Fire extinguishing paint

Abstract

To provide a fire extinguishing paint capable of freely coating without restriction on a shape or amount of such as places, installations, devices, tools, materials, structures and so on where fire disaster can occur, containing a fire extinguishing agent having initial fire extinguishing function, and preferable in productivity / mass productivity and high volume production.SOLUTION: A fire extinguishing paint containing a fire extinguishing agent that self-heats and decomposes to generate extinguishing components upon reaching a specified temperature after application.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a fire extinguishing paint that has an initial fire extinguishing function and can be applied to various materials and shapes, such as places, facilities, equipment, tools, materials, and structures where a fire may occur. [Background technology]

[0002] There is known a fire extinguishing sheet containing a fire extinguishing agent that thermally decomposes to generate a fire extinguishing component when a certain temperature is reached (for example, Patent Document 1). Such a fire extinguishing sheet can be used by being placed in contact with or adjacent to a lithium ion battery mounted in, for example, a facility, device, machine, tool, or structure. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-118847 Summary of the Invention [Problem to be solved by the invention]

[0004] Here, the raw materials for the fire extinguishing sheet described in Patent Document 1 need to be processed to obtain a sheet-like molded product. In order to contact and place the sheet adjacent to a lithium-ion battery or the like, the sheet needs to be shaped according to the structure and size of the target object, and the fire extinguishing sheet needs to be fixed with an adhesive or glue, etc., so there is still room for improvement.

[0005] Therefore, the present invention aims to provide a fire-extinguishing paint that can be applied flexibly in the required amount depending on the various materials and shapes of locations, equipment, materials, structures, etc. where a fire may occur, has an early stage fire extinguishing function, and is suitable for productivity, mass production, and mass production. [Means for solving the problem]

[0006] In order to solve the above-mentioned problems, the present invention provides a fire-extinguishing paint containing a fire-extinguishing agent that is thermally decomposed to generate a fire-extinguishing component when a predetermined temperature is reached.

[0007] In the fire-extinguishing paint of the present invention, the fire-extinguishing component is preferably an aerosol.

[0008] In the fire-extinguishing paint of the present invention, it is preferable that the fire-extinguishing agent contains at least a potassium compound and a binder.

[0009] In the fire-extinguishing coating material of the present invention, it is preferable that the potassium compound contains at least a potassium-containing organic compound and potassium chlorate.

[0010] In addition, in the fire extinguishing paint of the present invention, the binder is preferably one or more of polyester resin, polystyrene, polyolefin resin, polyurethane resin, polyisocyanate, polyimide resin, acrylic resin, cellulose compound, vinyl chloride, ethylene vinyl acetate copolymer, polyvinylidene fluoride resin, fluororesin binder, synthetic latex, rosin, epoxy resin, phenol resin, polyvinyl alcohol resin, polyvinyl acetal resin, olefin thermoplastic resin, butadiene thermoplastic resin, styrene thermoplastic resin, styrene-butadiene thermoplastic resin, isoprene thermoplastic resin, urethane thermoplastic resin, ester thermoplastic resin, amide thermoplastic resin, vinyl chloride thermoplastic resin, thermoplastic resin mixed with process oil or tackifying resin, alloy type thermoplastic elastomer, dynamically crosslinked thermoplastic elastomer, bentonite, and biobinder Biopoly B.

[0011] In addition, the fire extinguishing paint of the present invention preferably contains at least tripotassium citrate and potassium chlorate as the potassium compounds, and at least polyvinyl butyral as the binder.

[0012] In the fire-extinguishing paint of the present invention, it is preferable that the boiling point of the dispersion medium is 60° C. or higher and 150° C. or lower, and that the paint is composed of one or more of such dispersion mediums.

[0013] In addition, in the fire-extinguishing paint of the present invention, it is desirable that the volume average particle size D50 of the solid content in the fire-extinguishing paint is 2 micrometers or more and 6 micrometers or less.

[0014] In addition, the fire-extinguishing paint of the present invention desirably has a viscosity of 1,000 mPa-s or more and 12,000 mPa-s or less when measured at 25 revolutions per minute using a Brookfield viscometer. Effect of the Invention

[0015] According to the present invention, a fire-extinguishing paint that has an early stage fire extinguishing function and can be applied to various materials and shapes such as places, equipment, materials, and structures where a fire may occur can be realized, and which is suitable for productivity, mass production, and mass production. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] Hereinafter, a fire-extinguishing paint according to a representative embodiment of the present invention will be described in detail.

[0017] The extinguishing paint contains an extinguishing agent that thermally decomposes to generate an extinguishing component when a predetermined temperature is reached. Alternatively, the extinguishing paint may be said to be a liquid extinguishing agent. The extinguishing paint generates an aerosol as the extinguishing component. The extinguishing paint contains at least a potassium compound, a binder, and a dispersion medium in the extinguishing agent.

[0018] More specifically, the extinguishing agent contains, for example, 0.5 to 30 mass% of a binder (component A), 20 to 40 mass% of potassium chlorate (component B), and 30 to 60 mass% of a potassium salt (component C), and further contains 10 to 900 parts by mass of a dispersion medium (component D) per 100 parts by mass of the binder, the potassium chlorate, and the potassium salt.

[0019] The binder of component A is preferably at least one selected from the group consisting of polyester resin, polystyrene, polyolefin resin, polyurethane resin, polyisocyanate, polyimide resin, acrylic resin, cellulose compound, vinyl chloride, ethylene-vinyl acetate copolymer, polyvinylidene fluoride resin, fluororesin binder, synthetic latex, rosin, epoxy resin, phenol resin, polyvinyl alcohol resin, polyvinyl acetal resin, olefin thermoplastic resin, butadiene thermoplastic resin, styrene thermoplastic resin, styrene-butadiene thermoplastic resin, isoprene thermoplastic resin, urethane thermoplastic resin, ester thermoplastic resin, amide thermoplastic resin, vinyl chloride thermoplastic resin, thermoplastic resin mixed with process oil or tackifying resin, alloy thermoplastic elastomer, dynamically crosslinked thermoplastic elastomer, bentonite, and biobinder Biopoly B.

[0020] The chlorate salt, component B, is a strong oxidizing agent that generates thermal energy by burning with the potassium salt, component C, to generate an aerosol (potassium radical). This aerosol releases the potassium radical (potassium compound), a fire-extinguishing component, and breaks the chain reaction of combustion through a negative catalytic effect, realizing rapid extinguishing.

[0021] The potassium salt of component C is a component for generating an aerosol (potassium radical) by thermal energy generated by the combustion of component B. The potassium salt of component C is preferably selected from at least one of potassium acetate, potassium propionate, monopotassium citrate, dipotassium citrate, tripotassium citrate, monopotassium trihydrogen ethylenediaminetetraacetate, dipotassium dihydrogen ethylenediaminetetraacetate, tripotassium monohydrogen ethylenediaminetetraacetate, tetrapotassium ethylenediaminetetraacetate, potassium hydrogen phthalate, dipotassium phthalate, potassium hydrogen oxalate, dipotassium oxalate, potassium hydrogen carbonate, and potassium bicarbonate.

[0022] The content ratios of the binder (A), the chlorate (B), the potassium salt (C) and the residual ash (D) in a total of 100 mass % are as follows: Component A: 0.5 to 30% by mass, preferably 1 to 20% by mass, more preferably 3 to 10% by mass Component B: 20 ​​to 40% by mass, preferably 22.5 to 37.5% by mass, more preferably 25 to 35% by mass Component C: 40 to 60 mass%, preferably 42.5 to 57.5 mass%, more preferably 45 to 55 mass% The content of component D is 10 to 900 parts by mass, preferably 50 to 500 parts by mass, and more preferably 100 to 300 parts by mass, per 100 parts by mass of the contents of components A, B and C.

[0023] When considering safety during manufacturing and the evaporation rate of the dispersion medium after application, it is desirable for the boiling point of the dispersion medium of component D to be between 60°C and 150°C, and it is desirable for the fire-extinguishing paint to be composed of one or more types of dispersion medium.

[0024] It is desirable for the volume average particle size D50 of the solid content in the fire extinguishing paint to be 2 micrometers or more and 6 micrometers or less, preferably 2.5 micrometers or more and 5 micrometers or less, and more preferably 3 micrometers or more and 4 micrometers or less, in terms of uniformity during application and the finish after the dispersion medium has evaporated.

[0025] The viscosity of the fire-extinguishing paint, measured using a B-type viscometer at 25 revolutions per minute, should be 1,000 millipascal-second or more and 12,000 millipascal-second or less, preferably 2,000 to 10,000 millipascals, and more preferably 3,000 to 9,000 millipascals, in terms of uniformity during application and the finish after the dispersion medium has evaporated.

[0026] Furthermore, the extinguishing agent composition after application of the coating material of this embodiment has a thermal decomposition onset temperature in the range of 120° C. to 350° C., preferably 170° C. to 300° C. Such a thermal decomposition onset temperature range can be adjusted by combining the above-mentioned components A, B and C in the above-mentioned ratio.

[0027] The extinguishing agent may be prepared by mixing the components of the extinguishing agent composition. The concentration or viscosity of the paint relative to the dispersion medium may be appropriately adjusted depending on the object to be extinguished, such as equipment, devices, machines, tools, materials, and structures, and the purpose of use. The extinguishing paint may be repeatedly applied and laminated for use. In addition, in order to protect the applied part from external impacts and humid environments, it is also possible to make it durable for long-term use by covering it with a protective film or forming a coating such as spraying a waterproofing agent or coating agent.

[0028] The fire extinguishing paint of the present invention may be applied to easily ignite locations of objects to be extinguished, such as equipment, devices, machines, tools, materials, structures, etc. For example, in the case of devices or tools, the paint may be applied to or applied to components that may ignite, such as battery cells including secondary batteries such as lithium ion batteries and all-solid-state batteries, which may catch fire due to some malfunction such as an accident, their cases, electrodes, connection terminals, circuit boards, and other additional parts.

[0029] In order to exert a fire-extinguishing effect by the aerosol, the fire-extinguishing agent of the present invention may be applied to the inside of an object such as equipment, devices, machines, tools, materials, structures, etc. Also, the fire-extinguishing agent may be applied to and placed on a flammable member as described above, and enclosed therein. EXAMPLES

[0030] The present invention will be described in more detail below with reference to examples and comparative examples. In these examples and comparative examples, fire extinguishing paints were prepared as described below in (1).

[0031] (1) Preparation of fire extinguishing paint (1-1) Preparation of fire extinguishing agent suspension by powder grinding 2.5 g of tripotassium citrate manufactured by Fuso Chemical Co., Ltd., 2.0 g of potassium chlorate manufactured by Nouryon Pulp and Performance Chemicals AB, 5.0 g of ethanol (boiling point: 78.5°C), 0.5 g of polyvinyl butyrate manufactured by Sekisui Chemical Co., Ltd. (product name: S-LEC B BH-3), and 5 g of zirconia balls YTZ with a particle size of 0.1 mm manufactured by Nikkato Corporation as dispersion media were placed in an 80 ml zirconia grinding container, and this was set in a rotation / revolution nano grinder "Grinding Nanotaro" (model NP-100) manufactured by Thinky Corporation, and stirred and ground at 2000 rpm for 2 minutes to obtain a fire-extinguishing paint.

[0032] (1-2) Separation (removal of dispersed media) Using a suitable stainless steel sieve, separate the paint and dispersion media obtained in (1-1) above. If the yield is 80% or more, proceed to the next filtration step.

[0033] (1-3) Filtration (separation of large particle size drugs and debris) The paint obtained in the separation step (1-2) above is filtered through a stainless steel sieve with a mesh size of 100 (approximately 200 μm) to remove coarse particles and debris.

[0034] (2) Analysis and Evaluation (2-1) Paint appearance It was visually confirmed that the suspension was white and free of foreign matter.

[0035] (2-2) Paint particle size Using a laser diffraction particle size distribution analyzer, the dispersion medium was ethanol, and the particle size distribution was measured under the following set conditions: particle refractive index 1.520, particle absorption rate 0.010, dispersion medium refractive index 1.360, residual (weighted) 0.20%, stirring speed 1000 rpm. The paint was diluted with dilution solvent ethanol at a dilution rate of approximately 0.005%, and then poured in to measure the particle size distribution. As a result, a single, roughly symmetrical particle size distribution was obtained, with the volume average particle size distribution data being D10: 1.25 micrometers, D50: 3.00 micrometers, D90: 6.06 micrometers, and MODE: 3.11 micrometers.

[0036] (2-3) Viscosity of paint When the viscosity of the paint was measured at room temperature at 25 revolutions per minute using a B-type viscometer, it was found to be 4,380 millipascal seconds.

[0037] (3) Fire extinguishing performance evaluation (3-1) Coating process (applying paint to materials) A 110 micrometer thick release paper with a coating of Si or F and release treatment is cut into a 10 cm square, and approximately 0.001 g of fire extinguishing paint is dropped onto the center of the coating surface and spread evenly over an area of ​​approximately 1 cm square.

[0038] (3-2) Drying process (removal of dispersion medium) The dispersion medium, ethanol, is removed using a general circulating thermostatic chamber. With the extinguishing agent applied to the release paper, a drying process is carried out at a set temperature of 100°C, resulting in a release paper with an extinguishing agent coating thickness of 200 micrometers in the center of approximately 1 cm square. This material is then used for the fire extinguishing test.

[0039] (3-3) Fire extinguishing performance test (evaluation test of applied fire extinguishing agent) The fire extinguishing agent coating materials prepared according to the above procedures (3-1) and (3-2) were tested as follows.

[0040] (3-4) Installation of a fire source Place a candle measuring 6 mm in outer diameter and 41 mm in height in the container and light it with a lighter.

[0041] (3-5) Contact with fire extinguishing agent coating material The edge of the release paper coated with the extinguishing agent was clamped with tweezers, and the part coated with the extinguishing agent was brought closer to the flame little by little, so that it was directly above the candle flame. When the part with the extinguishing agent came into contact with the flame, smoke instantly spurted out, the flame went out, and the fire was successfully extinguished. EXAMPLES

[0042] In the preparation of the fire extinguishing agent suspension by powder grinding in Example 1 (1-1), the type and weight of the raw materials were changed to 3.0 g of tripotassium citrate, 1.95 g of potassium chlorate, 0.5 g of ion-exchanged water, and 0.05 g of sodium carboxymethylcellulose (product name: CMC Daicel #2260) manufactured by Daicel Corporation. In the analysis evaluation, the appearance of the paint was a white suspension, with a particle size distribution D50 of 5.73 micrometers and a viscosity of 11230 millipascal seconds. In the fire extinguishing performance evaluation, the smoke generated by the flame of a candle was successfully extinguished. EXAMPLES

[0043] In the preparation of the fire extinguishing agent suspension by powder grinding in Example 1 (1-1), the type and weight of the raw materials were changed to 1.5 g of tripotassium citrate, 2.0 g of potassium chlorate, 45 g of isopropyl alcohol (boiling point: 83°C), and 1.5 g of a dispersant (product name: Disparlon DA-7301) manufactured by Kusumoto Chemical Co., Ltd., but the same procedure was followed to prepare a paint. (2) In the analytical evaluation, the paint had an appearance of a white suspension, a particle size distribution D50 of 2.51 micrometers, and a viscosity of 1360 millipascal seconds. (3) In the evaluation of fire extinguishing performance, the smoke generated by the flame of a candle was successfully used to extinguish the fire. Comparative Example 1

[0044] In the above evaluation test (3), a series of evaluation test operations was carried out as described above in (3-3) without applying paint to the release paper. The release paper burned violently, starting a fire that spread and burned out within one minute.

[0045] A paint was prepared in the same manner as in Example 1 (1-1) in the preparation of the fire extinguishing agent suspension by powder grinding, except that no polyvinyl butyrate was added, i.e., the amount added was changed to 0.0 g. However, (3-1) the paint's uniform retention during the application process to the release paper was significantly reduced, resulting in uneven application, (3-2) the paint cracked after drying and fell off the release paper, meaning that it was not suitable for evaluation, and (3) it was not possible to carry out a fire extinguishing performance evaluation.

[0046] In the (1-1) preparation of the fire extinguishing agent suspension by powder grinding in Example 1, a paint was prepared in the same manner, except that the dispersion medium was changed to acetone (boiling point: 56°C). (3-1) During the coating process onto the release paper, the dispersion medium volatilized rapidly, causing uneven coating, and (3-2) after drying, cracks occurred, resulting in noticeable uneven coating. (3) When a fire extinguishing performance evaluation was carried out, flames penetrated the cracks, etc., and the release paper exploded violently, starting and spreading a fire, which burned out within 30 seconds. Comparative Example 4

[0047] A paint was made in the same manner as in Example 1 (1-1) in making a fire extinguishing agent suspension by powder grinding, except that the dispersion medium was changed to cyclohexanone (boiling point: 156°C). (3-2) Even after drying, the paint contained a large amount of dispersion medium, causing uneven drying. (3) When a fire extinguishing performance evaluation was carried out, some of the fire extinguishing agent dripped, and the remaining dispersion medium ignited, causing a violent blast and spreading fire, which burned out within 10 seconds. Comparative Example 5

[0048] In Example 1 (1-1) Preparation of fire extinguishing agent suspension by powder grinding, a paint was prepared in the same manner except that the operating conditions of the rotation-revolution nano grinder "Granulation Nanotaro" (model NP-100) were changed to stirring and grinding for 20 minutes at 200 revolutions per minute. (2) In the analysis evaluation, the appearance of the paint was a white suspension, with a particle size distribution D50 of 7.01 micrometers and a viscosity of 880 millipascal seconds. (3) In the fire extinguishing performance evaluation, the rate and amount of smoke generation were insufficient, and the candle flame was not extinguished.

[0049] Representative embodiments of the present invention have been described above, but the present invention is not limited to these, and various design modifications are possible, which are also included in the present invention.

Claims

1. A fire extinguishing paint that contains a fire extinguishing agent that self-heats and decomposes to generate a fire-extinguishing component when a certain temperature is reached after application.

2. The fire-extinguishing paint of claim 1 , wherein the fire-extinguishing component is an aerosol.

3. The fire extinguishing paint according to claim 2, wherein the fire extinguishing agent comprises at least a potassium compound, a binder and a dispersion medium.

4. The fire-extinguishing paint according to claim 3, wherein the potassium compound comprises at least a potassium-containing organic compound and potassium chlorate.

5. The binder is polyester resin, polystyrene, polyolefin resin, polyurethane resin, polyisocyanate, polyimide resin, acrylic resin, cellulose compound, vinyl chloride, ethylene vinyl acetate copolymer, polyvinylidene fluoride resin, fluororesin binder, synthetic latex, rosin, epoxy resin, phenol resin, polyvinyl alcohol resin, polyvinyl acetal resin, olefin thermoplastic resin, butadiene thermoplastic resin, styrene thermoplastic resin, styrene-butadiene thermoplastic resin, isoprene thermoplastic resin, urethane thermoplastic resin, ester thermoplastic resin, amide thermoplastic resin, vinyl chloride thermoplastic resin, thermoplastic resin mixed with process oil or tackifying resin, alloy type thermoplastic elastomer, dynamically crosslinked thermoplastic elastomer, bentonite, biobinder Biopoly B. The fire extinguishing paint according to claim 3, which is composed of one or more of these.

6. 4. The fire extinguishing paint according to claim 3, wherein the boiling point of the dispersion medium is 60° C. or higher and 150° C. or lower, and the fire extinguishing paint is composed of one or more kinds of the dispersion medium.

7. The fire extinguishing paint according to claim 3, wherein the volume average particle size D50 of the insoluble components in the fire extinguishing paint is 2 micrometers or more and 6 micrometers or less.

8. 4. The fire extinguishing paint according to claim 3, wherein the viscosity of the fire extinguishing paint is 1,000 mPa-s or more and 12,000 mPa-s or less when measured with a Brookfield viscometer at 25 revolutions per minute.