JPS6146149B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a fire extinguishing agent composition, and more specifically, a specific perfluoroalkyl group-containing compound and a surfactant are combined and mixed in water to form an aqueous film on the surface of flammable oil. The present invention relates to possible fire extinguishing agent compositions. Conventionally, an aqueous foam consisting of water and a water-soluble compound containing a fluoroalkyl group, called so-called light water, has been used as a fire extinguishing agent to prevent ignition or re-ignition of gasoline, naphtha, ether, benzene, and other low flash point flammable oils. Compositions are known. For example, Special Publication No. 40-20080, Special Publication No. 48
-See Publication No. 23161, etc. Such aqueous foam compositions have been used as excellent fire extinguishing agents because they can form an aqueous film on the surface of flammable oils, thereby preventing the evolution of flammable vapors. . Such aqueous foam compositions are used in combination with powder fire extinguishers, protein foam fire extinguishers, and the like. For example, see the aforementioned Japanese Patent Publication No. 40-20080, Japanese Patent Publication No. 47-21078, Japanese Patent Publication No. 47-26160, etc. According to the research of the present inventor, in order to spread water on the surface of flammable oil such as gasoline and form an aqueous film, it is necessary to make the surface tension of water smaller than that of oil, and at the same time It is necessary to reduce the interfacial tension of Conventional water-soluble fluoroalkyl group-containing compounds can form aqueous films, but they form slowly, have insufficient sealing properties to prevent re-ignition, and require relatively large amounts to be added. It is. Moreover, it is difficult to obtain easily, and only a relatively small number of types are used effectively. The present inventor aimed to provide an easily available fire extinguishing agent composition that is capable of forming an aqueous film on the surface of flammable oil, that forms rapidly, and has excellent sealing properties to prevent re-ignition. Various studies and examinations were conducted.
As a result, compounds containing perfluoroalkyl groups that are insoluble in water, such as polyfluoroalcohols,
By solubilizing polyfluorocarboxylic acids, polyfluoroimidazolines, etc. with hydrocarbon and/or silicone surfactants, the surface tension of water is lowered than that of oil, and water-
It was also found that the interfacial tension of oil can be reduced. In other words, even if a polyfluoro compound (almost insoluble in water) cannot reduce the surface tension of water below that of flammable oil when added alone, it can be made possible by combining it with a specific surfactant. They have surprisingly found that they are effective at lower concentrations than conventional water-soluble fluorocompounds. The present invention was completed based on the above knowledge, and since the solubility in water is low when added alone, the surface tension of water is reduced by adding flammable oil (the surface tension at 25°C is
A perfluoroalkyl group-containing compound having 4 to 20 carbon atoms, which cannot have a surface tension lower than 20 to 25 dynes/cm), is dissolved in water together with a solubilizer consisting of a hydrocarbon and/or silicone surfactant. The object of the present invention is to provide a novel fire extinguishing agent composition capable of forming an aqueous film on the surface of the flammable oil, which is characterized in that it is formed by adding and mixing the above-mentioned combustible oil. The composition of the present invention is characterized in that, first, it uses a polyfluoro compound that is hardly soluble in water and cannot lower the surface tension of water than that of oil when added alone. Such polyfluoro compounds are readily available and their effective concentrations can be reduced by use in combination with specific solubilizers, making them highly advantageous for widespread commercial use. Secondly, it is characterized by the use of surfactants that are also easily available. When such a surfactant is added alone, it is impossible to form an aqueous film on the surface of the oil, but it becomes possible to form an aqueous film only when combined with the above-mentioned specific polyfluoro compound. Therefore, by adding the two in combination, the surface tension of water can be greatly reduced, the rate of aqueous film formation can be increased (expansion time shortened), and the sealing performance can be improved, as is clear from the examples described below. It is something. In the present invention, the perfluoroalkyl group-containing compound contains a perfluoroalkyl group having 4 to 20 carbon atoms. Therefore, when added alone, it is hardly soluble in water, and the surface tension of water cannot be made lower than that of flammable oil. Preferably, those containing a perfluoroalkyl group having 6 to 14 carbon atoms are employed, and such perfluoroalkyl group may be linear or branched. As such compounds, a wide variety of conventionally known or well-known compounds may be exemplified as long as they satisfy the above conditions. Perfluoroalkyl group-containing compounds that are advantageous in combination with specific solubilizers and other points include:
There are the following: For example, the general formula R _f AOH
Fluoroalcohols represented by the general formula R _f
(A) _o Fluorocarboxylic acids represented by COOX, general formula

The file represented by [formula] Luoroimidazolines, general formula

Examples include fluoroamides or fluorosulfonamides represented by the formula: In each of the above formulas, R _f is a perfluoroalkyl group having 4 to 20 carbon atoms, n is an integer of 0 or 1, A is a divalent organic group,
X is a hydrogen atom, an alkyl group, or -MOOC(A) _o
R _f , R is a hydrogen atom or an alkyl group, Q is

[Formula] or

[Formula] are shown respectively, Z is −AOH, −(A) _o COOX,

[Formula] or -R, and M is a divalent alkaline earth metal. A is preferably a linear or branched alkylene group having 1 to 10 carbon atoms. Usually, R _f
AOH, R _f COOX,

【formula】

[Formula] etc. are preferred, where R _f is a perfluoroalkyl group having 6 to 14 carbon atoms, and A is a perfluoroalkyl group having 2 carbon atoms.
~3 divalent alkylene groups, X is -
Particularly preferably employed is MOOCR _f , where R is a hydrogen atom and M is barium or calcium. or,
Fluoroacrylates represented by the general formula R _f AOCOCR'=CH ₂ (R' represents a hydrogen atom or a methyl group) or polymers or copolymers thereof may also be employed. In the present invention, the specific solubilizing agent is not particularly limited as long as it is a hydrocarbon-based or silicone-based surfactant, and various types can be employed. That is, various nonionic, anionic, cationic, and amphoteric hydrocarbon surfactants and water-soluble polysiloxanes, such as polysiloxane/polyalkylene glycol block copolymers and polysiloxanes having ionic groups, are widely used. can be illustrated. For example, dioctyl sodium sulfosuccinate, diamyl sodium sulfosuccinate, dihexyl sodium sulfosuccinate, octylphenoxypolyoxyethyleneoxyethanol, nonylphenoxypolyoxyethyleneoxyethanol, alkoxyphenoxypolyoxyethyleneoxyethanol , polyoxyethylene ether alcohol, C ₁₂ H ₂₅ N
_{( CH3} ) _{2CH2COO , C12H25N}
(CH ₃ ) ₂ C ₂ H ₄ SO ₃ , sodium salt of lauryl sulfate, sodium salt of higher fatty acids,
C ₁₁ H ₂₃ CON(CH ₂ CH ₂ OH) ₂ ,

[Formula] Others

[Formula] etc., especially

[Formula] (R ¹ is a higher alkyl group, especially an alkyl group having 8 to 9 carbon atoms,
m is 1 to 10),

[Formula] (R ² is a higher alkyl group, especially an alkyl group having 8 to 9 carbon atoms, l is 3
~30),

[Formula] (R ³ and R ⁴ are alkyl groups having 4 to 10 carbon atoms), R ⁵ N
(CH ₃ ) ₂ CH ₂ COO (R ⁵ is an alkyl group having 8 to 16 carbon atoms), R ⁶ CON (CH ₂ CH ₂ OH) ₂ (R ⁶ is an alkyl group having 12 to 16 carbon atoms)
18 alkyl group), a block copolymer of methylsiloxane and ethylene oxide, etc. are suitable. Usually, an ionic or nonionic surfactant with an HLB value of 10 or more, particularly 12 to 16 is desirable, and a hydrocarbon type and a silicone type surfactant may be used in combination. In the composition of the present invention, the specific perfluoroalkyl group-containing compound may be used in an amount of 0.01% by weight or more based on water, and since the effect is large when used at a low concentration, it is usually 0.05 to 1% by weight, preferably 0.05 to 0.5% by weight.
It is adopted at about % by weight. The optimum range is selected depending on the perfluoroalkyl group-containing compound and the type of specific solubilizer used in combination. Further, the solubilizing agent consisting of a specific surfactant is used in a proportion of 0.05 to 5% by weight, preferably 0.2 to 1% by weight, based on water. In the present invention, the addition ratio of perfluoroalkyl group-containing compound/specific solubilizer is 1/1.
-10 (weight ratio), preferably about 1/1 - 5 (weight ratio). It goes without saying that the composition of the present invention can be advantageously applied to extinguish the combustion of various flammable oils, and is also effective in preventing re-ignition based on the good sealing properties described below. The composition of the present invention can be applied alone, and
Of course, it is also possible to use it in combination with various fire extinguishing agents such as conventional protein foam and powder. Furthermore, various additives such as a foaming accelerator, a stabilizer, a water-soluble polymer for increasing sealing properties, and a freezing point depressant may be added to the composition of the present invention. The composition of the present invention has a surface tension of 20 to 25°C at 25°C.
Aqueous films can be rapidly formed on the surface of flammable liquids at a rate of 25 dynes/cm; examples of such flammable liquids include gasoline, light oil, heavy oil, thinner, benzene, toluene, and cyclohexane. It will be done. That is, in the composition of the present invention, the surface tension of water is 20 dynes/
cm or less, and at the same time, the interfacial tension between water and flammable oil is also small due to the presence of a specific solubilizer, so an aqueous film can be rapidly formed on the surface of the flammable oil. It is. Next, embodiments of the present invention will be described in more detail, but it goes without saying that the present invention is not limited by such explanations. In the following examples, the surface tension shows the value at 25° C. according to the Wilhelmy method, and the foaming property shows the value measured by the Ross-Miles method. In addition, the sealing property is
The expansion time was measured by forming an aqueous film on cyclohexane, bringing a small flame close to it, and measuring the time it took to ignite.The expansion time was measured by placing cyclohexane in a 10 cm diameter shear dish and applying the composition onto the surface. This is the measurement of the time it takes for one drop to cover the entire surface of the liquid. Examples 1 to 8 and Comparative Example 1 Regarding the compositions shown in Table 1 below, surface tension,
The results of measuring sealing performance, expansion time, and foaming property were
They are summarized in Table 1 below.

【table】

[Table] Examples 9 to 11 The same measurement results as in Example 1 are shown for the compositions shown in Table 2 below.

【table】

Claims (1)

[Claims] 1. Since the solubility in water is low when added alone, the surface tension of water is reduced by combustible oil (surface tension at 25°C is 20
A perfluoroalkyl group-containing compound having 4 to 20 carbon atoms that cannot have a surface tension lower than 25 dynes/cm) is added to water together with a solubilizer consisting of a hydrocarbon-based and/or silicone-based surfactant. A fire extinguishing agent composition capable of forming an aqueous film on the surface of the flammable oil. 2 Fluoroalcohol represented by the general formula R _f AOH (where R _f in the formula represents a perfluoroalkyl group having 4 to 20 carbon atoms, and A represents a divalent organic group, respectively) as a perfluoroalkyl group-containing compound. The extinguishing agent composition according to claim 1, which uses the following. 3 As a perfluoroalkyl group-containing compound, the general formula R _f (A) _o COOX (in the formula, R _f is a perfluoroalkyl group having 4 to 20 carbon atoms, n is 0 or 1, and A is a divalent organic The method according to claim 1, in which a fluorocarboxylic acid represented by a group, X is a hydrogen atom, an alkyl group, or -MOOC(A) _o R _f , M is a divalent alkaline earth metal, respectively) is used. Fire extinguishing agent composition. 4 As a perfluoroalkyl group-containing compound, the general formula [Formula] (wherein R _f is a perfluoroalkyl group having 4 to 20 carbon atoms, n is 0 or 1, A is a divalent organic group, and R is The fire extinguishing agent composition according to claim 1, which uses a fluoroimidazoline represented by a hydrogen atom or an alkyl group, respectively. 5 As a perfluoroalkyl group-containing compound, use the general formula [Formula] (wherein R _f is a perfluoroalkyl group having 4 to 20 carbon atoms, Q is [Formula] or [Formula] R is a hydrogen atom or an alkyl group) , Z is -AOH, -(A) _o COOX, [Formula] or -R, A is a divalent organic group, X is a hydrogen atom, an alkyl group or -MOOC(A) _o R _f ,
2. The fire extinguishing agent composition according to claim 1, which uses fluoroamides or fluorosulfonamides represented by (M is a divalent alkaline earth metal). 6 As a perfluoroalkyl group-containing compound, the general formula R _f AOCOCR'=CH ₂ (wherein, R _f is a perfluoroalkyl group having 4 to 20 carbon atoms, A is a divalent organic group, and R' is hydrogen 2. The fire extinguishing agent composition according to claim 1, which uses fluoroacrylates or polymers thereof represented by (respectively an atom or a methyl group). 7. The fire extinguishing agent composition according to claim 1, wherein the solubilizer is represented by the formula: (wherein R ¹ is a higher alkyl group and m is 1 to 10). 8. The fire extinguishing agent composition according to claim 1, wherein the solubilizer is represented by the formula: (wherein R ² is a higher alkyl group and l is 3 to 30). 9. The fire extinguishing agent composition according to claim 1, which uses the formula: (R ³ and R ⁴ are alkyl groups having 4 to 10 carbon atoms) as a solubilizer. 10 R ⁵ N(CH ₃ ) ₂ CH ₂ COO as solubilizer
( ^R5 is an alkyl group having 8 to 16 carbon atoms). 11 R ⁶ CON(CH ₂ CH ₂ OH) ₂ as a solubilizer
( ^R6 is an alkyl group having 12 to 18 carbon atoms). 12. The fire extinguishing composition according to claim 1, which uses a block copolymer of methylsiloxane and ethylene oxide as a solubilizer. 13. The fire extinguishing composition according to claim 1, wherein the perfluoroalkyl group-containing compound is used in an amount of 0.05 to 1% by weight based on water. 14. The fire extinguishing composition according to claim 1, wherein the solubilizer is used in an amount of 0.05 to 5% by weight based on water. 15. The fire extinguishing agent composition according to claim 1, wherein the addition ratio of perfluoroalkyl group-containing compound/solubilizer is 1/1 to 10 (weight ratio).