JP2024012106A - Fire extinguishing material composition and manufacturing method therefor, fire extinguishing material, binder selection method, and device having auto fire extinguishing function - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fire extinguishing material composition capable of demonstrating excellent fire extinguishing ability at an early stage of fire.

SOLUTION: A fire extinguishing material composition includes: a fire extinguisher containing at least one of organic salt and inorganic salt; and a binder. When the binder is heated from 30°C to 500°C at a rate of temperature increase 5°C/min in a thermogravimetric measurement of the fire extinguishing material composition under an atmospheric atmosphere, a weight reduction percentage of the binder until temperature reaches 400°C is 30% or more.

SELECTED DRAWING: Figure 1

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present disclosure relates to a composition for a fire extinguishing material, a method for manufacturing the same, a fire extinguishing material, a method for selecting a binder for the fire extinguishing material, and an apparatus having an automatic fire extinguishing function.

In recent years, with the advancement of technology, our lives have become more and more comfortable. On the other hand, a large amount of energy is required to create such comfort, and a high degree of safety is required in each scene, such as filling and storing it at a high density, moving it, and using it.

For example, when it comes to automobiles, the danger of ignition and fire lurks when fossil fuels such as gasoline are mined, when gasoline is refined from fossil fuels, and when it is transported. Taking electronics as an example, when electrical energy is transferred through electric wires, when electrical energy is adjusted at substations and transformers, when electrical energy is used in electrical equipment in homes and factories, or when electrical energy is temporarily used, Similarly, there is a lurking danger of ignition and fire when preparing storage batteries.

To address the above-mentioned ignition and fire problems, Patent Document 1 uses a fire extinguishing liquid and fire extinguisher, Patent Document 2 uses an automatic fire extinguishing device dropped from a helicopter, Patent Document 3 uses an aerosol fire extinguishing device, and Patent Document 4 uses a fire extinguishing sheet containing a fire extinguishing agent. It is proposed to use

Japanese Patent Application Publication No. 9-276440 Japanese Patent Application Publication No. 2015-6302 JP 2017-080023 Publication Japanese Patent Application Publication No. 2020-81809

All of the techniques described in Patent Documents 1 to 4 propose methods for dealing with fires after a certain amount of time has passed. On the other hand, from the viewpoint of minimizing damage caused by a fire, it is desirable that some kind of fire extinguishing work (initial fire extinguishing) be carried out soon after the fire ignites. Therefore, for example, a method may be considered in which the components of the extinguishing agent themselves are made to exist in advance near objects that are likely to ignite. By doing so, it is expected that the components of the fire extinguishing agent will be able to completely extinguish the fire before a human senses that the object has ignited. However, it is not practical to spray the extinguishing agent near the object, and it is necessary to provide it near the object in a shape that is reasonably easy to handle.

Patent Document 4 proposes a fire-extinguishing sheet formed by mixing microcapsules encapsulating a fire-extinguishing agent with ink consisting of a water-soluble resin and a hardening agent, kneading the mixture into fibers, and solidifying it into a plate shape. . However, according to studies conducted by the present inventors, when assuming a small source of fire at the initial stage of ignition, the reactivity of the fire extinguishing sheet may not be sufficient and the fire extinguishing sheet may not react. Furthermore, even if some of the microcapsules rupture due to the heat from the fire source and extinguishing agent is released, it is assumed that the fire will not spread to the sheet and sufficient extinguishing agent will not be released.

The present disclosure has been made in view of the above circumstances, and provides a fire extinguishing composition that can exhibit excellent extinguishing ability in the initial stage of ignition, a method for producing the same, a fire extinguishing material using the fire extinguishing composition, and the fire extinguishing composition. To provide a device having an automatic fire extinguishing function, which is equipped with a fire extinguisher. The present disclosure also provides a method for selecting a binder that can provide a fire extinguishing material with superior initial fire extinguishing ability.

One aspect of the present disclosure relates to a fire extinguishing composition containing a binder and a fire extinguishing agent containing at least one of an organic salt and an inorganic salt. This composition for fire extinguishing material satisfies the following requirements. In other words, when the binder is heated from 30°C to 500°C at a heating rate of 5°C/min in thermogravimetric measurement under atmospheric conditions, the weight reduction rate of the binder until the temperature reaches 400°C is 30% or more. It is. Such a fire extinguishing composition has excellent fire extinguishing ability at the initial stage of ignition.

One aspect of the present disclosure relates to a fire extinguishing composition containing a fire extinguishing agent containing at least one of an organic salt and an inorganic salt, a first binder, and a second binder. This composition for fire extinguishing material satisfies the following requirements. In other words, when the first binder is heated from 30°C to 500°C at a heating rate of 5°C/min, the weight of the first binder until the temperature reaches 400°C is determined by thermogravimetric measurement in the air atmosphere. The reduction rate is 50% or more. Weight reduction rate of the second binder until the temperature reaches 400°C when the second binder is heated from 30°C to 500°C at a heating rate of 5°C/min in thermogravimetric measurement under atmospheric conditions is 15% or less. When the mass of the first binder is 100 parts, the mass of the second binder is 250 parts or less. Such a composition for fire extinguishing material has excellent extinguishing ability at the initial stage of ignition, and depending on the type of the second binder, improves adhesion to the base material, improves workability, suppresses deliquescent property, and improves tackiness. It is possible to obtain desired physical properties such as a reduction in the amount of paint and an improvement in roll coating suitability.

The second binder may be a compound having an acid anhydride group. The second binder may be a silane coupling agent having a carboxylic acid anhydride group and an alkoxysilyl group. A fire extinguishing composition containing such a second binder has excellent extinguishing ability at the initial stage of ignition, and can suppress deliquescence of salt.

One aspect of the present disclosure relates to a fire extinguishing material containing the above composition for fire extinguishing material. One aspect of the present disclosure relates to a device having an automatic fire extinguishing function and including the above-mentioned fire extinguishing material.

One aspect of the present disclosure relates to a method for selecting a binder used in a fire extinguishing composition containing a binder and a fire extinguishing agent containing at least one of an organic salt and an inorganic salt. In this method, the binder to be evaluated is heated from 30°C to 500°C at a heating rate of 5°C/min, and the weight of the binder is measured until the temperature reaches 400°C by thermogravimetric measurement in the air. The method includes a step of measuring the weight reduction rate, and a step of determining that a fire extinguishing material composition exhibiting good initial fire extinguishing properties can be prepared for a binder whose weight reduction rate is 30% or more.

One aspect of the present disclosure relates to a method of manufacturing a fire extinguishing composition. This manufacturing method includes the steps of preparing a binder that is judged to be capable of preparing a fire extinguishing composition that exhibits good initial fire extinguishing properties, and combining the binder with an organic salt and an inorganic salt in the binder selection method described above. and a fire extinguishing agent containing at least one salt.

According to the present disclosure, there is provided a fire extinguishing composition that can exhibit excellent extinguishing ability in the initial stage of ignition, a method for producing the same, a fire extinguishing material using the fire extinguishing composition, and an automatic extinguishing function equipped with the fire extinguishing material. Equipment is provided. Further, according to the present disclosure, a method for selecting a binder that can impart excellent initial fire extinguishing ability to a fire extinguishing material is provided.

FIG. 1 is a cross-sectional view schematically showing an embodiment of a fire extinguishing material according to the present disclosure.

Embodiments of the present disclosure will be described in detail below. However, the present invention is not limited to the following embodiments.

<First embodiment>
[Composition for fire extinguishing material]
The composition for a fire extinguishing material according to the present embodiment contains a fire extinguishing agent containing at least one of an organic salt and an inorganic salt, and a binder, and has a heating rate of 5° C. When the binder is heated from 30°C to 500°C in minutes, the weight loss rate of the binder is 30% or more until the temperature reaches 400°C.

(extinguishing agent)
The fire extinguisher contains at least one of an organic salt and an inorganic salt, and an oxidizing agent. Examples of organic salts include potassium salts, sodium salts, ammonium salts, and the like. Among these, it is preferable to use potassium salt as the organic salt. Examples of organic potassium salts include potassium carboxylate salts such as potassium acetate, potassium citrate (monopotassium citrate, dipotassium citrate, tripotassium citrate), potassium tartrate, potassium lactate, potassium oxalate, potassium maleate, etc. It will be done. Among these, potassium acetate or potassium citrate is preferably used from the viewpoint of usefulness for negative catalytic effects of combustion.

Examples of inorganic salts include potassium salts, sodium salts, and the like. Among these, it is preferable to use potassium salt as the inorganic salt. Examples of the inorganic potassium salt include potassium tetraborate, potassium carbonate, potassium hydrogen carbonate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, and the like.

The organic salts and inorganic salts may be used alone or in combination of two or more.

Organic and inorganic salts may be particulate. The average particle diameter D50 of the organic salt and inorganic salt may be 1 μm or more and 100 μm or less, or 3 μm or more and 40 μm or less. When the average particle diameter D50 is at least the above lower limit, it is easy to disperse in the system, and when the average particle diameter D50 is at most the above upper limit, the stability when used as a coating liquid is improved and the smoothness of the coated surface is improved. tends to improve. The average particle diameter D50 can be calculated by wet measurement using a laser diffraction particle size distribution analyzer.

Oxidizing agents include potassium chlorate, sodium chlorate, strontium chlorate, ammonium chlorate, magnesium chlorate, potassium nitrate, sodium nitrate, strontium nitrate, ammonium perchlorate, potassium perchlorate, basic copper nitrate, copper oxide. (I), copper (II) oxide, iron (II) oxide, iron (III) oxide, molybdenum trioxide, and the like. Among these, it is preferable to use potassium chlorate.

The content of the fire extinguishing agent contained in the fire extinguishing composition may be 70 to 97% by mass, or 85 to 92 mass%, based on the total amount of the fire extinguishing composition. When the content of the fire extinguishing agent is below the above upper limit, it is easy to suppress the deliquescence of the salt, and the coating suitability of the fire extinguishing composition is increased, making it easier to form a film. This makes it easier to demonstrate sufficient fire extinguishing ability.

(binder)
Preferably, the binder is one whose weight is easily reduced by heat. In other words, when the binder is heated from 30°C to 500°C at a heating rate of 5°C/min in thermogravimetric measurement in the air, the weight reduction rate of the binder is 30% or more until the temperature reaches 400°C. It is. The weight reduction rate may be 32% or more. When the weight reduction rate is within the above range, the resulting fire extinguishing composition has excellent extinguishing ability at the initial stage of ignition. In addition, the weight reduction rate of a binder means the weight reduction rate of a mixture when there is a plurality of binders. The upper limit of this value is, for example, 88%, and may also be 46% or 32%.

In order to select a binder suitable for a fire extinguishing composition, the following selection method may be used. In other words, the method for selecting a binder is to heat the binder to be evaluated from 30°C to 500°C at a heating rate of 5°C/min by thermogravimetric measurement under atmospheric conditions, and then heat the binder to be evaluated until the temperature reaches 400°C. The method includes a step of measuring the weight reduction rate of the binder, and a step of determining that a fire extinguishing material composition exhibiting good initial extinguishing properties can be prepared using a binder having a weight reduction rate of 30% or more. The standard for the weight reduction rate may be set to 32% or more.

As the binder, thermoplastic resins and thermosetting resins can be used. Examples of thermoplastic resins include polyolefin resins such as polyvinyl alcohol resins, polypropylene resins, polyethylene resins, poly(1-)butene resins, and polypentene resins, polystyrene resins, acrylonitrile-butadiene-styrene resins, and methyl. Examples include methacrylate-butadiene-styrene resin, ethylene-vinyl acetate resin, ethylene-propylene resin, polycarbonate resin, polyphenylene ether resin, acrylic resin, polyamide resin, and polyvinyl chloride resin. Thermosetting resins include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-polybutadiene rubber (1,2-BR), styrene-butadiene rubber (SBR), and 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), polyvulcanized Rubbers such as rubber (T), silicone rubber (Q), fluororubber (FKM, FZ), urethane rubber (U), polyurethane resin, polyisocyanate resin, polyisocyanurate resin, phenol resin, epoxy resin, etc. . Among the above resins, one type may be used alone, or two or more types may be used in combination. Among these, from the viewpoint of coating suitability, it is preferable to use polyurethane resin or polyvinyl alcohol resin. Note that the binder may contain a curing agent component.

The weight average molecular weight of the binder may be 5,000 or more, 20,000 or more, or 150,000 or less, or 100,000 or less. When the weight average molecular weight is at least the above lower limit, it is easy to ensure the hydrophobicity of the resin, and when the weight average molecular weight is at most the above upper limit, it is easy to ensure appropriate resin flexibility, improving bending resistance and coating properties. It is easy to improve aptitude. The weight average molecular weight can be calculated by GPC method.

The glass transition temperature of the binder is not particularly limited, but may be -40°C or higher, 55°C or higher, 80°C or higher, or 110°C or lower. , 100°C or less. When the glass transition temperature is at least the above-mentioned lower limit, the crystallinity increases, so that it is easy to ensure the hydrophobicity of the resin, and when the glass transition temperature is at most the above-mentioned upper limit, the coating suitability is easily improved. Glass transition temperature can be measured by thermal analysis using a differential scanning calorimeter.

The viscosity of the binder at 20° C. may be 500 mPa·s or more, 1000 mPa·s or more, 10000 mPa·s or less, or 6000 mPa·s or less. The viscosity can be measured using a B-type rotational viscometer.

The content of the binder contained in the fire extinguishing composition may be 2 to 30% by mass, or 4 to 15 mass%, based on the total amount of the fire extinguishing composition. When the binder content is below the above upper limit, the surface smoothness of the coating film after drying can be easily improved (easily suppressing cracking and bubble generation in the coating film), and when the binder content is above the above lower limit As a result, the suitability for roll-to-roll coating when applying the composition for fire extinguishing material is likely to be improved, and the adhesion to the substrate and the suitability for cutting of the coating film are likely to be improved.

(liquid medium)
The fire extinguishing composition may further contain a liquid medium. Liquid media include organic solvents. Examples of organic solvents include water-soluble solvents, such as alcohols such as methanol, ethanol, isopropyl alcohol, and n-propyl alcohol; ketones such as acetone and methyl ethyl ketone; glycols such as ethylene glycol and diethylene glycol; Examples include glycol ethers such as methylpyrrolidone, tetrahydrofuran, and butyl cellosolve. From the viewpoint of being used together with a salt, the liquid medium may be an alcoholic solvent, specifically a mixed solvent of ethanol and isopropyl alcohol.

The amount of the liquid medium may be adjusted as appropriate depending on the method of using the fire extinguishing composition, but it can be 30 to 70% by mass based on the total amount of the fire extinguishing composition. A fire extinguishing composition containing a liquid medium can be referred to as a fire extinguishing coating liquid.

(Other ingredients)
Other components may be mixed in the fire extinguishing composition in addition to those mentioned above. Other ingredients include surfactants, silane coupling agents, anti-blocking agents, colorants, antioxidants, flame retardants, inorganic fillers, flow agents, moisture-proofing agents, dispersants, UV absorbers, and flexibility. Examples include imparting agents, catalysts, and the like. These other components can be appropriately selected depending on the type of fire extinguisher, binder, liquid medium, etc. The content of other components contained in the fire extinguishing composition is, for example, 10% by mass or less based on the total amount of the fire extinguishing composition.

[Method for producing composition for fire extinguishing material]
A fire extinguishing composition can be produced by mixing a fire extinguishing agent containing at least one of an organic salt and an inorganic salt, a binder, and other components used as necessary. The binder to be used may be any binder that is determined to be capable of preparing a fire extinguishing composition that exhibits good initial fire extinguishing properties in the binder selection method described above.

<Second embodiment>
The composition for a fire extinguishing material according to the present embodiment contains a fire extinguishing agent containing at least one of an organic salt and an inorganic salt, a first binder, and a second binder, and is thermogravimetrically measured in an atmospheric atmosphere. When the first binder is heated from 30°C to 500°C at a heating rate of 5°C/min, the weight reduction rate of the first binder until the temperature reaches 400°C is 50% or more, Weight reduction rate of the second binder until the temperature reaches 400°C when the second binder is heated from 30°C to 500°C at a heating rate of 5°C/min in thermogravimetric measurement in the air atmosphere is 15% or less, and when the mass of the first binder is 100 parts, the mass of the second binder is 250 parts or less.

As the fire extinguishing agent and the first binder according to this embodiment, the same ones as the fire extinguishing agent and binder explained in the above-mentioned first embodiment can be used, respectively.

Since the second binder is used in combination with the first binder whose weight is easily reduced by heat, it may be a binder whose weight is not easily reduced by heat. That is, in the thermogravimetric measurement conducted under the above conditions, the weight reduction rate of the second binder may be 15% or less, 13% or less, or 12% or less, as described above. The lower limit of this value is, for example, 0%, and may be 3% or 7%.

The content of the second binder contained in the composition for fire extinguishing material is, as described above, 250 parts or less, 200 parts or less, 150 parts or less, or 100 parts or less, with the mass of the first binder being 100 parts. There may be. By having the content of the second binder within the above range, desired physical properties depending on the type of the second binder can be achieved while maintaining a practically sufficient extinguishing ability at the initial stage of ignition in the obtained fire extinguishing material composition. can be obtained. The lower limit of this value is, for example, 10 copies, or may be 50 copies.

Note that the first binder used in combination with the second binder may be one whose weight is more easily reduced by heat. That is, in the thermogravimetric measurement conducted under the above conditions, the weight reduction rate of the first binder is preferably 50% or more, may be 52% or more, 54% or more, or 60% or more. You can.

As the second binder, for example, a compound having an acid anhydride group can be used. When the fire extinguishing material composition contains a compound having an acid anhydride group, the properties of the molded article can be stably maintained over a long period of time. The reason for this is not clear, but it is presumed that the acid anhydride group is capable of reacting with water, which traps the invading water and prevents the salt contained in the molded article from deliquescing. It is also assumed that hydrophobicity is improved by modifying the surface of the salt with a compound having an acid anhydride group, thereby suppressing contact with water.

The compound having an acid anhydride group is not particularly limited as long as it is a compound having one or more acid anhydride groups in the molecule formed by dehydration condensation of two molecules of oxoacid. Examples of the oxoacid constituting the acid anhydride group include carboxylic acid, sulfuric acid, nitric acid, and phosphoric acid. Among these, the oxoacid constituting the acid anhydride group is preferably a carboxylic acid. Examples of compounds having a carboxylic anhydride group include simple carboxylic anhydrides such as phthalic anhydride, succinic anhydride, and maleic anhydride, or carboxylic anhydrides having unsaturated bonds such as maleic anhydride. Examples include copolymers made into monomers. Note that a compound having an acid anhydride group may be used as the first binder.

The compound having an acid anhydride group may further have an alkoxysilyl group in the molecule. When the compound having an acid anhydride group contained in the fire extinguishing composition further has an alkoxysilyl group in the molecule, the properties of the molded article can be maintained more stably over a long period of time. The reason for this is not clear, but after the alkoxysilane is hydrolyzed, a self-reaction occurs and siloxane is formed, which improves water resistance and film density, allowing the deliquescent salt and water to form. It is presumed that contact with other people has been suppressed. As the compound having an acid anhydride group and an alkoxysilyl group in the molecule, for example, a silane coupling agent may be used. Note that the silane coupling agent used as the compound having an acid anhydride group may have the same function as the binder resin in the fire extinguishing material composition.

As the second binder, for example, thermoplastic resins and thermosetting resins can be used. In addition, from the viewpoint of facilitating coating film formation and stabilizing the properties after film formation, surfactants, silane coupling agents, anti-blocking agents, antioxidants, flame retardants, fluidity imparting agents, moisture proofing agents, dispersants, UV absorbers, softeners, etc. may also be used. By appropriately using or combining the second binders, desired physical properties can be imparted to the fire extinguishing material composition, such as improved adhesion to the base material, improved workability, reduced tackiness, and improved suitability for roll-to-roll coating. can do. Among these, the second binder is preferably a compound having an acid anhydride group, and particularly preferably a silane coupling agent having a carboxylic acid anhydride group and an alkoxysilyl group.

The fire extinguishing composition according to the second embodiment may further contain the same liquid medium or other components as the fire extinguishing composition according to the first embodiment. The amount of the liquid medium may be adjusted as appropriate depending on the method of using the fire extinguishing composition, but it can be 30 to 70% by mass based on the total amount of the fire extinguishing composition. The content of other components contained in the fire extinguishing composition is, for example, 10% by mass or less based on the total amount of the fire extinguishing composition.

<Fire extinguishing material>
The fire extinguishing material can be formed from a fire extinguishing composition. FIG. 1 is a cross-sectional view schematically showing one embodiment of a fire extinguishing material. The fire extinguishing material 1 includes a base material 2 and a fire extinguishing material layer 3 provided on one surface of the base material 2. The fire extinguishing material 1 can be manufactured through the steps of applying a fire extinguishing material coating liquid onto one surface of the base material 2 and drying the applied layer to form the fire extinguishing material layer 3. The material of the base material 2 is, for example, metal, resin, wood, ceramics, or glass, and may be non-porous or porous.

Application can be performed by a wet coating method. Examples of the wet coating method include a gravure coating method, a comma coating method, a spray coating method, a dip coating method, a curtain coating method, a spin coating method, a sponge roll method, a die coating method, and painting with a brush.

The viscosity of the coating liquid for fire extinguishing material is preferably 1 to 2,000 mPa·s for gravure coating, 500 to 100,000 mPa·s for comma coating, and 500 to 100,000 mPa·s for spray coating. It is preferable to set it to 0.1 to 4000 mPa·s. The amount of the liquid medium may be adjusted as appropriate so that the viscosity of the coating liquid falls within a desired range. Viscosity can be measured using a coaxial double cylinder rotational viscometer.

If the substrate 2 is porous, the fire extinguishing coating liquid can penetrate into the substrate 2. In that case, a part of the fire extinguishing material layer 3 may soak into the inside of the base material 2, and the rest may be laminated on the surface of the base material 2.

A fire extinguishing material can also be obtained by molding a composition for a fire extinguishing material into a predetermined shape. The shape of the fire extinguishing material may be selected depending on its use, and the fire extinguishing material may be a granular fire extinguishing material, a plate-like fire extinguishing material, a columnar fire extinguishing material, or the like.

<Equipment with automatic fire extinguishing function>
Devices with automatic fire extinguishing function are equipped with fire extinguishing material. Examples of devices having an automatic fire extinguishing function include electrical system equipment equipped with electrical wiring, cables, transformers, electrical circuits, and the like. Specific examples include switchboards, distribution boards, storage batteries (lithium ion batteries, etc.), batteries (mobile batteries, tool batteries, automotive EV batteries, etc.), power storage systems equipped with the above, and the like. Furthermore, there are places where there is a risk of unintentional ignition, such as collection boxes for storage batteries, trash cans, outlet covers, etc.

Hereinafter, the present disclosure will be explained in more detail based on Examples, but the present invention is not limited to the following Examples.

<Formation of fire extinguishing material>
(Example 1)
A fire extinguishing material composition was prepared by mixing the following components.
Fire extinguisher: mixture of potassium citrate and potassium chlorate (87.4 parts by mass)
First binder: ether-based urethane resin (12.6 parts by mass)
Liquid medium: ethanol (87 parts by mass)
Liquid medium: isopropyl alcohol (27 parts by mass)
The mixture of potassium citrate and potassium chlorate was ground in an agate mortar and then filtered through an 800 mesh to adjust the particle size D50 to 8 to 12 μm.

Use an applicator on one side of a polyethylene terephthalate (PET) base material (product name: E7002, manufactured by Toyobo Co., Ltd.) that has not been subjected to release treatment, so that the coating thickness after drying is 150 μm. After applying the fire extinguishing composition as described above, it was dried in an oven at 75° C. for 7 minutes. Thereby, a sheet-like fire extinguishing material was produced on the surface of the base material.

(Example 2)
12.6 parts by mass of acrylic resin was used instead of 12.6 parts by mass of ether-based urethane resin, and 23 parts by mass of ethyl acetate was used instead of 27 parts by mass of isopropyl alcohol as the liquid medium. Except for the above, a fire extinguishing material composition was prepared in the same manner as in Example 1, and a fire extinguishing material was produced using this composition.

(Example 3)
12.6 parts by mass of polyvinyl butyral (PVB) resin was used instead of 12.6 parts by mass of ether-based urethane resin, and the amount of ethanol was 179 parts by mass and the amount of isopropyl alcohol was 10 parts by mass as the liquid medium. A fire extinguishing material composition was prepared in the same manner as in Example 1 except that the composition was used to produce a fire extinguishing material.

(Example 4)
Instead of 12.6 parts by mass of ether-based urethane resin, 8.4 parts by mass of PVB resin was used, and 4.2 parts by mass of X-12-1287A (trade name, Shin-Etsu Chemical Co., Ltd.) was used as a second binder. A fire extinguishing composition was prepared in the same manner as in Example 1, except that 148 parts by mass of ethanol and 7 parts by mass of isopropyl alcohol were used as the liquid medium. A fire extinguishing material was also produced using this.

(Example 5)
Instead of 12.6 parts by mass of ether-based urethane resin, 12.6 parts by mass of polymethyl vinyl ether (PMVE)/maleic anhydride copolymer (Gantrez AN-139 (manufactured by Ashland Japan Co., Ltd.)) is used. At the same time, a fire extinguishing material composition was prepared in the same manner as in Example 1 except that the amount of ethanol was 150 parts by mass and the amount of isopropyl alcohol was 0 parts by mass, and a fire extinguishing material was produced using this composition.

(Example 6)
Example 1 was carried out in the same manner as in Example 1, except that the amount of 12.6 parts by mass of ether-based urethane resin was changed to 4.2 parts by mass, and 8.4 parts by mass of X-12-1287A was used as the second binder. A composition for a fire extinguishing material was prepared, and a fire extinguishing material was produced using this composition.

(Comparative example 1)
Example 1 was carried out in the same manner as in Example 1, except that the amount of 12.6 parts by mass of ether-based urethane resin was changed to 3.2 parts by mass, and 9.4 parts by mass of X-12-1287A was used as the second binder. A composition for a fire extinguishing material was prepared, and a fire extinguishing material was produced using this composition.

(Comparative example 2)
A fire extinguishing material composition was prepared in the same manner as in Example 1, except that 12.6 parts by mass of X-12-1287A was used instead of 12.6 parts by mass of ether-based urethane resin, and using this. We made fire extinguishing material.

<Measurement of weight change rate>
The first and second binders used in each Example and Comparative Example were measured at a heating rate of 5°C/min in an atmospheric atmosphere using a differential thermal thermogravimeter "STA7200RV" manufactured by Hitachi High-Tech Science Co., Ltd. When the temperature was raised from 30°C to 500°C, the weight change rate when the temperature was raised to 400°C was measured. The sampling period at this time was 1 second. The measurement results are shown in Tables 1 and 2. "Weight reduction rate of mixture" in the table means the weight reduction rate of the mixture of the first and second binders (Examples 4 and 6 and Comparative Example 1).

<Enclosure of fire extinguishing material>
A barrier film including a sealant layer (L-LDPE (linear low density polyethylene) resin, thickness 30 μm) and a base material layer (PET resin having a silica deposited film, thickness 12 μm) was prepared. The water vapor permeability of the barrier film was 0.2 to 0.6 g/m ² /day (under 40° C./90% RH conditions). Two of these barrier films were used to cover a sheet-like fire extinguishing material, and the four sides of the barrier film were heat-sealed to encapsulate the fire extinguishing material. Heat sealing conditions were 140° C. for 2 seconds. This was used as an evaluation sample.

<Fire extinguishing test>
An iron container measuring 20 cm in length, 30 cm in width, and 40 cm in height was prepared. To prevent ignited solid fuel from extinguishing due to suffocation, there are circular vents with a diameter of 8.5 mm on the side of the container at heights of 5, 12.5, 20.0, 27.5, and 35.0 cm from the top. There were five openings on each side. A fire extinguishing material with an area of 50 mm x 50 mm was attached to the center of the top of the container with double-sided tape. In the center of the bottom of the container, 1.5 g of solid fuel (solid fuel fireblock igniter manufactured by Captain Stag Co., Ltd.) with a length of 15 mm, a width of 15 mm, and a height of 10 mm was placed.
When the solid fuel was ignited, an evaluation was made to determine whether the fire extinguishing material could extinguish the fire within 180 seconds after the solid fuel was ignited, while adjusting the distance between the solid fuel and the fire extinguishing material. Evaluation was performed based on the following criteria.
A: A fire can be extinguished if the distance from the fire extinguishing material to the fire source is 20cm.
B: The fire can be extinguished when the distance from the fire extinguishing material to the fire source is 10 cm.
C: The fire cannot be extinguished if the distance from the fire extinguishing material is 10 cm.

<Deliquescent evaluation>
The total light transmittance of the obtained evaluation sample was measured using a haze meter (BYK-Gardner Haze-Guard Plus, manufactured by BYK) in accordance with JIS K 7361-1. Measurements were performed before placing the device in a constant temperature and humidity chamber (85°C/85% RH) (initial total light transmittance) and after 24 hours (total light transmittance after storage). The amount of change Δ in total light transmittance before and after storage was calculated according to the following. Since the transparency of the fire extinguishing material increases when moisture absorption (deliquescence) occurs, the degree of deliquescence was evaluated by checking the amount of change Δ. Evaluation was performed based on the following criteria.
Amount of change Δ = value of total light transmittance after storage - value of initial total light transmittance A: Amount of change Δ is 35 or less.
B: The amount of change Δ exceeds 35.

1... Fire extinguishing material, 2... Base material, 3... Fire extinguishing material layer.

Claims (8)

A fire extinguishing composition comprising a fire extinguishing agent containing at least one of an organic salt and an inorganic salt, and a binder,
When the binder is heated from 30°C to 500°C at a heating rate of 5°C/min by thermogravimetric measurement in the air, the weight loss rate of the binder until the temperature reaches 400°C is 30% or more. A composition for fire extinguishing material. A fire extinguishing composition comprising a fire extinguishing agent containing at least one of an organic salt and an inorganic salt, a first binder, and a second binder, the composition comprising:
The weight of the first binder until the temperature reaches 400°C when the first binder is heated from 30°C to 500°C at a heating rate of 5°C/min in thermogravimetric measurement in the air atmosphere. The reduction rate is 50% or more,
The weight of the second binder until the temperature reaches 400°C when the second binder is heated from 30°C to 500°C at a heating rate of 5°C/min in thermogravimetric measurement in the air atmosphere. The reduction rate is 15% or less,
A composition for a fire extinguishing material, wherein the mass of the second binder is 250 parts or less when the mass of the first binder is 100 parts. The fire extinguishing material composition according to claim 2, wherein the second binder is a compound having an acid anhydride group. The fire extinguishing material composition according to claim 2, wherein the second binder is a silane coupling agent having a carboxylic acid anhydride group and an alkoxysilyl group. A fire extinguishing material comprising the fire extinguishing material composition according to any one of claims 1 to 4. An apparatus having an automatic fire extinguishing function, comprising the fire extinguishing material according to claim 5. A method for selecting a binder used in a fire extinguishing composition containing a fire extinguishing agent containing at least one of an organic salt and an inorganic salt, and a binder, the method comprising:
Heat the binder to be evaluated from 30°C to 500°C at a temperature increase rate of 5°C/min by thermogravimetric measurement under atmospheric conditions, and measure the weight loss rate of the binder until the temperature reaches 400°C. The process of
A step of determining that a fire extinguishing composition that exhibits good initial fire extinguishing properties can be prepared using the binder having a weight reduction rate of 30% or more;
How to select a binder, including: In the method for selecting a binder according to claim 7, a step of preparing a binder that is determined to be capable of preparing a fire extinguishing composition that exhibits good initial fire extinguishing properties;
preparing a fire extinguishing composition comprising the binder and a fire extinguishing agent containing at least one of an organic salt and an inorganic salt;
A method for producing a composition for fire extinguishing material, including:

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