Self-extinguishing molded article

Abstract

To provide a self-extinguishing molded article which can activate a self-extinguishing function without using a fire extinguisher, fire-extinguishing device, etc., and enables a safety measure against fire.SOLUTION: The present invention is a sheet-like self-extinguishing molded article which includes a fire extinguishing composition that generates an aerosol by combustion to extinguish or suppress fire, and is used by being affixed to a component of an automobile or to a member in a building where fire risk is present.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a self-extinguishing molded article characterized by including a fire extinguishing agent composition that generates an aerosol by combustion to extinguish and suppress a fire.

Background Art

[0002] Many general fire extinguishers and fire extinguishing devices eject and disperse fire extinguishing agents and fire extinguishing gases by means of an ignition method using gas pressure or an electric circuit. For example, various components such as components for actuation, components for ejecting and dispersing fire extinguishing agents and fire extinguishing gases, components such as electric circuits for ignition, temperature and flame sensors, etc. are required.

[0003] Therefore, structurally, the device becomes bulky like a fire extinguisher or a fire extinguishing device, and it is necessary to design its structure and system. Also, the management of each component and the manufacturing process become complicated, and the cost burden is large.

[0004] On the other hand, for buildings such as automobiles and houses, safety measures against fires are always required. For example, fire extinguishers and fire extinguishing devices as described above are placed, or for example, non-combustible materials and flame-retardant materials are adopted as constituent members (for example, Patent Document 1). However, in such safety measures, a placement location for fire extinguishers and fire extinguishing devices is required, and at present, even materials that are difficult to burn have to be said to be insufficient.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] Therefore, an object of the present invention is to provide a self-extinguishing molded article that can activate a self-extinguishing function without using a fire extinguisher, a fire extinguishing device, etc. and can take safety measures against fire.

Means for Solving the Problems

[0007] However, as a result of repeatedly and intensively studying and experimenting on whether the "fire extinguishing agent composition that can make a fire extinguisher, a fire extinguishing device, etc. more compact and lightweight compared to the case of using a conventional powder-based fire extinguishing agent", which is the subject of a separate patent application, can be effectively used, the inventors have found that if this is used to give a self-extinguishing function to parts of an automobile or members constituting a building, it is effective for achieving the above object, and thus have completed the present invention.

[0008] That is, the present invention provides a self-extinguishing molded article characterized by including a fire extinguishing agent composition that generates an aerosol by combustion to extinguish and suppress a fire. The self-extinguishing molded article of the present invention having such a configuration can activate a self-extinguishing function by generating chemical species having a fire extinguishing function using the thermal energy of a fire when a fire occurs, and can take safety measures against fire without using a fire extinguisher, a fire extinguishing device, etc.

[0009] The self-extinguishing molded article of the present invention described above can have a planar shape (for example, a film shape, a sheet shape, a plate shape) or a three-dimensional shape (for example, a columnar shape), and can be adopted for various parts and members.

[0010] Further, in the self-extinguishing molded article of the present invention described above, the fire extinguishing agent composition contains 20 to 50% by mass of fuel and 80 to 50% by mass of chlorate, and further contains 6 to 1000 parts by mass of potassium salt with respect to 100 parts by mass of the total amount of the fuel and the chlorate, and the thermal decomposition start temperature is in the range of more than 90°C to 260°C, which is preferable.

[0011] If a fire extinguishing agent composition having such a configuration is used, the self-extinguishing function can be more reliably exhibited, and it is possible to achieve compactification and weight reduction as compared with the case of using a conventional powder-based fire extinguishing agent.

Advantages of the Invention

[0012] According to the present invention, it is possible to realize a self-extinguishing molded article that can activate a self-extinguishing function without using a fire extinguisher or a fire extinguishing device, etc., and can provide safety measures against fires.

Brief Description of the Drawings

[0013]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Modes for Carrying Out the Invention

[0014] Hereinafter, representative embodiments of the self-extinguishing molded article of the present invention will be described in detail with reference to the drawings. Note that redundant explanations in each embodiment may be omitted, the present invention is not limited to these drawings, and the drawings are for conceptually explaining the present invention, so for ease of understanding, dimensions, ratios, or numbers may be exaggerated or simplified as necessary.

[0015] ≪First Embodiment≫ FIG. 1 is a schematic view showing an embodiment of the self-extinguishing molded article of the present invention. The self-extinguishing molded article 1 in this embodiment is in the form of a sheet and can be used by being attached to an adherend 2 such as an automobile panel or a building wall.

[0016] This self-extinguishing molded article 1 can be produced by mixing a fire extinguishing agent composition with a binder and other components and molding the resulting mixture into a sheet form by a conventionally known method using a molding machine or the like. Hereinafter, the fire extinguishing agent composition, binder, and other components will be described.

[0017] (1) Fire extinguishing agent composition The fire extinguishing agent composition contains 20 to 50% by mass of a fuel (component A) and 80 to 50% by mass of a chlorate (component B), and further contains 6 to 1000 parts by mass of a potassium salt (component C) with respect to 100 parts by mass of the total amount of the fuel and the chlorate, and is characterized in that the thermal decomposition start temperature is in the range of more than 90°C to 260°C.

[0018] The fuel as component A is a component for generating thermal energy by combustion together with the chlorate as component B and generating an aerosol (potassium radical) derived from the potassium salt of component C.

[0019] Examples of such a fuel as component A include dicyandiamide, nitroguanidine, guanidine nitrate, urea, melamine, melamine cyanurate, avicel, guar gum, sodium carboxymethyl cellulose, potassium carboxymethyl cellulose, ammonium carboxymethyl cellulose, nitrocellulose, aluminum, boron, magnesium, magnesium, zirconium, titanium, titanium hydride, tungsten, and silicon Those selected from at least one of them are preferred. Among them, sodium carboxymethyl cellulose is particularly preferred from the viewpoint of more surely obtaining the effect of the present invention of generating an aerosol to extinguish the fire.

[0020] The chlorate of component B is a strong oxidizing agent and is a component for generating thermal energy by combustion together with the fuel of component A and generating an aerosol (potassium radical) derived from the potassium salt of component C.

[0021] As such a chlorate of component B, for example, those selected from at least one of potassium chlorate, sodium chlorate, strontium chlorate, ammonium chlorate, and magnesium chlorate are preferable. Among them, potassium chlorate is particularly preferable from the viewpoint of more surely obtaining the effects of the present invention.

[0022] Here, the content ratio in the total 100% by mass of the fuel of component A and the chlorate of component B is as follows. Component A: 20 to 50% by mass Preferably 25 to 40% by mass More preferably 25 to 35% by mass Component B: 80 to 50% by mass Preferably 75 to 60% by mass More preferably 75 to 65% by mass

[0023] Next, the potassium salt of component C is a component for generating an aerosol (potassium radical) by the thermal energy generated by the combustion of component A and component B.

[0024] As such a potassium salt of component C, for example, those selected from at least one of potassium acetate, potassium propionate, potassium dihydrogen citrate, potassium hydrogen citrate, potassium citrate, potassium ethylene diamine tetraacetate trihydrate, potassium ethylene diamine tetraacetate dihydrogenate, potassium ethylene diamine tetraacetate hydrogenate, potassium ethylene diamine tetraacetate, potassium hydrogen phthalate, dipotassium phthalate, potassium hydrogen oxalate, dipotassium oxalate, and potassium bicarbonate are preferable. Among them, potassium acetate or potassium citrate is particularly preferable from the viewpoint of more surely obtaining the effects of the present invention.

[0025] The content ratio of component C is preferably 6 to 1000 parts by mass, more preferably 10 to 900 parts by mass, and particularly preferably 10 to 100 parts by mass, based on 100 parts by mass of the total amount of component A and component B.

[0026] Furthermore, the fire extinguishing agent composition of the present invention has a thermal decomposition start temperature in the range of more than 90°C to 260°C, preferably more than 150°C to 260°C. Such a range of thermal decomposition start temperature can be adjusted by combining the above-mentioned component A, component B, and component C in the above-mentioned ratio.

[0027] By satisfying the above range of thermal decomposition start temperature, the fire extinguishing agent composition can, for example, automatically ignite and burn component A and component B upon receiving heat during a fire without using an ignition device or the like, generate an aerosol (potassium radical) derived from component C, and extinguish the fire.

[0028] Note that the ignition temperature of common wood as a combustible in a room is 260°C, and by setting the thermal decomposition start temperature under the condition that it does not start at 90°C or lower, which is the general operating temperature of the heat sensor of the automatic fire alarm equipment installed in a place where fire is handled, rapid fire extinguishing can be achieved and malfunction of the heat sensor can also be prevented. In particular, since the maximum setting temperature of the heat sensor is 150°C, By setting the lower limit value of the thermal decomposition start temperature to more than 150°C, high versatility can be obtained.

[0029] The form of the fire extinguishing agent composition having the above configuration is not particularly limited, and it can be used as a liquid such as a dispersion, a powder, or a solid such as a molded body having a desired shape. If it is a dispersion, it can also be used as a coating agent by spray spraying. In addition, the molded body can be in the form of granules, pellets having a desired shape (such as a cylindrical shape), tablets, spheres, disks, etc., and preferably has an apparent density of 1.0 g / cm 3 or more.

[0030] (2) Binder and other components As the binder and other components, various materials can be used as long as they enable the molding of the above fire extinguishing agent composition without impairing its function. In particular, the binder may be an inorganic binder or an organic binder. Note that even without using a binder, it is possible to produce the self-extinguishing molded article of the present invention by using a dispersant described later.

[0031] Examples of the inorganic binder include sinterable inorganic materials, etc. Specific examples of this sinterable inorganic material include, for example, electrically insulating glass, etc.

[0032] Specifically, as the electrically insulating glass, those called E glass containing silicon dioxide in the range of 50 to 60% by weight, aluminum oxide in the range of 10 to 20% by weight, calcium oxide in the range of 10 to 20% by weight, magnesium oxide in the range of 1 to 10% by weight, boron oxide in the range of 8 to 13% by weight, etc. can be cited.

[0033] Also, among the above sinterable inorganic materials, it is preferable that the content of the lead metal salt and the alkali metal oxide is less than 1% by weight each with respect to the weight of the sinterable inorganic material. Examples of such lead metal salts include PbO, PbO2, Pb3O4, etc., and examples of the alkali metal oxides include Na2O, K2O, etc.

[0034] Also, among the above sinterable inorganic materials, the E glass is preferable from the viewpoint that it has a low content of alkali metal oxides and has little influence on building materials such as fire doors made of fire prevention and fire-resistant panels.

[0035] Next, examples of the organic binder include, specifically, 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 and other thermoplastic resins, 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), highly vulcanized rubber (T), silicone rubber (Q), fluororubber (FKM, FZ), urethane rubber (U) and other rubbers, thermosetting resins such as polyurethane resins, polyisocyanate resins, polyisocyanurate resins, phenol resins, epoxy resins, latexes of the above thermoplastic resins, rubbers, etc., emulsions of the above thermoplastic resins, rubbers, etc., and cellulose derivatives such as CMC (carboxymethyl cellulose), HEC (hydroxyethyl cellulose), HPMC (hydroxypropyl methyl cellulose), etc.

[0036] These organic binders can be used singly or in combination of two or more. Among them, from the viewpoint of handleability, etc., latexes of rubbers, ethylene-vinyl acetate resins, acrylic resin emulsions, CMC, etc. are preferable.

[0037] Examples of other components include dispersants such as water, solvents, colorants, antioxidants, flame retardants, inorganic fillers, adhesives, etc., and they may be appropriately selected according to the composition of the fire extinguishing agent composition, the type of binder, the form of the desired molded product, etc.

[0038] ≪Second Embodiment≫ Figure 2 is a schematic diagram showing a second embodiment of the self-extinguishing molded article of the present invention. The self-extinguishing molded article 11 in this embodiment is formed by spraying a fire extinguishing composition into a film shape, and can be formed on an adherend 12 such as an automobile panel or a building wall and used.

[0039] This film-shaped self-extinguishing molded article 11 can be produced by mixing a binder and other components (especially a solvent or a dispersion medium) with the above fire extinguishing agent composition, and forming the resulting liquid mixture (solution or dispersion) into a film shape by a conventionally known method using a sprayer (Y in Fig. 2).

[0040] ≪Third Embodiment≫ Figure 3 is a schematic diagram showing a third embodiment of the self-extinguishing molded article of the present invention. The self-extinguishing molded article 21 in this embodiment is formed by molding a columnar mixture obtained by mixing the above fire extinguishing composition molded into granules with, for example, wood chips, a binder, and other components, and can be used as a building column or the like.

[0041] This self-extinguishing molded article 21 can be produced by mixing wood chips, a binder, and other components with the above fire extinguishing agent composition molded into granules, and forming the resulting mixture into a columnar shape by a conventionally known method using a molding machine. The granular fire extinguishing agent composition 21a is dispersed throughout.

[0042] ≪Fourth Embodiment≫ Figure 4 is a schematic diagram showing a fourth embodiment of the self-extinguishing molded article of the present invention. The self-extinguishing molded article 31 in this embodiment is formed by molding a columnar mixture obtained by mixing, for example, wood chips, a binder, and other components, and impregnating the vicinity of its surface with a fire extinguishing composition, and can be used as a building column or the like.

[0043] This self-extinguishing molded product 31 can be produced, for example, by mixing wood chips, a binder, and other components, molding the resulting mixture into a columnar shape by a conventionally known method using a molding machine, and immersing the shaped product in a liquid fire extinguishing agent composition (solution or dispersion). The fire extinguishing agent composition 31a is impregnated near the surface.

[0044] As described above, the representative self-extinguishing molded products of the present invention have all contained the above fire extinguishing agent composition. Therefore, when a fire occurs, a chemical species having a fire extinguishing function is generated using the thermal energy of the fire, thereby activating the self-extinguishing function (the X part in FIG. 1). It is possible to take safety measures against fires without using a fire extinguisher or a fire extinguishing device.

Example

[0045] ≪Experimental Example 1≫ (Sheet-like) <Examples 1 to 13 and Comparative Examples 1 to 4> The A component, B component, and C component shown in Table 1 were thoroughly mixed at the blending ratios shown in Table 1 (as dry matter excluding moisture). With respect to a total of 100 parts by mass of the A component, B component, and C component, 10 parts by mass equivalent of ion-exchanged water was added and further mixed. The obtained water-wet mixture was dried in a constant temperature bath at 110 °C for 16 hours to obtain a dried product with a moisture content of 1% by mass or less. Next, the dried product was crushed in an agate mortar and sized to a particle size of 500 μm or less to obtain a pulverized product. CMC was added to the pulverized product to obtain a clay-like mixture. This mixture was molded into a sheet with a thickness of 5 mm and sufficiently dried to produce the self-extinguishing molded products 1 to 9 of the present invention and the comparative self-extinguishing molded products 1, 3, and 4.

[0046] [Evaluation Test] (1) Apparent density The apparent density of the self-extinguishing molded product obtained as described above was measured with a digital vernier caliper for the area and thickness, and calculated by dividing the weight by the volume obtained from the measured values, and is shown in Table 1. (2) Fire extinguishing test Fire extinguishing test 1 was carried out using the apparatus shown in FIG. 5. An iron wire mesh 52 was placed on the support table 51, and the molded products 56 of the examples and comparative examples were placed at the center thereof. A transparent container (5L) made of heat-resistant glass was placed over the wire mesh 52, and the portion other than the part facing the wire mesh 52 was sealed. A dish 55 containing 100 ml of n-heptane as an ignition agent was placed directly below the molded product 6 through the wire mesh 52. In this state, n-heptane was ignited to generate a flame 57, the molded product 56 was heated to generate an aerosol, and it was observed whether the flame 57 could be extinguished. The results are shown in Table 1.

[0047] ≪Experimental Example 2≫ (film-like) <Examples 14 to 26 and Comparative Examples 5 to 8> In the same manner as in Experimental Example 1, the pulverized product was sized to a particle size of 100 μm or less, and a sufficient amount of CMC was added to obtain a dispersion-like mixture having a significantly lower viscosity than that of Experimental Example 1. This mixture was injected into a sprayer, sprayed onto a glass substrate, and sufficiently dried to produce film-like self-extinguishing molded products 14 to 26 of the present invention and comparative self-extinguishing molded products 5 to 8 with a thickness of 300 μm. When a fire extinguishing test similar to that of Experimental Example 1 was conducted on these, similar results were obtained.

[0048] ≪Experimental Example 3≫ (pellet-like) <Example 27 and Comparative Example 9> The pulverized product prepared in the same manner as in Example 1 of Experimental Example 1 was filled with 2.0 g of the pulverized product into a predetermined mold (mortar) having an inner diameter of 9.6 mm. After inserting a pestle, a surface pressure of 220.5 MPa (2250 kg / cm 2 ) was applied from both sides for 5 seconds each with a hydraulic pump to obtain a pellet-like self-extinguishing molded product 27 of the present invention. Also, a wood pellet of the same size was used as Comparative Molded Product 9. When a fire extinguishing test similar to that of Experimental Example 1 was conducted on these, the self-extinguishing molded product 27 was extinguished, and the comparative molded product 9 was not extinguished. In addition, when a fire extinguishing test similar to that of Experimental Example 1 was conducted on a mixture obtained by mixing the self-extinguishing molded product 27 with the comparative molded product 9, the greater the proportion of the self-extinguishing molded product 27, the more remarkable the fire extinguishing effect. That is, the smaller the proportion of the self-extinguishing molded product 27, the more time was required for fire extinguishing, and in some cases, it could not be extinguished.

[0049]

Table 1

[0050] From Table 1, it can be seen that all of the self-extinguishing molded products of the examples of the present invention were able to extinguish the fire instantaneously. In the comparative examples, although the fire intensity temporarily decreased, the fire could not be extinguished.

Industrial Applicability

[0051] However, the present invention is not limited to the above-mentioned sheet-like, film-like, and columnar self-extinguishing molded products, and various applications are possible. In addition, it is also applicable to various adhesives other than the walls of buildings and molded products other than columns. For example, it is also applicable to various resin products and wood products.

[0052] For example, for automobile parts, it is also possible to apply to the following parts. · Rearview mirror · Headrest · Wiper arm, wiper blade (front and rear) · Top cowl · Headlight, fog lamp, front side marker lamp, and other lamps · Radiator grille · Front turn signal · Front bumper, rear bumper, skirt · Side molding · Step · Mud flap · Door armrest, door inner handle, door lock knob · Steering wheel · Horn pad · Meter panel · Handbrake · Ventilator · Various control panels · Shift lever

[0053] In addition, examples of building materials include roofing materials, wall materials, floor materials, furniture, and the like. If the above fire extinguishing agent composition is formed into a sheet shape, it can be used as a wall material, and if it is formed into a plate shape, it can also be used as a roofing material, a floor material, furniture, and the like.

[0054] The embodiments of the present invention are as follows. (1) A self-extinguishing molded article characterized by including a fire extinguishing agent composition that generates an aerosol by combustion to suppress a fire. (2) The self-extinguishing molded article according to (1), wherein the molded article is planar or three-dimensional. (3) The fire extinguishing agent composition contains 20 to 50% by mass of fuel and 80 to 50% by mass of chlorate, further contains 6 to 1000 parts by mass of potassium salt with respect to 100 parts by mass of the total amount of the fuel and the chlorate, and has a thermal decomposition start temperature in the range of more than 90°C to 260°C. The self-extinguishing molded article according to (1) or (2), characterized by the above. (4) In the DSC (differential scanning calorimetry) analysis of the potassium salt with a temperature increase of 10°C per minute, the total amount of endothermic peaks appearing between 100°C and 440°C is 100 J / g to 900 J / g. The self-extinguishing molded article according to any one of (1) to (3), characterized by the above. (5) The potassium salt is a compound that generates potassium radicals by thermal energy. The self-extinguishing molded article according to any one of (1) to (4), characterized by the above. (6) The potassium salt is at least one of potassium acetate, potassium propionate, potassium dihydrogen citrate, potassium hydrogen citrate, potassium citrate, potassium trihydrogen ethylenediaminetetraacetate, potassium dihydrogen ethylenediaminetetraacetate, potassium hydrogen ethylenediaminetetraacetate, potassium ethylenediaminetetraacetate, potassium hydrogen phthalate, dipotassium phthalate, potassium hydrogen oxalate, dipotassium oxalate, and potassium bicarbonate. The self - extinguishing molded article according to any one of (1) to (5), characterized by (7) The fuel is a compound that burns with the chlorate to generate thermal energy, and the self - extinguishing molded article according to any one of (1) to (6), characterized by (8) The fuel is at least one of dicyandiamide, nitroguanidine, guanidine nitrate, urea, melamine, melamine cyanurate, avicel, guar gum, sodium carboxymethyl cellulose, potassium carboxymethyl cellulose, ammonium carboxymethyl cellulose, nitrocellulose, aluminum, boron, magnesium, magnesium, zirconium, titanium, titanium hydride, tungsten and silicon, The self - extinguishing molded article according to (7), characterized by (9) The chlorate is an oxidizing agent compound that burns with the fuel to generate thermal energy, and the self - extinguishing molded article according to any one of (1) to (8), characterized by (10) The chlorate is at least one of potassium chlorate, sodium chlorate, strontium chlorate, ammonium chlorate and magnesium chlorate, and the self - extinguishing molded article according to (9), characterized by

Explanation of symbols

[0055] 1, 11, 21, 31 ··· self - extinguishing molded article, 2, 12 ··· adherend, 21a, 31a ··· fire - extinguishing agent composition.

Claims

1. A fire extinguishing agent that decomposes thermally at a specified temperature to produce chemical species with fire-extinguishing properties.

2. A fire extinguishing agent that generates chemical species with fire-extinguishing properties when exposed to heat.

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