A processing technology for highly flame-retardant, high-temperature-resistant and highly breathable protective fabric for firefighting clothing

Abstract

The present invention relates to the technical field of fire-fighting composite fabrics, and discloses a processing technology for highly flame-retardant, high-temperature-resistant, and highly breathable firefighting suit protective fabrics. The outer layer of the firefighting suit protective fabric adopts a high-temperature flame-retardant layer fabric made of nitrogen-phosphorus composite flame-retardant fibers. Through the synergistic effect between the various components, a dense carbon layer can be formed when a fire occurs to delay combustion. Nano-silicon dioxide aerogel is added to the composite adhesive of the inner layer to further block heat transfer. A comfort layer fabric blended with menthol-modified bamboo fiber and spandex fiber is composited with the composite adhesive by spraying the adhesive in a diamond lattice. The fabric has uniform breathable pores, can bring a continuous cool feeling, is highly comfortable to wear, and effectively promotes sweat discharge. The prepared firefighting suit protective fabric has excellent flame retardancy, high-temperature resistance, and breathability, and can meet the use requirements in various environments.

Description

Technical Field

[0001] The present invention belongs to the technical field of fire-fighting composite fabrics, and in particular relates to a processing technology for highly flame-retardant, high-temperature-resistant and highly breathable protective fabrics for fire-fighting clothing. Background Art

[0002] With the increasing complexity of modern urban building structures, the intensification of industrial facilities, and the widespread use of new energy materials, the suddenness and danger of fire accidents are becoming more diverse. Firefighters are the core force of emergency rescue, and the performance of their protective equipment directly determines the success or failure of rescue operations and the probability of survival.

[0003] As the first line of defense against high temperatures, flames, and thermal radiation, firefighting clothing must simultaneously achieve multiple functions such as flame retardancy and heat insulation, sweat emission, and dynamic operation adaptation in fire environments. However, in order to enhance thermal insulation, traditional firefighting clothing fabrics often use multiple layers of dense fabrics stacked together. Although this can block heat transfer to a certain extent, it has poor air permeability and low comfort. During long-term rescue work, it often aggravates the heat stress response of firefighters. In addition, traditional firefighting clothing protective fabrics mostly use high-performance fibers such as aramid and polybenzimidazole as the base material, and introduce flame retardant ingredients through physical blending or surface coating. Although this method can improve the initial flame retardancy of fire protection fabrics, in actual use, the physically blended flame retardant is easily lost during fiber processing, and the bonding ability between the flame retardant and the matrix material is insufficient. After long-term use, phase separation is prone to occur, causing the flame retardant performance to decay over time, resulting in local protection failure.

[0004] For example, the patent with publication number CN103556470B discloses an outer fabric of a heat-insulating protective suit for firefighters and a method for making the same. This patent prepares aluminum glue A and aluminum glue B and coats them on the outer surface of aramid 313, so that the outer fabric of the heat-insulating protective suit prepared has excellent heat insulation and moisture permeability, enhances wearing comfort, and has excellent flame retardant ability, which can play a good protective effect. However, the outer fabric of the heat-insulating protective suit prepared by this patent still has the problem of partial shedding of the coating and migration of flame retardant active ingredients through the method of coating the fabric surface. Summary of the Invention

[0005] The purpose of the present invention is to provide a processing technology for highly flame-retardant, high-temperature-resistant and highly breathable firefighting clothing protective fabrics, which solves the technical problems that traditional firefighting clothing has average flame-retardant and high-temperature-resistant properties and poor breathability.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A processing technology for highly flame-retardant, high-temperature-resistant and highly breathable firefighting clothing protective fabric includes the following processing steps:

[0008] Step 1: Combing and drawing the nitrogen-phosphorus composite flame-retardant fiber, and then using a plain weaving process to make a woven fabric, which is then immersed in a sodium hydroxide solution for 0.5-1 hour, washed with water until neutral, and dried to form a high-temperature resistant flame-retardant layer fabric;

[0009] Step 2: Mix the polyurethane adhesive and the nano-silica aerogel and stir them evenly to obtain a composite adhesive;

[0010] Step 3: Blending menthol-modified bamboo fiber with spandex fiber to form yarn, weaving the yarn into fabric using an interlock knitting process, and then subjecting the fabric to a steam setting treatment at 95-100° C. for 25-30 seconds to obtain a comfort layer fabric;

[0011] 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 cured with 120-150 ℃ hot air for 3-5 minutes and then laminated with the comfort layer fabric. It is hot pressed for 30-40 seconds in a hot press laminating machine with a temperature of 130-135 ℃ and a pressure of 0.8-1MPa to obtain the protective fabric for fire protection clothing.

[0012] Furthermore, in step 1, the mass fraction of the sodium hydroxide solution is 5-6%.

[0013] Furthermore, in step 4, the lattice spacing of the diamond lattice spraying method is 9-16 mm 2 .

[0014] Furthermore, the preparation method of the nitrogen-phosphorus composite flame-retardant fiber comprises the following steps:

[0015] S1: Diphenyl chloromethyl phosphate and chitosan are placed in acetone, a promoter is added, the temperature is raised to 45-50°C, the reaction is carried out for 3-5 hours, the solvent is removed by rotary evaporation, and the product is collected to obtain phosphated chitosan;

[0016] S2: Soak the aramid fiber in acetone for 4-6 hours, filter, dry, and irradiate it under ultraviolet light. After taking it out, place it in N,N-dimethylformamide, add phosphated chitosan and p-toluenesulfonic acid, heat it to 90-100°C, mix and stir it thoroughly, filter, wash, and dry it to obtain a nitrogen-phosphorus composite flame-retardant fiber.

[0017] In this scheme, under the action of a promoter, the active chlorine in the diphenyl chloromethyl phosphate structure undergoes a substitution reaction with the amino group in the chitosan structure to obtain phosphated chitosan. Then, under ultraviolet irradiation, the surface of the aramid fiber is modified to generate carboxyl groups. After the catalysis of p-toluenesulfonic acid, the carboxyl groups on the surface of the aramid fiber undergo an esterification reaction with the phosphated chitosan to obtain a nitrogen-phosphorus composite flame-retardant fiber. This type of nitrogen-phosphorus composite fiber has excellent high-temperature resistance and thermal stability. When a fire occurs, it can effectively block the transfer of heat and delay the thermal decomposition of the fire suit protective fabric when a fire occurs. Under long-term high-temperature conditions, the nitrogen-phosphorus composite flame-retardant fiber decomposes, and the phosphate ester in its structure promotes dehydration and carbonization of the fiber surface to form a dense carbon layer, isolating oxygen and heat. The nitrogen element in the chitosan molecule releases non-combustible gas when heated, effectively diluting the concentration of combustible gas and inhibiting the combustion chain reaction. At the same time, the phosphated chitosan is connected to the fiber surface by chemical bonding, which can effectively form a stable flame retardant layer to avoid the migration of the flame retardant during long-term use. Through the synergistic effect of the three, the flame retardant properties of the fire suit protective fabric are effectively improved.

[0018] Furthermore, in step S1, the accelerator is potassium carbonate.

[0019] Furthermore, in step S2, the wavelength of the ultraviolet light irradiation is 313-350 nm, and the time is 8-10 min.

[0020] Furthermore, the preparation method of the menthol-modified bamboo fiber comprises the following steps:

[0021] SS1: Place bamboo fiber in deionized water, introduce nitrogen, add allyl isocyanate and catalyst, heat to 70-75°C and react for 3-5 hours. After cooling to room temperature, filter, wash, and dry to obtain allyl-modified bamboo fiber.

[0022] SS2: Place allyl-modified bamboo fiber in anhydrous ethanol, add isopulegol and initiator, heat to 55-60°C and stir for 5-6 hours, filter, wash and dry to obtain menthol-modified bamboo fiber.

[0023] In this solution, under the action of a catalyst, the hydroxyl groups on the bamboo fiber surface react with the isocyanate groups in the allyl isocyanate structure to produce allyl-modified bamboo fiber. Then, under the action of an initiator, the alkenyl groups in the allyl-modified bamboo fiber structure react with the alkenyl groups in the isopulegol structure to produce menthol-modified bamboo fiber. This menthol-modified bamboo fiber can slowly release isopulegol molecules, which can activate the skin's cold receptors, enhancing the skin's cooling sensation and continuously lowering the perceived temperature, effectively improving the comfort of firefighter uniforms. The hollow structure of bamboo fiber offers good breathability, and combined with the elasticity of spandex fiber, it can effectively enhance the breathability and wearing comfort of firefighter uniforms.

[0024] Furthermore, in step SS1, the catalyst is any one of dibutyltin dilaurate and stannous octoate.

[0025] Furthermore, in step SS2, the initiator is any one of benzoyl peroxide and dicumyl peroxide.

[0026] Beneficial effects of the present invention:

[0027] The outer layer of the fire-fighting suit protective fabric prepared by the present invention adopts a high-temperature resistant flame-retardant layer fabric made of nitrogen-phosphorus composite flame-retardant fiber. Through the synergistic effect of the various components, a dense carbon layer can be formed when a fire occurs to isolate the flame and high temperature and delay combustion. Nano-silica aerogel is added to the composite adhesive of the inner layer, which can further block heat transfer. At the same time, the comfort layer fabric blended by menthol-modified bamboo fiber and spandex fiber is compounded with it by the method of spraying adhesive in a diamond lattice. This comfort layer fabric can bring a continuous cool feeling, is highly comfortable to wear, has uniform air permeability, and can effectively promote the discharge of sweat, so that the prepared fire-fighting suit protective fabric can have excellent flame retardant properties, high temperature resistance and breathability, is highly comfortable to wear, and meets the use requirements in various environments.

[0028] Of course, any product implementing the present invention does not necessarily need to achieve all of the advantages described above at the same time. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0030] Figure 1 This is a schematic cross-sectional view of the protective fabric of the fire-fighting suit of the present invention. DETAILED DESCRIPTION

[0031] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0032] The preparation methods of the nitrogen-phosphorus composite flame-retardant fibers and menthol-modified bamboo fibers in the following examples and comparative examples of the present invention are as follows:

[0033] 1. Preparation of nitrogen-phosphorus composite flame retardant fiber

[0034] S1: 2.6 g of diphenyl chloromethyl phosphate and 3.2 g of chitosan were placed in 60 ml of acetone, 0.05 g of potassium carbonate was added, and the temperature was raised to 45°C for reaction for 3 h. The solvent was removed by rotary evaporation, and the product was collected to obtain phosphated chitosan;

[0035] S2: Soak 5g of aramid fiber in 20ml of acetone for 4h, filter and dry, irradiate under ultraviolet light with a wavelength of 313nm for 8min, take out and place in 100ml of N,N-dimethylformamide, add 4.2g of phosphated chitosan and 0.3g of p-toluenesulfonic acid, heat to 90℃, mix and stir thoroughly, filter, wash and dry to obtain nitrogen-phosphorus composite flame retardant fiber.

[0036] 2. Preparation of menthol-modified bamboo fiber

[0037] SS1: 3.2 g of bamboo fiber was placed in 80 ml of deionized water, and nitrogen was introduced. 4 g of allyl isocyanate and 0.1 g of dibutyltin dilaurate were added. The temperature was raised to 70°C for reaction for 3 h. After cooling to room temperature, the allyl-modified bamboo fiber was obtained by filtration, washing, and drying.

[0038] SS2: 3.5 g of allyl-modified bamboo fiber was placed in 100 ml of anhydrous ethanol, 3 g of isopulegol and 0.6 g of benzoyl peroxide were added, the temperature was raised to 55 °C and stirred for 5 h, and menthol-modified bamboo fiber was obtained after filtration, washing, and drying.

[0039] Example 1

[0040] Preparation of protective fabrics for firefighting uniforms

[0041] Step 1: 50 parts of nitrogen-phosphorus composite flame-retardant fibers are carded and drawn, and then made into a woven fabric using a plain weave process. The woven fabric is then immersed in a 5% by mass sodium hydroxide solution for 0.5 h, washed with water until neutral, and dried to form a high-temperature resistant flame-retardant layer fabric;

[0042] Step 2: Mix 60 parts of polyurethane adhesive and 10 parts of nano-silica aerogel and stir them evenly to obtain a composite adhesive;

[0043] Step 3: 40 parts of menthol-modified bamboo fiber and 20 parts of spandex fiber are blended to form yarn, which is knitted into fabric using an interlock knitting process, and then subjected to a steam setting treatment at 95° C. for 25 seconds to obtain a comfort layer fabric;

[0044] Step 4: Use the diamond dot spraying method to apply the composite adhesive at a rate of 10g / m 2 The coating amount is sprayed onto the inner surface of the high temperature resistant flame retardant layer fabric, and the dot spacing is 9mm 2 After curing with 120℃ hot air for 3 minutes, it was laminated with the comfort layer fabric and hot pressed for 30 seconds in a hot press laminating machine with a temperature of 130℃ and a pressure of 0.8MPa to obtain the protective fabric for firefighting clothing.

[0045] Example 2

[0046] Preparation of protective fabrics for firefighting uniforms

[0047] Step 1: 60 parts of nitrogen-phosphorus composite flame-retardant fibers are carded and drawn, and then made into a woven fabric using a plain weave process. The woven fabric is then immersed in a 5.5% by mass sodium hydroxide solution for 0.8 h, washed with water until neutral, and dried to form a high-temperature resistant flame-retardant layer fabric;

[0048] Step 2: Mix 70 parts of polyurethane adhesive and 15 parts of nano-silica aerogel and stir them evenly to obtain a composite adhesive;

[0049] Step 3: 50 parts of menthol-modified bamboo fiber and 25 parts of spandex fiber are blended to form yarn, which is knitted into fabric using an interlock knitting process, and then subjected to a steam setting treatment at 98° C. for 28 seconds to obtain a comfort layer fabric;

[0050] Step 4: Use the diamond dot spraying method to apply the composite adhesive at 11g / m 2 The coating amount is sprayed onto the inner surface of the high temperature resistant flame retardant layer fabric, and the dot spacing is 12mm 2 After curing with 130℃ hot air for 4 minutes, it was laminated with the comfort layer fabric and hot pressed for 35 seconds in a hot press laminating machine with a temperature of 132℃ and a pressure of 0.9MPa to obtain the protective fabric for firefighting clothing.

[0051] Example 3

[0052] Preparation of protective fabrics for firefighting uniforms

[0053] Step 1: 70 parts of nitrogen-phosphorus composite flame-retardant fibers are carded and drawn, and then made into a woven fabric using a plain weave process. The woven fabric is then immersed in a 6% by mass sodium hydroxide solution for 1 hour, washed with water until neutral, and dried to form a high-temperature resistant flame-retardant layer fabric;

[0054] Step 2: Take 80 parts of polyurethane adhesive and 20 parts of nano-silica aerogel and mix them evenly to obtain a composite adhesive;

[0055] Step 3: 60 parts of menthol-modified bamboo fiber and 30 parts of spandex fiber are blended to form yarn, which is knitted into fabric using an interlock knitting process, and then subjected to a steam setting treatment at 100° C. for 30 seconds to obtain a comfort layer fabric;

[0056] Step 4: Use the diamond dot spraying method to apply the composite adhesive at 12g / m 2 The coating amount is sprayed onto the inner surface of the high temperature resistant flame retardant layer fabric, and the dot spacing is 16mm 2 After curing with 150℃ hot air for 5 minutes, it was laminated with the comfort layer fabric and hot pressed for 40 seconds in a hot press laminating machine with a temperature of 135℃ and a pressure of 1MPa to obtain the protective fabric for firefighting clothing.

[0057] Comparative Example 1

[0058] Preparation of protective fabrics for firefighting uniforms

[0059] Step 1: 60 parts of aramid fibers are carded and drawn, and then made into a woven fabric using a plain weave process. The woven fabric is then immersed in a 5.5% by mass sodium hydroxide solution for 0.8 h, washed with water until neutral, and dried to form a high-temperature resistant flame-retardant layer fabric;

[0060] Step 2: Mix 70 parts of polyurethane adhesive and 15 parts of nano-silica aerogel and stir them evenly to obtain a composite adhesive;

[0061] Step 3: 50 parts of menthol-modified bamboo fiber and 25 parts of spandex fiber are blended to form yarn, which is knitted into fabric using an interlock knitting process, and then subjected to a steam setting treatment at 98° C. for 28 seconds to obtain a comfort layer fabric;

[0062] Step 4: Use the diamond dot spraying method to apply the composite adhesive at 11g / m 2 The coating amount is sprayed onto the inner surface of the high temperature resistant flame retardant layer fabric, and the dot spacing is 12mm 2 After curing with 130℃ hot air for 4 minutes, it was laminated with the comfort layer fabric and hot pressed for 35 seconds in a hot press laminating machine with a temperature of 132℃ and a pressure of 0.9MPa to obtain the protective fabric for firefighting clothing.

[0063] Comparative Example 2

[0064] Preparation of protective fabrics for firefighting uniforms

[0065] Step 1: 60 parts of nitrogen-phosphorus composite flame-retardant fibers are carded and drawn, and then made into a woven fabric using a plain weave process. The woven fabric is then immersed in a 5.5% by mass sodium hydroxide solution for 0.8 h, washed with water until neutral, and dried to form a high-temperature resistant flame-retardant layer fabric;

[0066] Step 2: Mix 70 parts of polyurethane adhesive and 15 parts of nano-silica aerogel and stir them evenly to obtain a composite adhesive;

[0067] Step 3: 75 parts of spandex fibers are blended to form yarn, which is woven into a fabric using an interlock knitting process, and then subjected to a steam setting treatment at 98° C. for 28 seconds to obtain a comfort layer fabric;

[0068] Step 4: Use the diamond dot spraying method to apply the composite adhesive at 11g / m 2 The coating amount is sprayed onto the inner surface of the high temperature resistant flame retardant layer fabric, and the dot spacing is 12mm 2 After curing with 130℃ hot air for 4 minutes, it was laminated with the comfort layer fabric and hot pressed for 35 seconds in a hot press laminating machine with a temperature of 132℃ and a pressure of 0.9MPa to obtain the protective fabric for firefighting clothing.

[0069] Performance testing

[0070] The fire-fighting protective fabrics prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were made into test samples that met the specifications. With reference to the standard GB / T5455-2014, the flame height was 4 cm and the samples were ignited for 12 seconds. The damaged length was recorded after the samples were carbonized. The shorter the damaged length, the stronger the flame retardant performance. The samples were placed in a 260°C blast oven for 5 minutes. The dimensional changes of the samples before and after heating were 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 samples. The air permeability of the samples was tested with reference to the standard GB38453-2019. The specific test results are shown in the table below:

[0071]

[0072] It can be seen from the above table that the samples prepared in Examples 1 to 3 all have excellent flame retardant properties, high temperature resistance and air permeability. In the sample prepared in Comparative Example 1, the aramid fiber was not flame retardantly modified, so the flame retardant performance was poor. In the sample prepared in Comparative Example 2, menthol-modified bamboo fiber was not added, and spandex fabric was directly used as the comfort layer. The comfort level was not high and the air permeability needed to be improved.

[0073] In the description of this specification, the reference terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" mean that the specific features, structures, materials or characteristics described in conjunction 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 any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in this specification and features of different embodiments or examples without contradiction.

[0074] The above content is merely an example and explanation of the concept of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in a similar manner. As long as they do not deviate from the scope defined by the concept of the invention, they should all fall within the scope of protection 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: Combing and drawing the nitrogen-phosphorus composite flame-retardant fiber, and then using a plain weaving process to make a woven fabric, which is then immersed in a sodium hydroxide solution for 0.5-1 hour, washed with water until neutral, and dried to form 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 the yarn into fabric using an interlock knitting process, and then subjecting the fabric to a steam setting treatment at 95-100° C. 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 hot air at 120-150℃ for 3-5 minutes. The laminated fabric is then hot pressed for 30-40 seconds in a hot press laminating machine at a temperature of 130-135℃ and a pressure of 0.8-1MPa to obtain the protective fabric for firefighting clothing. The preparation method of the nitrogen-phosphorus composite flame-retardant fiber comprises the following steps: S1: Diphenyl chloromethyl phosphate and chitosan are placed in acetone, a promoter is added, the temperature is raised to 45-50°C, the reaction is carried out for 3-5 hours, the solvent is removed by rotary evaporation, and the product is collected to obtain phosphated chitosan; S2: soaking the aramid fiber in acetone for 4-6 hours, filtering, drying, and irradiating the fiber under ultraviolet light. After removal, the fiber is placed in N,N-dimethylformamide, phosphated chitosan and p-toluenesulfonic acid are added, and the temperature is raised to 90-100° C. After thorough mixing and stirring, the fiber is filtered, washed, and dried to obtain a nitrogen-phosphorus composite flame-retardant fiber. 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 and react for 3-5 hours. After cooling 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 5-6 hours, filter, wash and dry to obtain menthol-modified bamboo fiber.

2. The processing technology of a 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: In step S1, the accelerator is potassium carbonate.

5. 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 S2, the wavelength of the ultraviolet light irradiation is 313-350 nm, and the time is 8-10 minutes.

6. 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 SS1, the catalyst is any one of dibutyltin dilaurate and stannous octoate.

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: In step SS2, the initiator is any one of benzoyl peroxide and dicumyl peroxide.

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