JP7313076B2 - Method for producing self-extinguishing molded article - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a self-extinguishing molded article, comprising a fire-extinguishing agent composition that generates an aerosol by burning to suppress a fire.

Many common fire extinguishers and fire extinguishing devices eject and diffuse fire extinguishing agents and fire extinguishing gases by ignition methods using gas pressure and electric circuits.

Therefore, structurally, the fire extinguisher and fire extinguishing device are bulky, and it is necessary to design the structure and system.In addition, the management and manufacturing process of each part become complicated, and the cost burden is large.

On the other hand, for example, in buildings such as automobiles and houses, fire safety measures are always required, and fire extinguishers and fire extinguishing devices such as those described above are placed, and noncombustible materials and flame-retardant materials are used as constituent members (for example, Patent Document 1).

JP 2014-5689 A

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a method for producing a self-extinguishing molded product capable of activating a self-extinguishing function without using a fire extinguisher or a fire extinguishing device, thereby enabling safety measures against fire.

However, the inventors of the present invention have applied for a separate patent, "A fire extinguishing agent composition that can make fire extinguishers and fire extinguishing devices more compact and lightweight compared to the use of conventional powder fire extinguishing agents".

That is, the present invention provides a method for producing a self-extinguishing molded article, comprising a fire-extinguishing agent composition that generates an aerosol upon combustion to suppress fire extinguishing. The self-extinguishing molded article of the present invention having such a configuration can activate the self-extinguishing function by generating chemical species having extinguishing function using the thermal energy of the fire when a fire occurs, and it is possible to take safety measures against fire without using a fire extinguisher or a fire extinguishing device.

The present invention provides a self-extinguishing molded article characterized by: (1) preparing a fire extinguishing agent composition containing 20 to 50% by mass of fuel and 80 to 50% by mass of chlorate, and further containing 6 to 1000 parts by mass of potassium salt with respect to 100 parts by mass of the total amount of said fuel and said chlorate; A manufacturing method is provided.
That is, the self-extinguishing molded article obtained by the method of the present invention can have a planar shape (e.g., film-like, sheet-like, plate-like) or three-dimensional shape (e.g., columnar shape), and can be used for various parts and members.

Further, in the self-extinguishing molded article of the present invention, the extinguishing agent composition is
Containing 20 to 50% by mass of fuel and 80 to 50% by mass of chlorate,
Further containing 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,
The thermal decomposition start temperature is in the range of more than 90 ° C. to 260 ° C.,
is preferred.

By using a fire extinguisher composition having such a configuration, it is possible to more reliably exhibit a self-extinguishing function, and to realize compactness and weight reduction compared to the case of using a conventional powder-based fire extinguisher.

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

1 is a schematic diagram showing one embodiment of a self-extinguishing molded article of the present invention. FIG. FIG. 4 is a schematic diagram showing another embodiment of the self-extinguishing molded article of the present invention; FIG. 4 is a schematic diagram showing yet another embodiment of the self-extinguishing molded article of the present invention; FIG. 4 is a schematic diagram showing still another embodiment of the self-extinguishing molded article of the present invention; FIG. 2 is a diagram for explaining a test method for confirming fire extinguishing performance using the self-extinguishing molded article of the present 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, overlapping descriptions in each embodiment may be omitted, and the present invention is not limited to these drawings, and since the drawings are for conceptually explaining the present invention, for ease of understanding, dimensions, ratios, or numbers may be exaggerated or simplified as necessary.

<<First Embodiment>>
FIG. 1 is a schematic diagram showing one embodiment of the self-extinguishing molded article of the present invention. The self-extinguishing molded product 1 in this embodiment is in the form of a sheet, and can be used by sticking it to an object 2 to be stuck such as a panel of an automobile or a wall of a building.

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

(1) Extinguishing agent composition The extinguishing agent composition contains 20 to 50% by mass of fuel (component A) and 80 to 50% by mass of chlorate (component B), and further contains 6 to 1000 parts by mass of potassium salt (component C) with respect to 100 parts by mass of the total amount of the fuel and the chlorate.

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

The fuel of component A is preferably selected from at least one of, for example, dicyandiamide, nitroguanidine, guanidine nitrate, urea, melamine, melamine cyanurate, Avicel, guar gum, sodium carboxymethylcellulose, potassium carboxymethylcellulose, ammonium carboxymethylcellulose, nitrocellulose, aluminum, boron, magnesium, magnalium, zirconium, titanium, titanium hydride, tungsten and silicon. Among them, sodium carboxymethylcellulose is particularly preferable from the viewpoint of more reliably obtaining the effect of the present invention of extinguishing a fire by generating an aerosol.

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

The chlorate of component B is preferably selected from at least one of potassium chlorate, sodium chlorate, strontium chlorate, ammonium chlorate and magnesium chlorate. Among them, potassium chlorate is particularly preferable from the viewpoint that the effects of the present invention can be obtained more reliably.

Here, the contents of the fuel as component A and the chlorate as component B in the total 100% by mass are 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 C component is a component for generating an aerosol (potassium radical) by thermal energy generated by combustion of the A component and the B component.

The potassium salt of component C is preferably selected from at least one of, for example, potassium acetate, potassium propionate, monopotassium citrate, dipotassium citrate, tripotassium citrate, tripotassium trihydrogen ethylenediaminetetraacetate, dipotassium dihydrogen ethylenediaminetetraacetate, tripotassium tripotassium monohydrogen ethylenediaminetetraacetate, 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 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 components A and B.

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

By satisfying the above range of the thermal decomposition initiation temperature, the fire extinguishing agent composition can be extinguished by generating an aerosol (potassium radical) derived from the C component by automatically igniting and burning the A component and the B component upon receiving the heat at the time of the fire, for example, without using an ignition device or the like.

In addition, the ignition temperature of general wood as a combustible material in the room is 260 ° C., and it is not activated at 90 ° C. or less, which is the general operating temperature of the heat sensor of the automatic fire alarm system installed in the place where fire is handled. In particular, since the maximum set temperature of the heat sensor is 150°C, high versatility can be obtained by setting the lower limit of the thermal decomposition start temperature to over 150°C.

The form of the fire-extinguishing agent composition having the above structure is not particularly limited, and it can be used as a liquid such as a dispersion, a powder such as 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 atomization. The molded body can be in the form of granules, pellets of desired shape (cylindrical shape, etc.), tablets, spheres, discs, etc., and preferably has an apparent density of 1.0 g/cm ³ or more.

(2) Binder and other components As the binder and other components, various materials can be used as long as they are materials that can be molded without impairing the function of the fire extinguishing agent composition. In particular, the binder may be an inorganic binder or an organic binder. The self-extinguishing molded article of the present invention can be produced without using a binder by using a dispersing agent to be described later.

Examples of inorganic binders include sinterable inorganic materials, and specific examples of sinterable inorganic materials include electrically insulating glass.

Specific examples of the electrically insulating glass include those called E-glass containing 50 to 60% by weight of silicon dioxide, 10 to 20% by weight of aluminum oxide, 10 to 20% by weight of calcium oxide, 1 to 10% by weight of magnesium oxide, and 8 to 13% by weight of boron oxide.

The sinterable inorganic material preferably has a lead metal salt content and an alkali metal oxide content of less than 1% by weight relative to the weight of the sinterable inorganic material. Examples of such lead metal salts include PbO, PbO ₂ and Pb3O ₄ , and examples of alkali metal oxides include Na ₂ O and K ₂ O.

Among the sinterable inorganic materials, the E-glass is preferable from the viewpoint that it has a low content of alkali metal oxides and has little effect on building materials such as fire doors made of fireproof and fireproof panels.

Examples of organic binders include thermoplastic resins such as polyolefin resins such as polypropylene resins, polyethylene resins, poly(1-)butene resins, and polypentene resins, polystyrene resins, acrylonitrile-butadiene-styrene resins, methyl methacrylate-butadiene-styrene resins, ethylene-vinyl acetate resins, ethylene-propylene resins, polycarbonate resins, polyphenylene ether resins, acrylic resins, polyamide resins, polyvinyl chloride resins, and 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), many Rubbers such as vulcanized rubber (T), silicone rubber (Q), fluororubber (FKM, FZ), urethane rubber (U), etc. Thermosetting resins such as polyurethane resin, polyisocyanate resin, polyisocyanurate resin, phenolic resin, epoxy resin, etc. Latexes such as the above thermoplastic resins, rubbers, etc. Emulsions such as the above thermoplastic resins, rubbers, etc., CMC (carboxymethyl cellulose), HEC (hydroxyethyl cellulose), HPMC (hydroxypropyl methyl cellulose), etc. Derivatives of cellulose etc. can be mentioned.

One or more of these organic binders can be used, and among them, rubber latexes, ethylene-vinyl acetate resins, acrylic resin emulsions, CMC and the like are preferable from the viewpoint of handleability.

Other components include dispersants such as water, solvents, colorants, antioxidants, flame retardants, inorganic fillers, adhesives, etc., and may be appropriately selected depending on the composition of the fire extinguishing agent composition, the type of binder, and the form of the desired molded article.

<<Second embodiment>>
FIG. 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 into a film by spraying a fire-extinguishing composition, and can be used by forming it on an adhered object 12 such as a panel of an automobile or a wall of a building.

This film-like self-extinguishing molded article 11 can be produced by mixing a binder and other components (particularly a solvent or a dispersion medium) with the fire extinguishing agent composition, and molding the resulting liquid mixture (solution or dispersion) into a film by a conventionally known method using a sprayer (Y in FIG. 2).

<<Third Embodiment>>
FIG. 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 the present embodiment is a mixture obtained by mixing the fire-extinguishing composition molded into granules with, for example, wood chips, a binder and other components, and molded into a columnar shape, which can be used as a building pillar or the like.

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

<<Fourth embodiment>>
FIG. 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 the present embodiment is obtained by molding a mixture obtained by mixing wood chips, a binder and other components into a columnar shape, and impregnating the vicinity of the surface with a fire extinguishing agent composition, and can be used as a building pillar or the like.

The self-extinguishing molded article 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 it in a liquid extinguishing agent composition (solution or dispersion), and impregnating the extinguishing agent composition 31a near the surface.

The representative self-extinguishing molded articles of the present invention have been described above, but since they all contain the fire extinguishing agent composition described above, when a fire breaks out, the thermal energy of the fire can be used to generate a chemical species that has a fire-extinguishing function.

<<Experimental example 1>> (sheet form)
<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 in the mixing ratio shown in Table 1 (as a dry product containing no water), and the total amount of A component, B component, and C component was 100 parts by mass. 10 parts by mass of ion-exchanged water was added and further mixed. The resulting wet and wet mixed product was dried in a constant temperature bath at 110° C. for 16 hours to obtain a dry product with a water content of 1% by mass or less.
Next, the dried product was pulverized 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.

[Evaluation test]
(1) Apparent density The apparent density of the self-digesting molded product obtained as described above is obtained by measuring the area and thickness with a digital caliper, and dividing the weight by the volume obtained from the measured values.
(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 a support base 51, and a molded product 56 of the example and the comparative example was placed in the center. The wire mesh 52 was covered with a transparent container (5 L) made of heat-resistant glass, and the portion other than the portion facing the wire mesh 52 was sealed. A plate 55 containing 100 ml of n-heptane as an ignition agent was placed directly 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. Table 1 shows the results.

<<Experimental example 2>> (membrane)
<Examples 14 to 26 and Comparative Examples 5 to 8>
In the same manner as in Experimental Example 1, a sufficient amount of CMC was added to the pulverized product, which was regulated so as to have a particle diameter of 100 μm or less, to obtain a dispersion-like mixture with significantly lower viscosity than in Experimental Example 1. This mixture was injected into a sprayer, sprayed onto a glass substrate, and sufficiently dried to prepare film-like self-extinguishing molded articles 14 to 26 of the present invention and comparative self-extinguishing molded articles 5 to 8 having a thickness of 300 μm.
A fire extinguishing test similar to that of Experimental Example 1 was conducted on these, and similar results were obtained.

<<Experimental Example 3>> (Pellet)
<Example 27 and Comparative Example 9>
2.0 g of the pulverized product prepared in the same manner as in Example 1 of Experimental Example 1 was filled into a predetermined mold (mortar) having an inner diameter of 9.6 mm, and after inserting a pestle, pressure was applied from both sides with a hydraulic pump at a surface pressure of 220.5 MPa (2250 kg/cm ² ) for 5 seconds at a time to obtain a pellet-shaped self-digesting molded product 21 of the present invention. A comparative molded product 9 was made of wood pellets of the same size.
A fire extinguishing test similar to Experimental Example 1 was conducted on these, and the self-extinguishing molding 21 was extinguished, while the comparative molding 9 was not extinguished.
A similar fire extinguishing test was conducted on a mixture obtained by mixing the self-extinguishing molded article 21 with the comparative molded article 9. As a result, the greater the proportion of the self-extinguishing molded article 21, the greater the fire extinguishing effect. In other words, the smaller the proportion of the self-extinguishing molded article 21, the longer it took to extinguish the fire, and in some cases, the fire could not be extinguished.

From Table 1, all the self-extinguishing molded articles of the examples of the present invention were extinguished instantaneously. In the comparative example, the fire was temporarily reduced, but could not be extinguished.

However, the present invention is not limited to the sheet-like, film-like, and column-like self-extinguishing molded articles described above, and can be applied in various ways, and can also be applied to various pasted materials other than walls of buildings and molded articles other than pillars. For example, it can be applied to various resin products and wood products.

For example, with regard to automobile parts, it is also possible to apply the following parts.
・Rearview mirror ・Headrest ・Wiper arm, wiper blade (front and rear)
・Top cowl ・Headlights, fog lights, front width lights, other lamps ・Radiator grille ・Front turn signals ・Front bumper, rear bumper, skirt
・Door armrest, door inner handle, door lock knob ・Handle ・Horn pad ・Meter panel ・Hand brake ・Ventilator ・Various control panels ・Shift lever

Building materials also include, for example, roof materials, wall materials, floor materials, fittings, and the like. When the fire extinguishing agent composition is formed into a sheet, it can be used as a wall material, and when formed into a plate, it can be used as a roofing material, a flooring material, a fitting, and the like.

1, 11, 21, 31 ... self-digesting molded articles,
2, 12 ... affixed object,
21a, 31a... Fire-extinguishing composition.

Claims (9)

(1) containing 20 to 50% by mass of fuel and 80 to 50% by mass of chlorate,
Further prepare a fire extinguishing agent composition containing 6 to 1000 parts by mass of a potassium salt with respect to 100 parts by mass of the total amount of the fuel and the chlorate,
(2) obtaining a self-extinguishing molded article by forming the fire extinguishing agent composition into a film by spraying or forming a mixture containing particles of the fire extinguishing agent composition;
A method for producing a self-extinguishing molded article characterized by The fire extinguishing agent composition has a thermal decomposition initiation temperature in the range of more than 90 ° C. to 260 ° C.;
The method for producing a self-extinguishing molded article according to claim 1 or 2, characterized by: The total amount of endothermic peaks expressed between 100° C. and 440° C. in DSC (differential scanning calorimetry) analysis with a temperature increase of 10 degrees per minute of the potassium salt is 100 J/g to 900 J/g;
The method for producing a self-extinguishing molded article according to claim 1 or 2, characterized by: The potassium salt is a compound that generates potassium radicals by thermal energy,
A method for producing a self-extinguishing molded article according to any one of claims 1 to 3, characterized by: The potassium salt (C) is at least one of potassium acetate, potassium propionate, monopotassium citrate, dipotassium citrate, tripotassium citrate, monopotassium trihydrogen ethylenediaminetetraacetate, dipotassium dihydrogen ethylenediaminetetraacetate, tripotassium tripotassium monohydrogen ethylenediaminetetraacetate, tetrapotassium ethylenediaminetetraacetate, potassium hydrogen phthalate, dipotassium phthalate, potassium hydrogen oxalate, dipotassium oxalate and potassium bicarbonate;
A method for producing a self-extinguishing molded article according to any one of claims 1 to 4, characterized by: 6. The method for producing a self-extinguishing molded article according to any one of claims 1 to 5, wherein said fuel is a compound that burns with said chlorate to generate thermal energy. The fuel (A) is at least one of dicyandiamide, nitroguanidine, guanidine nitrate, urea, melamine, melamine cyanurate, Avicel, guar gum, sodium carboxymethylcellulose, potassium carboxymethylcellulose, ammonium carboxymethylcellulose, nitrocellulose, aluminum, boron, magnesium, magnalium, zirconium, titanium, titanium hydride, tungsten and silicon;
7. The method for producing a self-extinguishing molded article according to claim 6. the chlorate is an oxidant compound that burns with the fuel to generate thermal energy;
A method for producing a self-extinguishing molded article according to any one of claims 1 to 7, characterized by: The chlorate (B) is at least one of potassium chlorate, sodium chlorate, strontium chlorate, ammonium chlorate and magnesium chlorate;
The method for producing a self-extinguishing molded article according to claim 8, characterized by: