Fire-resistant multilayer laminated film, thermal insulation felt and manufacturing method therefor

Abstract

A fire-resistant multilayer laminated film (1), a thermal insulation felt (3) and a manufacturing method therefor, relating to the technical field of flame-retardant thermal insulation materials. The fire-resistant multilayer laminated film (1) comprises, successively combined, a first high polymer film layer (111), a first grid cloth layer (121), an inorganic particle layer (13), a second grid cloth layer (122) and a second high polymer film layer (112). The first high polymer film layer (111) and the first grid cloth layer (121) are combined together by means of an adhesive, and so are the second high polymer film layer (112) and the second grid cloth layer (122). The inorganic particle layer (13) is combined between the first grid cloth layer (121) and the second grid cloth layer (122) by means of an adhesive. During the manufacturing process for the fire-resistant multilayer laminated film (1) comprising the inorganic particle layer (13), some inorganic particles fill or are embedded into grids of grid cloth, while another some inorganic particles adhere to surfaces of fibers constituting the grid cloth, so that the inorganic particles sufficiently envelop the fibers constituting the grid cloth, allowing the static structure of the fire-resistant multilayer laminated film (1) to have good compactness and stability and providing reliable fire protection. The inorganic particles of the inorganic particle layer (13) are an inorganic fire-resistant material, and have a particle size of 100-3000 meshes and an length-to-diameter ratio of 1-10. The fire-resistant multilayer laminated film (1) has excellent burn-through resistance and excellent fire-resistant performance.

Description

Fireproof multi-layer composite film, thermal insulation felt and preparation method thereof TECHNICAL FIELD

[0001] The present application relates to the technical field of fire-retardant thermal insulation materials, in particular to a fireproof multi-layer composite film, a thermal insulation felt and a preparation method thereof. BACKGROUND

[0002] According to the statistics of the Cabin Research Safety Technical Group (CRSTG) led by the FAA and widely participated by the world civil aviation field, 40% of passengers survive in the aircraft crash accident, but die in the subsequent fire. Whether the cabin decoration in the aircraft cabin environment is fireproof and flame-retardant seriously affects the safety of the passengers on board. Improving the burn-through resistance of the fuselage, i.e. delaying the time for the flame to enter the cabin, can provide time guarantee for the emergency evacuation of passengers.

[0003] The existing sound and heat insulation materials used in commercial aircraft are usually installed on the back side of the interior panel of the aircraft, mainly formed by wrapping high-performance fire-resistant composite film around flame-retardant inorganic materials, so as to realize the protection of passengers, cargo and equipment from the influence of environmental conditions and engine noise, and to prevent the burn-through of the thermal and sound insulation layer and stop the spread of fire.

[0004] For example, Chinese patent CN102405172B and French patent FR3126106A3 both disclose a sandwich structure composite laminate structure composed of a polymer moisture-proof layer with UL94 flame rating V-0, an inorganic flake layer with a certain aspect ratio, and a thermoplastic film layer with UL94 flame rating V-0. The difference between the two patents lies in the disclosure of different parameter ranges. The two polymer films on both sides play the role of moisture-proof and reducing surface flame burning, and the middle fireproof layer is composed of inorganic flake material with a certain particle aspect ratio. However, too high aspect ratio will make the inorganic material flowability poor, thereby reducing the uniformity of coating, and forming more pores when stacking, thereby reducing the tightness of the fireproof layer. In addition, particle shape, particle size distribution, etc. also have an impact on flowability and stacking characteristics. The particle accumulation is not uniform and not tight enough, which may lead to a decrease in fireproof stability.

[0005] Chinese patent CN105593016B discloses a flame-retardant and fire-retardant laminated film, which comprises a first layer of film, a second layer of silica cloth, a third layer of film and an adhesive compound containing at least one inorganic filler. The flame-retardant and fire-retardant laminated film uses a dense high-silicon fiber cloth as a fireproof layer, which has higher flexibility than the inorganic particle accumulation layer, but has higher manufacturing cost and higher requirements for weaving, and lower fireproof stability.

[0006] Therefore, there is an urgent need to provide a new type of fireproof multi-layer composite film, which can improve the uniformity of structure quality and the stability of product performance while meeting the anti-burn-through performance, and reduce the manufacturing cost.

[0007] SUMMARY

[0008] The present application aims at the above-mentioned problems, and provides a fireproof multi-layer composite film, a heat insulation felt and a preparation method thereof.

[0009] In order to achieve the above-mentioned purposes, the present application adopts the technical scheme of:

[0010] The fireproof multi-layer composite film comprises a first high polymer film layer, a first mesh cloth layer, an inorganic particle layer, a second mesh cloth layer and a second high polymer film layer which are sequentially compounded.

[0011] Preferably, the inorganic particle layer comprises a first inorganic particle layer and a second inorganic particle layer; the first high polymer film layer, the first mesh cloth layer and the first inorganic particle layer are sequentially compounded to form a first combined layer; the second high polymer film layer, the second mesh cloth layer and the second inorganic particle layer are sequentially compounded to form a second combined layer; the first inorganic particle layer and the second inorganic particle layer are bonded together by an adhesive, and the first combined layer and the second combined layer are bonded together to form the fireproof multi-layer composite film.

[0012] Preferably, the fireproof multi-layer composite film has a grammage of 75-135 g / m 2 and a thickness of 0.2-0.46 mm.

[0013] Preferably, the manufacturing material of the first high polymer film layer or the second high polymer film layer is selected from polyether ether ketone, polyether ketone ketone, polyether ketone, polyester, polyimide, polyvinyl fluoride, polyamide, polytetrafluoroethylene, polyaryl sulfone, polyester amide, polyester imide, polyether sulfone, polyphenylene sulfide, ethylene trifluoro chloroethylene.

[0014] Preferably, the first mesh cloth layer or the second mesh cloth layer has a thickness of 50-120 μm, a unit area mass of 5-30 g / m 2 , a mesh number of 6-18, a mesh shape of rectangle, circle, ellipse or polygon, a tensile strength of 85-273 N / 50 mm, and the meshes of the first mesh cloth layer and the second mesh cloth layer are staggered and arranged without complete overlap.

[0015] Preferably, the first mesh cloth layer or the second mesh cloth layer is a flat mesh cloth formed by weaving a plurality of fiber lines, and the fiber line material is organic fiber or inorganic fiber.

[0016] Preferably, the raw inorganic particles of the inorganic particle layer are inorganic refractory materials, the particle size is 100-3000 mesh, the aspect ratio is 1-10, and the glass melting speed constant τ of the inorganic particles is ≥4.

[0017] The second aspect of the present application provides a fireproof insulation felt, comprising at least two of the fireproof multilayer composite films, and a core material layer arranged between the two fireproof multilayer composite films, and the fireproof multilayer composite film and the core material layer are bonded together by an adhesive.

[0018] Preferably, the material of the core material layer is selected from foams, organic or inorganic fibers, and the thickness of the core material layer is 10-75 mm.

[0019] Preferably, the fireproof multilayer composite film comprises two, three, five or seven fireproof multilayer composite films, and the core material layer is arranged between the two fireproof multilayer composite films.

[0020] The beneficial effects of the present application are:

[0021] The fireproof multilayer composite film of the present application comprises an inorganic particle layer, and in the preparation process, part of the inorganic particles are filled or embedded in the meshes of the mesh cloth, and the other part of the inorganic particles are attached to the surface of the constituent fibers of the mesh cloth. The inorganic particles fully wrap the constituent fibers of the mesh cloth, so that the static structure of the composite film has good compactness and stability. Even if the composite film is damaged or destroyed (such as the melting of mesh cloth fibers at high temperature, mechanical damage, etc.), the inorganic particle layer can maintain the structural integrity (structural uniformity) of the composite film, avoid the formation of leakage points at the fiber defect, and provide reliable fire protection.

[0022] The mesh layer of the fireproof multilayer composite film of the present application can be prepared using mesh cloth, which has lower material requirements and effectively reduces the production cost on the basis of meeting the burn-through resistance performance, and has more market competitiveness. The prepared fireproof multilayer composite film meets the burn-through resistance performance, improves the structural uniformity, has good overall strength and stability, and reduces the production cost.

[0023] The third aspect of the present application provides a fireproof multilayer composite film, comprising a first high polymer film layer, a first mesh cloth layer, an inorganic particle layer, a second mesh cloth layer and a second high polymer film layer which are sequentially compounded; the first high polymer film layer and the first mesh cloth layer and the second high polymer film layer and the second mesh cloth layer are compounded together by an adhesive; and the inorganic particle layer is compounded between the first mesh cloth layer and the second mesh cloth layer by an adhesive.

[0024] Preferably, the raw inorganic particles of the inorganic particle layer are inorganic refractory materials, the particle size is 100-3000 mesh, the aspect ratio is 1-10, and the glass melting speed constant τ of the inorganic particles is ≥4.

[0025] Preferably, the manufacturing material of the first high polymer film layer or the second high polymer film layer is selected from polyether ether ketone, polyether ketone ketone, polyether ketone, polyester, polyimide, polyvinyl fluoride, polyamide, polytetrafluoroethylene, polyaryl sulfone, polyester amide, polyester imide, polyether sulfone, polyphenylene sulfide, ethylene trifluorochloroethylene;

[0026] The fireproof multi-layer composite film has a grammage of 75-135 g / m 2 and a thickness of 0.2-0.46 mm.

[0027] Preferably, the first or second scrim layer is a flat-laid scrim formed by weaving a plurality of fiber threads, and the fiber thread material is selected from organic fibers and inorganic fibers.

[0028] The organic fibers include PAI fibers, PBI fibers, PI fibers, PEEK fibers, PPS fibers, PTFE fibers, PSU fibers, PPSU fibers, and PEI fibers.

[0029] The inorganic fibers include glass fibers, high-silica fibers, quartz fibers, basalt fibers, and alkaline earth silicate fibers.

[0030] The first or second scrim layer has a thickness of 50-120 μm and a unit area mass of 5-30 g / m 2 , a mesh count of 6-18 meshes, and a tensile strength of 85-273 N / 50 mm.

[0031] During the compounding, the first and second scrim layers are arranged in a staggered manner and do not completely overlap.

[0032] Preferably, the glass melting speed constant τ of the inorganic particles is greater than or equal to 4.

[0033] The raw material sources of the inorganic particles include mica, vermiculite, talc, montmorillonite, feldspar, glass fibers, ceramic fibers, titanium dioxide, and fumed silica.

[0034] Preferably, the mass percentage of the adhesive in the fireproof multi-layer composite film is 15-36%.

[0035] The adhesive includes a binder selected from one or more of polyurethane, acrylic, vinyl acetate, aluminum silicate, and methyl organosilicon.

[0036] Preferably, the adhesive further includes one or more auxiliary materials selected from water-proofing agents, flame retardants, and defoaming agents.

[0037] The water-proofing agent is selected from one or more of silicon-based water-proofing agents, fluorocarbon-based water-proofing agents, and acrylic water-proofing agents.

[0038] The fourth aspect of the present application provides a preparation method of the fireproof multilayer composite film, comprising the following steps:

[0039] The first polymer film layer and the first grid cloth layer are combined together by using the adhesive;

[0040] The second polymer film layer and the second grid cloth layer are combined together by using the adhesive;

[0041] The inorganic particle mixture is coated on the first grid cloth layer and / or the second grid cloth layer, and is dried and shaped to obtain the inorganic particle layer;

[0042] The fireproof multilayer composite film is prepared by combining the layers through the adhesive, and the inorganic particle layer is sandwiched between the first grid cloth layer and the second grid cloth layer.

[0043] The preparation method of the fireproof multilayer composite film, the inorganic particle mixture comprises 35-65 wt% of inorganic particles, 1-10 wt% of a binder, 0-15 wt% of a waterproof agent, 0-10 wt% of a flame retardant, 0-1 wt% of an antifoaming agent, and the balance is water.

[0044] The fifth aspect of the present application provides a fireproof thermal insulation felt, comprising at least two fireproof multilayer composite films according to any one of the above, and a core material layer is arranged between the two fireproof multilayer composite films, and the fireproof multilayer composite films and the core material layer are combined together by using the adhesive.

[0045] Preferably, the material of the core material layer is selected from foams, organic or inorganic fibers;

[0046] Preferably, the preparation material of the core material layer is selected from polyimide foams, glass fibers, polyacrylonitrile fibers, carbon fibers and pre-oxidized filaments;

[0047] Preferably, the thickness of the core material layer is 10-75 mm.

[0048] The sixth aspect of the present application provides a preparation method of the fireproof thermal insulation felt, comprising the following steps: the fireproof multilayer composite films are arranged oppositely, the core material layer is wrapped, and the fireproof thermal insulation felt is prepared by using the adhesive and hot pressing.

[0049] The present application has the following beneficial effects:

[0050] The fireproof multilayer composite film of the present application comprises an inorganic particle layer, in the preparation process, part of the inorganic particles are filled or embedded in the meshes of the mesh cloth, and the other part of the inorganic particles are attached to the surface of the constituent fibers of the mesh cloth, the inorganic particles fully wrap the constituent fibers of the mesh cloth, so that the static structure of the composite film has good compactness and stability. Even if the composite film is damaged or destroyed (such as the mesh cloth fibers melting at high temperature, mechanical damage, etc.), the inorganic particle layer can maintain the structural integrity (structural uniformity) of the composite film, avoid the formation of leakage points at the fiber defect, and provide reliable fire protection.

[0051] The mesh layer of the fireproof multilayer composite film of the present application is prepared using mesh cloth, which has lower material requirements, effectively reduces the production cost on the basis of meeting the burn-through resistance performance, and has more market competitiveness. The prepared fireproof multilayer composite film meets the burn-through resistance performance, improves the structural uniformity, has good overall strength and stability, and reduces the production cost. BRIEF DESCRIPTION OF DRAWINGS

[0052] Figure 1 is a structural schematic diagram of the fireproof multilayer composite film of the present application;

[0053] Figure 2 is a structural schematic diagram of the fireproof insulation felt of the present application;

[0054] In the drawings,

[0055] 1-fireproof multilayer composite film, 111-first polymer film layer, 121-first mesh cloth layer, 13-inorganic particle layer, 131-first inorganic particle layer, 132-second inorganic particle layer, 122-second mesh cloth layer, 112-second polymer film layer;

[0056] 3-fireproof insulation felt, 2-core material layer. DETAILED DESCRIPTION

[0057] The present application will be further described below in conjunction with examples, but it is not limited by the present application.

[0058] In the following examples, the experimental methods are conventional methods unless otherwise specified.

[0059] Example 1, the fireproof multilayer composite film of the present application

[0060] First, the fireproof multilayer composite film of the present application

[0061] The fireproof multi-layer composite film 1 of the present application as shown in Fig. 1 comprises a first high polymer film layer 111, a first mesh cloth layer 121, an inorganic particle layer 13, a second mesh cloth layer 122 and a second high polymer film layer 112 which are sequentially compounded. Optionally, an adhesive layer is arranged outside the first high polymer film layer 111 or the second high polymer film layer 112. The first high polymer film layer 111 and the first mesh cloth layer 121 and the second high polymer film layer 112 and the second mesh cloth layer 122 are bonded together by an adhesive. The inorganic particle layer 13 is compounded between the first mesh cloth layer 121 and the second mesh cloth layer 122 by an adhesive.

[0062] In some embodiments, the inorganic particle layer 13 comprises a first inorganic particle layer 131 and a second inorganic particle layer 132. The first high polymer film layer 111, the first mesh cloth layer 121 and the first inorganic particle layer 131 are sequentially compounded to form a first combined layer. The second high polymer film layer 112, the second mesh cloth layer 122 and the second inorganic particle layer 132 are sequentially compounded to form a second combined layer. The first inorganic particle layer 131 and the second inorganic particle layer 132 are bonded together by an adhesive, so that the first combined layer and the second combined layer are bonded together to form the fireproof multi-layer composite film 1 of the present application.

[0063] The fireproof multi-layer composite film of the present application has a grammage of 75-135 g / m 2 and a thickness of 0.2-0.46 mm.

[0064] (1) High polymer film layer

[0065] The thickness of the first high polymer film layer or the second high polymer film layer is 6-10 μm, preferably 6 μm. The manufacturing material of the first high polymer film layer or the second high polymer film layer is selected from polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether ketone (PEK), polyester, polyimide, polyvinyl fluoride, polyamide, polytetrafluoroethylene, polyaryl sulfone, polyester amide, polyester imide, polyether sulfone, polyphenylene sulfide, ethylene trifluorochloroethylene, etc., and the surface combustion characteristics thereof meet the ASTM E84 Class A standard issued by the American ASTM International Standardization Organization.

[0066] (2) Mesh cloth layer

[0067] The first mesh cloth layer / second mesh cloth layer is a flat mesh cloth formed by weaving a plurality of fiber lines. The material of the fiber lines can be organic fiber or inorganic fiber.

[0068] The organic fiber includes PAI fiber, PBI fiber, PI fiber, PEEK fiber, PPS fiber, PTFE fiber, PSU fiber, PPSU fiber and PEI fiber.

[0069] The inorganic fiber includes glass fiber, high silica fiber, quartz fiber, basalt fiber, and alkaline earth silicate fiber.

[0070] The specification / property parameters of the first or second scrim layer are as follows:

[0071] The thickness is 50-120 μm, preferably 100 μm;

[0072] The mass per unit area is 5-30 g / m 2 , preferably 15 g / m 2 ;

[0073] The mesh count of the scrim is 6-18, and the mesh can be rectangular, circular, oval, or polygonal, preferably rectangular, and the mesh size is (1-3 x 1-3) mm, further preferably 3 x 3 mm;

[0074] The tensile strength is 85-273 N / 50 mm, preferably 150 N / 50 mm.

[0075] The scrim layer can increase the uniformity of the inorganic particle layer and also serve as a reinforcing material to provide mechanical support.

[0076] (3) Inorganic particle layer

[0077] The inorganic particle layer is a high-temperature-resistant inorganic particle. Microscopically, the inorganic particle fully wraps the constituent fibers of the scrim to improve the structural density and fire resistance of the composite film.

[0078] The property parameters of the inorganic particle are as follows:

[0079] The particle size of the inorganic particle should be between 100 and 3000 mesh. If the mesh count is too high, the particle is too small and cannot be overlapped on the surface of the fiber of the scrim layer. If the mesh count is too low, the particle is too large and cannot be filled into the mesh of the scrim.

[0080] The aspect ratio of the inorganic particle should be between 1 and 10. As the aspect ratio gradually increases, the shape of the particle gradually becomes longer. If a particle with a large aspect ratio is used to prepare a composite film, the inorganic particles cannot be effectively overlapped, resulting in pores in the inorganic particle layer, and the fireproof film prepared is prone to form leakage points when exposed to fire.

[0081] The glass melting rate constant τ of the inorganic particle layer is ≥4. The glass melting rate constant τ is a characteristic value indicating the relative difficulty of melting of the inorganic particle in the composite film. The smaller the τ value, the lower the melting temperature. The τ value can be calculated by the mass percentage of the oxides in the inorganic particle layer, as follows:

[0082] In the formula, SiO2, Al2O3, Na2O, K2O, B2O3, PbO, etc. represent the mass percentage (wt%) of the oxide in the glass.

[0083] SiO2 can provide the thermal stability, heat resistance, chemical stability, mechanical strength of the glass, but when the content is high, a higher melting temperature is required, and crystallization can occur. Al2O3 can reduce the tendency of glass crystallization, improve the chemical stability, thermal stability and mechanical strength of the glass.

[0084] The raw material source of the inorganic particles is: inorganic refractory material, which can be a mineral material, for example, inorganic mineral material such as mica, vermiculite, talc, montmorillonite, feldspar, etc. whose main components are SiO2 and Al2O3, or a high-temperature-resistant synthetic inorganic material, such as high-temperature-resistant micro glass fiber, etc.

[0085] In the formula, the main chemical components of common vermiculite raw materials are as follows: 37-43% SiO2, 9-17% Al2O3, 5-24% Fe2O3, 11-23% MgO, 11.8% K2O, 0.5-9% H2O by mass percentage.

[0086] The main chemical components of the glass fiber can be as follows: 45.3% SiO2, 51.3% Al2O3, 3.4% ZrO2 by mass percentage.

[0087] The main chemical components of white mica can be as follows: 45.2% SiO2, 38.5% Al2O3, 11.8% K2O, 4.5% H2O by mass percentage.

[0088] (4) Adhesive

[0089] The adhesive used in the multilayer composite film of the present application comprises a binder selected from one or more of polyurethane, acrylic, vinyl acetate, aluminum silicate, and methyl silicone.

[0090] The adhesive can also contain one or more auxiliary materials such as waterproofing agent, flame retardant, defoaming agent, etc. Among them, the flame retardant and defoaming agent mainly play the effect of fireproofing and flame retardation.

[0091] The waterproofing agent is selected from one or more of silicon-based waterproofing agent, fluorocarbon-based waterproofing agent, and acrylic-based waterproofing agent.

[0092] The mass percentage of the adhesive in the entire multilayer composite film product of the present application is 15-36%.

[0093] Second, the fireproof insulation felt of the present application

[0094] Using the fireproof multilayer composite film of the present application, a fireproof insulation felt can also be prepared:

[0095] The fireproof insulation felt 3 of the present application as shown in Figure 2 comprises at least two fireproof multilayer composite films 1, and a core material layer 2 is arranged between each two of the fireproof multilayer composite films 1, and the fireproof multilayer composite films 1 and the core material layer 2 are bonded together by adhesive.

[0096] The material of the core material layer 2 includes foam, organic or inorganic fibers, such as polyimide foam, glass fiber, polyacrylonitrile fiber, carbon fiber, pre-oxidized fiber, etc. The thickness of the core material layer 2 is 10-75 mm.

[0097] The number of the fireproof multilayer composite films 1 can be multiple (for example, three, five), and a core material layer 2 is arranged between each two of the fireproof multilayer composite films 1, forming a sandwich structure of the fireproof multilayer composite films 1 sandwiching the core material layer 2.

[0098] The preparation method of the fireproof insulation felt of the present application is as follows: coating adhesive on the first high polymer film layer 111 and / or the second high polymer film layer 112 of the fireproof multilayer composite film 1, arranging two fireproof multilayer composite films 1 opposite to each other, covering the core material layer 2, and bonding and hot-pressing to obtain the fireproof insulation felt 3, which is suitable for the insulation felt of the aircraft fuselage, and the two fireproof multilayer composite film 1 products are not easy to peel off and delaminate after hot-pressing, and have good heat sealing property.

[0099] Example 2, preparation method of the fireproof multilayer composite film of the present application

[0100] I. Preparation of the fireproof multilayer composite film of Example 1

[0101] The first preparation method of the fireproof multilayer composite film comprises the following steps:

[0102] The first high polymer film layer and the first grid cloth layer are bonded together by adhesive;

[0103] The second high polymer film layer and the second grid cloth layer are bonded together by adhesive;

[0104] An inorganic particle mixed solution is coated on the first grid cloth layer and / or the second grid cloth layer, and is dried and shaped to obtain an inorganic particle layer;

[0105] The layers are bonded by adhesive, and the inorganic particle layer is sandwiched between the first grid cloth layer and the second grid cloth layer to obtain the fireproof multilayer composite film.

[0106] Preferably, the fireproof multilayer composite film of the present application can also be prepared by the second preparation method, and the steps are as follows:

[0107] Step 1, the first high polymer film layer and the first grid cloth layer are bonded together by adhesive; the second high polymer film layer and the second grid cloth layer are bonded together by the same method.

[0108] Step 2, coating the inorganic particle mixture on the first mesh cloth layer, high temperature drying to get the first inorganic particle layer, the first polymer film layer, the first mesh cloth layer and the first inorganic particle layer constitute the first combined layer. Coating the inorganic particle mixture on the second mesh cloth layer, high temperature drying to get the second inorganic particle layer, the second polymer film layer, the second mesh cloth layer and the second inorganic particle layer constitute the second combined layer.

[0109] The inorganic particle mixture comprises 35-65wt% inorganic particles, 1-10wt% binder, 0-15wt% waterproof agent, 0-10wt% flame retardant, 0-1wt% defoaming agent, and the balance is water.

[0110] Step 3, coating the adhesive on the inorganic particle layer of the first combined layer and the second combined layer, and hot pressing the first combined layer and the second combined layer to obtain the fireproof multilayer composite film.

[0111] Preferably, the meshes of the first mesh cloth layer and the second mesh cloth layer are staggered. The mesh staggered arrangement means that the fiber lines of the mesh cloth layers in the same direction do not completely overlap. If the fiber lines completely overlap, one fiber line covers another fiber line, so that the inorganic particles cannot fully wrap the fibers. Once the fibers are heated and melted, defects are more likely to occur at the overlapping part of the fiber lines, increasing the risk of leakage and reducing the anti-burn-through performance of the product.

[0112] In the fireproof multilayer composite film, part of the inorganic particles are uniformly filled or embedded in the mesh of the mesh cloth, and another part of the inorganic particles are attached to the surface of the constituent fibers of the mesh cloth. The mesh size of the mesh cloth should not be too large or too small. When the mesh size is too large, the inorganic particles are more likely to gather in the mesh edges, intersection points or larger spaces inside the mesh, forming particle clusters or agglomerates. Uneven distribution of inorganic particles leads to thin inorganic particle thickness, which is prone to form leakage under high temperature, resulting in substandard flame burn-through radiation temperature. When the mesh size is too small, it will increase unnecessary weight and processing difficulty of staggered arrangement, and also directly affect the coating effect of inorganic particles, making it difficult for inorganic particles to fully wrap the fibers. Since the temperature resistance of part of the mesh fibers is not as good as that of inorganic particles (except high-silicon oxygen), under high temperature, the mesh melts to form more pores, resulting in reduced flame burn-through resistance.

[0113] In the preparation process of the fireproof multilayer composite film, the inorganic particles fully wrap the constituent fibers of the mesh cloth, so that the static structure of the composite film has good compactness and stability. Even if the composite film is damaged or destroyed (such as mesh cloth fibers melting under high temperature, mechanical damage, etc.), the inorganic particle layer can maintain the structural integrity (uniformity) of the composite film, avoid the formation of leakage at the fiber defect, and provide reliable fire protection.

[0114] The grid layer of the fireproof multi-layer composite film is prepared by using a grid cloth, and the material requirement is low. On the basis of meeting the burn-through resistance performance, the production cost is effectively reduced, and the market competitiveness is higher. The first polymer film layer, the first grid cloth layer, the second grid cloth layer, the second polymer film layer, the inorganic particle material and the adhesive raw material used in the composite film can be directly purchased.

[0115] The composite film products in Table 1-2 are prepared according to the second preparation method.

[0116] Table 1

[0117] Table 2

[0118] Note: The grammage of the inorganic particle layer in Table 2 refers to the grammage of the inorganic particle layer composed of the first inorganic particle layer and the second inorganic particle layer in the unit area of the fireproof multi-layer composite film product.

[0119] The inorganic particles used in Examples 1-9, Examples 11-15 and Comparative Examples 1-2 have the following composition: 41.73% SiO2, 12.54% Al2O3, 10.75% K2O, 0.21% Na2O, 0.45% CaO, 0.12% TFe2O3, 27.7% MgO, 0.45% P2O5, and are derived from fluorophlogopite.

[0120] The inorganic particles used in Example 10 have the following composition: 42.44% SiO2, 6.40% K2O, 4.21% Na2O, 45.95% BaO / C, 1.00% BaO / N, and are derived from silicate glass.

[0121] The inorganic particles used in Comparative Example 3 have the following composition: 41.19% SiO2, 13.81% Al2O3, 14.31% K2O, 11.80% Na2O, 0.32% CaO, 9.89% Fe2O3, 9.13% H2O, and are derived from feldspar.

[0122] The inorganic particles used in Comparative Example 4 have the following composition: 38.62% SiO2, 14.78% Al2O3, 9.41% Fe2O3, 22.16% MgO, 6.29% K2O, 2.02% Na2O, 1.45% CaO, 5.27% H2O, and are derived from vermiculite.

[0123] In the products of the embodiments and comparative examples, the polymer types of the first polymer film layer and the second polymer film layer of each product are the same, that is, the raw materials of the polymer film layers of the products are the same, and the mesh fabrics used in the first mesh fabric layer and the second mesh fabric layer are also the same. However, it should be understood that the above embodiments and comparative examples are not intended to limit the present invention. In some embodiments, the first polymer film and the second polymer film have different polymer types; similarly, the mesh fabrics of the first mesh fabric layer and the second mesh fabric layer may also have different specifications.

[0124] II. Fireproof membrane performance testing

[0125] The test methods or reference standards for the performance indicators of fire-resistant multilayer composite films are as follows:

[0126] Burn-through resistance test: The test shall be conducted in accordance with Part VII of Appendix F of the Airworthiness Standards for Transport Category Aircraft (CCAR 25) formulated by the Civil Aviation Administration of China (CAAC). The requirements are: neither of the two specimens shall be burned through by fire or flame within 4 minutes; or, the heat flux of either specimen at a point 30.5 cm (12 inches) from the test fixture surface on the side insulated from the cold side shall not exceed 2.27 W / cm². 2 (2.0 British thermal units / foot) 2 Second).

[0127] Test method for heat sealability (peel strength): ISO 11339.

[0128] Test method for tear resistance: ISO 13937-2.

[0129] Water resistance test method: In one test, a sample of fire-resistant multilayer composite membrane was weighed and then completely immersed in water at 23°C for 72 hours. After this period, the sample was weighed again, and the water absorption rate was calculated.

[0130] Test method for burst strength: Federal Standard Test Method FED-STD-191METHOD 5122.

[0131] The test results are shown in Table 3:

[0132] Table 3

[0133] As can be seen from Tables 1-3, the mesh size of the mesh cloth of Comparative Example 1 is too large, 5 mm*5 mm, leading to uneven distribution of inorganic particles, and inorganic particles at thin parts are prone to form leakage points under high temperature, so that the anti-penetration performance of the fireproof multi-layer composite film product does not meet the standard. Specifically, the mesh edges are protruding points on the mesh cloth structure, and particles are more likely to deposit and aggregate at these positions during solution flow or drying; in addition, due to the large mesh size, particles have more space to move during coating, so they can also form larger agglomerates inside the mesh, especially in the larger space at the center of the mesh or near the mesh edges, which will lead to a decrease in the anti-penetration performance of the product.

[0134] The mesh size of the mesh cloth of Comparative Example 2 is too small, leading to a large weight of the fireproof multi-layer composite film product, which does not meet the requirement of light weight and is not suitable for application in the field of light-weight fireproof film required by airplanes, trains and the like. Comparative Example 3 has a glass melting speed constant τ < 4 of the inorganic particle layer, so that the anti-penetration performance of the fireproof multi-layer composite film product does not meet the standard.

[0135] Comparative Example 4 is a sample prepared according to Example 2 of Chinese Patent CN102405172B. The structure of the fireproof film of Comparative Example 4 is different from that of the fireproof film of the present application, even though the temperature resistance of the inorganic particles in Comparative Example 4 is better (τ = 6.426), but its anti-penetration performance is still lower than that of Example 2, and the maximum heat flow reaches 2.21 W / cm 2 , close to failure (2.27 W / cm 2 ); in addition, the strength of Comparative Example 4 is also much lower than that of Example 2.

[0136] The fireproof film products of Examples 1-15 have excellent anti-penetration performance, and also have excellent tear resistance, burst strength and light weight.

Claims

1. A fire-resistant multilayer composite membrane, characterized in that, The assembly comprises a first polymer film layer, a first mesh fabric layer, an inorganic particle layer, a second mesh fabric layer, and a second polymer film layer, which are sequentially laminated together. The first polymer film layer and the first mesh fabric layer, as well as the second polymer film layer and the second mesh fabric layer, are bonded together by an adhesive. The inorganic particle layer is laminated between the first mesh fabric layer and the second mesh fabric layer by an adhesive.

2. The fire-resistant multilayer composite membrane according to claim 1, characterized in that: The inorganic particle layer includes a first inorganic particle layer and a second inorganic particle layer; the first polymer film layer, the first mesh fabric layer, and the first inorganic particle layer are sequentially composited to form a first combined layer; the second polymer film layer, the second mesh fabric layer, and the second inorganic particle layer are sequentially composited to form a second combined layer; the first inorganic particle layer and the second inorganic particle layer are bonded together with an adhesive, and the first combined layer and the second combined layer are bonded together to form a fireproof multilayer composite film.

3. The fire-resistant multilayer composite membrane according to claim 1 or 2, characterized in that: The fire-resistant multilayer composite membrane has a basis weight of 75-135 g / m³. 2 The thickness is 0.2 to 0.46 mm.

4. The fire-resistant multilayer composite film according to claim 1 or 2, characterized in that: The materials used to manufacture the first or second polymer film layer are selected from polyetheretherketone, polyetherketoneketone, polyetherketone, polyester, polyimide, polyfluorinated vinyl, polyamide, polytetrafluoroethylene, polyarylsulfone, polyesteramide, polyesterimide, polyethersulfone, polyphenylene sulfide, and ethylene trifluorochloroethylene.

5. The fire-retardant multilayer composite film according to claim 1 or 2, characterized in that: The thickness of the first or second mesh fabric layer is 50–120 μm; the mass per unit area is 5–30 g / m². 2 The mesh size is 6–18 mesh; the mesh can be rectangular, circular, elliptical, or polygonal; the tensile strength is 85–273 N / 50 mm. The first and second mesh layers are arranged with staggered grids that do not completely overlap.

6. The fire-retardant multilayer composite membrane according to claim 1 or 2, characterized in that: The first mesh layer or the second mesh layer is a flat mesh fabric formed by weaving multiple strands of fiber yarn, and the fiber yarn material is organic fiber or inorganic fiber.

7. The fire-retardant multilayer composite membrane according to claim 1, characterized in that: The inorganic particles used as raw material in the inorganic particle layer are inorganic refractory materials with a particle size of 100-3000 mesh, an aspect ratio of 1-10, and a glass melting rate constant τ ≥ 4.

8. A fire-resistant multilayer composite membrane, characterized in that, The assembly comprises a first polymer film layer, a first mesh fabric layer, an inorganic particle layer, a second mesh fabric layer, and a second polymer film layer, which are sequentially laminated together. The first polymer film layer and the first mesh fabric layer, as well as the second polymer film layer and the second mesh fabric layer, are bonded together by an adhesive. The inorganic particle layer is bonded between the first mesh fabric layer and the second mesh fabric layer by an adhesive. The inorganic particles in the inorganic particle layer are inorganic refractory materials, and the particle size of the inorganic particles is 100-3000 mesh, with an aspect ratio of 1-10.

9. The fire-resistant multilayer composite membrane according to claim 8, characterized in that, The material used to manufacture the first polymer film layer or the second polymer film layer is selected from polyetheretherketone, polyetherketoneketone, polyetherketone, polyester, polyimide, polyvinyl fluoride, polyamide, polytetrafluoroethylene, polyarylsulfone, polyesteramide, polyesterimide, polyethersulfone, polyphenylene sulfide, and ethylene trifluorochloroethylene; The fire-resistant multilayer composite membrane has a basis weight of 75-135 g / m³. 2 The thickness is 0.2 to 0.46 mm.

10. The fire-retardant multilayer composite membrane according to claim 8, characterized in that, The first or second mesh fabric layer is a flat mesh fabric formed by weaving multiple strands of fiber yarns, and the fiber yarn material is selected from organic fibers and inorganic fibers. The organic fibers include: PAI fiber, PBI fiber, PI fiber, PEEK fiber, PPS fiber, PTFE fiber, PSU fiber, PPSU fiber, and PEI fiber; The inorganic fibers include: glass fiber, high silica fiber, quartz fiber, basalt fiber, and alkaline earth silicate fiber; The thickness of the first or second mesh layer is 50–120 μm, and the mass per unit area is 5–30 g / m². 2 The mesh size of the fabric is 6-18 mesh, and the tensile strength is 85-273 N / 50 mm. During the composite process, the meshes of the first and second mesh layers are arranged alternately and do not completely overlap.

11. The fire-retardant multilayer composite membrane according to claim 8, characterized in that, The glass melting rate constant τ of the inorganic particles is ≥4; The raw material sources for inorganic particles include: mica, vermiculite, talc, montmorillonite, feldspar, glass fiber, ceramic fiber, titanium dioxide, and fumed silica.

12. The fire-retardant multilayer composite membrane according to claim 8, characterized in that, The adhesive in the fireproof multilayer composite film has a mass percentage of 15-36%. Adhesives include binders, wherein the binders are selected from one or more of the following: polyurethane, acrylic acid, vinyl acetate, aluminum silicate, and methyl silicone; Preferred adhesives also include one or more of the following excipients: waterproofing agents, flame retardants, and defoamers; The waterproofing agent is selected from one or more of the following: silicone-based waterproofing agents, fluorocarbon-based waterproofing agents, and acrylic-based waterproofing agents.

13. The method for preparing the fire-retardant multilayer composite film according to any one of claims 8 to 12, characterized in that, Includes the following steps: The first polymer film layer and the first mesh fabric layer are bonded together with an adhesive. The second polymer film layer and the second mesh fabric layer are bonded together with an adhesive. An inorganic particle mixture is coated onto a first mesh fabric layer and / or a second mesh fabric layer, and then dried and shaped to obtain an inorganic particle layer. Fire-resistant multilayer composite film is prepared by bonding the various layers with adhesives and sandwiching the inorganic particle layer between the first and second mesh fabric layers.

14. The method for preparing the fire-retardant multilayer composite film according to claim 13, characterized in that, The inorganic particle mixture comprises: 35-65 wt% inorganic particles, 1-10 wt% binder, 0-15 wt% waterproofing agent, 0-10 wt% flame retardant, 0-1 wt% defoamer, and the balance being water.

15. A fireproof and heat-insulating felt, characterized in that: It includes at least two fire-resistant multilayer composite films as described in any one of claims 1 to 12, wherein a core material layer is disposed between each pair of fire-resistant multilayer composite films, and the fire-resistant multilayer composite films and the core material layers are bonded together by an adhesive.

16. The fireproof and heat-insulating felt according to claim 15, characterized in that: The core material is selected from foam, organic or inorganic fibers; the core material thickness is 10-75 mm.

17. The fireproof and heat-insulating felt according to claim 15, characterized in that: It includes two, three, five or seven fire-resistant multilayer composite films, with the core material layer disposed between each pair of fire-resistant multilayer composite films.

18. The fireproof and heat-insulating felt according to claim 15 or 16, characterized in that: The core material is made from polyimide foam, glass fiber, polyacrylonitrile fiber, carbon fiber, and pre-oxidized fiber.

19. The method for preparing the fireproof and heat-insulating felt according to claim 15, characterized in that, The process includes the following steps: placing two fire-resistant multilayer composite films opposite each other to cover the core material layer, and then bonding them together with adhesive and hot pressing to obtain the fire-resistant and heat-insulating felt.

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