Fire extinguishing material composition, fire extinguishing material, and device having automatic fire extinguishing function

Abstract

To provide a composition for a fire extinguishing material having highly stable properties.SOLUTION: A composition for a fire extinguishing material comprising a fire extinguishing agent containing at least one salt selected from an organic salt having deliquescence and an inorganic salt having deliquescence, and a deliquescence-inhibiting component that inhibits deliquescence of the salt, wherein the deliquescence-inhibiting component comprises a first component which is a compound having an acid anhydride group and an alkoxysilyl group, and a second component which is a copolymer containing a structural unit derived from a vinyl ether monomer and a structural unit derived from an unsaturated anhydrous carboxylic acid monomer, and when the content of the second component in the composition for the fire extinguishing material is B pts.mass and the content of the first component is A pts.mass, the value of B is greater than the value of A.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a composition for a fire extinguishing material, a fire extinguishing material, and an apparatus having an automatic fire extinguishing function.

Background Art

[0002] There is known a self-extinguishing molded article obtained by mixing a fire extinguishing agent composition that generates an aerosol by combustion with a binder and molding the mixture into a sheet shape (for example, Patent Documents 1 and 2).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] The fire extinguishing agent compositions described in Patent Documents 1 and 2 contain salts such as potassium nitrate and sodium nitrate. Since these salts are deliquescent, there is room for improvement in maintaining the properties of the self-extinguishing molded article stably over a long period. Further, according to the studies by the present inventors, when assuming a small ignition source at the initial stage of ignition, there is room for improvement in that the reactivity of the above self-extinguishing molded article is not sufficient and there is a case where initial fire extinguishing cannot be achieved with a certain probability.

[0005] The present disclosure has been made in view of the above circumstances, and provides a composition for a fire extinguishing material having excellent property stability, a fire extinguishing material containing the composition for a fire extinguishing material, and an apparatus having an automatic fire extinguishing function including the fire extinguishing material.

Means for Solving the Problems

[0006] The inventors have found that by adding a compound having an acid anhydride group and an alkoxysilyl group (hereinafter sometimes referred to as the "first component") to a fire extinguishing composition containing at least one of an organic salt and an inorganic salt having deliquescence, although the fire extinguishing performance of the fire extinguishing agent slightly decreases, the property stability can be imparted. The inventors have conducted studies to further improve the fire extinguishing performance of the fire extinguishing agent while maintaining the effect of improving the property stability by the first component. As a result, by adding an appropriate amount of a copolymer containing a structural unit derived from a vinyl ether monomer and a structural unit derived from an unsaturated carboxylic acid monomer (hereinafter sometimes referred to as the "second component") to the fire extinguishing composition, it has been found that a fire extinguishing composition excellent in property stability can be obtained while covering the decrease in the fire extinguishing performance caused by the first component. According to the studies of the inventors, both the above-mentioned first and second components play a role in suppressing the deliquescence of the salt, that is, they play a role in improving the performance stability of the fire extinguishing agent. Therefore, both the first and second components can be referred to as deliquescence suppressing components. The first component exhibits an excellent effect on improving the performance stability of the fire extinguishing agent, while the degree of decreasing the fire extinguishing performance of the fire extinguishing agent is stronger than that of the second component. On the other hand, although the degree of improving the performance stability of the fire extinguishing agent by the second component is weaker than that of the first component, it can maintain the fire extinguishing performance of the fire extinguishing agent without decreasing it, or the degree is weaker than that of the first component.

[0007] The fire extinguishing composition according to one aspect of the present disclosure is made based on the above findings, and includes a fire extinguishing agent containing at least one of an organic salt and an inorganic salt having deliquescence, and a deliquescence suppressing component for suppressing the deliquescence of the salt. The deliquescence suppressing component includes a first component that is a compound having an acid anhydride group and an alkoxysilyl group, and a second component that is a copolymer containing a structural unit derived from a vinyl ether monomer and a structural unit derived from an unsaturated carboxylic acid monomer. When the content of the second component in the fire extinguishing composition is B parts by mass and the content of the first component is A parts by mass, the value of B is larger than the value of A. According to the fire extinguishing composition satisfying this condition, excellent property stability is imparted by the first and second components, and the fire extinguishing performance that the fire extinguishing agent should originally exhibit can be maintained.

[0008] The fire extinguishing material composition preferably further contains a binder resin which is a component different from the second component. When the total mass of the first and second components and the binder resin is 100 parts by mass, the amount of the first component is 10 parts by mass or more and less than 25 parts by mass, the amount of the second component is 25 parts by mass or more and less than 90 parts by mass, and the amount of the binder resin is preferably 3 parts by mass or more and less than 40 parts by mass. The binder resin serves to bind the fire extinguishing agent and the first and second components. When the total mass of the first, second, and binder resin is 100 parts by mass, the amount of the binder resin is preferably 10 parts by mass or more. When the amount of the binder resin is 10 parts by mass or more, it is easy to produce a sheet-shaped fire extinguishing material from the fire extinguishing material composition, and this fire extinguishing material has the advantages of excellent cutting suitability and being less likely to crack.

[0009] The vinyl ether monomer may be methyl vinyl ether, and the unsaturated carboxylic anhydride monomer may be maleic anhydride. The acid anhydride group may be a carboxylic anhydride group, and the first component may be a silane coupling agent. The salt may be a potassium salt. The fire extinguishing material composition may further contain a liquid medium.

[0010] One aspect of the present disclosure relates to a fire extinguishing material containing the above fire extinguishing material composition. One aspect of the present disclosure relates to an apparatus having an automatic fire extinguishing function including the above fire extinguishing material.

Advantages of the Invention

[0011] According to the present disclosure, there are provided a fire extinguishing material composition excellent in property stability, a fire extinguishing material containing the fire extinguishing material composition, and an apparatus having an automatic fire extinguishing function including the fire extinguishing material.

Brief Description of the Drawings

[0012]

Figure 1

Figure 2

Embodiments for Carrying out the Invention

[0013] Hereinafter, embodiments of the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments.

[0014] <Fire extinguishing material composition> The fire extinguishing material composition according to the present embodiment includes a fire extinguishing agent containing at least one of an organic salt and an inorganic salt having deliquescence, and a deliquescence suppressing component that suppresses the deliquescence of the salt. The deliquescence suppressing component includes a first component that is a compound having an acid anhydride group and an alkoxysilyl group, and a second component that is a copolymer containing a structural unit derived from a vinyl ether monomer and a structural unit derived from an unsaturated carboxylic acid monomer. When the content of the second component in the fire extinguishing material composition is B parts by mass and the content of the first component is A parts by mass, the value of B is larger than the value of A. From the viewpoint of the balance between the property stability and the fire extinguishing performance of the fire extinguishing material, the value of B / A is preferably 1.5 to 10.0, more preferably 1.7 to 6.0, and still more preferably 2.0 to 4.6.

[0015] The fire extinguishing material composition preferably further includes a binder resin which is a component different from the second component. When the total mass of the first and second components and the binder resin is 100 parts by mass, the content of the first component is 10 parts by mass or more and less than 25 parts by mass. The lower limit of the above content may be 13 parts by mass, or may be 15 parts by mass. By the content being not less than the above lower limit, it is easy to suppress the deliquescence of the salt. Also, the upper limit of the above content may be 23 parts by mass, or may be 20 parts by mass or 18 parts by mass. By the content being not more than the above upper limit, it is easy to exhibit sufficient fire extinguishing performance.

[0016] When the total amount of the first and second components and the binder resin in the composition for a fire extinguishing material is 100 parts by mass, the content of the second component is 25 parts by mass or more and less than 90 parts by mass. The lower limit of the above content may be 30 parts by mass, or may be 40 parts by mass or 50 parts by mass. By the content being not less than the above lower limit, it is easy to suppress the deliquescence of the salt. Further, the upper limit of the above content may be 89 parts by mass, or may be 81 parts by mass or 75 parts by mass. By the content being not more than the above upper limit, not only is it easy to suppress the deliquescence of the salt, but also it becomes possible to add a sufficient amount of the binder resin to the composition for a fire extinguishing material, the coating suitability of the composition for a fire extinguishing material is enhanced, film formation is easy, and cracking of the film can also be suppressed.

[0017] When the total amount of the first and second components and the binder resin in the composition for a fire extinguishing material is 100 parts by mass, the content of the binder resin is, for example, 3 parts by mass or more and less than 40 parts by mass. The lower limit of the above content may be 10 parts by mass, or may be 20 parts by mass or 25 parts by mass. By the content being not less than the above lower limit, the binder resin can play a role as a binder, not only the coating suitability of the composition for a fire extinguishing material is enhanced and film formation is easy, but also cracking of the film can be suppressed. Among them, from the viewpoint of cutting suitability, the content is preferably 10 parts by mass or more. Further, the upper limit of the above content may be 33 parts by mass, or may be 30 parts by mass. By the content being not more than the above upper limit, it becomes possible to add a sufficient amount of the first and second components to the composition for a fire extinguishing material, and it becomes easy to achieve both property stability and fire extinguishing performance at the initial stage of ignition.

[0018] (Fire extinguishing agent) The fire extinguishing agent contains at least one of an organic salt and an inorganic salt having deliquescence, and an oxidizing agent. Examples of the organic salt include potassium salts, sodium salts, ammonium salts, and the like. Among these, it is preferable to use a potassium salt as the organic salt. Examples of the organic potassium salt include potassium carboxylate salts such as potassium acetate, potassium citrate (monopotassium citrate, dipotassium citrate, tripotassium citrate), potassium tartrate, potassium lactate, potassium oxalate, and potassium maleate. Among them, from the viewpoint of the usefulness for the negative catalytic effect of combustion, it is preferable to use potassium acetate or potassium citrate.

[0019] Examples of the inorganic salt include potassium salts, sodium salts, and the like. Among these, it is preferable to use a 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.

[0020] The organic salt and the inorganic salt may be used alone or in combination of two or more. The organic salt and the inorganic salt may be granular. The average particle diameter D50 of the organic salt and the inorganic salt may be 1 μm or more and 100 μm or less, or may be 3 μm or more and 40 μm or less. When the average particle diameter D50 is not less than the above lower limit, it is easy to disperse in the system. Further, when the average particle diameter D50 is not more than the above upper limit, the stability when made into a coating liquid is improved, and the smoothness of the coated surface tends to be improved. The average particle diameter D50 can be calculated by wet measurement using a laser diffraction particle size distribution measuring device.

[0021] Examples of the oxidizing agent 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(I) oxide, copper(II) oxide, iron(II) oxide, iron(III) oxide, molybdenum trioxide, and the like. Among them, it is preferable to use potassium chlorate.

[0022] The content of the fire extinguishing agent contained in the fire extinguishing material composition may be 70% by mass or more and 97% by mass or less, or may be 85% by mass or more and 92% by mass or less, based on the total amount (solid content) of the fire extinguishing material composition. When the content of the fire extinguishing agent is below the above upper limit, it is easy to suppress the deliquescence of salts, and the coating applicability of the fire extinguishing material composition is enhanced and film formation is easy. Also, when the content of the fire extinguishing agent is above the above lower limit, it is easy to exhibit sufficient fire extinguishing performance.

[0023] (First component: a compound having an acid anhydride group and an alkoxysilyl group) By containing the first component, the fire extinguishing material composition can maintain the properties of the molded article stably over a long period. Although the reason for this is not clear, since the acid anhydride group can react with water, it traps the water that has penetrated through the barrier film used to package the fire extinguishing material, preventing the deliquescence of the salts contained in the molded article, and / or after the alkoxysilane is hydrolyzed, self-reaction occurs to form siloxane, which is presumed to affect the improvement of water resistance and film density, and the suppression of the contact between the deliquescent salt and water.

[0024] The first component is preferably one that is difficult to lose weight by heat compared to the second component and the binder resin. That is, in thermogravimetric measurement under an air atmosphere, when the first component is heated from 30°C to 500°C at a heating rate of 5°C / min, the weight loss rate of the first component until the temperature reaches 400°C is, for example, less than 50%. The upper limit of the above weight loss rate may be 40%, or may be 30%, 20%, or 15%. When the above weight loss rate is within the above range, the property stability of the obtained fire extinguishing material composition is excellent. Note that the weight loss rate of the first component means the weight loss rate of the mixture when there are a plurality of first components. The lower limit of the above weight loss rate may be, for example, 0%, or may be 3% or 7%.

[0025] As the first component, there is no particular limitation as long as it is a compound having one or more acid anhydride groups formed by dehydration condensation of two molecules of oxo acid in the molecule and further having one or more alkoxysilyl groups in the molecule. Examples of the oxo acid constituting the acid anhydride group include carboxylic acid, sulfuric acid, nitric acid, phosphoric acid and the like. Among these, the oxo acid constituting the acid anhydride group is preferably a carboxylic acid. Examples of the compound having a carboxylic acid anhydride group include simple substances of carboxylic acid anhydrides such as phthalic anhydride, succinic anhydride, maleic anhydride, or copolymers having an unsaturated bond-containing carboxylic acid anhydride such as maleic anhydride as a monomer.

[0026] As the first component, for example, a silane coupling agent may be used. Note that the silane coupling agent used as the first component may have the same function as the binder resin in the fire extinguishing material composition.

[0027] (Second component: Copolymer containing a structural unit derived from a vinyl ether monomer and a structural unit derived from an unsaturated carboxylic acid anhydride monomer) By including the second component, the fire extinguishing material composition can maintain the properties of the molded article stably over a long period of time and can achieve initial fire extinguishing with a sufficiently high probability. The reason for this is not clear, but it is presumed that the structural unit derived from the vinyl ether monomer contributes to the improvement of the fire extinguishing performance, and the structural unit derived from the unsaturated carboxylic acid anhydride monomer contributes to the improvement of the property stability. The second component may have the same function as the binder resin in the fire extinguishing material composition, but is distinguished from the binder resin in that it is a copolymer containing a structural unit derived from a vinyl ether monomer and a structural unit derived from an unsaturated carboxylic acid anhydride monomer.

[0028] The second component preferably has a property of being liable to lose weight by heat. That is, in thermogravimetric measurement under an air atmosphere, when the second component is heated from 30°C to 500°C at a heating rate of 5°C / min, the weight loss rate of the second component until the temperature reaches 400°C is, for example, 50% or more. The lower limit of the above weight loss rate may be 55%. When the above weight loss rate is within the above range, the fire extinguishing performance at the initial stage of ignition in the obtained fire extinguishing composition is excellent. Note that the weight loss rate of the second component means the weight loss rate of the mixture when there are a plurality of second components. The upper limit of the above weight loss rate may be, for example, 80%, or may be 70% or 60%.

[0029] The second component is obtained, for example, by copolymerizing a vinyl ether monomer and an unsaturated carboxylic anhydride monomer. Examples of the vinyl ether monomer include alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether. Among these, the vinyl ether monomer is preferably methyl vinyl ether. Examples of the unsaturated carboxylic anhydride monomer include maleic anhydride and citraconic anhydride. Among these, the unsaturated carboxylic anhydride monomer is preferably maleic anhydride.

[0030] (Binder resin) As the binder resin, a thermoplastic resin and a thermosetting resin can be used. Examples of the thermoplastic resin include polyolefin resins such as polyvinyl alcohol-based resins, polyvinyl acetal-based resins, polypropylene-based resins, polyethylene-based resins, poly(1-)butene-based resins, polypentene-based resins, etc., polystyrene-based resins, acrylonitrile-butadiene-styrene-based resins, methyl methacrylate-butadiene-styrene-based resins, ethylene-vinyl acetate resins, ethylene-propylene resins, polycarbonate-based resins, polyphenylene ether-based resins, acrylic resins, polyamide-based resins, polyvinyl chloride-based resins, etc. Examples of the thermosetting resin include rubbers such as 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), multi-vulcanized rubber (T), silicone rubber (Q), fluororubber (FKM, FZ), urethane rubber (U), etc., polyurethane-based resins, polyisocyanate-based resins, polyisocyanurate-based resins, phenolic resins, epoxy resins, etc. Among the above resins, one kind may be used alone, or a plurality of kinds may be used in combination. Among these, according to the findings of the present inventors, from the viewpoint of coating applicability, it is preferable to use polyurethane-based resins, polyvinyl alcohol-based resins, and polyvinyl acetal-based resins, and from the viewpoint of proper cutting of the sheet-shaped fire extinguishing material, it is preferable to use polyurethane-based resins and acrylic resins. Note that the binder resin may contain a curing agent component.

[0031] The binder resin preferably has a property of being easily weight-reduced by heat. That is, in thermogravimetric measurement under an air atmosphere, when the binder resin is heated from 30°C to 500°C at a heating rate of 5°C / min, the weight reduction rate of the binder resin until the temperature reaches 400°C is, for example, 50% or more. The lower limit of the above weight reduction rate may be 60%. When the above weight reduction rate is within the above range, the fire extinguishing performance at the initial stage of ignition in the obtained fire extinguishing composition is excellent. Note that when a plurality of binder resins are used, the weight reduction rate of the binder resin means the weight reduction rate of the mixture. The upper limit of the above weight reduction rate may be, for example, 88%, or may be 80% or 70%.

[0032] The weight average molecular weight of the binder resin may be 5000 or more, may be 20000 or more, may be 150000 or less, or may be 100000 or less. When the weight average molecular weight is above the above lower limit, it is easy to ensure the hydrophobicity of the resin. Also, when the weight average molecular weight is below the above upper limit, it is easy to ensure appropriate resin flexibility, and the flexural resistance and coating applicability are likely to be improved. The weight average molecular weight can be calculated by the GPC method.

[0033] The glass transition temperature of the binder resin is not particularly limited, but may be -40°C or more, may be 55°C or more or 80°C or more, may be 110°C or less, or may be 100°C or less. When the glass transition temperature is above the above lower limit, the crystallinity increases, so it is easy to ensure the hydrophobicity of the resin. Also, when the glass transition temperature is below the above upper limit, the coating applicability is likely to be improved. The glass transition temperature can be measured by thermal analysis using a differential scanning calorimeter.

[0034] The viscosity of the resin solution obtained by dissolving the binder resin in a liquid medium at 20°C may be 500 mPa·s or more, may be 1000 mPa·s or more, may be 10000 mPa·s or less, or may be 6000 mPa·s or less. The viscosity can be measured by a B-type rotational viscometer.

[0035] (Liquid medium) The fire extinguishing composition may further contain a liquid medium. Examples of the liquid medium include organic solvents. Examples of the organic solvent 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; and glycol ethers such as N-methylpyrrolidone, tetrahydrofuran, and butyl cellosolve. From the viewpoint of being used together with the salt, the liquid medium may be an alcohol-based solvent.

[0036] The amount of the liquid medium may be appropriately adjusted according to the usage method of the fire extinguishing composition, but it can be 30% by mass or more and 70% by mass or less based on the total amount (including the liquid medium) of the fire extinguishing composition. The fire extinguishing composition containing the liquid medium can be referred to as a coating liquid for fire extinguishers.

[0037] (Other components) Other components may be mixed in the fire extinguishing composition in addition to those described above. Examples of other components include surfactants, anti-blocking agents, colorants, antioxidants, flame retardants, inorganic fillers, fluidity imparting agents, moisture-proof agents, dispersants, UV absorbers, flexibility imparting agents, catalysts, etc. These other components can be appropriately selected according to the type of the fire extinguishing agent, the first and second components, the binder resin, or the liquid medium. The content of other components contained in the fire extinguishing composition can be 10% by mass or less based on the total amount of the fire extinguishing composition.

[0038] The fire extinguishing composition can be produced by mixing a fire extinguishing agent containing at least one of an organic salt and an inorganic salt having deliquescence, the first and second components, the binder resin, and other components used as necessary.

[0039] <Fire extinguisher> The fire extinguishing material can be formed from a fire extinguishing material composition. FIG. 1 is a cross-sectional view schematically showing an embodiment of the 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 a process of applying a coating liquid for the fire extinguishing material on one surface of the base material 2 and a process of 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 it may be non-porous or porous.

[0040] The 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, painting with a brush, and the like.

[0041] For the viscosity of the coating liquid for the fire extinguishing material, for example, in the case of the gravure coating method, it is preferably 1 to 2000 mPa·s, in the case of the comma coating method, it is preferably 500 to 100000 mPa·s, and in the case of the spray coating method, it is preferably 0.1 to 4000 mPa·s. The amount of the liquid medium may be appropriately adjusted so that the coating liquid viscosity is within the desired range. The viscosity can be measured by a coaxial double cylinder rotational viscometer.

[0042] When the base material 2 is porous, the coating liquid for the fire extinguishing material can penetrate into the base material 2. In that case, a part of the fire extinguishing material layer 3 may penetrate into the interior of the base material 2 and the rest may be laminated on the surface of the base material 2.

[0043] The fire extinguishing material can also be obtained by shaping the fire extinguishing material composition into a predetermined shape. The shape of the fire extinguishing material may be selected according to its use, and the fire extinguishing material may be a granular fire extinguishing material, a plate-shaped fire extinguishing material, a columnar fire extinguishing material, or the like.

[0044] <Device with automatic fire extinguishing function> The device having an automatic fire extinguishing function is equipped with a fire extinguishing material. Examples of the device having an automatic fire extinguishing function include electrical system facilities such as those equipped with electrical wiring, cables, transformers, and electrical circuits. Specifically, distribution boards, sub-distribution boards, storage batteries (such as lithium-ion batteries), batteries (such as mobile batteries, tool batteries, and automotive EV batteries), and power storage systems equipped with the above are included. Further, locations where there is a risk of unintended ignition, such as collection boxes for storage batteries, trash cans, and outlet covers, are included.

[0045] This disclosure relates to the following matters. [1] A fire extinguishing agent containing at least one of an organic salt and an inorganic salt having deliquescence, A deliquescence suppressing component for suppressing the deliquescence of the salt, A composition for a fire extinguishing material, comprising: The deliquescence suppressing component includes a first component which is a compound having an acid anhydride group and an alkoxysilyl group, and a second component which is a copolymer containing a structural unit derived from a vinyl ether monomer and a structural unit derived from an unsaturated carboxylic acid monomer, A composition for a fire extinguishing material, wherein when the content of the second component in the composition for the fire extinguishing material is B parts by mass and the content of the first component is A parts by mass, the value of B is greater than the value of A. [2] Further comprising a binder resin which is a component different from the second component, When the total mass of the first and second components and the binder resin is 100 parts by mass, The amount of the first component is 10 parts by mass or more and less than 25 parts by mass, The amount of the second component is 25 parts by mass or more and less than 90 parts by mass, The amount of the binder resin is 3 parts by mass or more and less than 40 parts by mass. The composition for a fire extinguishing material according to [1]. [3] When the total mass of the first and second components and the binder resin is 100 parts by mass, the amount of the binder resin is 10 parts by mass or more. The composition for a fire extinguishing material according to [2]. [4] The content of the fire extinguishing agent is 70% by mass or more and 97% by mass or less based on the solid content of the total amount of the fire extinguishing material composition, the fire extinguishing material composition according to any one of [1] to [3]. [5] The vinyl ether monomer is methyl vinyl ether, the fire extinguishing material composition according to any one of [1] to [4]. [6] The unsaturated carboxylic anhydride monomer is maleic anhydride, the fire extinguishing material composition according to any one of [1] to [5]. [7] The acid anhydride group is a carboxylic anhydride group, the fire extinguishing material composition according to any one of [1] to [6]. [8] The first component is a silane coupling agent, the fire extinguishing material composition according to any one of [1] to [7]. [9] The salt is a potassium salt, the fire extinguishing material composition according to any one of [1] to [8].

[10] Further comprising a liquid medium, the fire extinguishing material composition according to any one of [1] to [9].

[11] A fire extinguishing material comprising the fire extinguishing material composition according to any one of [1] to

[10] .

[12] An apparatus having an automatic fire extinguishing function, comprising the fire extinguishing material according to

[11] .

Examples

[0046] Hereinafter, the present disclosure will be described more specifically based on examples, but the present disclosure is not limited to the following examples.

[0047] The following materials were used in the examples and comparative examples. (1) Fire extinguishing agent Organic potassium salt: tripotassium citrate Oxidizing agent: potassium chlorate (KClO3) Tripotassium citrate is a deliquescent salt. (2) First component: a compound having an acid anhydride group and an alkoxysilyl group A silane coupling agent having an acid anhydride group and an alkoxysilyl group (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-12-1287A) (weight loss rate: 11.8%) (3) Second component: A copolymer containing a structural unit derived from a vinyl ether monomer and a structural unit derived from an unsaturated carboxylic anhydride monomer Polymethyl vinyl ether (PMVE) / maleic anhydride copolymer (manufactured by Ashland Japan Co., Ltd., trade name: Gantrez AN-119) (weight loss rate: 60.0%) (4) Binder resin (4-1) Ether-based polyurethane resin (weight loss rate: 88.0%) (4-2) Acrylic resin (weight loss rate: 76.3%) (4-3) Polyvinyl butyral resin (PVB resin) (weight loss rate: 54.1%) When preparing the fire extinguishing composition, a solution of the above binder resin was used. (4-1) Ether-based polyurethane resin solution obtained by dissolving 100 parts by mass of the above ether-based polyurethane resin in 210 parts by mass of isopropyl alcohol (4-2) Solution containing the above acrylic resin (manufactured by Siden Chemical Co., Ltd., trade name: Cybinol TPO-3183) (4-3) PVB resin solution obtained by dissolving 100 parts by mass of the above PVB resin in 910 parts by mass of a mixed solution of ethanol and isopropyl alcohol (5) Liquid medium Ethanol (6) Resin substrate Polyethylene terephthalate (PET) substrate (manufactured by Toyobo Co., Ltd., trade name: E7002, thickness 50 μm)

[0048] <Measurement of weight change rate> Regarding the first and second components and the binder resin, when heating from 30 °C to 500 °C at a heating rate of 5 °C / min under an air atmosphere using a differential thermal thermogravimetric analyzer "STA7200RV" manufactured by Hitachi High-Technologies Corporation, the weight change rate when heating to 400 °C was measured. The sampling period at this time was set to 1 second.

[0049] <Preparation of fire extinguishing composition> (Example 1) A mixture of tripotassium citrate and KClO3 was ground in an agate mortar so that the average particle size D50 was 12 μm or less. A fire extinguishing composition was obtained, which contained 87.4 parts by mass of the ground mixture and 12.6 parts by mass of the solids of the first and second components and the binder resin. When the solids of the first and second components and the binder resin were set to 100 parts by mass, the contents of these components were as shown in Table 1. In addition, when preparing the fire extinguishing composition, 87 parts by mass of ethanol was used per 100 parts by mass of the solids. In the table, the notation in parentheses for the "second component" means the value of the ratio (B / A) of the content (B parts by mass) of the second component to the content (A parts by mass) of the first component.

[0050] (Examples 2 to 9 and Comparative Examples 1 to 5) A fire extinguishing composition was obtained in the same manner as in Example 1, except that the contents of the first and second components and the binder resin were changed to the contents shown in Table 1. Note that the contents shown in Table 1 mean the contents of each component when the total mass of the first and second components and the binder resin is 100 parts by mass.

[0051] (Examples 10 to 12) A fire extinguishing composition was obtained in the same manner as in Example 1, except that an acrylic resin was used instead of the ether-based polyurethane resin as the binder resin, and the contents of the first and second components and the binder resin were as shown in Table 2. In addition, when preparing the fire extinguishing composition, the amount of ethanol used per 100 parts by mass of the solids was appropriately adjusted.

[0052] (Examples 13 to 15) A fire extinguishing composition was obtained in the same manner as in Example 10, except that a PVB resin was used instead of the acrylic resin as the binder resin, and the contents of the first and second components and the binder resin were as shown in Table 3. In addition, when preparing the fire extinguishing composition, the amount of ethanol used per 100 parts by mass of the solids was appropriately adjusted.

[0053] <Preparation of Fire Extinguishing Material> Using an applicator, the fire extinguishing material composition obtained in each example was applied onto a PET substrate, and then dried in an oven at 75 °C for 7 minutes to obtain a laminate in which a sheet-like fire extinguishing material with a thickness of 150 μm was formed on the PET substrate.

[0054] <Various Tests> A barrier film (water vapor transmission rate is 0.2 - 0.6 g / (m 2 ·day), compliant with JIS K 7129 under the conditions of 40 °C / 90%RH) was prepared. Using two pieces of this barrier film, a sheet-like fire extinguishing material (50 mm × 50 mm) was covered, and the four sides of the barrier film were heat-sealed to enclose the sheet-like fire extinguishing material. The heat-sealing conditions were 140 °C for 2 seconds. The heat-sealing width of each side was 10 mm. As a result, a fire extinguishing material package 20 as shown in Figure 2 with an outer dimension of 70 mm × 70 mm (sheet-like fire extinguishing material 10 housed in packaging bag 4) was obtained. This was used as an evaluation sample. The following tests were conducted on the evaluation samples obtained from each example. The results are shown in Table 1.

[0055] <Stability of Properties Test> The total light transmittance of the evaluation sample was measured using a haze meter (BYK-Gardner Haze-Guard Plus manufactured by BYK) in accordance with the method compliant with JIS K 7361-1. The measurement was carried out after 168 hours of being placed in a thermostatic and humidistatic chamber (under the conditions of 85 °C / 85%RH). This operation was performed 3 times by changing the measurement location, and the average value was recorded. Since the transparency of the fire extinguishing material increases and the value of the total light transmittance rises as the deliquescence of the salt progresses, the degree of deliquescence was evaluated by measuring the total light transmittance. It can be said that the fire extinguishing material with a lower value of the total light transmittance has higher stability of properties. The total light transmittance of the barrier film was 85%.

[0056] <Fire Extinguishing Performance Test> A 20 cm long, 30 cm wide, and 40 cm high iron container was prepared. To prevent the ignited solid fuel from being extinguished by asphyxiation, five circular vents with a diameter of 8.5 mm were provided on each side of the container at heights of 5.0 cm, 12.5 cm, 20.0 cm, 27.5 cm, and 35.0 cm from the top surface. A fire extinguishing material package (evaluation sample) was attached to the center of the top surface of the container with double-sided tape. 1.5 g of solid fuel (solid fuel fire block 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 at the center of the bottom surface of the container. After the solid fuel was ignited, the distance between the solid fuel and the evaluation sample was adjusted to 20 cm, and a test was conducted to determine whether the evaluation sample could be extinguished within 180 seconds. The above test was repeated multiple times, and the fire extinguishing success probability was recorded. In the table, the notation in parentheses for the fire extinguishing success probability means (number of successful fire extinguishings / number of tests).

[0057] <Cutting Suitability Evaluation Test> When the laminated body formed with the fire extinguishing material was cut with a cutter by inserting the blade from the fire extinguishing material surface side, the presence or absence of chipping of the fire extinguishing material coating film and peeling from the base material was visually confirmed. The evaluation was conducted based on the following criteria. A: No chipping of the coating film and peeling from the base material are observed. B: Chipping of the coating film and peeling from the base material occur partially. C: Chipping of the coating film and peeling from the base material occur throughout the area.

[0058]

Table 1

[0059]

Table 2

[0060]

Table 3

Explanation of Symbols

[0061] 1... Fire extinguishing material, 2... Base material, 3... Fire extinguishing material layer, 4... Packaging bag, 5... Sealant layer, 6... Base material layer, 10... Fire extinguishing material, 20... Fire extinguishing material package.

Claims

1. A fire extinguishing composition comprising a fire extinguishing agent containing at least one of an organic salt and an inorganic salt having deliquescence, a deliquescence-inhibiting component for suppressing deliquescence of the salt, wherein the deliquescence-inhibiting component comprises a first component which is a compound having an acid anhydride group and an alkoxysilyl group, and a second component which is a copolymer containing a structural unit derived from a vinyl ether monomer and a structural unit derived from an unsaturated carboxylic acid monomer, and when the content of the second component in the fire extinguishing composition is B parts by mass and the content of the first component is A parts by mass, the value of B is greater than the value of A.

2. The fire extinguishing composition according to claim 1, further comprising a binder resin which is a component different from the second component, wherein when the total mass of the first and second components and the binder resin is 100 parts by mass, the amount of the first component is 10 parts by mass or more and less than 25 parts by mass, the amount of the second component is 25 parts by mass or more and less than 90 parts by mass, and the amount of the binder resin is 3 parts by mass or more and less than 40 parts by mass.

3. The fire extinguishing composition according to claim 2, wherein when the total mass of the first and second components and the binder resin is 100 parts by mass, the amount of the binder resin is 10 parts by mass or more.

4. The fire extinguishing composition according to claim 1, wherein the content of the fire extinguishing agent is 70% by mass or more and 97% by mass or less based on the solid content of the total amount of the fire extinguishing composition.

5. The fire extinguishing composition according to claim 1, wherein the vinyl ether monomer is methyl vinyl ether.

6. The fire extinguishing composition according to claim 1, wherein the unsaturated carboxylic acid monomer is maleic anhydride.

7. The fire extinguishing composition according to claim 1, wherein the acid anhydride group is a carboxylic acid anhydride group.

8. The fire extinguishing composition according to claim 1, wherein the first component is a silane coupling agent.

9. The fire extinguishing composition according to claim 1, wherein the salt is a potassium salt.

10. The fire extinguishing composition according to claim 1, further comprising a liquid medium.

11. A fire extinguisher comprising the fire extinguishing composition according to any one of claims 1 to 10.

12. An apparatus having an automatic fire extinguishing function, comprising the fire extinguisher according to claim 11. ​

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