Foam fire extinguishing agent

Abstract

The present invention provides a foam fire extinguishing agent which is able to satisfy a specific performance and heat resistance without containing a fluorine compound. A foam fire extinguishing agent according to the present invention is characterized by containing from 0.1% by mass to 2% by mass of a phosphorus-containing compound and from 1% by mass to 10% by mass of a cationic polymer.

Description

Technical Field

[0001] The present invention relates to a foam fire extinguishing agent, and particularly to a fluorine-free foam fire extinguishing agent having excellent heat resistance without containing a fluorine-based compound.

Background Art

[0002] Foam fire extinguishing agents are mainly used for fires of flammable liquids belonging to Class 4 dangerous goods and are supplied in a foamed state. The supplied foam extinguishes the fire by quickly spreading over the flammable liquid.

[0003] Here, in order to quickly extinguish the fire, it is required that the foam fire extinguishing agent has excellent heat resistance. In addition, various performances as a fire extinguishing agent are required, such as satisfying predetermined foaming performance, not dissolving in flammable dangerous goods, and not separating or precipitating components over a long period of time. Therefore, there is a problem that the foam fire extinguishing agent needs to satisfy these various performances in a well-balanced manner while increasing the heat resistance.

[0004] In order to meet such requirements, as a conventional foam fire extinguishing agent, for example, as proposed in Patent Document 1 (Japanese Patent Application Laid-Open No. 2007-252731), a surfactant containing a fluorine-based compound is used as one of the components (for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, in recent years, due to the influence of the Stockholm Convention on Persistent Organic Pollutants (POPs Convention), there has been a movement to regulate the production and use of organofluorine compounds such as perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA), and perfluorohexanesulfonic acid (PFHxS), as well as related substances thereof.

[0007] Therefore, an object of the present invention is to provide a foam fire extinguishing agent that can satisfy predetermined performance without containing a fluorine compound.

Means for Solving the Problems

[0008] In order to solve the above-described problems, the inventors have intensively conducted tests and research, and found that a fire extinguishing agent containing a predetermined amount of a non-fluorine-based cationic polymer and a non-fluorine-based phosphorus-containing compound can satisfy the performance as a foam fire extinguishing agent and has excellent heat resistance even without containing a fluorine compound, and thus the present invention has been completed.

[0009] That is, the foam fire extinguishing agent of the present invention contains 0.1 to 2% by mass of a phosphorus-containing compound and 1 to 10% by mass of a cationic polymer, and is characterized by containing the same.

[0010] In the foam fire extinguishing agent of the present invention, it is preferable that the phosphorus-containing compound is at least one of trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, naphthyldiphenyl phosphate, dinaphthyldiphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, cresyl 2,6-xylenyl phosphate, tributoxyethyl phosphate, 2-ethylhexyl diphenyl phosphate, 1,3-phenylene bis(diphenyl phosphate), 1,3-phenylene bis(di-2,6-xylenyl phosphate), bisphenol A bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate), hydroquinone bis(bis(2,6-dimethylphenyl)phosphate), biphenol bis(bis(2,6-dimethylphenyl)phosphate), octyl diphenyl phosphate, diethylene ethyl ester phosphate, dihydroxypropylene butyl ester phosphate, ethylene disodium ester phosphate, t-butyl phenyl diphenyl phosphate, bis-(t-butylphenyl)phenyl phosphate, tris-(t-butylphenyl)phosphate, isopropyl phenyl diphenyl phosphate, bis-(isopropylphenyl)diphenyl phosphate, tris-(isopropylphenyl)phosphate, tris(2-ethylhexyl)phosphate, tris(butoxyethyl)phosphate, tris(isobutyl)phosphate, methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, 2-methyl-propylphosphonic acid, t-butylphosphonic acid, 2,3-dimethylbutylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, diethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctylphosphinic acid, phenylphosphinic acid, diethylphenylphosphinic acid, diphenylphosphinic acid and alkyl phosphate esters, and condensates containing these structures.

[0011] In addition, in the foam extinguishing agent of the present invention, the cationic polymer includes (meth)acrylic acid ester and (meth)acrylaminoethyltrimethylammonium copolymer, (meth)acrylamide and (meth)acrylaminoethyltrimethylammonium copolymer, (meth)acrylaminodialkyl and (meth)acrylaminoethyltrimethylammonium copolymer, (meth)acrylaminoethyltrimethylammonium copolymer containing poly(meth)acrylaminoethyltrimethylammonium; dicyandiamide and formaldehyde condensate, dicyandiamide-based condensate containing dicyandiamide and diethylenetriamine condensate, dimethylamine-epichlorohydrin condensate, diethylamine and epichlorohydrin condensate, dimethylamine and epichlorohydrin and ammonia condensate, dialkylamine and epihalohydrin condensate containing diethylamine and epichlorohydrin and ammonia condensate; polydiallyldimethylammonium chloride, diallyldimethylammonium chloride and acrylamide copolymer, diallyldimethylammonium chloride and sulfur dioxide copolymer, diallyldimethylammonium chloride and (meth)acrylamide copolymer, diallyldimethylammonium chloride and (meth)acrylic acid copolymer, diallyldimethylammonium chloride copolymer containing diallyldimethylammonium chloride and (meth)acrylic acid and (meth)acrylamide copolymer; polyalkylamine containing polyethyleneimine, polyallylamine, polyvinylamine is preferably at least one of them.

Effect of the Invention

[0012] According to the present invention, it is possible to provide a foam extinguishing agent that satisfies predetermined performance without containing a fluorine compound and is particularly excellent in heat resistance.

Mode for Carrying Out the Invention

[0013] Hereinafter, the foam extinguishing agent according to a typical embodiment of the present invention will be described in detail with reference to the table. However, the present invention is not limited thereto.

[0014] The foam fire extinguishing agent according to this embodiment contains 0.1 to 2% by mass of a phosphorus-containing compound, 1 to 10% by mass of a cationic polymer, 1 to 10% by mass of a carbitol-based organic solvent, and 1 to 10% by mass of a surfactant, and the balance is mainly water for a total of 100% by mass (all of the balance may be water). In such a formulation, excellent heat resistance and other properties (foaming performance, foam durability, etc.) can be achieved while not containing a fluorine compound. As a factor for obtaining good results with the above formulation, the inventors presume that the combined raw materials form a complex, thereby improving the heat resistance.

[0015] Further, the foam fire extinguishing agent of the present invention preferably contains 0.1 to 2% by mass of a phosphorus-containing compound and 1 to 10% by mass of a cationic polymer.

[0016] Examples of the phosphorus-containing compound include various phosphorus-containing compounds, such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, naphthyldiphenyl phosphate, dinaphthylphenyl phosphate, tricresyl phosphate, cresylphenyl phosphate, cresyl 2,6-xylenyl phosphate, tributoxyethyl phosphate, 2-ethylhexyldiphenyl phosphate, 1,3-phenylenebis(diphenyl phosphate), 1,3-phenylenebis(di-2,6-xylenyl phosphate), bisphenol A bis(diphenyl phosphate), resorcinol bisdiphenyl phosphate, hydroquinone bis(bis(2,6-dimethylphenyl) phosphate), biphenol bis(bis(2,6-dimethylphenyl) phosphate), octyldiphenyl phosphate, diethylene ethyl ester phosphate, dihydroxypropylene butyl ester phosphate, ethylene disodium ester phosphate, t-butylphenyldiphenyl phosphate, bis-(t-butylphenyl)phenyl phosphate, tris-(t-butylphenyl) phosphate, isopropylphenyldiphenyl phosphate, bis-(isopropylphenyl)diphenyl phosphate, tris-(isopropylphenyl) phosphate, tris(2-ethylhexyl) phosphate, tris(butoxyethyl) phosphate, tris(isobutyl) phosphate, methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, 2-methyl-propylphosphonic acid, t-butylphosphonic acid, 2,3-dimethylbutylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, diethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctylphosphinic acid, phenylphosphinic acid, diethylphenylphosphinic acid, diphenylphosphinic acid, and alkyl phosphate esters, and at least one of condensates containing these structures may be used.

[0017] As the phosphorus-containing compound, it is preferable to use resorcinol bis(diphenyl phosphate) in consideration of its high solubility in water, ease of obtaining raw materials, and compatibility with other raw materials.

[0018] Examples of the cationic polymer include various cationic polymers. For example, (meth)acrylate and (meth)acrylaminoethyltrimethylammonium copolymer, (meth)acrylamide and (meth)acrylaminoethyltrimethylammonium copolymer, (meth)acrylaminodialkyl and (meth)acrylaminoethyltrimethylammonium copolymer, (meth)acrylaminoethyltrimethylammonium copolymer containing poly((meth)acrylaminoethyltrimethylammonium); dicyandiamide and formaldehyde condensate, dicyandiamide-based condensate containing dicyandiamide and diethylenetriamine condensate, dimethylamine-epichlorohydrin condensate, diethylamine and epichlorohydrin condensate, dimethylamine and epichlorohydrin and ammonia condensate, dialkylamine and epihalohydrin condensate containing diethylamine and epichlorohydrin and ammonia condensate; diallyldimethylammonium chloride copolymer including polydiallyldimethylammonium chloride, diallyldimethylammonium chloride and acrylamide copolymer, diallyldimethylammonium chloride and sulfur dioxide copolymer, diallyldimethylammonium chloride and (meth)acrylamide copolymer, diallyldimethylammonium chloride and (meth)acrylic acid copolymer, diallyldimethylammonium chloride and (meth)acrylic acid and (meth)acrylamide copolymer; at least one of polyalkylamines including polyethyleneimine, polyallylamine, and polyvinylamine may be used.

[0019] As the cationic polymer, considering its high solubility in water, ease of obtaining raw materials, and compatibility with other raw materials, polyethyleneimine and polyallylamine are preferable.

[0020] According to the experimental results obtained by the inventors of the present invention, the most preferable combination is that the phosphorus-containing compound is resorcinol bis(diphenyl phosphate) and the cationic polymer is polyethyleneimine.

[0021] Here, regarding the lower limits of the contents of the cationic polymer and the phosphorus-containing compound, if the cationic polymer is less than 1% by mass, there is a demerit that the foam disappearance time becomes short and the required performance cannot be obtained. Also, if the phosphorus-containing compound is less than 0.1% by mass, there is a demerit that sufficient heat resistance performance cannot be obtained.

[0022] Regarding the upper limits of the contents of the cationic polymer and the phosphorus-containing compound, if the cationic polymer exceeds 10% by mass, there is a demerit that the foam disappearance time becomes short and the required performance cannot be obtained. Also, if the phosphorus-containing compound exceeds 2% by mass, there is a demerit that the solution separates and it cannot be formed as a foam fire extinguishing agent.

[0023] Thus, the foam fire extinguishing agent of the present embodiment has excellent heat resistance, which was conventionally difficult, and also has good other performances, despite not containing a fluorine-based compound in its formulation. Moreover, it is excellent in the ease of obtaining raw materials.

Examples

[0024] 10% by mass of butyl carbitol, 10% by mass of a surfactant, polyethyleneimine which is a cationic polymer and resorcinol bis(diphenyl phosphate) which is a phosphorus-containing compound in the contents shown in Table 1 were mixed to form a mixture, and water was added (made up) to this mixture to prepare 25 kinds of foam fire extinguishing agent samples (foam aqueous solutions) in total of 100% by mass, and the following heat resistance test was conducted.

[0025] Note that butyl carbitol is a solvent that is also formulated in actual fire extinguishing agents. In addition, in actual fire extinguishing agents, components such as organic solvents such as carbitol, surfactants, water, and ethylene glycol may be added.

[0026] [Heat Resistance Test] The heat resistance test was carried out using each foam fire extinguishing agent sample according to the following procedure. (1) n-Heptane was put into a round dish with a diameter of 11 cm (95 cm 2 ) and ignited. (2) The foam fire extinguishing agent foamed by a juice mixer was scooped up with a spoon and put into the round dish 1 minute after ignition. (3) The foam agent was continuously added until the fire was extinguished. (4) After extinguishing the fire, the foam in the center of the round dish was extracted, and the oil surface with a diameter of about φ3 cm (7 cm 2 ) was exposed. (5) The exposed oil surface was ignited again. (6) The area of the oil surface 5 minutes after ignition or the time when all the foam disappeared was measured.

[0027] In the above heat resistance test, the pass or fail was judged and the state of the solution was observed. Regarding the criteria for pass or fail, · When the oil surface area 5 minutes after ignition is 50 cm 2 or less, it is marked as 〇 · When the oil surface area 5 minutes after ignition is 30 cm 2 or less, it is marked as ◎ · When there is still foam on the oil surface 5 minutes after ignition, it is marked as △ · When the foam disappeared within 5 minutes after ignition or the solution was separated and evaluation was impossible, it is marked as × It was determined as such. If the evaluation is ◎, 〇 or △, it has heat resistance to withstand practical use, and ◎ or 〇 is particularly preferable. The results are shown in Table 1.

[0028]

Table 1

[0029] From the results shown in Table 1, it can be seen that the foam fire extinguishing agent according to the present invention can excellently exhibit the fire extinguishing function with heat resistance when it contains 0.1 to 2% by mass of a phosphorus-containing compound and 1 to 10% by mass of a cationic polymer. Further, it can be seen that the foam fire extinguishing agent according to the present invention is more excellent when it contains 1 to 2% by mass of a phosphorus-containing compound and 5 to 10% by mass of a cationic polymer.

Claims

【Claim 1】 A foam fire extinguishing agent containing no fluorine-based compound, characterized by containing 0.1 to 2% by mass of resorcinol bis(diphenyl phosphate) as a phosphorus-containing compound and 1 to 10% by mass of polyethyleneimine as a cationic polymer.

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