JP2022009928A - Manufacturing method of self-extinguishing molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a self-extinguishing molding capable of applying safety measure to a fire capable of activating a self-extinguishing function without using a fire extinguisher or a fire extinguishing device.

SOLUTION: A manufacturing method of a self-extinguishing molding characterized in that (1) a fire extinguishing agent composition that contains 20 to 50 mass% of fuel and 80 to 50 mass% of chlorate, and further, contains 6 to 1000 pts.mass of potassium salt relative to a total 100 pts.mass of the fuel and the chlorate is prepared, (2) the fire extinguishing composition is molded into plate-like or stereo-like shape by a molder, or spray atomization, or by impregnating in the molding to obtain the self-extinguishing molding.

SELECTED DRAWING: None

COPYRIGHT: (C)2022,JPO&INPIT

Description

The present invention relates to a method for producing a self-extinguishing molded product, which comprises a fire extinguishing agent composition that generates an aerosol by combustion and suppresses fire extinguishing.

Many general fire extinguishers and fire extinguishing devices eject and diffuse fire extinguishing agents and fire extinguishing gas by ignition method using gas pressure or electric circuit. It is necessary to use various parts such as parts for ejecting and diffusing gas, parts such as electric circuits for ignition, and temperature and flame detectors.

Therefore, due to the structure, the fire extinguisher and the fire extinguisher become bulky, it is necessary to design the structure and system, and the management and manufacturing process of each part becomes complicated, which is costly. The burden is also heavy.

On the other hand, for example, buildings such as automobiles and houses are always required to have safety measures against fire, and fire extinguishers and fire extinguishing devices as described above may be installed, for example, nonflammable materials and flame retardant materials. Materials are used for constituent members (for example, Patent Document 1), but such safety measures require a place for a fire extinguisher, a fire extinguisher, etc., or are hard to burn. The current situation is that it is inadequate.

Japanese Unexamined Patent Publication No. 2014-5689

Therefore, an object of the present invention is to provide a method for manufacturing a self-extinguishing molded product capable of invoking a self-extinguishing function without using a fire extinguisher, a fire extinguishing device, or the like and capable of taking safety measures against a fire.

However, the present inventors have separately applied for a patent, "A fire extinguisher composition capable of making a fire extinguisher, a fire extinguisher, etc. more compact and lightweight than the case of using a conventional powder-based fire extinguishing agent. As a result of repeated diligent studies and experiments to see if it can be used effectively, it was found that if the parts of automobiles and the members that make up the building have a self-fire extinguishing function, it would be effective to achieve the above objectives. We have found and completed the present invention.

That is, the present invention provides a method for producing a self-extinguishing molded product, which comprises a fire extinguishing agent composition that generates an aerosol by combustion and suppresses fire extinguishing. The self-extinguishing molded product of the present invention having such a configuration can activate the self-fire extinguishing function by generating a chemical species having a fire extinguishing function by using the heat energy of the fire when a fire occurs, and is a fire extinguisher. It is possible to take safety measures against fire without using a fire extinguisher or a fire extinguisher.

The present invention contains (1) 20 to 50% by mass of fuel and 80 to 50% by mass of chlorate, and 6 to 1000 parts by mass with respect to 100 parts by mass of the total amount of the fuel and the chlorate. A fire extinguishing agent composition containing a potassium salt is prepared, and (2) the fire extinguishing agent composition is molded into a flat or three-dimensional shape by a molding machine or spray spray, or by impregnating the molded body. Provided is a method for manufacturing a self-extinguishing molded product, which comprises obtaining a self-extinguishing molded product.
That is, the self-extinguishing molded product obtained by the method of the present invention 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 various parts and members. Can be adopted for.

Further, in the self-extinguishing molded product of the present invention, the fire extinguishing agent composition is used.
Contains 20-50% by mass of fuel and 80-50% by mass of chlorate,
Further, 6 to 1000 parts by mass of potassium salt is contained 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 over 90 ° C to 260 ° C.
Is preferable.

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

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

It is a schematic diagram which shows one Embodiment of the self-fire 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 the still 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 5L).

Hereinafter, a typical embodiment of the self-extinguishing molded product of the present invention will be described in detail with reference to the drawings. It should be noted that duplicate explanations may be omitted in each embodiment, and the present invention is not limited to these drawings, and the drawings are for conceptually explaining the present invention. For convenience, dimensions, ratios or numbers may be exaggerated or simplified as needed.

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

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

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

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

Examples of the fuel for the component A include dicyandiamide, nitroguanidine, guanidine nitrate, urea, melamine, melamine cyanurate, avicel, guagam, sodium carboxylmethylcellulose, potassium carboxylmethylcellulose, ammonium carboxylmethylcellulose, nitrocellulose, aluminum, boron, and magnesium. , Magnalium, zirconium, titanium, titanium hydride, tungsten and silicon are preferably selected from at least one. Of these, sodium carboxylmethylcellulose is particularly preferable from the viewpoint of more reliably obtaining the effect of the present invention of generating an aerosol to extinguish a fire.

Chlorate of component B is a powerful oxidizing agent, and is a component for generating thermal energy by combustion together with fuel of component A and generating aerosol (potassium radical) derived from the potassium salt of component C.

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

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

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

Examples of the potassium salt of the C component include potassium acetate, potassium propionate, monopotassium citrate, dipotassium citrate, tripotassium citrate, monopotassium trihydrogen tetraacetate ethylenediamine, dipotassium dihydrogen tetraacetate ethylenediamine, and tetratetraethylenediamine. It is preferably selected from at least one of tripotassium monohydrogen acetate, tetrapotassium ethylenediamine tetraacetate, potassium hydrogen phthalate, dipotassium phthalate, potassium hydrogen oxalate, dipotassium oxalate and potassium bicarbonate. Of these, potassium acetate or tripotassium citrate is particularly preferable from the viewpoint of more reliably obtaining the effects of the present invention.

The content ratio of the C component 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 with respect to 100 parts by mass of the total amount of the A component and the B component. Is.

Further, 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. The range of such a thermal decomposition start temperature can be adjusted by combining the above-mentioned A component, B component and C component in the above ratio.

By satisfying the range of the above-mentioned pyrolysis start temperature, the above-mentioned fire extinguishing agent composition automatically ignites and burns the components A and B by receiving the heat at the time of a fire without using, for example, an ignition device. Therefore, the fire can be extinguished by generating an aerosol (potassium radical) derived from the C component.

The ignition temperature of wood, which is generally used as a combustible material in a room, is 260 ° C, and it does not start at 90 ° C or lower, which is the general operating temperature of a heat detector of an automatic fire alarm system installed in a place where fire is handled. By setting the thermal decomposition start temperature as a condition, the fire can be extinguished quickly and the malfunction of the heat detector can be prevented. In particular, since the maximum set temperature of the heat detector is 150 ° C., high versatility can be obtained by setting the lower limit of the thermal decomposition start temperature to more than 150 ° C.

The form of the fire extinguishing agent composition having the above-mentioned structure is not particularly limited, and can be used as a liquid or powder such as a dispersion 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 spraying. Further, the molded body can be formed into granules, pellets having a desired shape (cylindrical shape, etc.), tablets, spheres, disks, etc., and the apparent density is preferably 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 can be molded without impairing the function of the fire extinguishing agent composition, and particularly as the binder. It may be an inorganic binder or an organic binder. It is possible to produce the self-extinguishing molded product of the present invention by using the dispersant described later without using a binder.

Examples of the inorganic binder include a sinterable inorganic material, and specific examples of the sinterable inorganic material include electrically insulating glass and the like.

Specific examples of the electrically insulating glass include silicon dioxide in an amount of 50 to 60% by weight, aluminum oxide in an amount of 10 to 20% by weight, calcium oxide in an amount of 10 to 20% by weight, magnesium oxide in an amount of 1 to 10% by weight, and boron oxide in an amount of 1 to 10% by weight. Can be mentioned as E-glass, which is contained in the range of 8 to 13% by weight or the like.

Further, the sinterable inorganic material is preferably such that the content of the lead metal salt and the alkali metal oxide is less than 1% by weight, respectively, with respect to the weight of the sinterable inorganic material. Examples of the lead metal salt include PbO, PbO ₂ , Pb3O ₄ , and the like, and examples of the alkali metal oxide include Na ₂ O, K ₂ O, and the like.

Further, among the sintered inorganic materials, the E glass is preferable from the viewpoint that the content of the alkali metal oxide is small and the influence on the building material such as a fire door made of a fireproof / fireproof panel is small.

Next, as the organic binder, for example, specifically, a polypropylene resin, a polyethylene resin, a poly (1-) butene resin, a polyolefin resin such as a polypentene resin, a polystyrene resin, and an acrylonitrile-butadiene-styrene resin. Thermoplastic resins such as resins, 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 (IIR), ethylene-propylene rubber (EPR, EPDM), chlorosulfonated polyethylene (CSM), acrylic rubber (ACM, ANM), epichlorohydrin rubber (CO, ECO), polysulfide rubber (T), silicone rubber. (Q), rubbers such as fluororubber (FKM, FZ), urethane rubber (U), thermosetting resins such as polyurethane resin, polyisocyanate resin, polyisocyanurate resin, phenol resin, epoxy resin, and the above-mentioned thermoplasticity. Examples include latexes such as resins and rubbers, emulsions such as the thermoplastic resins and rubbers, and cellulose derivatives such as CMC (carboxymethyl cellulose), HEC (hydroxyethyl cellulose), and HPMC (hydroxypropyl methyl cellulose). can.

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

Examples of other components include dispersants such as water, solvents, colorants, antioxidants, flame retardants, inorganic fillers, adhesives and the like, and the composition of the fire extinguishing agent composition, the type of binder and the desired one. It may be appropriately selected depending on 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 product of the present invention. The self-extinguishing molded product 11 in the present embodiment is formed by spraying a fire-extinguishing composition into a film shape, and can be formed on an attached object 12 such as an automobile panel or a building wall and used. It is a thing.

The film-like self-extinguishing molded product 11 is obtained by mixing a binder and other components (particularly a solvent or a dispersion medium) with the above-mentioned fire extinguishing agent composition, and spraying the obtained liquid mixture (solution or dispersion) with a sprayer (FIG. It can be produced by molding into a film by a conventionally known method using Y) of 2.

<< Third Embodiment >>
FIG. 3 is a schematic view showing a third embodiment of the self-extinguishing molded product of the present invention. The self-extinguishing molded product 21 in the present embodiment is obtained by molding a mixture obtained by mixing the above-mentioned fire-extinguishing composition formed in a granular form with, for example, wood chips, a binder and other components in a columnar shape. It can be used as a pillar of a building.

The self-extinguishing molded product 21 is obtained by mixing wood chips, a binder and other components with the above-mentioned fire extinguishing agent composition molded into granules, and molding the obtained mixture into columns by a conventionally known method using a molding machine. The granular fire extinguishing agent composition 21a is dispersed throughout.

<< Fourth Embodiment >>
FIG. 4 is a schematic view showing a fourth embodiment of the self-extinguishing molded product of the present invention. The self-extinguishing molded product 31 in the present embodiment is obtained by molding a mixture obtained by mixing, for example, wood chips, a binder and other components into columns and impregnating the surface thereof with a fire extinguishing agent composition. It can be used as a pillar of a building.

In this self-extinguishing molded product 31, for example, wood chips, binders and other components are mixed, and the obtained mixture is formed into columns by a conventionally known method using a molding machine, and this is formed into a liquid fire extinguishing agent composition (solution). Alternatively, it can be produced by immersing it in a dispersion liquid) or the like, and the fire extinguishing agent composition 31a is impregnated in the vicinity of the surface.

The typical self-extinguishing molded products of the present invention have been described above, but since they all contain the above-mentioned fire extinguishing agent composition, they are chemical species having a fire extinguishing function by using the heat energy of the fire in the event of a fire. The self-fire extinguishing function can be activated by generating the above (part X in FIG. 1), and safety measures against fire can be taken without using a fire extinguisher or a fire extinguisher.

<< 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 are sufficiently mixed in the blending ratio shown in Table 1 (as a dry product containing no water), and the total amount of the A component, B component and C component is 100 parts by mass. Ion-exchanged water corresponding to 10 parts by mass 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 having a water 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 crushed product, and CMC was added to the crushed product to obtain a clay-like mixture, and this mixture was thickened. It was formed into a sheet having a size of 5 mm and dried sufficiently to prepare the autolytic molded products 1 to 9 of the present invention and the comparative autolytic molded products 1, 3 and 4.

[Evaluation test]
(1) Apparent density The apparent density of the autolytic molded product obtained as described above was obtained by measuring the area and thickness with a digital caliper and dividing the weight by the volume obtained from the measured values, and Table 1 shows. Described.
(2) Fire extinguishing test Fire extinguishing test 1 was carried out with the device shown in FIG.
An iron wire mesh 52 was placed on the support base 51, and the molded products 56 of Examples and Comparative Examples were placed in the center thereof. A transparent container (5 L) made of heat-resistant glass was placed on the wire mesh 52 and sealed except for the portion facing the wire mesh 52. A dish 55 containing 100 ml of n-heptane as an ignition agent was placed directly under the molded product 6 via 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.

<< Experimental Example 2 >> (Membrane)
<Examples 14 to 26 and Comparative Examples 5 to 8>
In the same manner as in Experimental Example 1, the particles were sized so as to have a particle size of 100 μm or less, and a sufficient amount of CMC was added to the pulverized product to obtain a dispersed liquid mixture having a significantly lower viscosity than Experimental Example 1. .. This mixture is injected into a sprayer, sprayed onto a glass substrate, and sufficiently dried to prepare a film-shaped self-extinguishing molded product 14 to 26 and a comparative self-digesting molded product 5 to 8 having a thickness of 300 μm. did.
When the same fire extinguishing test as in Experimental Example 1 was performed on these, the same results were obtained.

<< Experimental Example 3 >> (Pellet)
<Example 27 and Comparative Example 9>
The crushed product prepared in the same manner as in Example 1 of Experimental Example 1 is filled with 2.0 g of the crushed product into a predetermined mold (mortar) having an inner diameter of 9.6 mm, a pestle is inserted, and a surface pressure is applied by a hydraulic pump. Pressurization was performed from both sides at 220.5 MPa (2250 kg / cm ² ) for 5 seconds to obtain a pellet-shaped self-extinguishing molded product 21 of the present invention. Further, wood pellets of the same size were designated as comparative molded products 9.
When the same fire extinguishing test as in Experimental Example 1 was carried out, the self-extinguishing molded product 21 was extinguished and the comparative molded product 9 was not extinguished.
Further, when the same fire extinguishing test was performed on the mixture obtained by mixing the self-extinguishing molded product 21 with the comparative molded product 9, the fire extinguishing effect was more remarkable as the proportion of the self-extinguishing molded product 21 was larger. That is, the smaller the proportion of the self-extinguishing molded product 21, the longer it took to extinguish the fire, and in some cases the fire could not be extinguished.

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

However, the present invention is not limited to the above-mentioned sheet-shaped, film-shaped, and columnar self-extinguishing molded products, and various applications are possible, and other than various pasted objects and pillars other than the walls of buildings. It can also be applied to molded products of. For example, it can be applied to various resin products and wood products.

For example, automobile parts can be applied to the following parts.
・ Room mirror ・ Headrest ・ Wiper arm, wiper blade (front and rear)
・ Top cowl headlights, fog lamps, front side lights, other lamps ・ Radiator grille ・ Front turn signals ・ Front bumper, rear bumper, skirt ・ Side molding ・ Step mudflap (mudguard)
・ Door armrest, door inner handle, door lock knob ・ Handle ・ Horn pad ・ Meter panel ・ Handbrake ・ Ventilator ・ Various control panels ・ Shift lever

Further, as the building material, for example, roofing material, wall material, floor material, fittings and the like can be mentioned. If the above fire extinguishing agent composition is molded into a sheet shape, it can be used as a wall material, and if it is molded into a plate shape, it can be used as a roofing material, a floor material, a fitting, or the like.

1, 11, 21, 31 ... Self-extinguishing molded product,
2, 12 ... Attached material,
21a, 31a ... Fire extinguishing agent composition.

Claims (9)

(1) Contains 20 to 50% by mass of fuel and 80 to 50% by mass of chlorate.
Further, 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 was prepared.
(2) A self-extinguishing molded product can be obtained by molding the fire extinguishing agent composition into a planar or three-dimensional shape by a molding machine or spray spray, or by impregnating the molded body with the fire extinguishing agent composition.
A method for manufacturing a self-extinguishing molded product. The digestive composition has a thermal decomposition initiation temperature in the range of over 90 ° C to 260 ° C.
The method for producing a self-extinguishing molded product according to claim 1 or 2. The total amount of endothermic peaks expressed between 100 ° C and 440 ° C in the DSC (differential scanning calorimetry) analysis of the potassium salt raised at 10 ° C / min is 100 J / g to 900 J / g.
The method for producing a self-extinguishing molded product according to claim 1 or 2. The potassium salt is a compound that generates potassium radicals by heat energy.
The method for producing a self-extinguishing molded product according to any one of claims 1 to 3. The potassium salt (C) is potassium acetate, potassium propionate, monopotassium citrate, dipotassium citrate, tripotassium citrate, monopotassium trihydrogen tetraacetate ethylenediamine, dipotassium dihydrogen tetraacetate ethylenediamine, dipotassium tetraacetate ethylenediamine. Being at least one of tripotassium hydrogen, tetrapotassium ethylenediamine tetraacetate, potassium hydrogen phthalate, dipotassium phthalate, potassium hydrogen oxalate, dipotassium oxalate and potassium bicarbonate.
The method for producing a self-extinguishing molded product according to any one of claims 1 to 4. The method for producing a self-extinguishing molded product according to any one of claims 1 to 5, wherein the fuel is a compound that burns together with the chlorate to generate heat energy. The fuel (A) is dicyandiamide, nitroguanidine, guanidine nitrate, urea, melamine, melamine cyanurate, avicell, guagam, sodium carboxylmethylcellulose, potassium carboxylmethylcellulose, ammonium carboxylmethylcellulose, nitrocellulose, aluminum, boron, magnesium, magnalium, Being at least one of zirconium, titanium, titanium hydride, tungsten and silicon,
6. The method for manufacturing a self-extinguishing molded product according to claim 6. The chlorate is an oxidant compound that burns together with the fuel to generate thermal energy.
The method for producing a self-extinguishing molded product according to any one of claims 1 to 7. The chlorate (B) is at least one of potassium chlorate, sodium chlorate, strontium chlorate, ammonium chlorate and magnesium chlorate.
8. The method for manufacturing a self-extinguishing molded product according to claim 8.

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