environment polluted by dangerous chemicals.

According to the protection mechanism, the biochemical protection materials can be divided into four categories: the biochemical protective material comprises an isolation type biochemical protective material, a ventilation type biochemical protective material, a semi-ventilation type biochemical protective material and a selective ventilation type biochemical protective material. The isolated biochemical protective material is a chemical protective composite fabric obtained by compounding airtight rubber, polymer coating or polymer film with fabric in a surface coating or laminating compounding mode. Due to the good air tightness and chemical stability of the material, the material can provide effective protection for personnel at site in environments with high risk of chemical leakage or unknown chemical pollution.

The isolated biochemical protective fabric used in China at present generally has the problems of short protective time, narrow protective pedigree, thick and heavy material and the like. For rubber-based isolated protective materials, butyl rubber, fluororubber and the like are mostly adopted and prepared by a mode of coating fabrics on two sides of rubber. The rubber material is widely applied to airtight (heavy) biochemical protection equipment, molecular chains of the rubber material are arranged neatly and tightly, gaps among the molecular chains are few, and the rubber material has high airtightness and good corrosion resistance. Although rubber materials are widely favored in the field of biochemical protection by virtue of their many advantages, there are still some problems in application and production processes. On the one hand, a single rubber material has performance deficiencies. For example, butyl rubber has a slow cure rate, is poorly compatible with other rubbers, and is not resistant to benzene-based organic solvents; fluororubbers are not resistant to low temperature and are easily corroded by ketone solvents. On the other hand, the processing of rubber materials requires a vulcanization process, and rubber such as butyl rubber which is inherently low in vulcanization speed needs to be vulcanized under a high temperature condition, so that the production process of rubber becomes more complicated. In addition, the thick fabric is a disadvantage of the rubber-based biochemical protective clothing, and the flexibility of action is reduced in the actual wearing process, so that the burden of wearing, using, carrying and transporting is increased.

Disclosure of Invention

The invention aims to further improve the contradiction between prolonging the protection time and reducing the material surface density of the existing isolated biochemical protection composite fabric, and also considers the flame-retardant hydrophobic property of the material. The isolated chemical protective fabric produced in China mostly adopts rubber composite fabric and polymer coating fabric, the material is thick and heavy, and the produced equipment cannot be worn for a long time. The invention adopts the polymer film with high barrier property as the main protective material, and carries out hot-pressing compounding on the polymer film and the textile fabric through reasonable structural design and hot-pressing compounding process, thereby endowing the material with excellent protective property and mechanical property, and simultaneously achieving the effect of reducing the surface density of the composite fabric.

The technical scheme of the invention is as follows:

a preparation method of a hydrophobic flame-retardant high-barrier biochemical protective composite fabric comprises the following steps:

step 1, bonding a high-strength nylon fabric and a light and thin nylon fabric on two sides of a polymer barrier film to obtain a composite sample;

step 2, curing the composite sample at room temperature to obtain a multilayer composite fabric;

step 3, adopting solvent type hydrophobic flame retardant coating to perform surface coating finishing on both sides of the multilayer composite fabric;

and 4, drying the multilayer composite fabric with the finished surface coating to obtain the hydrophobic flame-retardant high-barrier biochemical protection composite fabric.

Further, in the preparation method of the hydrophobic flame-retardant high-barrier biochemical protective composite fabric, in the step 1, the polymer barrier film is any one of EVOH, PVDC or PA.

Further, in the preparation method of the hydrophobic flame-retardant high-barrier biochemical protection composite fabric, in the step 1, the high-strength nylon fabric is a nylon fabric with the yarn fineness of 70-250D, the warp-direction strength of more than 800N and the weft-direction strength of more than 500N. Further preferably, the high-strength nylon fabric is a nylon 66 woven fabric with the yarn fineness of 100D.

Further, in the preparation method of the hydrophobic flame-retardant high-barrier biochemical protective composite fabric, in the step 1, the light and thin nylon fabric is a nylon fabric with a yarn fineness of 15-40D, and further preferably, the light and thin nylon fabric is a nylon 6 or nylon 66 woven fabric with a yarn fineness of 30D.

Further, in the preparation method of the hydrophobic flame-retardant high-barrier biochemical protective composite fabric, the adhesive used for bonding in the step 1 is a TPU hot melt adhesive film with the thickness of 6-10 filaments, and more preferably, the adhesive used for bonding is a TPU hot melt adhesive film with the thickness of 8 filaments.

Further, in the preparation method of the hydrophobic flame-retardant high-barrier biochemical protection composite fabric, in the step 1, the high-strength nylon fabric and the light and thin nylon fabric are bonded on both sides of the polymer barrier film in a hot-pressing mode, the hot-pressing temperature is 110-150 ℃, and the hot-pressing time is 10-60 s.

Further, in the preparation method of the hydrophobic flame-retardant high-barrier biochemical protective composite fabric, the room-temperature curing time in the step 2 is 8-24 hours.

Further, in the preparation method of the hydrophobic flame-retardant high-barrier biochemical protective composite fabric, in the step 3, the solvent-based hydrophobic flame-retardant coating is hydrophobic flame-retardant polyurethane coating, and further can be flame-retardant polyurethane composite coating.

Further, the preparation method of the hydrophobic flame-retardant high-barrier biochemical protective composite fabric comprises the step 4 of drying the fabric in two stages, wherein the drying temperature in the first stage is 50-80 ℃, the drying time is 20-40 min, and the drying temperature in the second stage is 90-160 ℃, and the drying time is 2-6 min.

The composite fabric obtained by the preparation method provided by the invention has a 7-layer structure of 'functional layer/bearing layer/bonding layer/barrier layer/bonding layer/protective layer/functional layer', a thermoplastic polyurethane adhesive film is used as an adhesive, a polymer barrier film is compounded with a high-strength nylon fabric and a light and thin nylon fabric in a hot-pressing compounding mode, and hydrophobic flame-retardant coating finishing is carried out on two sides of the compounded fabric to obtain the hydrophobic flame-retardant high-barrier protective composite fabric. The barrier layer is a polymer barrier film, the bonding layer is a thermoplastic polyurethane film, the bearing layer is a high-strength nylon fabric, the protective layer is a light and thin nylon fabric, and the functional layer is a hydrophobic flame-retardant coating. The hydrophobic flame-retardant protective composite fabric can avoid the situation that the fabric is damaged due to accumulation of liquid harmful chemicals on the surface of the material, and meanwhile, the polymer film of the barrier layer can effectively prevent the permeation of gaseous harmful chemicals and has good chemical protection capability.

The flame-retardant hydrophobic high-barrier protective composite fabric prepared by the preparation method has good mechanical property and barrier property, and the surface of the material has a hydrophobic flame-retardant effect. The nylon fabric of the bearing layer has high mechanical strength, good toughness and friction resistance, corrosion resistance, alkali resistance and low relative density, and can provide high mechanical property for the composite fabric. The polymer barrier film of the barrier layer has the characteristics of high crystallinity and chemical resistance, and can provide good barrier property for the composite fabric. The light and thin nylon fabric of the protective layer has low surface density, is adhered to the inner side of the barrier film, can prevent the barrier film from being scratched by sharp objects, and can not bring too much weight load to the composite fabric. The polyurethane hot melt adhesive film of the adhesive layer contains strongly polar isocyanate groups and urethane groups, has excellent adhesive force on various materials, is easy to infiltrate, has good manufacturability and long service life, has the advantages of impact resistance, fatigue resistance, chemical resistance and the like, and can well adhere all the materials. The functional layer is a hydrophobic flame-retardant polyurethane composite coating. The materials of each layer act synergistically in a whole to form excellent protective capability.

Compared with the prior art, the invention has the following beneficial effects:

1. the structure is optimized, and the material areal density is low.

The conventional rubber-based protective composite fabric has high areal density and limited protective performance of a single rubber material. According to the invention, through structural optimization design, a structure of compounding a single polymer barrier layer and a fabric is adopted, compared with a rubber-based composite fabric, the polymer barrier film material can reduce the weight of the barrier material while ensuring the protective performance, and the problem of contradiction between the protective performance and the material areal density is solved.

2. The non-solvent type hot melt adhesive film is selected as the adhesive, so that the operation is simple and convenient, and the environment is protected.

3. The high-barrier polymer film is used as a barrier material, and the production process is simple.

The production of the rubber-based protective composite fabric needs a vulcanization process, the production process is complex, the protective performance of a single rubber material is limited, and the rubber-based protective composite fabric is hot-pressed and bonded with a fabric after a polymer is blown into a film, so that the production efficiency is high.

The performance test of the composite fabric prepared by the preparation method provided by the invention specifically comprises the following steps:

according to GB/T3923.1-2013 textile fabric tensile Properties part 1: the composite fabric is subjected to tensile breaking strength test, and the warp tensile strength is greater than 1200N and the weft tensile strength is greater than 1000N.

According to GB/T3917.2-1997 textile fabric tear Performance part 2: the tearing strength of the composite fabric is tested by a trouser-shaped sample (single slit) tearing strength test, the longitudinal tearing strength of the composite fabric prepared by the invention is more than 50N, and the latitudinal tearing strength is more than 45N.

According to a GB/T2791 and 1995 adhesive T peel strength test method, a peel strength test is carried out on a force bearing layer/barrier layer interface of a composite fabric according to a flexible material to flexible material, and the warp and weft peeling strengths prepared by the method are all larger than 14N.

According to the GB/T1037-1988 plastic film and sheet water vapor permeability test method cup method, the composite fabric is subjected to moisture permeability test, and the water vapor permeability of the composite fabric prepared by the invention is in the range of 2-6 g/(m.24 h).

According to the GB/T1038 plastic film and sheet gas permeability test method-pressure difference method for testing the air permeability of the composite fabric, the oxygen permeability of the composite fabric prepared by the method is 10-20 cm in dry labor/(m) by year²24h 0.1 MPa).

According to the GB/T30447 and 2013 nanometer film contact angle measurement method, the static contact angle of the water drop on the outer surface of the composite fabric prepared by the method is tested, and the static contact angle is larger than 100 degrees.

And (3) testing the flame retardant property of the composite fabric according to GB/T5456 plus 2009 textile flame spread performance test of a test sample in the vertical direction of the combustion property, wherein the smoldering and afterburning time of the composite fabric prepared by the invention is in the range of 0-3 s, and the damage length is in the range of 30-100 mm.

According to the invention, the single polymer barrier layer is adopted, so that the processing complexity of the composite fabric can be reduced, and the using amount of the adhesive is reduced, thereby reducing the surface density of the composite fabric; the high-barrier polymer with excellent protective performance is used as the barrier material, the material weight is small, and the composite process is simple; the non-solvent type hot melt adhesive film is used as the adhesive, and the compounding process is convenient to operate and environment-friendly.

The specific implementation mode is as follows:

example 1

A preparation method of a hydrophobic flame-retardant high-barrier biochemical protective composite fabric comprises the following steps:

step 1, on PVDC barrier film (19.76 g/m)²) Bonding 100D nylon 66 woven fabric on one side, bonding 30D light and thin nylon woven fabric on the other side, bonding by adopting a polyurethane hot-melt adhesive film with the thickness of 8 threads, specifically, performing hot-pressing bonding on the 100D nylon 66 woven fabric on one side of a PVDC barrier film and the 30D light and thin nylon woven fabric on the other side on a flat hot press by taking the polyurethane hot-melt adhesive film as an adhesive, wherein the hot-pressing temperature is 125 ℃, and the hot-pressing time is 30 s, so as to obtain a composite sample;

step 2, placing the composite sample in a room temperature environment until the composite sample is completely cured to obtain a multilayer composite fabric;

step 3, adopting hydrophobic flame-retardant polyurethane coating to perform flame-retardant hydrophobic coating finishing on both sides of the multilayer composite fabric, wherein the using amount of the double-sided flame-retardant coating is 200 g/m²；

Step 4, drying the finished fabric, wherein the first stage is drying: 60 ℃, 30 min, and second stage drying: and (3) obtaining the hydrophobic flame-retardant high-barrier biochemical protection composite fabric at 90 ℃ for 2 min.

Water vapor transmission amount of prepared composite fabric is 4.3814 g/(m.24 h), and oxygen transmission amount is 12.35 cm dry weight/(m.24 h)²24 h.0.1 MPa). The warp stretching strength of the composite fabric is 1250N, and the weft stretching strength is 1509N; the warp tearing strength is 56N, and the weft tearing strength is 59N; the warp peel strength was 16N and the weft peel strength was 18N.

The contact angle of the left side of the surface of the material is 108.8 degrees, and the contact angle of the right side of the surface of the material is 108.3 degrees; the after-burning time was 2.5 s, the smoldering time was 2.3 s, and the damaged length was 82 mm.

Example 2

A preparation method of a hydrophobic flame-retardant high-barrier biochemical protective composite fabric comprises the following steps:

step 1, on PVDC barrier film (19.76 g/m)²) One side of the fabric is bonded with 100D nylon 66 woven fabric, the other side is bonded with 30D light and thin nylon woven fabric, and 8-filament-thick polyurethane is adoptedBonding a hot melt adhesive film, specifically, on a flat hot press, using a polyurethane hot melt adhesive film as an adhesive, performing hot-pressing bonding on 100D nylon 66 woven fabric on one side of a PVDC barrier film, and performing hot-pressing bonding on 30D light and thin nylon woven fabric on the other side of the PVDC barrier film, wherein the hot-pressing temperature is 135 ℃, and the hot-pressing time is 30 s, so as to obtain a composite sample;

step 2, placing the composite sample in a room temperature environment until the composite sample is completely cured to obtain a multilayer composite fabric;

step 3, adopting hydrophobic flame-retardant polyurethane coating to perform flame-retardant hydrophobic coating finishing on both sides of the multilayer composite fabric, wherein the using amount of the double-sided flame-retardant coating is 226 g/m²；

Step 4, drying the finished fabric, wherein the first stage is drying: 60 ℃, 30 min, and second stage drying: and (3) obtaining the hydrophobic flame-retardant high-barrier biochemical protection composite fabric at 90 ℃ for 2 min.

The water vapor transmission amount of the prepared composite fabric is 2.4250 g/(m.24 h), and the oxygen transmission amount is 18.23 cm bulks/(m.24 h.0.1 MPa). The warp stretching strength of the composite fabric is 1584N, and the weft stretching strength is 1250N; the warp tearing strength is 54N, and the weft tearing strength is 49N; the warp peel strength was 16N and the weft peel strength was 29N.

The contact angle of the left side of the surface of the material is 114.5 degrees, and the contact angle of the right side of the surface of the material is 115.8 degrees; the after-burning time was 1.1 s, the smoldering time was 0 s, and the destruction length was 44 mm.

Example 3

A preparation method of a hydrophobic flame-retardant high-barrier biochemical protective composite fabric comprises the following steps:

step 1, on PVDC barrier film (19.76 g/m)²) Bonding 100D nylon 66 woven fabric on one side, bonding 30D light and thin nylon woven fabric on the other side, bonding by adopting a polyurethane hot-melt adhesive film with the thickness of 8 threads, specifically, on a flat hot press, using the polyurethane hot-melt adhesive film as an adhesive, performing hot-pressing bonding on the 100D nylon 66 woven fabric on one side of a PVDC barrier film, and performing hot-pressing bonding on the 30D light and thin nylon woven fabric on the other side, wherein the hot-pressing temperature is 110 ℃, and the hot-pressing time is 60 s, so as to obtain a composite sample;

step 2, placing the composite sample in a room temperature environment until the composite sample is completely cured to obtain a multilayer composite fabric;

step 3, adopting hydrophobic flame-retardant polyurethane coating to perform flame-retardant hydrophobic coating finishing on both sides of the multilayer composite fabric, wherein the using amount of the double-sided flame-retardant coating is 220 g/m²；

Step 4, drying the finished fabric, wherein the first stage is drying: 50 ℃, 40 min, and second stage drying: and (3) obtaining the hydrophobic flame-retardant high-barrier biochemical protection composite fabric at 90 ℃ for 6 min.

The water vapor transmission of the prepared composite fabric is 4.5750 g/(m)²24 h), oxygen transmission capacity is 19.94 cm through (m.24 h.0.1 MPa). The warp stretching strength of the composite fabric is 1226N, and the weft stretching strength is 1078N; the warp tearing strength is 77N, and the weft tearing strength is 79N; the warp peel strength was 14N and the weft peel strength was 15N.

The contact angle of the left side of the surface of the material is 116.8 degrees, and the contact angle of the right side of the surface of the material is 116.8 degrees; the after-burning time is 1.7 s, the smoldering time is 1.4 s, and the damage length is 70 mm.

In addition, EVOH and PA are also adopted as a polymer barrier film in the preparation process, and finally the warp stretching strength of the composite fabric is more than 1200N, the weft stretching strength is more than 1000N, the warp tearing strength is more than 50N, the weft tearing strength is 45N, the warp peeling strength and the weft peeling strength are both more than 14N, the left static contact angle and the right static contact angle are more than 100 degrees, the smoldering and afterburning time of the composite fabric is in the range of 0-3 s, and the damage length is in the range of 30-100 mm.