A protective composite material with high anti-toxic and high flame-retardant properties and its preparation method

Abstract

The present invention relates to the technical field of protective materials, and discloses a protective composite material with high anti-toxic and high flame-retardant properties, which includes a gas-proof layer, a flame-retardant layer, a skeleton layer, a flame-retardant layer, and a gas-proof layer laminated in sequence; the gas-proof layer uses a gas-proof co-extruded film, and the gas-proof co-extruded film is prepared by multi-layer co-extrusion of TPU, PVDC, and PE materials; the flame-retardant layer uses a flame-retardant film; the skeleton layer uses an aramid skeleton material. A manufacturing method of a protective composite material with high anti-toxic and high flame-retardant properties includes the following steps: selecting a multi-layer co-extrusion composite process of TPU, PVDC, and PE materials to prepare a gas-proof co-extruded film; mixing and stirring TPU and a flame retardant; adding a DMAC solvent and fully mixing and stirring; selecting an aramid skeleton material as the skeleton layer, and thermally melting and gluing the flame-retardant film and the gas-proof co-extruded film on both sides of the skeleton layer in sequence. This material meets national standards, while retaining the original anti-toxic and flame-retardant protective properties, reduces problems such as creases and delamination during product use, improves product quality, and extends product life.

Description

Technical Field

[0001] The present invention relates to the technical field of protective materials, in particular to the technical field of anti-toxic and flame-retardant protective materials, and specifically provides a protective composite material with high anti-toxic and high flame-retardant properties and a preparation method thereof. Background Art

[0002] In places where operations are carried out near open flames, spark-emitting sources, molten metals, and where there is a risk of ignition of flammable substances, it is necessary for working staff to wear protective clothing made of flame-retardant materials. The national standard GB8965.1-2009 "Protective Clothing - Flame Retardant Protection" stipulates the grading standards for protective clothing. Flame-retardant material Class A is applicable to flame-retardant clothing worn in occasions where there are open flames, spark emissions, operations near molten metals, and there is radiant heat and convective heat, and it belongs to the highest grade of flame-retardant materials. According to the flame-retardant performance items and indicators stipulated in the GB8965.1-2009 "Protective Clothing - Flame Retardant Protection" standard, the Class A standard indicators are: damage length ≤ 50 mm, afterglow and continued burning time ≤ 2 s. This kind of flame-retardant composite material usually adds a flame retardant to the outer composite material to meet the corresponding flame-retardant requirements.

[0003] In actual work, the on-site working environment is complex, and toxic and harmful substances are generated in dangerous places at high temperatures, which may threaten the personal safety of working staff and cause irreversible effects. Protective clothing with only flame-retardant effects cannot meet the actual on-site requirements. Currently, the anti-toxic products on the market use a composite single-layer anti-toxic film, and then a layer of materials such as TPU or PVC is compounded outside the anti-toxic film. Due to the brittle nature of the anti-toxic film material, poor cold resistance, and low peel strength between the anti-toxic film and the framework material, the product often has problems such as creases and delamination during use, affecting the product's performance, and further leading to a series of problems such as short service life. Summary of the Invention

[0004] In order to solve the problems that the existing protective materials currently on the market cannot meet the requirements of flame retardancy and anti-toxicity in a complex working environment, and due to the structural characteristics of the anti-toxic film material, there are problems such as brittleness, easy folding, and poor cold resistance, and quality problems such as creases and delamination often occur during use, resulting in frequent replacement, short service life, and increased use costs, the present invention provides a protective composite material with high anti-toxic and high flame-retardant properties and a preparation method thereof.

[0005] The present invention is implemented as follows:

[0006] The present invention provides a protective composite material with high anti - toxicity and high flame - retardancy performance, which includes a skeleton layer in the middle. On both sides of the skeleton layer, an anti - poison layer and a flame - retardant layer are sequentially compounded. The anti - poison layer uses an anti - poison co - extrusion film, and the anti - poison co - extrusion film is prepared by multi - layer co - extrusion of TPU, PVDC, and PE. The flame - retardant layer uses a flame - retardant film, and the flame - retardant film is made by mixing various flame - retardants. The skeleton layer uses an aramid skeleton material.

[0007] During implementation, a protective composite material with high anti - toxicity and high flame - retardancy performance designed by the present invention is prepared by a multi - layer composite process. It includes a skeleton layer in the middle. On both sides of the skeleton layer, an anti - poison layer and a flame - retardant layer are sequentially compounded. The anti - poison layers on both sides are exactly the same, and the flame - retardant layers on both sides are exactly the same. The front and back sides of the protective composite material are symmetrically compounded.

[0008] The anti - poison layer uses an anti - poison co - extrusion film, and the anti - poison co - extrusion film is prepared by multi - layer co - extrusion of TPU (polyurethane), PVDC (polyvinylidene chloride), and PE (polyethylene) film materials. This can improve the problems that the anti - poison film material is brittle and has poor cold resistance, and can also improve the peel strength between it and the skeleton material, solve quality problems such as creases and delamination that occur during product use, reduce the primary composite process, lower costs, and improve product quality.

[0009] The anti - poison co - extrusion film uses five - layer composite co - extrusion, including a base layer and a functional layer. The base layer is a PE layer, which has good support and retention effects on the functional layer. The functional layer includes a TPU layer and a PVDC layer. The TPU layer and the PVDC layer are sequentially compounded on both sides of the PE layer. When PVDC is used as a barrier material, its oxygen permeability and water vapor permeability are very low, effectively playing a barrier role.

[0010] The flame - retardant layer uses a flame - retardant film, and the flame - retardant film is obtained by mixing various flame - retardants and directly compounded on the skeleton material, meeting the high requirements of the composite material for flame - retardancy. At the same time, compared with the existing technology using a flame - retardant coating, the tear strength of the composite material is improved.

[0011] The skeleton layer uses an aramid skeleton material.

[0012] A manufacturing method of a protective composite material with high anti - toxicity and high flame - retardancy performance includes the following steps:

[0013] a. Preparation of the anti - poison layer;

[0014] Select TPU, PVDC, and PE materials as raw materials, and use a multi - layer co - extrusion compounding process to prepare an anti - poison co - extrusion film. Specifically, the TPU, PVDC, and PE raw materials are respectively added to their respective extruders, melted and plasticized in their respective extruders, then flow into a multi - layer co - extrusion compound die head and are distributed according to the interlayer structure, and then after extrusion compounding and cooling forming, an anti - poison co - extrusion film is obtained.

[0015] b, Preparation of the flame retardant layer;

[0016] Add 100 parts of TPU to a mixing blender, add a flame retardant, and mix preliminarily; then add a total of 100 parts of DMAC solvent in three portions, mix thoroughly, and coat on a centrifugal paper to form a film. The weight of the flame retardant layer is 45 - 70 g / m 2 ; Further, the weight of the flame retardant layer is selected to be 50 - 60 g / m 2 ; Even further, the weight of the flame retardant layer is selected to be 53 g / m 2 ;

[0017] c, Composite process;

[0018] Select an aramid skeleton material as the skeleton layer, and the weight of the skeleton layer is 200 - 260 g / m 2 , Further, the weight of the skeleton layer is selected to be 220 - 230 g / m 2 ; Even further, the weight of the skeleton layer is selected to be 228 g / m 2 ; Use a hot melt adhesive spraying and compounding machine to glue the flame retardant film and the gas - proof co - extruded film on both sides of the skeleton layer in sequence; specifically, install the aramid skeleton material, the flame retardant film, and the gas - proof co - extruded film on the bracket, align the line positions, then put the cloth from the pre - heating cylinder to the drying port, place the glue well, turn on the return glue motor, and the amount of glue applied is 8 - 10 g / m 2 , Pre - heat, tighten the belt, turn on the power supply, start the motor, run at a low speed, the composite temperature is 95 - 100 °C, and the weight of the composite protective composite material is 550 - 600 g / m 2 , Further, the weight of the protective composite material is 550 - 560 g / m 2 , Even further, the weight of the protective composite material is 550 g / m 2 .

[0019] A protective composite material with high gas - resistance and high flame - retardant performance is applied to a flexible shelter or tent in collective protection equipment.

[0020] Compared with the prior art, the present invention has the following beneficial effects: A protective composite material with high anti-toxic and high flame-retardant properties designed by the present invention uses a process of co-extruding materials such as TPU, PE, and PVDC together, replacing the most commonly used single-layer composite anti-toxic film in the current market and the process of further compounding a layer of materials such as TPU or PVC outside the anti-toxic film. The flame-retardant performance of this material can reach a damage length of ≤1 mm and a smoldering time of 0 s. The protection level is far greater than the performance indicators required by the highest level A in the "Protective Clothing - Flame Retardant Protection" standard GB8965.1-2009, which requires a damage length of ≤50 mm and a smoldering and afterflame time of ≤2 s. It meets the national standards, has excellent flame-retardant effects, and for the first time applies a composite material with high anti-toxic and higher flame-retardant properties to collective protection equipment. While retaining the original anti-toxic and flame-retardant protection properties, there will be no quality defects such as creases and delamination, greatly reducing the problems of creases and delamination during product use, improving product quality, extending product life, reducing usage costs, being safe and reliable, and suitable for wide promotion and use. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is a schematic structural diagram of the present invention.

[0022] Figure 2 It is a schematic structural diagram of the anti-toxic co-extruded film in the present invention.

[0023] In the figure: 1 - anti-toxic layer, 2 - flame-retardant layer, 3 - skeleton layer, 4 - TPU layer, 5 - PVDC layer, 6 - PE layer. DETAILED DESCRIPTION OF THE INVENTION

[0024] The following details the specific embodiments of the present invention.

[0025] Embodiment 1

[0026] A protective composite material with high anti-toxic and high flame-retardant properties, as Figure 1 shown: This composite material is prepared by a multi-layer composite process, including a skeleton layer 3 in the middle. On both sides of the skeleton layer 3, an anti-toxic layer 1 and a flame-retardant layer 2 are sequentially compounded. The anti-toxic layers 1 on both sides are completely the same, and the flame-retardant layers 2 on both sides are completely the same. The front and back sides of the protective composite material are symmetrically compounded;

[0027] As Figure 2 shown: The anti-toxic layer 1 uses an anti-toxic co-extruded film, and the anti-toxic co-extruded film is prepared by multi-layer co-extrusion of TPU (polyurethane), PVDC (polyvinylidene chloride), and PE (polyethylene) thin film materials, which can improve the problems of brittleness and poor cold resistance of the anti-toxic film material, can also improve the peel strength between it and the skeleton material, solve quality problems such as creases and delamination during product use, and can also reduce one composite process, reduce costs and improve product quality;

[0028] The anti-toxic co-extrusion film adopts five-layer composite co-extrusion, including a base layer and a functional layer. The base layer is a PE layer 6, which has a good support and retention effect on the functional layer; the functional layer includes a TPU layer 4 and a PVDC layer 5. The two sides of the PE layer 6 are compounded with the TPU layer 4 and the PVDC layer 5 in sequence. When PVDC (polyvinylidene chloride) is used as a barrier material, its oxygen permeability and water vapor permeability are very low, which effectively plays a barrier role;

[0029] The flame retardant layer 2 uses a flame retardant film, which is made by mixing a variety of flame retardants. The flame retardant film is directly compounded on the skeleton material to meet the high flame retardancy requirements of the composite material. At the same time, compared with the flame retardant coating used in the prior art, the tear strength of the composite material is improved;

[0030] The skeleton layer is made of aramid skeleton material.

[0031] A method for manufacturing a protective composite material with high anti-toxic and high flame retardant properties comprises the following steps:

[0032] a, preparation of anti-virus layer;

[0033] TPU, PVDC and PE materials are selected as raw materials, and a multi-layer co-extrusion composite process is adopted to prepare a poison-proof co-extrusion film. Specifically, TPU, PVDC and PE raw materials are added to their respective extruders, melted and plasticized in their respective extruders, flowed into a multi-layer co-extrusion composite die head and distributed according to the interlayer structure, and then extruded, composited and cooled to obtain the poison-proof co-extrusion film;

[0034] b, preparation of flame retardant layer;

[0035] Add 100 parts of TPU and flame retardant into a mixing mixer and mix them preliminarily; then add 100 parts of DMAC solvent in three times, mix them thoroughly, and apply them on centrifugal paper to form a film. The weight of the flame retardant layer is 45~70g / m 2 Preferably, the weight of the flame retardant layer is 50-60 g / m 2 More preferably, the weight of the flame retardant layer is 53g / m 2 ;

[0036] c, composite process;

[0037] Aramid skeleton material is selected as the skeleton layer, and the weight of the skeleton layer is 200~260g / m 2 Preferably, the weight of the skeleton layer is 220-230 g / m 2 More preferably, the weight of the skeleton layer is 228 g / m 2; Use a hot melt adhesive spraying laminating machine to glue the flame retardant film and the gas-proof co-extruded film on both sides of the skeleton layer in sequence; specifically, the aramid skeleton material, the flame retardant film, and the gas-proof co-extruded film are installed on the bracket, align the line positions, then put the cloth from the preheating cylinder to the drying port, place the glue well, turn on the return glue motor, and the glue application amount is 8g / m 2 , preheat, tighten the belt, turn on the power supply, start the motor, run at low speed, the lamination temperature is 100°C, and the weight of the laminated protective composite material is 550 - 600g / m 2 , preferably, the weight of the protective composite material is 550 - 560g / m 2 , more preferably, the weight of the protective composite material is 550g / m 2 , control the overall weight of the material to avoid the reduction of material portability caused by excessive weight. While taking into account high anti-toxicity and high flame retardancy, try to reduce the weight of raw materials as much as possible for the application of the composite material and improve portability.

[0038] A protective composite material with high anti-toxic and high flame retardant properties is applied to flexible shelters or tents in collective protection equipment.

[0039] Inspect according to the various indicators specified in the standard of GB8965.1 - 2009 "Protective Clothing - Flame Retardant Protection" to detect its flame retardant effect.

[0040] I. Flame Retardant Performance Detection

[0041] 1. Afterflame Time

[0042] Cut samples in the radial (longitudinal) and weft (transverse) directions respectively, and measure the time that the material continues to burn with a flame after removing (igniting) the fire source under the specified test conditions.

[0043] After testing, the afterflame times in the warp and weft directions are T ≤ 5.1 seconds and W ≤ 2 seconds respectively.

[0044] 2. Afterglow Time

[0045] Cut samples in the radial (longitudinal) and weft (transverse) directions respectively, and measure the time that the material continues to burn without a flame after the flaming combustion terminates or after removing (igniting) the fire source under the specified test conditions.

[0046] After testing, the afterglow times in both the warp and weft directions are 0 seconds.

[0047] 3. Damaged Length

[0048] Cut samples in the radial (longitudinal) and weft (transverse) directions respectively, and measure the maximum length of the damaged area of the material in the specified direction under the specified test conditions.

[0049] After testing, the damaged lengths in the warp and weft directions are T ≤ 1mm and W ≤ 1mm respectively.

[0050] II. Poison agent resistance penetration performance

[0051] Measured through tests, the penetration time of "liquid - gas" mustard gas resistance > 24h.

[0052] III. Tear strength

[0053] Samples are respectively cut in the radial (longitudinal) and weft (transverse) directions, and the tear strengths in the warp and weft directions are measured under specified test conditions.

[0054] Measured through tests, the tear strengths in the warp and weft directions are respectively T≥480N and W≥370N.

[0055] Example 2

[0056] A manufacturing method of a protective composite material with high anti - poison and high flame - retardant properties, including the following steps:

[0057] a. Preparation of the gas - proof layer;

[0058] Select TPU, PVDC, and PE materials as raw materials, and use a multi - layer co - extrusion compounding process to prepare a gas - proof co - extrusion film. Specifically, the TPU, PVDC, and PE raw materials are respectively added to their respective extruders. After being melted and plasticized in their respective extruders, they flow into a multi - layer co - extrusion die head and are distributed according to the interlayer structure. Then, after extrusion compounding and cooling and forming, a gas - proof co - extrusion film is obtained;

[0059] b. Preparation of the flame - retardant layer;

[0060] Add 100 parts of TPU to a mixing and stirring machine, and add a flame retardant for preliminary mixing; subsequently, add 100 parts of DMAC solvent in three times and mix thoroughly. Coat it on a centrifugal paper to form a film. The weight of the flame - retardant layer is 60g / m 2 ;

[0061] c. Compounding process;

[0062] Select an aramid skeleton material as the skeleton layer, and the weight of the skeleton layer is 225g / m 2 ; Use a hot - melt adhesive spraying compounding machine to glue the flame - retardant film and the gas - proof co - extrusion film on both sides of the skeleton layer in sequence. Specifically, the aramid skeleton material, the flame - retardant film, and the gas - proof co - extrusion film are installed on a bracket, aligned in position. Then, put the cloth from the pre - heating cylinder to the drying port, put on the glue, turn on the return glue motor, the amount of glue applied is 10g / m 2 , pre - heat, tighten the belt, turn on the power supply, start the motor, run at a low speed, the compounding temperature is 95°C, and the weight of the composite protective composite material is 555g / m 2 ..

[0063] The scope of protection claimed by the present invention is not limited to the above specific embodiments, and for those skilled in the art, the present invention can have various modifications and changes. Any modification, improvement, and equivalent replacement made within the concept and principle of the present invention should be included in the scope of protection of the present invention.

Claims

1. A protective composite material with high anti - toxicity and high flame - retardant properties, characterized in that: It includes a middle skeleton layer (3), with a flame-retardant layer (2) and a gas-proof layer (1) successively laminated on both sides of the skeleton layer (3). The gas-proof layers on both sides are exactly the same, and the flame-retardant layers on both sides are exactly the same. The anti-protection composite material is symmetrically laminated on both the front and back sides. The gas-proof layer (1) uses a gas-proof co-extruded film, which is prepared by multi-layer co-extrusion of TPU, PVDC, and PE. The gas-proof co-extruded film is prepared by five-layer composite co-extrusion, including a base layer and a functional layer. The base layer is a PE layer (6), and the functional layer includes a TPU layer (4) and a PVDC layer (5). The PVDC layer (5) and the TPU layer (4) are successively laminated on both sides of the PE layer. The flame-retardant layer (2) uses a flame-retardant film, which is made by mixing various flame retardants with TPU. The skeleton layer (3) uses an aramid skeleton material.

2. A manufacturing method of a protective composite material with high anti - toxicity and high flame - retardant performance as described in claim 1, characterized in that: It includes the following steps: a. Preparation of the gas-proof layer Select TPU, PVDC, and PE materials as raw materials, and use a multi-layer co-extrusion composite process to prepare a gas-proof co-extruded film. b. Preparation of the flame-retardant layer Add 100 parts of TPU into a mixing blender, and add a flame retardant for preliminary mixing; then add 100 parts of DMAC solvent in three portions in total, mix well, coat on a centrifugal paper to form a film, and the weight of the flame retardant layer (2) is 45-70 g / m 2 ; c. Composite process Select the aramid fiber skeleton material as the skeleton layer (3), and the weight of the skeleton layer (3) is 200-260 g / m 2 , and use a hot melt adhesive spraying and laminating machine to glue the flame retardant film and the gas-proof co-extruded film on both sides of the skeleton layer (3) in sequence. The weight of the composite protective composite material is 550-600 g / m 2 .

3. The manufacturing method of a protective composite material with high anti-toxic and high flame-retardant properties according to claim 2, characterized in that: In step a, the TPU, PVDC, and PE raw materials are respectively added to their respective extruders. After being melted and plasticized in their respective extruders, they flow into a multi-layer co-extrusion composite die head and are distributed according to the interlayer structure, and then through extrusion compounding and cooling forming, a gas-proof co-extruded film is obtained.

4. The manufacturing method of a protective composite material with high anti-toxic and high flame-retardant properties according to claim 2, characterized in that: In step c, the aramid fiber skeleton material, the flame retardant film, and the gas-proof co-extruded film are installed on the bracket, the line positions are aligned, then the cloth is placed from the preheating cylinder to the drying port, the glue is placed, the glue return motor is turned on, and the glue application amount is 8-10 g / m 2 , preheat, tighten the belt, turn on the power supply, start the motor, and run at a low speed.

5. The manufacturing method of a protective composite material with high anti-toxic and high flame-retardant properties according to claim 4, characterized in that: The composite temperature is 95 - 100 °C.

6. Application of the anti-protection composite material with high anti-toxic and high flame-retardant performance described in claim 1 in collective protection equipment.

7. Application of the protective composite material with high anti - toxicity and high flame - retardancy performance according to claim 6 in collective protection equipment, characterized in that: The collective protection equipment is a flexible shelter or a tent.

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