Processing technology of high-flame-retardant high-temperature-resistant high-breathability firefighter uniform protective fabric

Abstract

The invention relates to the technical field of fire-fighting composite fabrics, and discloses a processing technology of a high-flame-retardant, high-temperature-resistant and high-air-permeability firefighter uniform protective fabric. The outer layer of the firefighter uniform protective fabric is a high-temperature-resistant and flame-retardant layer fabric made of nitrogen-phosphorus composite flame-retardant fibers; a compact carbon layer can be formed when a fire disaster occurs, combustion is delayed, nano silicon dioxide aerogel is added into the composite adhesive of the inner layer, heat transfer can be further blocked, the comfortable layer fabric formed by blending menthol modified bamboo fibers and spandex fibers is compounded with the composite adhesive in a rhombic dot matrix spraying mode, and the heat transfer can be further blocked. According to the present invention, the prepared firefighter uniform protection fabric has characteristics of uniform ventilation pore channel, continuous cooling feeling, high wearing comfort, and effective sweat gas discharge promoting, such that the prepared firefighter uniform protection fabric has advantages of excellent flame retardation, excellent high temperature resistance, excellent gas permeability, and meeting of use requirements in various environments.

Description

Technical Field

[0001] The present invention belongs to the technical field of fire-fighting composite fabrics, and particularly relates to a processing technology for a fire-fighting suit protective fabric with high flame retardancy, high temperature resistance and high breathability. Background Art

[0002] With the complication of modern urban building structures, the intensification of industrial facilities, and the extensive application of new energy materials, the suddenness and danger of fire accidents show a diversified development trend. As the core force of emergency rescue, the performance of firefighters' protective equipment directly determines the success or failure of rescue operations and the survival probability of personnel.

[0003] As the first line of defense against high temperature, flames and heat radiation, fire-fighting suits need to achieve multiple functions such as flame retardancy and heat insulation, sweat and gas emission, and dynamic operation adaptation in a fire environment. However, in order to enhance the heat insulation ability, traditional fire-fighting suit fabrics often adopt the method of stacking multiple dense fabrics. Although it can block the transfer of heat to a certain extent, it has poor breathability and low comfort. During long-term rescue work, it often exacerbates the heat stress reaction of firefighters. Moreover, most traditional fire-fighting suit protective fabrics use high-performance fibers such as aramid and polybenzimidazole as basic materials, and introduce flame retardant components through physical blending or surface coating. Although this method can improve the initial flame retardancy level of fire-fighting protective fabrics, in actual use, the flame retardants in physical blending are easy to lose during fiber processing, and the binding ability with the matrix material is insufficient. After long-term use, phase separation is likely to occur, resulting in the attenuation of flame retardancy over time and causing local protection failure.

[0004] For example, the patent with the publication number CN103556470B discloses an outer layer fabric for a fireman's heat-insulating protective suit and its manufacturing method. This patent coats aluminosilicate A and aluminosilicate B on the outer surface of aramid 313, making the prepared outer layer fabric for the heat-insulating protective suit have excellent heat insulation ability and moisture permeability, enhancing the wearing comfort, and having excellent flame retardancy, and being able to well play the protective effect. However, the outer layer fabric for the heat-insulating protective suit prepared by this patent by coating a coating on the fabric surface still has problems such as local peeling of the coating and migration of flame retardant active ingredients. Summary of the Invention

[0005] The purpose of the present invention is to provide a processing technology for a fire-fighting suit protective fabric with high flame retardancy, high temperature resistance and high breathability, and solve the technical problems of general flame retardancy and high temperature resistance and poor breathability of traditional fire-fighting suits.

[0006] The purpose of the present invention can be achieved by the following technical solutions: A processing technology for a fire-fighting suit protective fabric with high flame retardancy, high temperature resistance and high breathability, comprising the following processing steps: Step 1: Comb and draw the nitrogen-phosphorus composite flame-retardant fiber, and then use the plain weaving process to make a woven fabric. Immerse the fabric in a sodium hydroxide solution for 0.5 - 1 h, wash it with water until neutral, and then dry and shape it to obtain a high-temperature resistant flame-retardant fabric. Step 2: Mix and stir polyurethane adhesive and nano-silica aerogel evenly to obtain a composite adhesive. Step 3: Blended-spin menthol-modified bamboo fiber and spandex fiber to form a yarn. Weave the yarn into a fabric using the double rib knitting process, and then perform steam setting treatment at 95 - 100 °C for 25 - 30 s to obtain a comfortable fabric. Step 4: Use the diamond dot spraying method to spray the composite adhesive onto the inner surface of the high-temperature resistant flame-retardant fabric at a coating amount of 10 - 12 g / m 2 . After curing with hot air at 120 - 150 °C for 3 - 5 min, laminate it with the comfortable fabric, and then hot press it for 30 - 40 s under a hot press laminator at a temperature of 130 - 135 °C and a pressure of 0.8 - 1 MPa to obtain a fire-fighting suit protective fabric.

[0007] Further, in Step 1, the mass fraction of the sodium hydroxide solution is 5 - 6%.

[0008] Further, in Step 4, the dot spacing of the diamond dot spraying method is 9 - 16 mm 2 .

[0009] Further, the preparation method of the nitrogen-phosphorus composite flame-retardant fiber includes the following steps: S1: Place diphenylchloromethyl phosphate and chitosan in acetone, add a promoter, heat up to 45 - 50 °C and react for 3 - 5 h, rotate and evaporate to remove the solvent, and collect the product to obtain phosphorylated chitosan. S2: Immerse aramid fiber in acetone for 4 - 6 h, filter and dry it, irradiate it under ultraviolet light, take it out and place it in N,N-dimethylformamide, add phosphorylated chitosan and p-toluenesulfonic acid, heat up to 90 - 100 °C, fully mix and stir, then filter, wash and dry to obtain the nitrogen-phosphorus composite flame-retardant fiber.

[0010] In this solution, under the action of a promoter, the active chlorine in the structure of diphenyl chloromethyl phosphate reacts with the amino group in the structure of chitosan to obtain phosphorylated chitosan. Then, under ultraviolet irradiation, carboxyl groups are generated on the surface of aramid fibers. Through the catalytic action of p-toluenesulfonic acid, the carboxyl groups on the surface of aramid fibers react with phosphorylated chitosan to obtain a nitrogen-phosphorus composite flame-retardant fiber. This kind of nitrogen-phosphorus composite fiber has excellent high-temperature resistance and thermal stability. In case of a fire, it can effectively block the transfer of heat, delay the time of thermal decomposition of the protective fabric of the fire-fighting suit during a fire. In a long-term high-temperature environment, the nitrogen-phosphorus composite flame-retardant fiber decomposes, and the phosphate ester in its structure promotes dehydration and carbonization on the fiber surface to form a dense carbon layer, isolating oxygen and heat. The nitrogen element in the chitosan molecule releases non-combustible gases when heated, effectively diluting the concentration of combustible gases and inhibiting the combustion chain reaction. At the same time, phosphorylated chitosan is connected to the fiber surface in a chemical bonding manner, which can effectively form a stable flame-retardant layer and prevent the migration of the flame retardant during long-term use. Through the synergistic effect of the three, the flame-retardant performance of the protective fabric of the fire-fighting suit is effectively improved.

[0011] Further, in step S1, the promoter is potassium carbonate.

[0012] Further, in step S2, the wavelength of the ultraviolet irradiation is 313 - 350 nm, and the time is 8 - 10 min.

[0013] Further, the preparation method of the menthol-modified bamboo fiber includes the following steps: SS1: Place the bamboo fiber in deionized water, introduce nitrogen, add allyl isocyanate and a catalyst, heat up to 70 - 75 °C and react for 3 - 5 h. After cooling to room temperature, filter, wash, and dry to obtain allyl-modified bamboo fiber; SS2: Place the allyl-modified bamboo fiber in absolute ethanol, add isopulegol and an initiator, heat up to 55 - 60 °C and stir for 5 - 6 h. Filter, wash, and dry to obtain menthol-modified bamboo fiber.

[0014] In this solution, under the action of a catalyst, the hydroxyl group on the surface of the bamboo fiber reacts with the isocyanate group in the structure of allyl isocyanate to obtain allyl-modified bamboo fiber. Then, under the action of an initiator, the alkenyl group in the structure of the allyl-modified bamboo fiber reacts with the alkenyl group in the structure of isopulegol to undergo a free radical polymerization reaction to obtain menthol-modified bamboo fiber. This kind of menthol-modified bamboo fiber can slowly release isopulegol molecules, and the menthol molecules can activate the cold receptors on the skin, enhance the cool feeling of the skin and continuously reduce the body temperature, effectively improving the comfort of wearing the fire-fighting suit. At the same time, the bamboo fiber has a hollow structure, has good air permeability, combined with the elasticity of spandex fiber, can effectively enhance the air permeability and wearing comfort of the protective fabric of the fire-fighting suit.

[0015] Further, in step SS1, the catalyst is any one of dibutyltin dilaurate and stannous octoate.

[0016] Further, in step SS2, the initiator is any one of benzoyl peroxide and dicumyl peroxide.

[0017] Advantages of the present invention: The outer layer of the fire-fighting suit protective fabric prepared by the present invention is a high-temperature resistant flame-retardant fabric made of nitrogen-phosphorus composite flame-retardant fibers. Through the synergistic effect among the components, a dense carbon layer can be formed during a fire, isolating the flame and high temperature, and delaying combustion. Nano-silica aerogel is added to the inner composite adhesive, which can further block heat transfer. At the same time, by spraying the adhesive in a diamond lattice pattern, a comfortable fabric blended with menthol-modified bamboo fiber and spandex fiber is laminated thereto. This kind of comfortable fabric can bring a continuous sense of coolness, has high wearing comfort, has uniform air-permeable pores, and can effectively promote the discharge of sweat gas, so that the prepared fire-fighting suit protective fabric can have excellent flame-retardant performance, high temperature resistance and air permeability, high wearing comfort, and meet the use requirements in various environments.

[0018] Of course, it is not necessary for any product implementing the present invention to achieve all the above-mentioned advantages simultaneously. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for describing the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present invention, and those of ordinary skill in the art can obtain other drawings based on these drawings without creative efforts.

[0020] Figure 1 It is a schematic cross-sectional view of the fire-fighting suit protective fabric of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0021] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the scope of protection of the present invention.

[0022] The preparation methods of the nitrogen-phosphorus composite flame-retardant fiber and the menthol-modified bamboo fiber in the following embodiments and comparative examples of the present invention are as follows: I. Preparation of nitrogen-phosphorus composite flame-retardant fiber S1: Place 2.6 g of diphenyl chloromethyl phosphate and 3.2 g of chitosan in 60 ml of acetone, add 0.05 g of potassium carbonate, raise the temperature to 45 °C and react for 3 h. Rotate and evaporate to remove the solvent, and collect the product to obtain phosphorylated chitosan. S2: Soak 5 g of aramid fiber in 20 ml of acetone for 4 h, filter and dry it, irradiate it under ultraviolet light with a wavelength of 313 nm for 8 min, take it out and place it in 100 ml of N,N-dimethylformamide, add 4.2 g of phosphorylated chitosan and 0.3 g of p-toluenesulfonic acid, raise the temperature to 90 °C, fully mix and stir, then filter, wash and dry to obtain a nitrogen-phosphorus composite flame-retardant fiber.

[0023] II. Preparation of menthol-modified bamboo fiber SS1: Place 3.2 g of bamboo fiber in 80 ml of deionized water, introduce nitrogen, add 4 g of allyl isocyanate and 0.1 g of dibutyltin dilaurate, raise the temperature to 70 °C and react for 3 h. After cooling to room temperature, filter, wash and dry to obtain allyl-modified bamboo fiber. SS2: Place 3.5 g of allyl-modified bamboo fiber in 100 ml of absolute ethanol, add 3 g of isopulegol and 0.6 g of benzoyl peroxide, raise the temperature to 55 °C and stir for 5 h. Filter, wash and dry to obtain menthol-modified bamboo fiber.

[0024] Example 1

[0025] Preparation of fire-fighting suit protective fabric Step 1: Take 50 parts of nitrogen-phosphorus composite flame-retardant fiber, after carding and drawing, use a plain weaving process to make a woven fabric, immerse it in a sodium hydroxide solution with a mass fraction of 5% for 0.5 h, wash it with water until neutral, and then dry and shape it to obtain a high-temperature resistant flame-retardant surface fabric. Step 2: Take 60 parts of polyurethane adhesive and 10 parts of nano-silica aerogel, mix and stir evenly to obtain a composite adhesive. Step 3: Blend 40 parts of menthol-modified bamboo fiber and 20 parts of spandex fiber to form a yarn, use a double-rib knitting process to weave it into a fabric, and then perform steam setting treatment at 95 °C for 25 s to obtain a comfortable surface fabric. Step 4: Use the diamond dot spraying method to spray the composite adhesive onto the inner surface of the high-temperature resistant flame-retardant surface fabric at a coating amount of 10 g / m 2 , with a dot spacing of 9 mm 2 , after curing with hot air at 120 °C for 3 min, laminate it with the comfortable surface fabric, and hot press it for 30 s under a hot press at a temperature of 130 °C and a pressure of 0.8 MPa to obtain the fire-fighting suit protective fabric.

[0026] Example 2

[0027] Preparation of fire-fighting suit protective fabric Step 1: Take 60 parts of nitrogen-phosphorus composite flame-retardant fibers. After carding and drawing, a woven fabric is made by plain weaving process. Immerse it in a sodium hydroxide solution with a mass fraction of 5.5% for 0.8 h. After washing with water until neutral, dry and shape it to obtain a high-temperature resistant flame-retardant surface fabric. Step 2: Take 70 parts of polyurethane adhesive and 15 parts of nano-silica aerogel, mix and stir evenly to obtain a composite adhesive. Step 3: Blend 50 parts of menthol-modified bamboo fibers and 25 parts of spandex fibers to form a yarn. After weaving it into a fabric using double rib knitting process, subject it to steam setting treatment at 98 °C for 28 s to obtain a comfortable surface fabric. Step 4: Using the diamond dot spraying method, spray the composite adhesive onto the inner surface of the high-temperature resistant flame-retardant surface fabric at a coating amount of 11 g / m 2 , with a dot spacing of 12 mm 2 . After curing with hot air at 130 °C for 4 min, laminate it with the comfortable surface fabric, and hot press it for 35 s under a hot press laminator at a temperature of 132 °C and a pressure of 0.9 MPa to obtain the fire-fighting suit protective fabric.

[0028] Example 3

[0029] Preparation of Fire-fighting Suit Protective Fabric Step 1: Take 70 parts of nitrogen-phosphorus composite flame-retardant fibers. After carding and drawing, a woven fabric is made by plain weaving process. Immerse it in a sodium hydroxide solution with a mass fraction of 6% for 1 h. After washing with water until neutral, dry and shape it to obtain a high-temperature resistant flame-retardant surface fabric. Step 2: Take 80 parts of polyurethane adhesive and 20 parts of nano-silica aerogel, mix and stir evenly to obtain a composite adhesive. Step 3: Blend 60 parts of menthol-modified bamboo fibers and 30 parts of spandex fibers to form a yarn. After weaving it into a fabric using double rib knitting process, subject it to steam setting treatment at 100 °C for 30 s to obtain a comfortable surface fabric. Step 4: Using the diamond dot spraying method, spray the composite adhesive onto the inner surface of the high-temperature resistant flame-retardant surface fabric at a coating amount of 12 g / m 2 , with a dot spacing of 16 mm 2 . After curing with hot air at 150 °C for 5 min, laminate it with the comfortable surface fabric, and hot press it for 40 s under a hot press laminator at a temperature of 135 °C and a pressure of 1 MPa to obtain the fire-fighting suit protective fabric.

[0030] Comparative Example 1 Preparation of Fire-fighting Suit Protective Fabric Step 1: Take 60 parts of aramid fibers. After carding and drawing, a woven fabric is made using a plain weave process. Immerse it in a sodium hydroxide solution with a mass fraction of 5.5% for 0.8 h. After washing with water until neutral, dry and shape it to obtain a high-temperature resistant and flame-retardant surface fabric; Step 2: Take 70 parts of polyurethane adhesive and mix it evenly with 15 parts of nano-silica aerogel to obtain a composite adhesive; Step 3: Blend 50 parts of menthol-modified bamboo fibers and 25 parts of spandex fibers to form a yarn. After weaving it into a fabric using a double rib knitting process and subjecting it to steam setting treatment at 98 °C for 28 s, a comfortable surface fabric is obtained; Step 4: Using the diamond dot spraying method, spray the composite adhesive onto the inner surface of the high-temperature resistant and flame-retardant surface fabric at a coating amount of 11 g / m 2 , with a dot spacing of 12 mm 2 . After curing with hot air at 130 °C for 4 min, laminate it with the comfortable surface fabric and hot press it for 35 s under a hot press laminator at a temperature of 132 °C and a pressure of 0.9 MPa to obtain a fire-fighting suit protective fabric.

[0031] Comparative Example 2 Preparation of Fire-fighting Suit Protective Fabric Step 1: Take 60 parts of nitrogen-phosphorus composite flame-retardant fibers. After carding and drawing, a woven fabric is made using a plain weave process. Immerse it in a sodium hydroxide solution with a mass fraction of 5.5% for 0.8 h. After washing with water until neutral, dry and shape it to obtain a high-temperature resistant and flame-retardant surface fabric; Step 2: Take 70 parts of polyurethane adhesive and mix it evenly with 15 parts of nano-silica aerogel to obtain a composite adhesive; Step 3: Blend 75 parts of spandex fibers to form a yarn. After weaving it into a fabric using a double rib knitting process and subjecting it to steam setting treatment at 98 °C for 28 s, a comfortable surface fabric is obtained; Step 4: Using the diamond dot spraying method, spray the composite adhesive onto the inner surface of the high-temperature resistant and flame-retardant surface fabric at a coating amount of 11 g / m 2 , with a dot spacing of 12 mm 2 . After curing with hot air at 130 °C for 4 min, laminate it with the comfortable surface fabric and hot press it for 35 s under a hot press laminator at a temperature of 132 °C and a pressure of 0.9 MPa to obtain a fire-fighting suit protective fabric.

[0032] Performance Testing The fire-fighting suit protective fabrics prepared in Examples 1 - 3 and Comparative Examples 1 - 2 were made into specimens that met the specifications. Referring to the standard GB / T5455 - 2014, with a flame height of 4 cm, it was ignited for 12 s, and the char length was recorded after the sample was carbonized. The shorter the char length, the stronger the flame retardancy; the sample was placed in a forced-air oven at 260 °C for 5 min, and the dimensional change of the specimen before and after heating was measured. The change rate was calculated with reference to the following formula: change rate = (size before heating - size after heating) × 100% / size before heating. The smaller the change rate, the better the high-temperature resistance of the sample; referring to the standard GB38453 - 2019, the air permeability of the sample was tested; the specific test results are shown in the following table:

[0033] As can be seen from the above table, the samples prepared in Examples 1 - 3 all have excellent flame retardancy, high-temperature resistance, and air permeability. In the sample prepared in Comparative Example 1, the aramid fiber was not flame-retardant modified, so the flame retardancy was poor. In the sample prepared in Comparative Example 2, menthol-modified bamboo fiber was not added, and the spandex fabric was directly used as the comfort layer, so the comfort level was not high and the air permeability needed to be improved.

[0034] In the description of this specification, the description with reference to terms such as "one embodiment", "some embodiments", "example", "specific example", or "some examples" means that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples. In addition, without contradiction, those skilled in the art can combine and combine the different embodiments or examples described in this specification and the features of different embodiments or examples.

[0035] The above content is only an example and illustration of the concept of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the scope defined by the concept of the invention, they should all fall within the protection scope of the present invention.

Claims

1. A processing technology for highly flame-retardant, high-temperature-resistant and highly breathable firefighting clothing protective fabric, characterized in that: The processing steps include: Step 1: After the nitrogen-phosphorus composite flame-retardant fiber is combed and drawn, a plain weaving process is used to make a woven fabric, which is then immersed in a sodium hydroxide solution for 0.5-1h, washed with water until neutral, and dried to obtain a high-temperature resistant flame-retardant layer fabric; Step 2: Mix the polyurethane adhesive and the nano-silica aerogel and stir them evenly to obtain a composite adhesive; Step 3: Blending menthol-modified bamboo fiber with spandex fiber to form yarn, weaving into fabric using double rib knitting process, and subjecting to 95-100° C. steam setting treatment for 25-30 seconds to obtain a comfort layer fabric; Step 4: Use the diamond dot spraying method to apply the composite adhesive at a rate of 10-12g / m 2 The coating amount is sprayed onto the inner surface of the high temperature resistant flame retardant layer fabric, and then laminated with the comfort layer fabric after being cured with 120-150℃ hot air for 3-5min. It is then hot pressed for 30-40s in a hot pressing laminating machine at a temperature of 130-135℃ and a pressure of 0.8-1MPa to obtain the protective fabric for firefighting clothing.

2. The processing technology of the highly flame-retardant, high-temperature-resistant and highly breathable firefighting clothing protective fabric according to claim 1 is characterized in that: In step 1, the mass fraction of the sodium hydroxide solution is 5-6%.

3. The processing technology of the highly flame-retardant, high-temperature-resistant and highly breathable firefighting clothing protective fabric according to claim 1 is characterized in that: In step 4, the dot spacing of the diamond dot spraying method is 9-16mm 2 .

4. The processing technology of the highly flame-retardant, high-temperature-resistant and highly breathable firefighting clothing protective fabric according to claim 1 is characterized in that: The preparation method of the nitrogen-phosphorus composite flame-retardant fiber comprises the following steps: S1: placing diphenyl chloromethyl phosphate and chitosan in acetone, adding a promoter, heating to 45-50°C for reaction for 3-5h, removing the solvent by rotary evaporation, and collecting the product to obtain phosphated chitosan; S2: Soak the aramid fiber in acetone for 4-6 hours, filter, dry, and irradiate under ultraviolet light. Take it out and place it in N,N-dimethylformamide, add phosphated chitosan and p-toluenesulfonic acid, heat it to 90-100°C, mix and stir thoroughly, filter, wash, and dry to obtain nitrogen-phosphorus composite flame-retardant fiber.

5. The processing technology of the highly flame-retardant, high-temperature-resistant and highly breathable firefighting clothing protective fabric according to claim 4 is characterized in that: In step S1, the accelerator is potassium carbonate.

6. The processing technology of the highly flame-retardant, high-temperature-resistant and highly breathable protective fabric for fire-fighting clothing according to claim 4 is characterized in that: In step S2, the wavelength of the ultraviolet light irradiation is 313-350nm, and the time is 8-10min.

7. The processing technology of the highly flame-retardant, high-temperature-resistant and highly breathable firefighting clothing protective fabric according to claim 1 is characterized in that: The preparation method of the menthol modified bamboo fiber comprises the following steps: SS1: Place bamboo fiber in deionized water, introduce nitrogen, add allyl isocyanate and catalyst, heat to 70-75°C for reaction for 3-5h, cool to room temperature, filter, wash and dry to obtain allyl modified bamboo fiber; SS2: Place allyl-modified bamboo fiber in anhydrous ethanol, add isopulegol and initiator, heat to 55-60°C and stir for 5-6h, filter, wash and dry to obtain menthol-modified bamboo fiber.

8. The processing technology of the highly flame-retardant, high-temperature-resistant and highly breathable firefighting clothing protective fabric according to claim 7 is characterized in that: In step SS1, the catalyst is any one of dibutyltin dilaurate and stannous octoate.

9. The processing technology of the highly flame-retardant, high-temperature-resistant and highly breathable protective fabric for fire-fighting clothing according to claim 7 is characterized in that: In step SS2, the initiator is any one of benzoyl peroxide and diisopropylbenzene peroxide.

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