FOAM FIRE EXTINGUISHING AGENT

Abstract

An object of the present invention is to provide a foam fire extinguishing agent that does not contain a fluorine compound and can satisfy predetermined performance. The foam fire extinguishing agent in accordance with the present invention is characterized by comprising 0.1 to 2% by mass of a phosphorus-containing compound, and 1 to 10% by mass of a cationic polymer.

Claims

1. A foam fire extinguishing agent, characterized by comprising 0.1 to 2% by mass of a phosphorus-containing compound, and 1 to 10 by mass of a cationic polymer.

2. The foam fire extinguishing agent in accordance with claim 1, wherein the phosphorus-containing compound is at least one of trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresidyl phosphate, trixylenyl phosphate, naphthyl diphenyl phosphate, dinaphthyl phenyl 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(di2,6-xylenyl phosphate), bisphenol A bis(diphenyl phosphate), resorcinol bisdiphenyl phosphate, hydroquinone bis(bis(2,6-dimethylphenyl) phosphate), biphenol bis(bis(2,6-dimethylphenyl) phosphate), octyl diphenyl phosphate, diethylene ethyl ester phosphate, dihydroxypropylene butyl ester phosphate, ethylene disodium ester phosphate, t-butylphenyl diphenyl phosphate, bis-(t-butylphenyl) phenyl phosphate, tris-(t-butylphenyl)) phenyl phosphate, isopropylphenyl diphenyl phosphate, bis-(isopropylphenyl) diphenyl phosphate, tris-(isopropylphenyl) phosphate, tris(2-ethylhexyl) phosphate, tris(butoxyethyl) phosphate, trisisobutyl 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 alkylphosphate esters, and condensates containing these structures.

3. The foam fire extinguishing agent in accordance with claim 1, wherein the cationic polymer is at least one of a copolymer of (meth)acrylaminoethyltrimethylammonium including a copolymer of (meth)acrylic acid ester and (meth)acrylaminoethyltrimethylammonium, a copolymer of (meth)acrylamide and (meth)acrylaminoethyltrimethylammonium, a copolymer of (meth)acrylaminodialkyl and (meth)acrylaminoethyltrimethylammonium, poly(meth)acrylaminoethyltrimethylammonium; a dicyandiamide-based condensate including a condensate of dicyandiamide and formaldehyde, a condensate of dicyandiamide and diethylenetriamine, a condensate of dialkylamine and epihalohydrin including dimethylamine-epichlorohydrin condensate, a condensate of diethylamine, epichlorohydrin, a condensate of dimethylamine, epichlorohydrin and ammonia, a condensate of diethylamine, epichlorohydrin and ammonia; a copolymer of diallyldimethylammonium chloride including polydiallyldimethylammonium chloride, a copolymer of diallyldimethylammonium chloride and acrylamide, a copolymer of diallyldimethylammonium chloride and sulfur dioxide, a copolymer of diallyldimethylammonium chloride and (meth)acrylamide, a copolymer of diallyldimethylammonium chloride and (meth)acrylic acid, a copolymer of diallyldimethylammonium chloride, (meth)acrylic acid and (meth)acrylamide; and polyalkylamine including polyethyleneimine, polyallylamine, polyvinylamine.

Description

EMBODIMENTS FOR ACHIEVING THE INVENTION

[0015] Hereinafter, the foam fire extinguishing agent in accordance with a representative embodiment of the present invention will be described in detail with reference to the Table. However, the present invention is not limited to these examples.

[0016] The foam fire extinguishing agent in accordance with the present embodiment contains 0.1 to 2% by mass of the phosphorus-containing compound, 1 to 10% by mass of the 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 and 100% by mass in total (all of the balance may be water). In such a formulation, excellent heat resistance and other performances (e.g., foaming performance and foam durability) can be achieved while containing no fluorine compound. As a factor that the favorable result is obtained by the above-described blending, the present inventors have presumed that heat resistance is improved by forming a complex from the combined raw materials.

[0017] Further, it is preferable that the foam fire extinguishing agent of the present invention contains 0.1 to 2% by mass of the phosphorous-containing compound and 1 to 10% by mass of the cationic polymer.

[0018] Examples of the phosphorus-containing compound may be at least one of trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresidyl phosphate, trixylenyl phosphate, naphthyl diphenyl phosphate, dinaphthyl phenyl 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(di2,6-xylenyl phosphate), bisphenol A bis(diphenyl phosphate), resorcinol bisdiphenyl phosphate, hydroquinone bis(bis(2,6-dimethylphenyl) phosphate), biphenol bis(bis(2,6-dimethylphenyl) phosphate), octyl diphenyl phosphate, diethylene ethyl ester phosphate, dihydroxypropylene butyl ester phosphate, ethylene disodium ester phosphate, t-butylphenyl diphenyl phosphate, bis-(t-butylphenyl) phenyl phosphate, tris-(t-butylphenyl) phenyl phosphate, isopropylphenyl diphenyl phosphate, bis-(isopropylphenyl) diphenyl phosphate, tris-(isopropylphenyl) phosphate, tris(2-ethylhexyl) phosphate, tris(butoxyethyl) phosphate, trisisobutyl 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 alkylphosphate esters, and condensates containing these structures.

[0019] As the phosphorus-containing compound, it is preferable to use resorcinol bisdiphenyl phosphate in consideration of solubility in water, availability of raw material, and compatibility with other raw materials.

[0020] Further, the cationic polymer may include various cationic polymers, and examples thereof may be at least one of a copolymer of (meth)acrylaminoethyltrimethylammonium including a copolymer of (meth)acrylic acid ester and (meth)acrylaminoethyltrimethylammonium, a copolymer of (meth)acrylamide and (meth)acrylaminoethyltrimethylammonium, a copolymer of (meth)acrylaminodialkyl and (meth)acrylaminoethyltrimethylammonium, poly(meth)acrylaminoethyltrimethylammonium; a dicyandiamide-based condensate including a condensate of dicyandiamide and formaldehyde, a condensate of dicyandiamide and diethylenetriamine, a condensate of dialkylamine and epihalohydrin including dimethylamine-epichlorohydrin condensate, a condensate of diethylamine, epichlorohydrin, a condensate of dimethylamine, epichlorohydrin and ammonia, a condensate of diethylamine, epichlorohydrin and ammonia; a copolymer of diallyldimethylammonium chloride including polydiallyldimethylammonium chloride, a copolymer of diallyldimethylammonium chloride and acrylamide, a copolymer of diallyldimethylammonium chloride and sulfur dioxide, a copolymer of diallyldimethylammonium chloride and (meth)acrylamide, a copolymer of diallyldimethylammonium chloride and (meth)acrylic acid, a copolymer of diallyldimethylammonium chloride, (meth)acrylic acid and (meth)acrylamide; and polyalkylamine including polyethyleneimine, polyallylamine, polyvinylamine.

[0021] As the cationic polymer, polyethyleneimine, or polyallylamine is preferable in consideration of solubility in water, availability of raw material, and compatibility with other raw materials.

[0022] In accordance with the experimental results by the present inventors, the most preferable combination is resorcinol bisdiphenyl phosphate as the phosphorus-containing compound and polyethyleneimine as the cationic polymer.

[0023] Here, with respect to the lower limits of the contents of the cationic polymer and the phosphorus-containing compound, when the cationic polymer is less than 1% by mass, there is a disadvantage that the foam disappearance time is shortened and required performance cannot be obtained, and when the phosphorus-containing compound is less than 0.1% by mass, there is a disadvantage that sufficient heat resistance performance cannot be obtained.

[0024] In addition, with respect to the upper limits of the contents of the cationic polymer and the phosphorus-containing compound, when the cationic polymer exceeds 10% by mass, there is a disadvantage that the foam disappearance time is shortened and the required performance cannot be obtained, and when the phosphorus-containing compound exceeds 2% by mass, there is a disadvantage that the solution is separated and a foam fire extinguishing agent cannot be formed.

[0025] As described above, despite the formulation that does not contain a fluorine-based compound, the foam fire extinguishing agent of the present embodiment has excellent heat resistance and other performances that have been difficult to achieve in the past. Further, the raw materials are excellent in availability.

EXAMPLE

[0026] 10% by mass of butyl carbitol, 10% by mass of a surfactant, and polyethyleneimine as the cationic polymer and resorcinol bisdiphenyl phosphate as the phosphorus-containing compound in the contents shown in Table 1 were mixed to obtain a mixture, and water was added (measured up) to the mixture to prepare 25 foam fire extinguishing agent samples (foam aqueous solutions) of a total of 100% by mass, and the samples were subjected to the following heat resistance test.

[0027] Butyl carbitol is a solvent also blended in an actual fire extinguishing agent. Further, in addition to an organic solvent such as a carbitol, a surfactant, and water, ingredients such as ethylene glycol may be added to the actual fire extinguishing agent.

Heat Resistance Test

[0028] A heat resistance test, was performed in accordance with the following procedure by using each foam fire extinguishing agent sample. [0029] (1) n-Heptane was put into a round dish having a diameter of 11 cm (95 cm.sup.2) and ignited. [0030] (2) The foam fire extinguishing agent foamed with a jouser mixer was taken up with a spoon and put into the round dish after 1 minute from the ignition. [0031] (3) The foam agent was continuously added until the fire was extinguished. [0032] (4) After extinguishing the fire, the foam at the center of the round dish was removed to expose an oil surface of about φ3 cm (7 cm.sup.2). [0033] (5) The exposed oil surface was ignited again. [0034] (6) The area of the oil surface after 5 minutes from the ignition or the time for all foam to disappear was measured.

[0035] In the above-described heat resistance test, the success or failure was determined, and the state of the solution was observed. The criteria for determining the success or failure were as follows: [0036] A case where the oil surface area after 5 minutes from the ignition was 50 cm.sup.2 or less was defined as ◯; [0037] A case where the oil surface area after 5 minutes from the ignition was 30 cm.sup.2 or less was defined as ⊚; [0038] A case where the foam remained on the oil surface after 5 minutes from the ignition was defined as Δ; [0039] A case where foam disappeared or the solution was separated not to be evaluated within 5 minutes after the ignition was defined as x.
When the evaluation is ⊚, ◯, or Δ the heat resistance is practically acceptable, and when being or ⊚ or ◯, the heat resistance is particularly preferable. The results are shown in Table 1.

TABLE-US-00001 TABLE 1 Phosphorous containing compound Cationic (Resorcinol Oil surface Foam polymer bisdiphenyl State of area after disappearance No (Polyethyleneimine) phosphate) solution 5 min. time Evaluation 1  0%   0% Good — 1 min 12 sec × 2  0% 0.1% Separated — — × 3  0% 0.5% Separated — — × 4  0%   1% Separated — — × 5  0%   2% Separated — — × 6  0%   3% Separated — — × 7  1%   0% Good — 4 min 22 sec × 8  1% 0.1% Good 72.3 cm.sup.2 — Δ 9  1% 0.5% Good 69.3 cm.sup.3 — Δ 10  1%   1% Good 63.5 cm.sup.2 — Δ 11  1%   2% Good 56.7 cm.sup.2 — Δ 12  1%   3% Separated — — × 13  5%   0% Good — 3 min 21 sec × 14  5% 0.1% Good 78.5 cm.sup.2 — Δ 15  5% 0.5% Good 50.2 cm.sup.2 — Δ 16  5%   1% Good 9.6 cm.sup.2 — ⊚ 17  5%   2% Good 1.8 cm.sup.2 — ⊚ 18  5%   3% Separated — — × 19 10%   0% Good — 4 min 2 sec × 20 10% 0.1% Good 63.5 cm.sup.2 — Δ 21 10% 0.5% Good 49.6 cm.sup.2 — ◯ 22 10%   1% Good 3.1 cm.sup.2 — ⊚ 23 10%   2% Good 38.5 cm.sup.2 — ◯ 24 10%   3% Separated — — × 25 15%   0% Good — 3 min 37 sec × 26 15% 0.1% Good — 1 min 58 sec × 27 15% 0.5% Good — 2 min 4 sec × 28 15%   1% Good — 1 min 46 sec × 29 15%   2% Good — 2 min 25 sec × 30 15%   3% Good — 2 min 45 sec ×

[0040] From the results shown in Table 1, it is found that when the foam fire extinguishing agent in accordance with the present invention contains 1 to 2% by mass of the phosphorus-containing compound and 1 to 10% by mass of the cationic polymer, the agent is excellent in heat resistance and can suitably exhibit the fire extinguishing function. Further, it is found that when the foam fire extinguishing agent in accordance with the present invention contains 1 to 2% by mass of the phosphorus-containing compound and 5 to 10% by mass of the cationic polymer, the agent is further excellent.