JPWO2018047762A1 - Self-extinguishing molded articles - Google Patents

Abstract

Providing a self-extinguishing molded article that can activate a self-extinguishing function without using a fire extinguisher or a fire extinguisher, etc. The present invention provides a self-extinguishing molded article characterized by comprising an extinguishant composition that generates an aerosol by combustion to suppress a fire.

Description

  The present invention relates to a self-extinguishing molded article characterized by comprising an extinguishant composition that generates an aerosol by combustion to suppress a fire.

  Many common fire extinguishers and fire extinguishing devices expel and diffuse a fire extinguishing agent and fire extinguishing gas by a gas pressure and an ignition method using an electric circuit, for example, parts for operating, fire extinguishing agent and fire extinguisher It is necessary to use various parts such as parts for injecting and diffusing gas, parts such as an electric circuit for igniting, and sensors for temperature and flame.

  Therefore, due to the structure, it is necessary for the device to make the fire extinguisher and the fire extinguishing device bulky, and to design the structure and system, and the management of each part and the manufacturing process become complicated. The burden is also great.

  On the other hand, safety measures against fires are always required, for example, in buildings such as cars and homes, and such fire extinguishers and fire extinguishing devices as described above may be placed, for example, nonflammable materials and flame retardants. Although materials have been adopted as component members (for example, Patent Document 1), such safety measures require a place for placing a fire extinguisher, a fire extinguishing device, etc. It is the present condition that you can not but say that it is insufficient.

JP, 2014-5689, A

  Then, an object of the present invention is to provide a self-extinguishing molded article capable of activating a self-extinguishing function without using a fire extinguisher or a fire extinguishing device, etc. and capable of safety measures against fire.

  However, the inventors of the present invention have filed patent applications separately "extinguishing agent composition capable of making a fire extinguisher, an extinguishing device, etc. more compact and lighter than when using a conventional powder-type extinguishing agent. It is effective to achieve the above-mentioned purpose if self-extinguishing function is given to automobile parts and building components using this as a result of earnestly repeating examination and experiment whether it can not use effectively. The present invention has been completed.

  That is, the present invention provides a self-extinguishing molded article characterized by containing an extinguishant composition that generates an aerosol by combustion to suppress a fire. The self-extinguishing molded article of the present invention having such a configuration can activate the self-extinguishing function by generating chemical species having an extinction function using thermal energy of the fire when a fire occurs, and a fire extinguisher Safety measures against fires are possible without using fire extinguishers or fire extinguishers.

  The self-extinguishing molded article of the present invention can have a planar (eg, film, sheet, plate) or three-dimensional (eg, columnar) shape, and can be employed for various parts and members. .

Further, in the self-extinguishing molded article of the present invention, the extinguishant composition is
20 to 50% by mass of fuel and 80 to 50% by mass of chlorate,
Furthermore, 6 to 1000 parts by mass of potassium salt is contained with respect to a total amount of 100 parts by mass of the fuel and the chlorate,
The thermal decomposition start temperature is in the range of more than 90 ° C. to 260 ° C.,
Is preferred.

  With the use of the extinguishant composition having such a configuration, the self-extinguishing function can be more reliably exhibited, and compactness and weight reduction can be realized as compared with the case where a conventional powder-type extinguishant is used. .

  According to the present invention, it is possible to realize a self-extinguishing molded article capable of activating a self-extinguishing function without using a fire extinguisher or a fire extinguisher or the like, and capable of taking safety measures against fire.

It is a schematic diagram which shows one Embodiment of the self-extinguishing molded article of this invention. It is a schematic diagram which shows another embodiment of the self-extinguishing molded article of this invention. It is a schematic diagram which shows another embodiment of the self-extinguishing molded article of this invention. It is a schematic diagram which shows another embodiment of the self-extinguishing molded article of this invention. It is a figure for demonstrating the test method of the confirmation test of the fire extinguishing performance using the self-extinguishing molded article of this invention (combustion space volume is 5 L).

  Hereinafter, representative embodiments of the self-extinguishing molded article of the present invention will be described in detail with reference to the drawings. In addition, since the description which overlaps in each embodiment may be abbreviate | omitted, this invention is not limited to these drawings, Moreover, since drawing is for describing this invention notionally, it is understood. For the sake of simplicity, dimensions, ratios or numbers may be exaggerated or simplified as necessary.

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 the present embodiment is in the form of a sheet, and can be used by being attached to an object to be attached 2 such as a panel of a car or a wall of a building.

  This self-extinguishing molded article 1 can be produced by mixing the binder and other components with the extinguishant composition and forming the resulting mixture into a sheet by a conventionally known method using a molding machine etc. is there. Hereinafter, the extinguishant composition, the binder and the other components will be described.

(1) Fire extinguisher composition The fire extinguisher composition contains 20 to 50% by mass of fuel (component A) and 80 to 50% by mass of chlorate (component B), and the total of the fuel and the chlorate It is characterized by containing 6-1000 mass parts potassium salt (C component) with respect to 100 mass parts, and the thermal decomposition start temperature being the range of more than 90 degreeC-260 degreeC.

  The fuel which is the component A is a component for generating thermal energy by combustion with the chlorate which is the component B to generate an aerosol (potassium radical) derived from the potassium salt of the component C.

  Such fuels for component A include, for example, dicyandiamide, nitroguanidine, guanidine nitrate, urea, melamine, melamine cyanurate, avicel, guar gum, sodium carboxymethylcellulose, potassium carboxymethylcellulose, ammonium carboxymethylcellulose, nitrocellulose, aluminum, boron, magnesium Preferably, at least one selected from magnarium, zirconium, titanium, titanium hydride, tungsten and silicon. Among them, sodium carboxymethylcellulose is particularly preferable from the viewpoint of more reliably achieving the effects of the present invention of generating and extinguishing an aerosol.

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

  As the chlorate of component B, for example, one selected from at least one of potassium chlorate, sodium chlorate, strontium chlorate, ammonium chlorate and magnesium chlorate is preferable. Among them, potassium chlorate is particularly preferable from the viewpoint of obtaining the effects of the present invention more reliably.

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

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

  Such potassium salts of component C include, for example, potassium acetate, potassium propionate, monopotassium citrate, dipotassium citrate, tripotassium citrate, monopotassium trihydrogen ethylenediaminetetraacetate, dipotassium diethylenediaminetetraacetate, ethylenediaminetetra Preferred is at least one selected from tripotassium monohydrogen acetate, tetrapotassium ethylenediaminetetraacetate, potassium hydrogen phthalate, dipotassium phthalate, potassium hydrogen oxalate, dipotassium oxalate and potassium bicarbonate. Among them, potassium acetate or tripotassium citrate is particularly preferable from the viewpoint that the effects of the present invention can be obtained more reliably.

  The content ratio of the component C is preferably 6 to 1000 parts by mass, more preferably 10 to 900 parts by mass, particularly preferably 10 to 100 parts by mass with respect to 100 parts by mass of the total amount of the components A and B. It is.

  Furthermore, the fire extinguishant composition of the present invention has a thermal decomposition onset temperature in the range of more than 90 ° C. to 260 ° C., preferably more than 150 ° C. to 260 ° C. The range of such a thermal decomposition start temperature can be adjusted by combining said A component, B component, and C component in said ratio.

  When the extinguishant composition satisfies the above range of the thermal decomposition start temperature, for example, the A and B components are automatically ignited and burned by receiving heat at the time of fire occurrence without using an igniter or the like. Thus, an aerosol (potassium radical) derived from the component C can be generated and extinguished.

  The ignition temperature of wood generally used as combustibles in the room is 260 ° C, and it does not start below 90 ° C, which is the general operating temperature of the heat detector of an automatic fire alarm system installed in a place handling fire By setting the thermal decomposition start temperature as the condition, it is possible to quickly extinguish the fire and to prevent the malfunction of the heat sensor. In particular, since the maximum set temperature of the heat sensor is 150 ° C., high versatility can be obtained by setting the lower limit value of the thermal decomposition start temperature to 150 ° C. or more.

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

(2) Binder and Other Components As the binder and the other components, various materials can be used as long as they can be formed without impairing the function of the above-mentioned extinguishant composition, and in particular as the binder It may be an inorganic binder or an organic binder. In addition, even if it does not use a binder, it is possible to produce the self-extinguishing molded article of this invention, if the dispersing agent mentioned later is used.

  As an inorganic binder, a sinterable inorganic material etc. can be mentioned, for example, As a specific example of this sinterable inorganic material, electrically insulating glass etc. can be illustrated, for example.

  Specifically as said electrically insulating glass, 50 to 60 weight% of silicon dioxide, 10 to 20 weight% of aluminum oxide, 10 to 20 weight% of calcium oxide, 1 to 10 weight% of magnesium oxide, boron oxide Can be mentioned, for example, those called E-glass, which are contained in the range of 8 to 13% by weight.

Further, it is preferable that the sinterable inorganic material has a lead metal salt and an alkali metal oxide content less than 1% by weight with respect to the weight of the sinterable inorganic material. Examples of such a lead metal salt include PbO, PbO ₂ , Pb ₃ O _{4 and the} like, and examples of the alkali metal oxide include Na ₂ O, K ₂ O and the like.

  Further, among the sinterable inorganic materials, the E glass is preferable from the viewpoint of having a low content of alkali metal oxide and having little influence on building materials such as fire doors made of fireproof / fireproof panels.

  Next, as the organic binder, for example, specifically, polyolefin resin such as polypropylene resin, polyethylene resin, poly (1-) butene resin, polypentene resin, polystyrene resin, acrylonitrile-butadiene-styrene resin Thermoplastic resins such as resin, methyl methacrylate-butadiene-styrene resin, ethylene-vinyl acetate resin, ethylene-propylene resin, polycarbonate resin, polyphenylene ether resin, acrylic resin, polyamide resin, polyvinyl chloride resin, etc. 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 (I IR), ethylene-propylene rubber (EPR, EPDM), chlorosulfonated polyethylene (CSM), acrylic rubber (ACM, ANM), epichlorohydrin rubber (CO, ECO), multiple vulcanized rubber (T), silicone rubber (Q), Rubbers such as fluorine rubber (FKM, FZ), urethane rubber (U), polyurethane resin, polyisocyanate resin, polyisocyanurate resin, thermosetting resin such as phenol resin, epoxy resin, etc., the above-mentioned thermoplastic resins, rubber And latexes such as thermoplastic resins, emulsions such as rubbers, cellulose derivatives such as CMC (carboxymethylcellulose), HEC (hydroxyethylcellulose), HPMC (hydroxypropylmethylcellulose), and the like.

  These organic binders may be used alone or in combination of two or more. Among them, latexes of rubbers, ethylene-vinyl acetate resin, acrylic resin emulsion, CMC and the like are preferable from the viewpoint of handleability and the like.

  Examples of other components include dispersants such as water, solvents, colorants, antioxidants, flame retardants, inorganic fillers, adhesives, etc. The composition of the extinguishant composition, the type of binder and desired It may be appropriately selected according to the form of the molded product and the like.

Second Embodiment
FIG. 2 is a schematic view showing a second embodiment of the self-extinguishing molded article of the present invention. The self-extinguishing molded article 11 in the present embodiment is formed into a film by spraying the fire-extinguishing composition, and can be used by forming it on the adherend 12 such as a panel of a car or a wall of a building. It is a thing.

  This film-like self-extinguishing molded article 11 is obtained by mixing the above-described extinguishant composition with a binder and other components (particularly, a solvent and a dispersion medium), and a liquid mixture (solution or dispersion) obtained with a sprayer (figure It is possible to produce by shape | molding to a film form by the conventionally well-known method using Y of 2).

Third Embodiment
FIG. 3 is a schematic view showing a third embodiment of the self-extinguishing molded article of the present invention. The self-extinguishing molded article 21 in the present embodiment is formed into a columnar shape, for example, a mixture obtained by mixing the above-described extinguishing composition molded into particles with a wood chip, a binder and other components, It can be used as a pillar of a building.

  This self-extinguishing molded article 21 is prepared by mixing wood chips, binders and other components with the above-described extinguishant composition molded into granules, and molding the obtained mixture into columns by a conventionally known method using a molding machine The particulate extinguishant composition 21a is dispersed throughout.

Fourth Embodiment
FIG. 4 is a schematic view showing a fourth embodiment of the self-extinguishing molded article of the present invention. The self-extinguishing molded article 31 in the present embodiment is, for example, a mixture obtained by mixing wood chips, a binder and other components, formed into a columnar shape, and impregnated with a extinguishant composition near its surface, It can be used as a pillar of a building.

  This self-extinguishing molded article 31 is, for example, a mixture of wood chips, a binder and other components, and the resulting mixture is formed into a columnar shape by a conventionally known method using a molding machine, and this is a liquid extinguishant composition (solution Alternatively, it can be prepared by immersion in a dispersion liquid, etc., and the fire extinguishing agent composition 31a is impregnated near the surface.

  As mentioned above, although a representative self-digestible molded article of the present invention has been described, since all of them contain the above-described fire extinguishing agent composition, chemical species having a fire extinguishing function using heat energy of fire at the time of fire occurrence The self-extinguishing function can be activated by generating (Fig. 1, X portion), and safety measures against fire can be made without using a fire extinguisher or a fire extinguisher.

«Experimental example 1» (sheet-like)
<Examples 1 to 13 and Comparative Examples 1 to 4>
Ingredients A, B and C shown in Table 1 are sufficiently mixed (as a dry matter not containing water) shown in Table 1 and thoroughly mixed with respect to a total amount of 100 parts by mass of A, B and C components, 10 parts by mass of ion exchange water was added and further mixed. The obtained water-wet mixture was dried in a thermostat at 110 ° C. for 16 hours to obtain a dried product having a water content of 1% by mass or less.
Next, the dried product is crushed in an agate mortar and sized to a particle size of 500 μm or less to obtain a ground product, CMC is added to the ground product to obtain a clay-like mixture, and this mixture is thickened It was formed into a sheet of 5 mm in size and sufficiently dried to produce the self-digestible molded articles 1 to 9 of the present invention and the comparative self-digestible molded articles 1, 3 and 4.

[Evaluation test]
(1) Apparent density The apparent density of the self-digestible molded article obtained as described above is determined by measuring the area and thickness with a digital caliper and dividing the weight by the volume obtained from the measured values. Described.
(2) Fire extinguishing test Fire extinguishing test 1 was carried out using the apparatus shown in FIG.
An iron wire mesh 52 was placed on the support table 51, and the molded articles 56 of the example and the comparative example were placed at the center thereof. A transparent container (5 L) made of heat resistant glass was placed on the wire mesh 52, and the portion other than the portion facing the wire mesh 52 was sealed. A tray 55 containing 100 ml of n-heptane as an ignition agent was placed immediately below the molded product 6 through a wire mesh 52. In this state, n-heptane was ignited to generate a flame 57, the molded article 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.

<< Experimental example 2 >> (film-like)
Examples 14 to 26 and Comparative Examples 5 to 8
In the same manner as in Example 1, a sufficient amount of CMC was added to the pulverized material so as to obtain a particle diameter of 100 μm or less, and a dispersion liquid mixture having a significantly lower viscosity than in Example 1 was obtained. . The mixture is poured into a sprayer, sprayed onto a glass substrate, and sufficiently dried to prepare a 300 μm thick film of the self-digestible molded articles 14 to 26 of the present invention and the comparative self-digestible molded products 5 to 8 did.
About these, when the same fire-extinguishing test as Experimental example 1 was done, the same result was obtained.

«Experimental Example 3» (Pelleted)
Example 27 and Comparative Example 9
A pulverized material prepared in the same manner as in Example 1 of Experimental Example 1 is filled with 2.0 g of the pulverized product in a predetermined die (die) with an inner diameter of 9.6 mm, and after inserting a punch, the surface pressure is obtained by a hydraulic pump. The pressure was applied from both sides for 5 seconds at 220.5 MPa (2250 kg / cm ² ) to obtain pellets of the self-digestible molded article 27 of the present invention. In addition, wood pellets of the same size were used as comparative molded products 9.
About these, when the fire extinguishing test similar to Experimental example 1 was done, it extinguished about the self-digestible molded article 27, and about the comparative molded article 9, it did not extinguish.
The same fire extinguishing test was conducted on the mixture obtained by mixing the self-digestible molded product 27 with the comparative molded product 9; the larger the ratio of the self-digestible molded product 27, the more effective the fire extinguishing. That is, as the proportion of the self-digestible molded product 27 is smaller, it takes more time to extinguish the fire, and in some cases the fire can not be extinguished.

  From Table 1, all of the self-digestible molded articles of the examples of the present invention could be extinguished instantly. In the comparative example, although the fire was temporarily reduced, it was not possible to extinguish the fire.

  However, the present invention is not limited to the above-mentioned sheet-like, film-like, and columnar self-digestible molded articles, and various applications are possible, and various pastes and columns other than walls of buildings are also possible. The invention is also applicable to molded articles of For example, it is applicable also to various resin products and wood products.

For example, with regard to parts of a car, it is also possible to apply to the following parts.
-Rearview mirror-Headrest-Wiper arm, Wiper blade (front and rear)
-Top cowl-Headlights, fog lights, front car side lights, other lamps-Radiator grille-Front turn signals-Front bumpers, Rear bumpers, Skirts-Side moldings-Step mud flaps
-Door arm rest, door inner handle, door lock knob-handle-horn pad-meter panel-hand brake-ventilator-various control panel-shift lever

  Moreover, as a building material, a roof material, a wall material, a floor material, a fitting etc. are mentioned, for example. The above extinguishant composition can be used as a wall material if it is formed into a sheet, and it can also be used as a roofing material, a floor material, a fitting or the like if it is formed into a plate.

1, 11, 21, 31 · · · self-digestible molded articles,
2, 12 ... material to be affixed,
21a, 31a ... extinguishant composition.

Claims (10)

  What is claimed is: 1. A self-extinguishing molded article comprising an extinguishant composition that generates an aerosol by burning to suppress a fire.   The self-extinguishing molded article according to claim 1, wherein the molded article is flat or three-dimensional. The above-mentioned digestive agent composition contains 20 to 50% by mass of fuel and 80 to 50% by mass of chlorate,
Furthermore, 6 to 1000 parts by mass of potassium salt is contained with respect to a total amount of 100 parts by mass of the fuel and the chlorate,
The thermal decomposition start temperature is in the range of more than 90 ° C. to 260 ° C.,
The self-extinguishing molded article according to claim 1 or 2, characterized in that The total amount of endothermic peaks expressed between 100 ° C. and 440 ° C. in a 10 ° C.-minute temperature rising DSC (differential scanning calorimetry) analysis of the potassium salt is 100 J / g to 900 J / g,
The self-extinguishing molded article according to any one of claims 1 to 3, characterized in that The potassium salt is a compound that generates a potassium radical by thermal energy;
The self-extinguishing molded article according to any one of claims 1 to 4, characterized in that The potassium salt is potassium acetate, potassium propionate, monopotassium citrate, dipotassium citrate, tripotassium citrate, monopotassium trihydrogen ethylenediaminetetraacetate, dipotassium diethylenediaminetetraacetate, trihydrogenpotassium ethylenediaminetetraacetate And ethylenediaminetetraacetic acid tetrapotassium, potassium hydrogen phthalate, dipotassium phthalate, potassium hydrogen oxalate, dipotassium oxalate and at least one of potassium bicarbonate,
The self-extinguishing molded article according to any one of claims 1 to 5, characterized in that   The self-extinguishing molded article according to any one of claims 1 to 6, wherein the fuel is a compound which burns together with the chlorate to generate thermal energy. The fuel is dicyandiamide, nitroguanidine, guanidine nitrate, urea, melamine, melamine cyanurate, avicel, guar gum, sodium carboxymethylcellulose, potassium carboxymethylcellulose, ammonium carboxymethylcellulose, nitrocellulose, aluminum, boron, magnesium, magnalium, zirconium, titanium Or at least one of titanium hydride, tungsten and silicon;
The self-extinguishing molded article according to claim 7, characterized in that   The self-extinguishing molded article according to any one of claims 1 to 8, wherein the chlorate is an oxidant compound that burns with the fuel to generate thermal energy.   The self-extinguishing molded article according to claim 9, wherein the chlorate is at least one of potassium chlorate, sodium chlorate, strontium chlorate, ammonium chlorate and magnesium chlorate.