Method for manufacturing a laminate for fire extinguishing

Abstract

To provide a method for efficiently manufacturing a fire extinction film allowing easy installation at a location with a likelihood of inflammation and capable of exerting an excellent effect in an initial fire extinction at inflammation.SOLUTION: A manufacturing method of a fire extinction film includes: (A) a step of preparing a coating liquid containing a binder resin and a fire-extinguishing agent component configured to generate aerosol by burning; (B) a step of forming a coating film on a surface of a base material using the coating liquid; and (C) a step of applying a drying treatment to a coating film to form a fire-extinguishing agent-containing layer containing a fire-extinguishing agent component and a binder resin on the surface of the base material. The step (B) and the step (C) are conducted by a roll-to-roll method.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a fire extinguishing laminate, a method for manufacturing the same, and a wound body of the fire extinguishing laminate.

Background Art

[0002] In recent years, with the progress of technology, while our lives are becoming increasingly comfortable, a large amount of energy is required to create this comfort. High safety is required for the handling of energy in each scenario of densely filling, storing, moving, and using a large amount of energy.

[0003] Taking automobiles as an example, when extracting fossil fuels, purifying gasoline from fossil fuels, transporting gasoline, or burning gasoline in an engine, there are potential risks of ignition and fire. Also, taking electronics as an example, when moving electrical energy through wires, adjusting electrical energy at substations or transformers, using electrical energy in electrical appliances in homes or factories, or temporarily storing it in batteries, there are similarly potential risks of ignition and fire.

[0004] Regarding the problems of ignition and fire, Patent Document 1 proposes using a fire extinguishing liquid and a fire extinguisher. Patent Document 2 proposes an automatic fire extinguishing device dropped from a helicopter. Patent Document 3 proposes an aerosol fire extinguishing device.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0006] All of the prior arts propose methods for dealing with fires after a certain period of time has passed. On the other hand, from the perspective of minimizing damage caused by fires, it is desirable that some kind of fire extinguishing operation (initial fire extinguishing) be carried out at a stage shortly after ignition.

[0007] Therefore, for example, a method of pre-existing the components of the fire extinguishing agent disclosed in the prior art itself in the vicinity of an object that may catch fire can be considered. By doing so, it is expected that the fire extinguishing will be completed by the components of the fire extinguishing agent before a person perceives that the object has caught fire. However, it is necessary to address the problem that the fire extinguishing agent placed in the open space deteriorates over time. In addition, of course, it is not realistic to simply spray the fire extinguishing agent in the vicinity of the object, and it is necessary to provide it in a moderately handleable shape in the vicinity of the object.

[0008] The present invention has been made in view of the above circumstances, and provides a fire extinguishing laminate that can be easily installed at a site where there is a concern of ignition and exhibits an excellent effect of initial fire extinguishing at the time of ignition, and a method for efficiently manufacturing the same. Further, the present invention provides a fire extinguishing composition, a fire extinguishing sheet, and a fire extinguishing molded article having excellent fire extinguishing performance.

Means for Solving the Problems

[0009] The method for manufacturing a fire-extinguishing laminate according to one aspect of the present invention includes: (A) a step of preparing a coating liquid containing a fire-extinguishing agent component that generates an aerosol by combustion and a binder resin; (B) a step of forming a coating film on the surface of a base material using the coating liquid; and (C) a step of forming a fire-extinguishing agent-containing layer containing a fire-extinguishing agent component and a binder resin on the surface of the base material by drying the coating film. The steps (B) and (C) are carried out by roll-to-roll. By carrying out the steps (B) and (C) by roll-to-roll, a fire-extinguishing laminate having excellent fire-extinguishing performance can be manufactured in large quantities and efficiently. One aspect of the present invention relates to a roll weight of a fire-extinguishing laminate (for example, having a length of 100 to 12,000 m).

[0010] The fire-extinguishing laminate according to one aspect of the present invention includes a base material layer and a fire-extinguishing agent-containing layer provided on the surface of the base material layer and containing a fire-extinguishing agent component that generates an aerosol by combustion and a binder resin. This fire-extinguishing laminate can be easily installed at a site where there is a concern of ignition and exhibits an excellent effect on initial fire extinguishing at the time of ignition.

[0011] The fire-extinguishing agent component includes, for example, at least an inorganic oxidizing agent that burns together with the binder resin to generate thermal energy and a radical generator, and the decomposition start temperature of the radical generator is in the range of 90°C to 260°C. Such a fire-extinguishing agent component has excellent fire-extinguishing performance. The fire-extinguishing agent component includes, for example, at least one of potassium salts and sodium salts as the radical generator. Potassium salts and sodium salts have an effect (negative catalytic effect) of stabilizing combustion radicals and suppressing the chain reaction of combustion.

[0012] The binder resin is preferably an epoxy resin. Since the epoxy resin has excellent compatibility with potassium salts and sodium salts (radical generators), it is easy to obtain a fire extinguishing agent-containing layer with a uniform thickness. In addition, since the epoxy resin does not undergo hydrolysis and embrittlement due to wet heat, the fire extinguishing agent-containing layer containing the epoxy resin as a binder resin has excellent stability. Further, during the combustion of the fire extinguishing agent-containing layer, thermal decomposition starts at about 260 to 350 °C, and aerosols can be generated without impairing the fire extinguishing performance. The binder resin preferably has a water vapor barrier property.

[0013] The content of the binder resin in the fire extinguishing agent-containing layer is preferably 3 to 30% by mass. The content of the fire extinguishing agent component in the fire extinguishing agent-containing layer is preferably 70 to 97% by mass. When the content of the binder resin in the fire extinguishing agent-containing layer is 3% by mass or more, excellent coatability can be achieved. When the content of the fire extinguishing agent component in the fire extinguishing agent-containing layer is 70% by mass or more, excellent fire extinguishing performance can be achieved.

Advantages of the Invention

[0014] According to the present invention, there are provided a fire extinguishing laminate that can be easily installed at a site where there is a concern of ignition and exhibits excellent effects in initial fire extinguishing at the time of ignition, and a method for efficiently manufacturing the same. Further, according to the present invention, there are provided a fire extinguishing composition, a fire extinguishing sheet, and a fire extinguishing molded article having excellent fire extinguishing performance.

Brief Description of the Drawings

[0015]

Figure 1

Figure 2

Figure 3

Figure 4

Mode for Carrying Out the Invention

[0016] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, as a laminate having at least one fire extinguishing agent-containing layer, a fire extinguishing film (the thickness of the fire extinguishing agent-containing layer is, for example, 1 mm or less) is exemplified.

[0017] <Fire extinguishing film> FIG. 1 is a schematic cross-sectional view of the fire extinguishing film according to the present embodiment. The fire extinguishing film 10 (fire extinguishing laminate) includes a base material 1 (base material layer) and a fire extinguishing agent-containing layer 3 in this order. The fire extinguishing agent-containing layer 3 may be provided on at least a part of one surface 1a of the base material 1, but as shown in FIG. 1, it may be provided on the entire surface 1a.

[0018] FIG. 2 is a schematic cross-sectional view showing a method of using the fire extinguishing film 10. As shown in FIG. 2, the fire extinguishing film 10 is used such that the object X, which may catch fire on the side of the fire extinguishing agent-containing layer 3, faces it. When a fire breaks out from the object X, initial fire extinguishing is performed by the previously provided fire extinguishing film 10. The object X is not particularly limited as long as it may catch fire and has a surface (plane or curved surface) on which the fire extinguishing film 10 can be placed. For example, examples of the object include electric wires, switchboards, distribution boards, control panels, storage batteries (such as lithium-ion batteries), building materials such as wall papers for building materials and ceiling materials, and each member of a recovery box for lithium-ion batteries.

[0019] (Base material) As the base material 1, a resin base material can be selected. For example, as the material of the resin base material, polyolefins (LLDPE, PP, COP, CPP, etc.), polyesters (PET, etc.), fluororesins (PTFE, ETFE, EFEP, PFA, FEP, PCTFE, etc.), PVC, PVA, acrylic resins, epoxy resins, polyamides, polyimides, etc. can be mentioned. Among these, from the viewpoint of low water vapor permeability and easy suppression of the deterioration of the fire extinguishing agent component, the resin base material may contain at least one selected from the group consisting of LLDPE, PP, COP, CPP, PET, PTFE, ETFE, EFEP, PFA, FEP, PCTFE, and PVC. Also, by selecting a material with high transparency, it becomes easier to perform an appearance inspection of the fire extinguishing film 10 and to confirm the replacement timing. The resin base material may contain a fire extinguishing agent. The material of the base material 1 may be a metal such as aluminum and stainless steel, or may be non-combustible paper or glass cloth.

[0020] The thickness, breaking strength, etc. of the resin base material can be appropriately selected according to the heat quantity, impact, allowable space, etc. at the time of fire outbreak. For example, if it is a thick resin base material, it is easy to suppress water vapor permeation, strength and rigidity can be obtained, a form with high flatness can be obtained, and handling becomes easy. Also, if it is a thin resin base material, a fire extinguishing body can be provided in a narrow space. The thickness of the resin base material can be, for example, 4.5 to 100 μm, and may be 12 to 50 μm. The resin base material may be a laminate of a plurality of resin base materials.

[0021] The resin base material may be a resin base material having heat resistance and impact resistance (high-strength heat-resistant resin base material). As the high-strength heat-resistant base material, it is preferable to satisfy at least one of a tensile strength of 20 N / cm or more and a melting point of 500 °C or more. The resin base material may contain, as a reinforcing material, materials such as carbon, glass, stainless steel, aluminum, ceramics, etc., particularly a woven fabric (cloth) of fibers made of these materials. By the resin base material having heat resistance and impact resistance, it is possible to suppress the formation of holes on the resin base material side due to heat and impact at the time of ignition. Thereby, it is possible to suppress the ejection of the fire extinguishing agent in the direction opposite to the object.

[0022] The resin base material preferably has a water vapor barrier property such that the properties of the fire extinguishing agent component contained in the fire extinguishing agent-containing layer 3 do not change significantly regardless of the installation location and use environment of the fire extinguishing film 10. The water vapor permeability of the resin base material (under the conditions of 40 °C / 90% RH in accordance with JIS K 7129) is not particularly limited because it can be designed according to the type of the fire extinguishing agent component, but it can be 2×10 2 g / m 2 / day or less, and may be 1×10 2 g / m 2 / day or less. From the viewpoint of adjusting the water vapor permeability, a vapor deposition layer (aluminum oxide vapor deposition layer or silica vapor deposition layer) having a water vapor barrier property may be provided on the resin base material.

[0023] (Fire extinguishing agent-containing layer) The fire extinguishing agent-containing layer 3 is a layer containing a fire extinguishing agent component and a binder resin. The fire extinguishing agent component generates an aerosol by combustion. The fire extinguishing agent component includes, for example, at least an inorganic oxidizing agent and a radical generator. The radical generator has an action (negative catalytic action) of stabilizing combustion radicals and suppressing the chain reaction of combustion.

[0024] The thickness of the fire extinguishing agent-containing layer 3 may be appropriately set according to the fire extinguishing target, installation location of the fire extinguishing film 10, and the amount of the fire extinguishing agent component to be blended. The thickness of the fire extinguishing agent-containing layer 3 may be, for example, 1 mm or less, can be 30 to 1000 μm, and may be 120 to 500 μm.

[0025] The content rate of the fire extinguishing agent component in the fire extinguishing agent-containing layer 3 (based on the mass of the fire extinguishing agent-containing layer 3) is, for example, 70 to 97% by mass, preferably 80 to 95% by mass, and more preferably 85 to 92% by mass. By the content rate of the fire extinguishing agent component being 70% by mass or more, excellent fire extinguishing performance can be achieved. On the other hand, by being 97% by mass or less, excellent film formability can be achieved. The amount of the fire extinguishing agent component per unit area may be set according to the object to be extinguished. For example, for a fire extinguishing film formed on a PET base material with a thickness of 15 μm and a content rate of the fire extinguishing agent component of 95% by mass, the weight per unit area required to extinguish a fire with a relatively small firepower such as a candle is 25 g / m2 This shall be sufficient. For the firepower of 1 g of solid fuel, it is 90 g / m 2 This shall be sufficient. For large firepower such as large-scale fires and ignition from lithium-ion batteries, it is 100 g / m 2 It is preferably the above.

[0026] [Fire extinguishing agent component] As described above, the fire extinguishing agent-containing layer 3 contains an inorganic oxidizing agent and a radical generator as fire extinguishing agent components. Hereinafter, these components will be described.

[0027] The inorganic oxidizing agent (hereinafter, sometimes referred to as the “component (A)”) is a component that burns together with the binder resin to generate thermal energy. Examples of the inorganic oxidizing agent include potassium chlorate, sodium chlorate, strontium chlorate, ammonium chlorate, and magnesium chlorate. Among these, one kind may be used alone, or two or more kinds may be used in combination.

[0028] The radical generator (hereinafter, sometimes referred to as the “component (B)”) is a component for generating an aerosol (radical) by the thermal energy generated by the combustion of the binder resin and the inorganic oxidizing agent. It is preferable to use a radical generator having a decomposition start temperature in the range of 90°C to 260°C. Examples of the radical generator include potassium salts and sodium salts. Examples of the potassium salts include potassium acetate, potassium propionate, monopotassium citrate, dipotassium citrate, tripotassium citrate, monopotassium trihydrogen ethylenediaminetetraacetate, dipotassium dihydrogen ethylenediaminetetraacetate, tripotassium monohydrogen ethylenediaminetetraacetate, potassium ethylenediaminetetraacetate, potassium hydrogen phthalate, dipotassium phthalate, potassium hydrogen oxalate, dipotassium oxalate, and potassium bicarbonate. Examples of the sodium salts include sodium acetate, sodium citrate, and sodium bicarbonate. Among these, one kind may be used alone, or two or more kinds may be used in combination.

[0029] The content of component (A) is, for example, 10 to 60 parts by mass, preferably 20 to 50 parts by mass, more preferably 35 to 45 parts by mass, based on 100 parts by mass of the total amount of components (A) and (B). The content of component (B) is, for example, 40 to 90 parts by mass, preferably 50 to 80 parts by mass, more preferably 55 to 65 parts by mass, based on 100 parts by mass of the total amount of components (A) and (B).

[0030] [Binder resin] As the binder resin, a thermoplastic resin and a thermosetting resin can be used. Examples of the thermoplastic resin include polyolefin resins such as polypropylene-based resins, polyethylene-based resins, poly(1-)butene-based resins, polypentene-based resins, polystyrene-based resins, acrylonitrile-butadiene-styrene-based resins, methyl methacrylate-butadiene-styrene resins, ethylene-vinyl acetate resins, ethylene-propylene resins, polycarbonate-based resins, polyphenylene ether-based resins, acrylic resins, polyamide-based resins, polyvinyl chloride-based resins, etc. Examples of the thermosetting resin include rubbers such as natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-polybutadiene rubber (1,2-BR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), nitrile rubber (NBR), butyl rubber (IIR), ethylene-propylene rubber (EPR, EPDM), chlorosulfonated polyethylene (CSM), acrylic rubber (ACM, ANM), epichlorohydrin rubber (CO, ECO), multi-vulcanized rubber (T), silicone rubber (Q), fluororubber (FKM, FZ), urethane rubber (U), etc., polyurethane resins, polyisocyanate resins, polyisocyanurate resins, phenolic resins, epoxy resins, etc.

[0031] The epoxy resin is suitable as the binder resin because it has excellent compatibility with the fire extinguishing agent component, is soluble in the alcohol solvent described later, and has high stability.

[0032] As the binder resin, it is preferable to use one having a water vapor barrier property. When a single-layer film made of the binder resin is produced, the binder resin preferably has a water vapor permeability of 5 g·mm / m 2 / day or less, more preferably 1 g·mm / m 2 / day or less (under the conditions of 40 °C / 90%RH in accordance with JIS K 7129). As a commercially available product of such a binder resin, Maxiseal (trade name, manufactured by Mitsubishi Gas Chemical) can be mentioned.

[0033] The content rate of the binder resin in the fire extinguishing agent-containing layer 3 (based on the mass of the fire extinguishing agent-containing layer 3) is, for example, 3 to 30% by mass, preferably 5 to 20% by mass, and more preferably 8 to 15% by mass. When the content rate of the binder resin is 3% by mass or more, excellent film formability can be achieved. On the other hand, when it is 30% by mass or less, excellent fire extinguishing performance can be achieved.

[0034] [Other components] Examples of other components to be blended in the fire extinguishing agent-containing layer 3 include dispersants such as water, solvents, colorants, antioxidants, flame retardants, inorganic fillers, and adhesives. These components may be appropriately selected according to the composition of the fire extinguishing agent-containing layer 3 and the type of the binder resin. The content rate of other components in the fire extinguishing agent-containing layer 3 (based on the mass of the fire extinguishing agent-containing layer 3) is, for example, 10% by mass or less.

[0035] [Manufacturing method of the fire extinguishing film] The manufacturing method of the fire extinguishing film 10 includes: (A) a step of preparing a coating liquid containing the above fire extinguishing agent component and the above binder resin; (B) a step of forming a coating film on the surface 1a of the base material 1 using the coating liquid; and (C) a step of forming the fire extinguishing agent-containing layer 3 on the surface 1a by drying the coating film, and the steps (B) and (C) are carried out by roll-to-roll.

[0036] (A) In the process, as the solvent used for preparing the coating liquid, it is preferable to use an alcohol solvent (for example, ethanol, IPA). Since the alcohol solvent has excellent dispersibility of the fire extinguishing agent component and low volatility, it is suitable as a solvent for preparing the coating liquid. Ethyl acetate may be used as the solvent.

[0037] (B) The process may be carried out by wet coating or by impregnating the substrate 1 with the coating liquid. By carrying out the (B) process and the (C) process by roll-to-roll, a fire extinguishing film 10 with excellent fire extinguishing performance can be manufactured in large quantities and efficiently. That is, a roll body (roll) of the fire extinguishing film 10 can be manufactured efficiently and inexpensively. The length of the roll body is, for example, 100 to 1000 m, and may be 1000 to 12000 m. The width of the roll body is, for example, 0.01 to 0.3 m, and may be 0.3 to 1.5 m. When using the fire extinguishing film 10, it may be cut to the size according to the use and installation location.

[0038] According to the manufacturing method according to this embodiment, the fire extinguishing film 10 can be efficiently manufactured by extrusion molding. The fire extinguishing film 10 can be easily installed at a site where there is a concern of ignition and exhibits an excellent effect on initial fire extinguishing at the time of ignition. Therefore, it is useful in that it can suppress the spread of fire.

[0039] As described above, the embodiments of the present invention have been described in detail, but the present invention is not limited to the above embodiments. For example, in the above embodiment, a fire extinguishing film having a two-layer structure of a base material 1 and a fire extinguishing agent-containing layer 3 was exemplified, but the fire extinguishing film may further include an adhesive layer or an adhesive layer. The fire extinguishing film 20A shown in Fig. 3(a) includes a base material 1, a fire extinguishing agent-containing layer 3, an adhesive layer 4, and a release film 5 in this order. The fire extinguishing film 20B shown in Fig. 3(b) includes a release film 5, an adhesive layer 4, a base material 1, and a fire extinguishing agent-containing layer 3 in this order. The release film 5 is peeled off when the fire extinguishing films 20A and 20B are used, and may be made of resin or paper. By having the adhesive layer 4 or the adhesive layer in the fire extinguishing film, the fire extinguishing film can be more easily installed at a location where there is a concern of ignition.

[0040] As shown in Fig. 4, the fire extinguishing film may be in a form in which the fire extinguishing agent-containing layer 3 is sandwiched between other layers. The fire extinguishing film 30 shown in Fig. 4 includes a fire extinguishing agent-containing layer 3 and surface layers 6a and 6b arranged so as to sandwich the fire extinguishing agent-containing layer 3. As the surface layers 6a and 6b, for example, a resin base material similar to the base material 1 can be used. By providing the surface layers 6a and 6b, the durability or designability of the fire extinguishing agent-containing layer 3 can be enhanced, and a fire extinguishing film 30 having high strength can be obtained.

Examples

[0041] The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

[0042] <Examples 1 to 12 and Comparative Examples 1 and 2> The following materials were prepared. [Base material] · Base material 1: PET film (thickness: 4.5 μm) · Base material 2: PET film (thickness: 15 μm) · Base material 3: PET film (thickness: 50 μm) · Base material 4: Aluminum foil (thickness: 150 μm) [Fire extinguishing agent component] · Aerosol fire extinguishing agent (manufactured by Yamato Protec Co., Ltd.) [Solvent] · Solvent 1: Ethyl acetate · Solvent 2: Ethanol [Binder resin] · Resin 1: Epoxy resin (trade name: K468, manufactured by Toyo Ink Co., Ltd.) · Resin 2: Epoxy resin (trade name: Maxieve, manufactured by Mitsubishi Gas Chemical Co., Ltd.)

[0043] Coating liquids were respectively prepared using the components shown in Table 1. After forming a coating film on the surface of the substrate, a fire extinguishing agent-containing layer (uncured) was formed on the substrate by drying at 90°C for 2 minutes. Thereafter, the fire extinguishing agent-containing layer was cured by performing a curing treatment at 50°C for 48 hours. Thereby, a fire extinguishing laminated body of the substrate and the fire extinguishing agent-containing layer was obtained. In Table 1, the "binder content" means the content of the binder resin contained in the dried coating film. The "coating amount" in Table 1 means the mass per unit area of the dried coating film.

[0044] <Evaluation of coating appearance> It was visually confirmed whether there were streaks on the coating film. The evaluation results are shown in Table 1.

[0045] <Evaluation of fire extinguishing performance> (Candle) The fire extinguishing laminated bodies of the examples and comparative examples were respectively cut into a size of 20 mm in length × 20 mm in width to obtain samples. While holding the sample with tweezers, it was brought close to the position of 20 mm in height with respect to the flame of the candle. Thereby, after burning the sample, it was confirmed whether it could be extinguished. The evaluation results are shown in Table 1. (Solid fuel) The fire extinguishing laminated bodies of the examples and comparative examples were respectively cut into a size of 20 mm in length × 20 mm in width to obtain samples. After placing 1 g of solid fuel in a pan installed inside an aluminum container, the solid fuel was ignited to generate a flame. While holding the sample with tweezers, it was brought close to the position of 20 mm in height with respect to the burning solid fuel. Thereby, after burning the sample, it was observed whether it could be extinguished. The evaluation results are shown in Table 1.

[0046]

Table 1

Industrial Applicability

[0047] According to the present invention, there are provided a fire extinguishing film that can be easily installed at a site where there is a concern of ignition and exhibits an excellent effect on initial fire extinguishing at the time of ignition, and a method for efficiently manufacturing the same. Further, according to the present invention, there are provided a fire extinguishing composition, a fire extinguishing sheet, and a fire extinguishing molded article having excellent fire extinguishing performance.

Explanation of Reference Numerals

[0048] 1... base material (base material layer), 1a... surface, 3... fire extinguishing agent-containing layer, 4... adhesive layer, 5... release film, 6a, 6b... surface layer, 10, 20A, 20B, 30... fire extinguishing film (fire extinguishing laminate), X... object

Claims

【Claim 1】 (A) A step of preparing a coating liquid containing a fire extinguishing agent component that generates an aerosol by combustion and a binder resin; (B) A step of forming a coating film on the surface of the resin base material supplied from a wound body in which the resin base material is wound in a roll shape using the coating liquid; (C) By drying the coating film, a fire extinguishing agent-containing layer containing the fire extinguishing agent component and the binder resin is formed on the surface of the resin base material to obtain a fire extinguishing laminate, and the fire extinguishing laminate is wound in a roll shape to obtain a wound body of the fire extinguishing laminate. A method for producing a fire extinguishing laminate, comprising: ​

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