Aqueous foam fire extinguisher

Abstract

An aqueous foam fire extinguisher comprising (A) a surface-active agent having an anionic hydrophilic group, (B) a cationic water-soluble polymeric substance, and, optionally, (C) a polybasic acid compound.

Description

This invention relates to an aqueous foam fire extinguisher composition having an excellent fire extinguishing effect against fires of non-polar solvents, especially polar solvents.

Various fire extinguisher foams have been developed for use against fires of non-polar solvents such as gasoline, kerosene, light oils, heavy oils, crude oils, etc. However, when such fire extinguishers are applied to fires of polar solvents such as alcohols, ketones, esters, ethers and amines, the polar solvents take away water from the foam films, and the foams break instantaneously or become very weak. Hence, they can scarcely exhibit a fire extinguishing effect.

For this reason, protein foam fire extinguishers or synthetic surface active agent foam fire extinguishers containing water-insoluble metal soaps are now mainly used against the fires of polar solvents. The effect of these fire extinguishers is ascribed to the fact that when a concentrated solution of such a fire extinguisher is foamed by diluting it with water, the metal soap precipitates on the film surface of the foams and thus produces a barrier against the polar solvent, whereby the foams can be spread afloat on the liquid surface without being broken.

These fire extinguishers, however, have the serious defect unless they are used within 2 to 3 minutes after dilution with water at the site of fire, a precipitate forms in the water stream and markedly reduces their fire extinguishing effect, and that their foams disappear rapidly because they do not have sufficient solvent resistance. In order, therefore, to inject the foams onto the burning liquid surface, large quantities of foams must be placed very gently on the burning liquid surface, and special contrivances are required in the design of a foam discharge nozzle and in the method of installing it. Consequently, a large quantity of the fire extinguisher and a long period of time are required for fire extinguishing. For example, in extinguishing the fire of methanol, the spreading of the extinguisher foams becomes possible only after methanol has been diluted to about 75 to 80% with the fire extinguisher, and fire extinguishing takes a long time. Moreover, since such a large amount of the fire extinguisher is injected, the solvent is likely to overflow when fire takes place in a tank filled fully with the solvent.

There is also known a fluorinated foam fire extinguisher for use against the fire of polar solvents obtained by adding a certain kind of fluorine-type surface-active agent to a protein foam fire extinguisher thereby imparting resistance to polar solvents. This fluorinated protein foam fire extinguisher has not come into practical use because it also has the serious defect that it does not have a sufficient ability to extinguish fires of polar solvents, the foams do not have sufficient solvent resistance, a concentrated solution of the fire extinguisher lacks storage stability, and when it is diluted with sea water, the diluted solution is not stable.

In order to overcome these defects, it was proposed to add a thixotropic water-soluble polymeric substance (polysaccharide) to a water film-type foam fire extinguisher based on a fluorine-type surface-active agent. It is believed that when this type of fire extinguisher contacts a polar solvent, it is dehydrated on the interface to form a gel-like mat of the water-soluble polymeric substance in the interface, and the gel-like mat protects the foams existing thereon, whereby it covers the burning surface and finally extinguishes the fire. Thus, this fire extinguisher permits better spreading of foams than fire extinguishers of the metal soap type, and has an improved fire extinguishing effect. However, as will be anticipated from the mechanism by which the foams are protected by a gel-like mat of a thixotropic water-soluble polymeric substance, this fire extinguisher has a reduced fire extinguishing effect against fires of solvents having high volatility or generating high heat of combustion, such as alcohols (e.g., isopropanol, t-butanol, etc.), ketones, propylene oxide, etc.

Furthermore, since this type of fire extinguisher requires a large amount of the thixotropic water-soluble polymeric substance, its concentrated solution has a very high viscosity (more than 3,000 centistokes). Its viscosity, therefore, varies greatly with temperature, and it lends itself to difficult handling in practical applications. Furthermore, it cannot withstand storage for a long period of time because a thin layer (skin) of it is likely to form on the wall surface of the tank and the liquid surface during storage. This fire extinguisher cannot be used in a concentration lower than 6% because if the concentration of the thixotropic water-soluble polymeric substance is decreased, no gel-like mat is formed, or only a weak gel-like mat results. In addition, since this fire extinguisher has a freezing temperature of as high as about 0.degree. C., does not reversibly freeze and melt. For this reason, special considerations are required in using or storing it in districts of cold climate.

The present inventors have made extensive investigations in order to solve the above problems, and discovered the unique mutual action of (A) a surface-active agent containing an anionic hydrophilic group and (B) a cationic water-soluble polymeric substance. This has led to the discovery that an aqueous foam fire extinguisher based on a mixture of these compounds (A) and (B) produces very stable foams not only on non-polar solvents but also on polar solvents.

Thus, according to this invention, there is provided an aqueous foam fire extinguisher comprising (A) a surface-active agent containing an anionic hydrophilic group and (B) a cationic water-soluble polymeric substance, which can form tough, stable foams having excellent flame resistance.

According to another aspect of this invention, there is provided an aqueous foam fire extinguisher of better performance comprising the aforesaid components (A) and (B) and as a third component, (C) a polybasic acid compound.

The surface-active agent having an anionic hydrophilic group used in this invention includes those which can electrostatically act on the cationic water-soluble polymeric substance. In this sense, it is essential that the surface-active agents should have at least one anionic hydrophilic group. Preferred anionic hydrophilic groups are, for example, --COOH, --SO.sub.3 H, --OSO.sub.3 H and --PO(OH).sub.2. There may also be used those anionic hydrophilic groups which have an inorganic or organic cation as a counter ion for the anionic group.

The surface-active agent may be those which contain one or more anionic groups of the same or different kinds as the hydrophilic group, or amphoteric ion-type surface-active agents which contain one or both of a cationic hydrophilic group (such as an amino group or an ammonium group) and a nonionic group in addition to the anionic hydrophilic group.

The hydrophobic group of the surface-active agent may, for example, be an aliphatic hydrocarbon group having at least 6 carbon atoms, a dihydrocarbyl polysiloxane chain and/or a fluorinated aliphatic group having 3 to 20 carbon atoms. The surface-active agent may be a mixture of various kinds of compounds having these different hydrophobic groups.

Examples of especially useful surface active agents (A) having an anionic hydrophilic group are the following (A-1) to (A-4).

(A-1) Fluorine-containing amino acid-type amphoteric surface-active agents ##STR1## wherein Rf represents a fluorinated aliphatic group having 3 to 20 carbon atoms, Y represents --SO.sub.2 -- or --CO--, Q.sub.1 and Q.sub.2 represent an organic divalent linking group and is selected from aliphatic hydrocarbon groups, hydroxyl-substituted aliphatic hydrocarbon groups, aromatic hydrocarbon groups and substituted aromatic hydrocarbon groups, preferably --CH.sub.2 --.sub.j in which j is an integer of 1 to 6, or ##STR2## in which R.sub.2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R.sub.1 and R.sub.2 represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an aliphatic hydrocarbon group substituted by a hydrophilic group, or R.sub.1 and R.sub.2 are linked to each other to form a ring together with the adjacent nitrogen atom, A represents an anionic hydrophilic group such as --COO.sup.-, --SO.sub.3.sup.-, --OSO.sub.3.sup.-, or --OPO(OH)O.sup.-, and M represents a hydrogen atom, an alkali metal, an alkali earth metal, an ammonium group or an organic cationic group.

Specific examples of these compounds are given below. ##STR3## wherein Rf represents a fluorinated aliphatic group having 3 to 20 carbon atoms, Z is a divalent linking group and represents --SO.sub.2 N(R.sub.1)--, CON(R.sub.1), --(CH.sub.2 CH.sub.2).sub.i --SO.sub.2 N(R.sub.1)--, ##STR4## (in which R.sub.1 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and i represents an integer of 1 to 10), Q.sub.1 represents --(CH.sub.2).sub.j -- (in which j is an integer of 1 to 6) or ##STR5## (R.sub.2 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), R represents a hydrogen atom, an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, --Q.sub.2 SO.sub.3 M or --(CH.sub.2).sub.k COOM (in which k represents an integer of 1 to 4), Q.sub.2 represents --(CH.sub.2).sub.l -- (in which l represents an integer of 1 to 4), ##STR6## (in which R.sub.3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), or ##STR7## M represents a cationic atom or atomic grouping, and represents a hydrogen atom, an alkali metal, an alkaline earth metal or --N(H).sub.m (R.sub.4).sub.n (in which R.sub.4 represents an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, and m and n are integers of 0 to 4 provided that m+n=4).

Specific examples of these compounds are given below. ##STR8## wherein Rf represents a polyfluoroalkyl group having 3 to 20 carbon atoms which may contain an oxygen atom, a polyfluoroalkenyl group, a polyfluorocyclohexyl group, a polyfluorocyclohexyl-alkyl group or a polyfluorocyclohexyl-alkenyl group, Z represents a divalent linking group selected from ##STR9## [in which R.sub.1 represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group, or a monovalent group containing an aromatic ring, or --CH.sub.2 CH.sub.2 --.sub.j R.sub.2 (in which R.sub.2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and j represents an integer of 1 to 6), and i represents an integer of 1 to 3], Q represents --CH.sub.2 --.sub.l, ##STR10## --CH.sub.2 --.sub.m O--CH.sub.2 --.sub.m or --CH.sub.2 --.sub.p O--CH.sub.2 --.sub.2 O--CH.sub.2 --.sub.q (in which l is an integer of 1 to 6, m and n are integers of 2 to 6, and p and q are 2 or 3), and each of Q.sub.1 and Q.sub.2 represents a divalent linking group --CH.sub.2 --.sub.r or --CH.sub.2 --.sub.s (in which r and s are integers of 1 to 3), and each of M.sub.1 and M.sub.2 represents a hydrogen atom or an inorganic or organic cation.

Specific examples of the compounds (A-3) are given below. ##STR11##

Specific examples of these compounds are given below. ##STR12##

The cationic water-soluble polymeric substance (B) used in this invention is a polyamine-type polymeric substance which contains a primary amino group, a secondary amino group, a tertiary amino group, an ammonium group, a pyridinium group or a quaternary ammonium group at the main chain or side chain and has a solubility in water of at least 0.1% by weight. The degree of polymerization of this polymeric substance is restricted by its solubility in water, but polymeric substances having a degree of polymerization in the oligomer region to a degree of polymerization of more than several hundred thousand may be used. Preferred polymeric substances have a molecular weight of about 600 to about 100,000.

Specific examples of especially useful polymeric substances as the cationic water-soluble polymeric substance (B) in this invention are the following B-I to B-X. ##STR13##

The unique synergistic effect of the surface-active agent containing an anionic hydrophilic group and the cationic water-soluble polymeric substance on the foam characteristics of the fire extinguisher is observed over a broad range of the bending ratios of the two. The preferred range of the blending ratio of the cationic water-soluble polymeric substance (B) to the surface-active agent (A), i.e. (B)/(A), varies depending upon the combination of the two components, and is difficult to determine unequivocally. Generally, the weight ratio of (B)/(A) is from 0.05 to 50, preferably from 0.1 to 10. If the proportion of the cationic water-soluble polymeric substance (B) is too low, a complex formed between it and the surface-active agent (A) becomes water-insoluble and its foamability is greatly reduced. If the above blending ratio exceeds 50, the synergistic effect of the two is not impaired, but the viscosity of the concentrated or diluted solution of the fire extinguisher increases remarkably to reduce the commercial value of the fire extinguisher.

The unique synergistic effect in accordance with this invention appears most at a pH of 6 to 8. Desirably, fire extinguishers are generally used in a pH range from weak acidity to weak alkalinity in order to secure safety to man and other living organisms and to inhibit the corrosion of storage containers. From this viewpoint, too, the fire extinguisher of this invention has utility.

The fire extinguisher of this invention, whether in a concentrated or diluted form, has excellent dissolution stability and outstanding long-term storage stability. A concentrated solution of the fire extinguisher which can be diluted to a high ratio can be easily produced because of the excellent solubility and the low viscosity of the individual components. The viscosity of a 3% type concentrated solution of the fire extinguisher of this invention can be adjusted to not more than 100 centistokes at 20.degree. C., and this solution has excellent handlability in practical applications. Another characteristic of this invention is that since the amount of the cationic water-soluble polymeric substance (B) can be small, it is easy to reduce the freezing point of the concentrated solution of the fire extinguisher to -10.degree. to -20.degree. C.

The polybasic acid compound (C) which can be used in combination with the surface-active agent (A) and the cationic water-soluble polymeric substance (B) in this invention is a non-surface active compound and includes, for example, aromatic, aliphatic, alicyclic, and heterocyclic dibasic, tribasic, tetrabasic, pentabasic and hexabasic acids, and their alkali metal and ammonium salts. A broad range of polybasic acid compounds ranging from low-molecular-weight compounds to polymeric compounds having a carboxyl group in the side chain may be used. Since, however, the polymeric compounds may frequently produce a water-insoluble gel-like precipitate as a result of increasing the viscosity of the fire extinguisher or its reaction with the cationic water-soluble polymeric compound, it is preferred to use polybasic acid compounds having a relatively low molecular weight, particularly dibasic acid compounds having 3 to 24 carbon atoms, preferably 4 to 18 carbon atoms. The acid groups of the polybasic acid compounds include carboxylic, sulfonic, and phosphoric acid groups. Specific examples of the polybasic acid compound (C) are given below. ##STR14## (R.sub.1 represents hydrogen or a methyl group, R.sub.2 represents hydrogen or an alkali metal such as Li, Na, or K, or an ammonium group, and n is an integer of 5 to 100)

The mixing ratio of the cationic water-soluble polymeric substance (B) to the polybasic acid compound (C) is from 5:1 to 1:3, preferably from 4:1 to 1:1, by weight.

The fire extinguisher of this invention consists essentially of the surface-active agent (A) containing an anionic hydrophilic group and the cationic water-soluble polymeric substance (B), and its fire extinguishing performance is markedly increased by additionally including the polybasic acid compound (C). The mixing proportion of the polybasic acid (C) is such that the weight ratio of the component (A) to the components (B)+(C), i.e. A/B+C, is from 0.01 to 10, preferably from 0.1 to 2.

The advantages of the fire extinguisher of this invention are as follows:

(1) The fire extinguishing time can be shortened.

(2) It has increased liquid resistance. In other words, the life of its foams in contact with a polar solvent such as methanol and acetone is prolonged.

(3) Its foams have increased stability. Specifically, at the same foaming ratio, the 25% drainage time, 50% drainage time and 75% drainage time, as measures of foam stability, are prolonged.

(4) It has increased economy. Since the amount of a fluorine-containing surface-active agent which is more than 100 times as costly as ordinary surface-active agents (for example, detergents) can be decreased, the fire extinguisher can be supplied at a lower cost.

In addition to the surface-active agent (A), the water-soluble polymeric substance (B) and the polybasic acid compound (C) as an optional component, various additives may be included in the fire extinguisher of this invention. Examples of the additives include foam stabilizers, freezing point depressants, rust inhibitors and pH adjusting agents. The foam stabilizers are added to adjust the foam expansion ratio of the fire extinguisher, and may, for example, be nonionic surface active agents, cationic surface active agents, polyethylene glycol and polyvinyl alcohol. Examples of the freezing point depressants are ethylene glycol, propylene glycol, ethers of the Cellosolve type, carbitols, lower alcohols, and urea. The rust inhibitors and pH adjusting agents may be various compounds known in the art.

The fire extinguisher of this invention is applied to the site of fire by a known method, specifically by blowing or mixing air, carbon dioxide gas, nitrogen, a low-boiling fluorocarbon such as difluorodichloromethane, or another suitable incombustible gas into or with it. For example, when the fire extinguisher of this invention is stored as a concentrated solution, it is diluted to a suitable ratio by usual methods (for example, by causing it to be drawn into a water stream being sent toward a fire extinguishing device or a foam nozzle), and mixed with an incombustible gas such as air to foam it, and the resulting foams are jetted or sent to a burning surface from above or into below the burning surface.

If desired, the fire extinguisher of this invention may be used in combination with powdery fire extinguishers, protein foam extinguishers, foam fire extinguishers for use against fires of wooden materials, etc.

The following examples illustrate the present invention in greater detail. All percentages in these examples are by weight.

EXAMPLE 1

______________________________________C.sub.8 F.sub.17 SO.sub.2 NH(CH.sub.2).sub.3 N(CH.sub.3)(CH.sub.2).sub.3SO.sub.3 Na 5%Polyethylenimine (molecular weight: 6%40,000 to 70,000)Ethylene glycol 15%Butyl carbitol 15%Water 59%______________________________________

A mixture of the above ingredients was stirred at room temperature to form a clear solution. A very small amount of 1:1 HCl (water:HCl=1:1) was added to the solution to adjust its pH to 7.5. The properties of the resultant fire extinguisher (3% type concentrated solution) are shown in Table 1.

EXAMPLE 2

______________________________________ ##STR15## 5%Polyethylenimine (molecular weight 6%40,000 to 70,000)Ethylene glycol 15%Butyl carbitol 15%Water 59%______________________________________

A mixture of these ingredients was stirred at room temperature to form a clear solution. A very small amount of 1:1 HCl was added to the solution to adjust its pH to 7.5. The properties of the resulting fire extinguisher (3% type concentrated solution) are shown in Table 1.

EXAMPLE 3

______________________________________C.sub.8 F.sub.17 SO.sub.2 NH(CH.sub.2).sub.3 N(CH.sub.2 COONa).sub.2 5%Polyethylenimine (molecular weight 6%40,000 to 70,000)Ethylene glycol 15%Butyl carbitol 15%Water 51%______________________________________

A mixture of these ingredients was stirred at room temperature to form a clear solution. A very small amount of 1:1 HCl was added to adjust its pH to 7.5. The properties of the resulting fire extinguisher (3% type concentrated solution) are shown in Table 1.

TABLE 1______________________________________ Freezing Viscosity Test for the point at-10.degree. C. amount of aExample Appearance at -C.) (cst) precipitate (*1)______________________________________1 Completely -18 165 Trace clear2 Completely -18 170 Trace clear3 Completely -17 180 Trace Clear______________________________________ (*1): Conducted in accordance with the method described in Ordinance No. 26 of Ministry of Home Affairs, Japan on the concentrated solutions which had been subjected to a degeneration test.

EXAMPLES 4 to 100

______________________________________Surface-active agent (A-1 to A-4) 5%Cationic water-soluble polymer 6%(B-I to B-VIII)Ethylene glycol 15%Butyl carbitol 15%Water 59%______________________________________

The surface-active agent and the cationic water-soluble polymer were mixed in the above proportions with stirring. A very small amount of 1:1 HCl was added to adjust the pH of the solution to 7.5.

The properties of the resulting fire extinguishers (3% type concentrated solutions) obtained in the above manner are shown in Table 2. The polymers used had the following molecular weights.

______________________________________Polymer Molecular weight______________________________________B-I 40,000-70,000B-II-(a).about.(c) 30,000-70,000 (partially acylated product; ##STR16##B-III 9,000-10,000B-IV 10,000-12,000B-V 11,000-17,000B-VI 5,000-8,000B-VII 7,000-9,000B-VIII 7,500-9,500______________________________________ TABLE 2__________________________________________________________________________ Test for the amount Cationic water- Freezing Viscosity of a Surface-active soluble polymer Appear- point at -10.degree. C. precipitateExample agent (A) (B) ance (.degree.C.) (cst) (*1)__________________________________________________________________________ 4 A-1-a I Completely -17 170 Trace clear 5 A-1-c I Completely -17 170 " clear 6 A-1-d I Completely -16 165 " clear 7 A-1-m I Completely -17 170 " clear 8 A-1-p I Completely -18 165 " clear 9 A-1-r I Completely -14 164 " clear10 A-1-t I Completely -17 167 " clear11 A-1-u I Completely -16 165 " clear12 A-1-v I Completely -16 171 " clear13 A-1-b II-a(a) Completely -15 170 " clear14 A-1-e II-(b) Completely -16 174 " clear15 A-1-f II-(c) Completely -17 166 " clear16 A-1-g II-(a) Completely -18 168 " clear17 A-1-h II-(a) Completely -13 172 " clear18 A-1-j II-(b) Completely -16 170 " clear19 A-1-k II-(b) Completely -17 165 " clear20 A-1-n II-(c) Completely -14 167 " clear21 A-1-o I Completely -14 164 " clear22 A-1-s I Completely -14 170 " clear23 A-1-c II-(a) Completely -15 164 " clear24 A-1-c III Completely -14 167 " clear25 A-1-c IV Completely -16 169 " clear26 A-1-c V Completely -16 170 " clear27 A-1-c VI Completely -16 164 " clear28 A-1-c VII Completely -18 164 " clear29 A-1-c VIII Completely - 17 167 " clear30 A-1-d III Completely -16 169 " clear31 A-1-m IV Completely -16 170 " clear32 A-1-r V Completely -17 167 " clear33 A-1-t VII Completely -16 173 " clear34 A-1-u VI Completely -17 174 " clear35 A-1-v VIII Completely -15 170 " clear36 A-2-a I Completely -14 169 " clear37 A-2-c I Completely -17 169 " clear38 A-2-d I Completely -19 166 " clear39 A-2-f I Completely -15 167 " clear40 A-2-h I Completely -18 163 " clear41 A-2-i I Completely -17 170 " clear42 A-2-j I Completely -15 180 " clear43 A-2-k I Completely -16 170 " clear44 A-2-l I Completely -16 172 " clear45 A-2-n I Completely -14 169 " clear46 A-2-o I Completely -15 167 " clear47 A-2-a II-(a) Completely -16 167 " clear48 A-2-f II-(b) Completely -15 160 " clear49 A-2-g II-(a) Completely -15 168 " clear50 A-2-m II-(b) Completely -16 169 " clear51 A-2-o II-(a) Completely -17 165 " clear52 A-2-c II-(a) Completely -16 180 " clear53 A-2-c III Completely -17 172 " clear54 A-2-c IV Completely -17 170 " clear55 A-2-d II-(a) Completely -17 173 " clear56 A-2-c V Completely -17 174 " clear57 A-2-c VI Completely -16 165 " clear58 A-2-c VIII Completely -17 167 " clear59 A-2-c VIII Completely -15 168 " clear60 A-2-e VI Completely -16 170 " clear61 A-2-i VII Completely -14 163 " clear62 A-2-k V Completely -14 164 " clear63 A-2-n IV Completely -17 165 " clear64 A-3-a I Completely -14 170 " clear65 A-3-b I Completely -15 173 " clear66 A-3-d I Completely -15 174 " clear67 A-3-f I Completely -14 173 " clear68 A-3-h I Completely -16 181 " clear69 A-3-i I Completely -16 163 " clear70 A-3-k I Completely -11 173 " clear71 a-3-c II-(b) Completely -14 174 " clear72 A-3-d II-(b) Completely -15 171 " clear73 A-3-e II-(a) Completely -14 166 " clear74 A-3-g II-(c) Completely -13 165 " clear75 A-3-j II-(c) Completely -14 171 " clear76 A-3-b III Completely -16 175 " clear77 A-3-b IV Completely -13 164 " clear78 A-3-b V Completely -15 163 " clear79 A-3-b VI Completely -14 167 " clear80 A-3-b VII Completely -13 170 " clear81 A-3-b VIII Completrly -17 180 " clear82 A-3-c V Completely -16 164 " clear83 A-3-f IV Completely -14 160 " clear84 A-3-h VI Completely -15 154 " clear85 A-3-j VII Completely -16 170 " clear86 A-4-a I Completely -16 146 " clear87 A-4-b I Completely -16 140 " clear88 A-4-c I Completely -17 150 " clear89 A-4-d I Completely -16 148 " clear90 A-4-e I Completely -17 149 " clear91 A-4-f II-(a) Completely -15 150 " clear92 A-4-g II-(b) Completely -15 143 " clear93 A-4-b II-(a) Completely -16 144 " clear94 A-4-c III Completely -16 146 " clear95 A-4-d II-(c) Completely -17 153 " clear96 A-4-f III Completely -15 154 " clear97 A-4-g IV Completely -16 170 " clear98 A-4-c III Completely -16 153 " clear99 A-4-c IV Completely -15 155 " clear100 A-4-c VII Completely -15 159 " clear__________________________________________________________________________ (*1): Same as the footnote to Table 1.

The fire extinguishers of this invention obtained in Examples 1 to 100 were subjected to a fire extinguishing test in accordance with the method described in Ordinance No. 26 of the Ministry of Home Affairs. For comparison, a fire extinguisher containing a thixotropic water-soluble polymeric material (a commercial product containing a fluorine-type surface-active agent) was also tested. The outline of the experimental procedure was as follows:

The scale of fire was such that a B-20 model having a combustion area of 4 m.sup.2 was used and 400 liters of a fuel (solvent) was charged. But in the case of propylene oxide as a fuel, the fire size was 2 m.sup.2 (B-10 model) and 200 liters of the fuel was charged. The pre-burning time was 5 minutes. Each of the concentrated solutions of fire extinguishers was diluted with fire extinguishing water and filled in a pressure container. It was foamed under a nitrogen pressure of 7.0 kg/cm.sup.2 by passing it through a standard foaming nozzle for testing water-film type extinguisher foams, and the foams were supplied to the burning liquid surface. The rate of discharge was adjusted to 10 liters/min and the total discharge time was adjusted to 5 minutes. The results are shown in Table 3.

TABLE 3__________________________________________________________________________ Dilution Foam Extinguishing Heat Dilution ratio expansion time Vapor sealing resistance (*2)Example water (%) Burning solvent ratio (min./sec.) property (*1) (cm .phi.)__________________________________________________________________________ 1 Sea water 3 iso-Propanol 5.7 4/12 Did not ignite 25 Fresh water " " 6.1 2/50 " 17 2 Sea water " iso-Propanol 5.9 3/50 " 23 Fresh water " " 6.3 3/13 " 15 3 Sea water " iso-Propanol 5.6 3/10 " Self- extinguishing Fresh water " " 6.0 3/5 " Self- extinguishing Sea water " Acetone 5.6 3/25 " Self- extinguishing Sea water 4.5 Propylene oxide 5.7 4/7 " 19Com- Sea water 9 iso-Propanol 6.2 Did not -- --para- extinguishtive Fresh water " 6.3 Did not -- --Example extinguish 1 4 Sea water 3 " 6.2 3/14 Did not ignite 22 Fresh water " " 6.3 3/33 " 19 5 Sea water " " 6.0 4/03 " 23 Fresh water " " 6.3 4/13 " 22 6 Sea water " " 6.1 3/36 " 17 Fresh water " " 6.2 3/33 " 18 7 Sea water " " 5.9 4/03 " 19 Fresh water " " 6.2 3/49 " 19 8 Sea water " " 5.9 2/19 " 21 Fresh water " " 6.3 2/46 " 24 9 Sea water " Methanol 5.8 3/09 " 20 Fresh water " " 6.0 3/12 " 2110 Sea water " " 5.7 3/42 " 15 Fresh water " " 5.8 3/43 " 1711 Sea water " " 5.6 3/22 " 19 Fresh water " " 5.6 3/35 " 2112 Sea water " Acetone 6.3 2/16 " 18 Fresh water " " 6.4 2/19 " 1813 Sea water " " 6.1 3/22 " 23 Fresh water " " 6.0 3/33 " 2314 Sea water " " 5.8 3/13 " 25 Fresh water " " 6.3 3/17 " 2615 Sea water " " 6.1 2/53 " 24 Fresh water " " 5.7 2/34 " 2116 Sea water " iso-Propanol 6.0 3/09 " 20 Fresh water " " 6.1 3/18 " 2517 Sea water " " 5.7 2/26 " 27 Fresh water " " 5.9 2/33 " 2618 Sea water " " 6.1 3/41 " 20 Fresh water " " 6.0 3/47 " 1919 Sea water 4.5 Propylene oxide 5.8 3/56 " 18 Fresh water " " 5.7 3/48 " 2320 Sea water " " 5.9 3/11 " 21 Fresh water " " 6.0 3/21 " 1821 Sea water 3 Methanol 5.7 3/40 " 19 Fresh water " " 5.6 3/51 " 2322 Sea water " " 5.9 3/21 " 19 Fresh water " " 5.7 3/24 " 2023 Sea water " " 5.9 3/36 " 23 Fresh water " " 6.3 3/42 " 2424 Sea water " " 6.1 3/16 " 25 Fresh water " " 6.4 3/18 " 2125 Sea water " " 5.8 4/06 " 22 Fresh water " " 5.6 4/32 " 2426 Sea water " Acetone 6.3 2/38 " 22 Fresh water " " 6.1 2/44 " 2427 Sea water " " 6.2 2/56 " 21 Fresh water " " 6.4 3/08 " 2028 Sea water " iso-Propanol 5.8 4/01 " 20 Fresh water " " 5.7 4/22 " 2029 Sea water " " 5.3 3/06 " 18 Fresh water " " 5.5 3/18 " 1830 Sea water " " 5.7 3/13 " 19 Fresh water " " 5.9 3/56 " 1631 Sea water " Acetone 6.0 3/17 " 23 Fresh water " " 5.9 3/19 " 2132 Sea water " " 6.1 3/06 " 18 Fresh water " " 5.8 3/33 " 1733 Sea water " " 5.7 3/42 " 18 Fresh water " " 5.6 3/56 " 2034 Sea water " Methanol 5.8 3.52 " 18 Fresh water " " 5.9 3/50 " 1935 Sea water " " 6.0 3/48 " 22 Fresh water " " 6.1 3/49 " 2436 Sea water " " 6.2 3/33 " 21 Fresh water " " 6.3 3/16 " 2637 Sea water " " 6.4 3/15 " 23 Fresh water " " 6.6 3/10 " 2438 Sea water " " 5.4 3/20 " 21 Fresh water " " 5.3 3/29 " 2439 Sea water " " 5.7 3/51 " 25 Fresh water " " 5.6 3/57 " 2640 Sea water " Acetone 5.9 3/19 " 18 Fresh water " " 5.6 4/00 " 1941 Sea water " " 5.8 3/44 " 20 Fresh water " " 5.8 3/38 " 2142 Sea water " " 5.9 3/48 " 26 Fresh water " " 5.5 3/25 " 2543 Sea water " iso-Propanol 6.0 3/18 " 23 Fresh water " " 6.1 3/31 " 2244 Sea water 4.5 Propylene oxide 5.3 2/16 " 19 Fresh water " " 5.4 2/19 " 1845 Sea water 3 Methanol 6.0 3/26 " 21 Fresh water " " 6.1 3/24 " 2046 Sea water " " 5.6 3/19 " 20 Fresh water " " 5.8 3/17 " 1947 Sea water " " 5.9 3/19 " 18 Fresh water " " 5.8 3/42 " 1748 Sea water 4.5 Propylene oxide 6.1 2/00 " 19 Fresh water " " 6.3 2/32 " 2049 Sea water 3 Methanol 6.1 3/16 " 18 Fresh water " " 6.0 3/19 " 2050 Sea water " " 5.8 3/18 " 21 Fresh water " " 5.7 3/32 " 2251 Sea water " " 5.7 3/54 " 24 Fresh water " " 5.9 3/06 " 2552 Sea water " " 6.0 3/47 " 24 Fresh water " " 5.8 3/16 " 2553 Sea water " " 5.7 3/37 " 26 Fresh water " " 5.3 3/26 " 2354 Sea water " " 6.1 3/36 " 27 Fresh water " " 6.3 3/18 " 2755 Sea water " " 6.0 3/46 " 25 Fresh water " " 6.0 3/14 " 2556 Sea water " iso-Propanol 5.6 4/07 " 20 Fresh water " " 5.7 4/06 " 2657 Sea water " " 5.9 3/58 " 27 Fresh water " " 5.8 3/42 " 2658 Sea water " " 5.9 3/53 " 25 Fresh water " " 5.7 3/55 " 2459 Sea water " Acetone 6.0 3/11 " 27 Fresh water " " 6.1 3/12 " 2860 Sea water " " 5.9 3/31 " 21 Fresh water " " 6.3 3/27 " 2061 Sea water " " 5.8 3/24 " 23 Fresh water " " 5.9 3/22 " 2062 Sea water " " 5.5 3/18 " 21 Fresh water " " 5.6 3/16 " 2263 Sea water " " 5.8 3/14 " 24 Fresh water " " 6.0 3/18 " 2364 Sea water " Methanol 5.6 3/43 " 24 Fresh water " " 5.7 3/14 " 2365 Sea water " " 5.5 3/17 " 24 Fresh water " " 5.7 3/19 " 2166 Sea water " " 5.6 4/03 " 24 Fresh water " " 6.0 3/59 " 2267 Sea water " " 5.8 3/19 " 23 Fresh water " " 5.8 3/26 " 1968 Sea water " " 5.9 3/34 " 22 Fresh water " " 5.6 3/38 " 1969 Sea water " " 5.5 3/20 " 20 Fresh water " " 5.4 3/17 " 2170 Sea water " Acetone 6.0 3/08 " 19 Fresh water " " 6.1 3/11 " 1871 Sea water 4.5 Propylene oxide 6.3 2/46 " 18 Fresh water " " 6.4 2/33 " 1972 Sea water " " 6.7 2/16 " 18 Fresh water " " 6.5 2/30 " 2073 Sea water 3 iso-Propanol 5.6 3/44 " 25 Fresh water " " 5.4 3/56 " 2674 Sea water 4.5 Propylene oxide 6.1 2/11 " 18 Fresh water " " 6.2 2/40 " 2175 Sea water 3 Acetone 5.8 3/12 " 21 Fresh water " " 5.9 3/19 " 2276 Sea water " iso-Propanol 5.7 3/49 " 20 Fresh water " " 5.7 3/55 " 1977 Sea water " " 5.8 3/18 " 21 Fresh water " " 5.9 3/19 " 2278 Sea water " " 5.7 3/20 " 23 Fresh water " " 5.6 3/37 " 2479 Sea water " " 5.6 3/39 " 21 Fresh water " " 5.7 3/42 " 2680 Sea water " Acetone 5.9 3/55 " 25 Fresh water " " 6.0 3/46 " 2581 Sea water " " 6.0 3/56 " 24 Fresh water " " 5.8 3/33 " 2482 Sea water " Methanol 6.1 3/12 " 21 Fresh water " " 6.0 3/06 " 2283 Sea water " " 6.2 3/09 " 20 Fresh water " " 6.0 3/13 " 1984 Sea water " iso-Propanol 5.8 3/23 " 20 Fresh water " " 5.7 3/16 " 1985 Sea water " " 5.9 3/15 " 18 Fresh water " " 5.9 3/06 " 1986 Sea water 4.5 Methanol 6.0 3/56 " 16 Fresh water " " 6.2 3/54 " 1787 Sea water " " 6.0 3/49 " 19 Fresh water " " 5.7 3/46 " 2288 Sea water 3 Acetone 5.6 3/18 " 23 Fresh water " " 5.7 3/49 " 2689 Sea water " " 5.9 3/14 " 25 Fresh water " " 6.0 3/23 " 2490 Sea water 4.5 Propylene oxide 6.3 2/19 " 27 Fresh water " " 6.4 2/13 " 2291 Sea water " " 6.2 2/31 " 26 Fresh water " " 6.0 2/33 " 2392 Sea water 3 Acetone 5.9 3/43 " 21 Fresh water " " 5.7 3/41 " 2393 Sea water " Methanol 5.6 3/56 " 22 Fresh water " " 5.7 4/02 " 2394 Sea water " " 5.5 3/42 " 19 Fresh water " " 5.7 3/16 " 1995 Sea water " " 5.9 3/35 " 19 Fresh water " " 5.8 3/32 " 2096 Sea water " " 5.9 3/31 " 22 Fresh water " " 6.0 3/56 " 2497 Sea water " " 5.7 3/12 " 23 Fresh water " " 5.7 3/16 " 2298 Sea water " " 5.5 3/19 " 20 Fresh water " " 5.9 3/21 " 2199 Sea water " " 6.0 3/29 " 19 Fresh water " " 5.7 3/32 " 20100 Sea water " iso-Propanol 5.3 3/52 " 22 Fresh water " " 5.5 3/48 " 23__________________________________________________________________________ (*1): Vapor sealing property For 15 minutes after the application of the fire extinguisher, a flame wa made to approach the foam surface by using a torch, and it was determined whether the solvent caught fire. (*2): Heat resistance Fifteen minutes after the application of the fire extinguisher, a liquid surface of a square shape with one side measuring 15 cm was exposed at th central part of the foam surface. It was ignited, and the burning area wa measured 5 minutes later.

EXAMPLES 101 TO 195

______________________________________Surface-active agent (A-1 to A-4) 3%Cationic water-soluble polymer 6%(B-I to B-VIII)Polybasic acid (C-1 to C-32) 4%Ethylene glycol 15%Butyl carbitol 15%Water 57%______________________________________

In each run, a fire extinguisher was prepared in accordance with the above formulation containing the polybasic acid, and tested in the same way as in Examples 1 to 100. The properties of the resulting fire extinguishers are shown in Table 4, and the results of the fire extinguishing test are shown in Table 5.

TABLE 4__________________________________________________________________________ Test for the Cationic Freezing Viscosity amount of aEx- Surface-active water-soluble Polybasic point at -10.degree. C. precipitateample agent (A) polymer (B) acid Appearance (.degree.C.) (cst) (*1)__________________________________________________________________________101 A-1-a I C-1 (n = 4) Completely clear -15 156 Trace102 A-1-c I " " -15 150 "103 A-1-d I " " -13 160 "104 A-1-m I " " -14 172 "105 A-1-p I " " -14 163 "106 A-1-r I C-1 (n = 6) " -16 162 "107 A-1-t I " " -14 165 "108 A-1-u I " " -14 164 "109 A-1-v I " " -14 167 "110 A-1-b II-(a) C-2 " -14 166 "111 A-1-e II-(b) " " -15 172 "112 A-1-f II-(c) " " -16 163 "113 A-1-g II-(a) C-4 " -16 162 "114 A-1-h II-(a) " " -16 176 "115 A-1-j II-(b) " " -14 179 "116 A-1-k II-(b) C-3 " -15 167 "117 A-1-n II-(c) " " -13 169 "118 A-1-o I " " -13 170 "119 A-1-s I C-8 " -12 180 "120 A-1-c II-(a) C-6 " -13 165 "121 A-1-c III C-8 " -14 170 "122 A-1-c IV C-10 " -15 171 "123 A-1-c V C-9 " -16 173 "124 A-1-c VII C-7 " -16 165 "125 A-1-c VIII " " -15 166 "126 A-1-d III " " -14 170 "127 A-1-m IV C-13 " -14 175 "128 A-1-r V C-15 " -15 176 "129 A-1-t VII C-16 " -14 173 "130 A-1-u VI C-20 " -15 180 "131 A-1-v VIII C-22 " -16 180 "132 A-2-a I C-23 " -14 180 "133 A-2-c I C-1 (n = 4) " -17 179 "134 A-2-d I " " -11 179 "135 A-2-f I C-25 " -13 169 "136 A-2-h I C-24 " -16 173 "137 A-2-i I " " -16 172 "138 A-2-j I " " -15 173 "139 A-2-k I " " -16 175 "140 A-2-l I C-30 (p = 4) " -16 176 "141 A-2-n I " " -14 179 "142 A-2-o I C-31 (q = 2) " -14 180 "143 A-2-a II-(a) " " -14 173 "144 A-2-f II-(b) C-27 " -14 174 "145 A-2-g II-(a) C-28 " -14 175 "146 A-2-m II-(b) C-19 (n = 4) " -14 176 "147 A-2-o II-(a) C-24 " -15 176 "148 A-2-c II-(a) C-1 (n = 6) " -15 182 "149 A-2-c III " " -16 183 "150 A-2-c IV " " -16 183 "151 A-2-c V " " -16 180 "152 A-2-c VI C-16 " -15 186 "153 A-2-c VII " " -16 172 "154 A-2-c VIII " " -15 173 "155 A-2-e VI C-10 " -16 171 "156 A-2-i VII " " -13 176 "157 A-2-k V " " -13 175 "158 A-2-n IV " " -13 175 "159 A-3-a I C-13 " -13 175 "160 A-3-b I " " -15 176 "161 A-3-d I " " -13 175 "162 A-3-f I C-17 " -14 176 "163 A-3-h I " " -14 182 "164 A-3-i I " " -10 175 "165 A-3-k I C-18 " -13 176 "166 A-3-c II-(b) C-7 " -12 175 "167 A-3-d II-(b) " " -13 175 "168 A-3-e II-(a) C-14 " -12 176 "169 A-3-g II-(c) C-22 " -12 170 "170 A-3-j II-(c) C-23 " -13 173 "171 A-3-b III C-26 " -15 176 "172 A-3-b III C-27 " -12 165 "173 A-3-b V " " -14 165 "174 A-3-b VI " " -13 170 "175 A-3-b VII C-29 (l = 4) " -12 172 "176 A-3-b VIII C-31 (q = 4) " -15 182 "177 A-3-c V " " -14 170 "178 A-3-f IV " " -12 163 "179 A-3-h VI C-28 " -12 160 "180 A-3-j VII C-24 " -15 180 "181 A-4-a I " " -16 153 "182 A-4-b I " " -14 150 "183 A-4-c I " " -15 160 "184 A-4-d I C-16 " -14 152 "185 A-4-e I C-14 " -16 156 "186 A-4-f I " " -15 160 "187 A-4-g I " " -15 153 "188 A-4-b II-(a) C-12 (P-type) " -14 154 "189 A-4-c II-(b) C-10 " -13 157 "190 A-4-d II-(c) " " -15 159 "191 A-4-f III " " -14 172 "192 A-4-g IV C-2 " -14 172 "193 A-4-c III C-1 (n = 4) " -15 155 "194 A-4-c IV " " -14 160 "195 A-4-c VII " " -14 163 "__________________________________________________________________________ (*1): Same as the footnote to Table 2. TABLE 5__________________________________________________________________________ Dilution Foam Extinguishing Heat Dilution ratio expansion time Vapor sealing resistance (*2)Example water (%) Burning solvent ratio (min./sec.) property (*1) (cm .phi.)__________________________________________________________________________101 Sea water 3 iso-Propanol 6.3 2/16 Did not ignite 11 Fresh water " " 6.4 2/56 " 9102 Sea water " " 6.2 3/42 " 4 Fresh water " " 6.3 3/43 " 6103 Sea water " " 6.2 2/18 " 3 Fresh water " " 6.4 2/19 " 3104 Sea water " " 6.3 3/12 " 8 Fresh water " " 6.4 3/19 " 8105 Sea water " " 6.6 1/56 " 11 Fresh water " " 6.7 1/58 " 13106 Sea water " Methanol 6.3 2/23 " 16 Fresh water " " 6.7 2/29 " 14107 Sea water " " 6.0 2/59 " 13 Fresh water " " 6.1 2/48 " 12108 Sea water " " 6.0 2/46 " 17 Fresh water " " 6.3 2/48 " 13109 Sea water " Acetone 6.7 2/00 " 9 Fresh water " " 2/56 1/59 "8 8110 Sea water " " 6.6 2/33 " 5 Fresh water " " 6.3 2/48 " 6111 Sea water " " 6.0 2/35 " 5 Fresh water " " 6.5 2/58 " 3112 Sea water " " 6.4 2/13 " 7 Fresh water " " 6.1 2/00 " 8113 Sea water " iso-Propanol 6.3 2/32 " 15 Fresh water " " 6.4 2/48 " 13114 Sea water " " 6.0 2/01 " 14 Fresh water " " 6.1 2/13 " 10115 Sea water " " 6.4 2/26 " 10 Fresh water " " 6.3 2/58 " 8116 Sea water 4.5 Propylene oxide 6.3 2/59 " 7 Fresh water " " 6.2 3/07 " 10117 Sea water " " 6.7 2/23 " 11 Fresh water " " 6.8 2/21 " 9118 Sea water 3 Methanol 6.9 2/59 " 9 Fresh water " " 6.3 2/53 " 7119 Sea water " " 6.6 2/18 " 9 Fresh water " " 6.5 2/32 " 10120 Sea water " " 6.7 2/46 " 11 Fresh water " " 6.3 2/48 " 13121 Sea water " " 6.5 2/33 " 14 Fresh water " " 6.5 2/30 " 10122 Sea water " " 6.3 3/18 " 10 Fresh water " " 6.0 3/43 " 8123 Sea water " Acetone 6.7 2/00 " 9 Fresh water " " 6.5 2/16 " 10124 Sea water " " 6.5 1/58 " 9 Fresh water " " 6.6 1/53 " 8125 Sea water " iso-Propanol 6.0 3/11 " 9 Fresh water " " 5.9 3/23 " 9126 Sea water " " 5.9 2/16 " 6 Fresh water " " 6.0 2/22 " 6127 Sea water " " 6.3 2/00 " 7 Fresh water " " 6.5 2/13 " 6128 Sea water " Acetone 6.9 2/00 " 7 Fresh water " " 6.8 1/58 " 8129 Sea water " " 6.9 1/56 " Self- extinguishing Fresh water " " 6.5 2/17 " Self- extinguishing130 Sea water " " 6.7 2/58 " Self- extinguishing Fresh water " " 6.6 2/57 " 3131 Sea water " Methanol 6.7 3/08 " 3 Fresh water " " 6.6 3/00 " 2132 Sea water " " 6.8 3/11 " 10 Fresh water " " 6.7 3/12 " 11133 Sea water " " 6.9 2/58 " 10 Fresh water " " 7.0 2/48 " 15134 Sea water " " 7.1 2/13 " 12 Fresh water " " 7.1 2/15 " 10135 Sea water " " 6.6 2.48 " 10 Fresh water " " 6.7 2/56 " 12136 Sea water " " 6.5 2/56 " 13 Fresh water " " 6.0 2/56 " 12137 Sea water " Acetone 6.3 3/01 " 9 Fresh water " " 6.2 3/48 " 8138 Sea water " " 6.6 2/58 " 10 Fresh water " " 6.6 2/46 " 11139 Sea water " " 6.8 3/16 " 9 Fresh water " " 6.5 2/46 " 9140 Sea water " iso-Propanol 6.8 2/46 " 9 Fresh water " " 6.9 2/45 " 9141 Sea water 4.5 Propylene oxide 6.3 1/46 " 10 Fresh water " " 6.5 1/33 " 10142 Sea water 3 Methanol 7.0 2/11 " 8 Fresh water " " 7.2 2/06 " 8143 Sea water " " 6.0 2/27 " 9 Fresh water " " 6.5 2/16 " 2/48144 Sea water " " 6.9 2/52 " Self- extinguishing Fresh water " " 7.0 2/52 " Self- 2/59 extinguishing145 Sea water 4.5 Propylene oxide 7.1 /59 " 11 Fresh water " " 6.9 /57 " 9146 Sea water 3 Methanol 7.0 1/16 " 2 Fresh water " " 6.6 1/28 " 4147 Sea water " " 6.3 2/32 " 6 Fresh water " " 6.7 2/46 " 4148 Sea water " " 6.6 2/59 " 8 Fresh water " " 6.9 2/13 " 8149 Sea water " " 6.6 2/33 " Self- extinguishing Fresh water " " 6.5 1/53 " Self- extinguishing150 Sea water " " 6.6 2/16 " Self- extinguishing Fresh water " " 6.4 2/33 " Self- extinguishing151 Sea water " " 7.2 2/42 " 3 Fresh water " " 7.5 2/17 " 4152 Sea water " " 7.2 2/32 " 5 Fresh water " " 7.2 1/59 " 8153 Sea water " iso-Propanol 6.9 3/13 " 8 Fresh water " " 7.0 3/18 " 10154 Sea water " " 7.0 3/01 " 8 Fresh water " " 7.1 3/06 " 12155 Sea water " " 7.3 3/00 " 13 Fresh water " " 7.2 2/47 " 12156 Sea water " Acetone 7.3 2/11 " 11 Fresh water " " 7.4 2/10 " 13157 Sea water " " 7.0 2/53 " 9 Fresh water " " 6.9 2/56 " 8158 Sea water " " 7.3 2/22 " 7 Fresh water " " 7.6 2/18 " 7159 Sea water " " 7.5 2/19 " 8 Fresh water " " 7.4 2/24 " 9160 Sea water " " 7.6 2/29 " 10 Fresh water " " 7.0 2/38 " 10161 Sea water " Methanol 6.3 2/38 " 11 Fresh water " " 6.6 2/56 " 12162 Sea water " " 6.5 2/48 " 13 Fresh water " " 6.7 2/32 " 13163 Sea water " " 6.6 2/39 " 12 Fresh water " " 6.8 2/56 " 11164 Sea water " " 6.7 2/48 " 13 Fresh water " " 6.7 2/27 " 8165 Sea water " " 6.6 2/36 " 9 Fresh water " " 6.7 2/39 " 9166 Sea water " " 6.5 2/16 " 10 Fresh water " " 6.4 2/19 " 11167 Sea water " Acetone 7.6 2/00 " Self- extinguishing Fresh water " " 7.3 1/56 " Self- extinguishing168 Sea water 4.5 Propylene oxide 8.0 1/12 " 11 Fresh water " " 8.3 1/13 " 10169 Sea water " " 8.0 1/07 " 10 Fresh water " " 7.9 /53 " 8170 Sea water 3 iso-Propanol 6.3 2/57 " 13 Fresh water " " 6.2 2/49 " 12171 Sea water 4.5 Propylene oxide 8.0 1/13 " 8 Fresh water " " 7.9 1/27 " 10172 Sea water 3 Acetone 6.6 2/16 " 11 Fresh water " " 6.3 2/17 " 10173 Sea water " iso-Propanol 6.3 3/00 " 10 Fresh water " " 6.2 3/11 " 9174 Sea water " " 6.7 2/49 " 8 Fresh water " " 6.8 2/59 " 12175 Sea water " " 6.2 2/16 " 11 Fresh water " " 6.6 2/33 " 13176 Sea water " " 6.7 2/46 " 10 Fresh water " " 6.8 2/43 " 13177 Sea water " Acetone 6.9 3/06 " 12 Fresh water " " 7.0 3/11 " 11178 Sea water " " 7.2 3/12 " 13 Fresh water " " 7.1 3/00 " 12179 Sea water " Methanol 6.9 2/48 " 10 Fresh water " " 7.0 2/46 " 11180 Sea water " " 7.1 2/18 " 10 Fresh water " " 7.0 2/16 " 9181 Sea water " iso-Propanol 6.6 2/23 " 8 Fresh water " " 6.7 2/26 " 9182 Sea water " " 6.9 2/27 " 7 Fresh water " " 6.9 2/16 " 8183 Sea water 4.5 Methanol 7.0 2.58 " 9 Fresh water " " 7.2 2/56 " 6184 Sea water " " 7.0 2/43 " 3 Fresh water " " 7.0 2/47 " 2185 Sea water 3 Acetone 6.6 2/16 " 12 Fresh water " " 6.3 2/32 " 13186 Sea water " " 6.7 2/14 " 9 Fresh water " " 6.9 2/16 " 10187 Sea water 4.5 Propylene oxide 7.8 1/27 " 10 Fresh water " " 7.9 1/33 " 10188 Sea water " " 7.3 /52 " 9 Fresh water " " 7.6 /46 " 11189 Sea water 3 Acetone 6.8 2/32 " 9 Fresh water " " 6.9 2/56 " 9190 Sea water " Methanol 7.2 2/48 " 11 Fresh water " " 7.2 2/59 " 12191 Sea water " " 7.3 2/37 " 10 Fresh water " " 7.0 2/19 " 8192 Sea water " " 6.6 2/46 " 9 Fresh water " " 6.7 2/43 " 10193 Sea water " " 6.9 2/18 " 7 Fresh water " " 7.0 2/11 " 6194 Sea water " " 6.9 2/28 " 9 Fresh water " " 6.3 2/17 " 8195 Sea water " " 6.5 2/32 " 7 Fresh water " " 6.9 2/38 " 6__________________________________________________________________________ (*1) and (*2): Same as the footnote to Table 3.

EXAMPLES 196 TO 233

Some of the fire extinguishers obtained in the foregoing Examples were subjected to a liquid resistance test and a test of determing the time (drainage time) which elapsed until the foams were converted to liquid. The results are shown in Table 6.

TABLE 6______________________________________Liquid resistance (*2)Time required until thefoams completely disap-peared (min./sec.)Ex- iso- Drainage timeam- No. Prop- (min./sec.)ple (*1) Methanol anol Acetone 25% 50% 75%______________________________________196 4 5/12 4/11 6/18 3/11 7/32 22/56197 10 5/46 4/08 6/19 3/31 7/18 22/48198 15 5/52 4/11 6/32 3/26 7/56 22/32199 19 5/11 4/18 6/34 3/46 7/31 22/16200 24 4/53 3/53 6/48 3/52 7/33 22/18201 28 5/16 4/52 6/13 2/48 7/48 22/22202 43 5/18 5/48 6/23 3/31 7/11 22/23203 46 5/43 5/43 6/56 3/18 7/08 22/26204 58 5/52 4/47 6/57 3/17 7/16 22/31205 62 6/48 4/56 6/16 3/16 7/51 22/33206 66 5/22 4/57 6/19 3/19 7/51 22/18207 67 5/17 5/33 6/21 3/08 7/32 22/52208 80 5/26 4/51 6/36 3/33 7/38 23/53209 85 5/56 4/53 6/33 3/39 7/29 22/18210 87 5/18 4/59 6/31 3/56 7/38 24/19211 90 6/20 4/41 6/30 3/51 7/21 22/27212 100 6/19 4/47 6/19 3/44 7/24 25/32213 110 >10 min. 8/11 >10 min. 5/56 10/53 40/17214 113 >10 min. 8/56 >10 min. 5/47 10/52 39/16215 118 >10 min. 7/32 >10 min. 6/11 10/56 39/46216 120 >10 min. 7/49 >10 min. 6/13 10/18 38/41217 125 >10 min. 8/56 >10 min. 6/16 10/23 41/33218 131 >10 min. 9/13 >10 min. 6/13 10/29 42/37219 134 >10 min. 9/59 >10 min. 6/08 10/16 43/19220 145 >10 min. 7/16 >10 min. 6/14 11/46 42/19221 148 >10 min. 8/42 >10 min. 6/17 11/21 41/17222 152 >10 min. 9/53 >10 min. 6/28 12/19 46/18223 156 >10 min. 7/48 >10 min. 6/29 13/21 45/21224 159 >10 min. 9/16 >10 min. 6/38 12/18 43/38225 160 >10 min. 8/16 >10 min. 6/43 11/33 40/39226 167 >10 min. 7/47 >10 min. 6/12 11/42 39/42227 173 >10 min. 8/51 >10 min. 5/19 11/47 41/44228 180 >10 min. 7/14 >10 min. 5/31 11/46 46/47229 182 >10 min. 8/14 >10 min. 6/42 11/50 48/16230 183 >10 min. 9/46 >10 min. 5/47 11/31 49/21231 188 >10 min. 8/33 >10 min. 6/51 11/40 40/27232 190 >10 min. 7/26 >10 min. 6/51 11/16 39/35233 191 >10 min. 9/27 >10 min. 5/48 10/10 40/55______________________________________ (*1): Showing the fire extinguishers by the numbers of the foregoing Examples. (*2): The liquid resistance was tested by the following procedure. An aqueous solution of the fire extinguisher diluted with fresh water to concentration of 3% was foamed by the method herein above described. Immediately then, 5 cc of the foams were collected and placed gently on 100 cc of a polar sovent. The time which elapsed from the placing until the foams completely disappeared was measured.

Claims

1. An aqueous foam fire extinguisher comprising (A) a fluorine-containing aminosulfonate-type surface-active agent of formula (A-2)

Rf--Z--Q.sub.1 --N(R)--Q.sub.2 SO.sub.3 M

wherein Rf represents a fluorinated aliphatic group having 3 to 20 carbon atoms, Z is a divalent linking group selected from the group consisting of --SO.sub.2 N(R.sub.1)--, --CON(R.sub.1)--, --(CH.sub.2 CH.sub.2).sub.i --SO.sub.2 N(R.sub.1)--, ##STR17## in which R.sub.1 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and i represents an integer of 1 to 10, Q.sub.1 represents (--CH.sub.2)j, in which j is an integer of 1 to 6 or ##STR18## in which j is an integer of 1 to 6 or ##STR19## in which R.sub.2 represents an hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R represents a hydrogen atom, an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, --Q.sub.2 SO.sub.3 M or --(CH.sub.2).sub.k COOM, in which k represents an integer of 1 to 4, Q.sub.2 represents (--CH.sub.2).sub.l -- in which l represents an integer of 1 to 4, ##STR20## in which R.sub.3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, or ##STR21## M represents a cationic atom or atomic grouping selected from the group consisting of a hydrogen atom, an alkaline earth metal and --N(H).sub.m (R.sub.4).sub.n, in which R.sub.4 represents an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, and m and n are integers of 0 to 4 provided that m+n=4,

and (B) a cationic water-soluble polymeric substance which is a polyamine-type polymeric substance having a primary amino group, a secondary amino group, a tertiary amino group, an ammonium group, a pyridinium group or a quaternary ammonium group in the main chain or side chain, the weight ratio of the component (B) to the component (A), B/A, being from 0.05 to 50.

2. An aqueous foam fire extinguisher comprising (A) a fluorine-containing aminosulfonate-type surface-active agent of formula (A-2)

Rf--Z--Q.sub.1 --N(R)--Q.sub.2 --SO.sub.3 M

wherein Rf represents a fluorinated aliphatic group having 3 to 20 carbon atoms, Z is a divalent linking group selected from the group consisting of --SO.sub.2 N(R.sub.1)--, --CON(R.sub.1)--, --(CH.sub.2 CH.sub.2).sub.i SO.sub.2 N(R.sub.1)--, ##STR22## in which R.sub.1 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and i represents an integer of 1 to 10, Q.sub.1 represents (--CH.sub.2).sub.j, in which j is an integer of 1 to 6 or ##STR23## in which R.sub.2 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R represents a hydrogen atom, an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, --Q.sub.2 SO.sub.3 M or --(CH.sub.2).sub.k COOM, in which k represents an integer of 1 to 4, Q.sub.2 represents (--CH.sub.2).sub.l -- in which l represents an integer of 1 to 4, ##STR24## in which R.sub.3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, or ##STR25## M represents a cationic atom or atomic grouping selected from the group consisting of a hydrogen atom, an alkaline earth metal and --N(H).sub.m (R.sub.4).sub.n, in which R.sub.4 represents an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, and m and n are integers of 0 to 4 provided that m+n=4,

(B) a cationic water-soluble polymeric substance which is a polyamine-type polymeric substance having a primary amino group, a secondary amino group, a tertiary amino group, an ammonium group, a pyridinium group or a quaternary ammonium group in the main chain or side chain, and (C) a polybasic acid compound which is an aromatic, aliphatic, alicyclic or heterocyclic dibasic, tribasic, tetrabasic, pentabasic or hexabasic acid having carboxylic, sulfonic or phosphoric acid groups, the weight ratio of the component (B) to the component (A), B/A, being from 0.05 to 50, the weight ratio of the component (A) to the component (B) plus the component (C), A/B+C being from 0.01 to 10, and the weight ratio of the component (B) to the component (C), B/C being from 5 to one-third.

3. An aqueous foam fire extinguisher comprising (A) a fluorine-containing aminocarboxylate-type surface-active agent of formula (A-3) ##STR26## wherein Rf represents a polyfluoralkyl group having 3 to 20 carbon atoms which may contain an oxygen atom, a polyfluoroalkenyl group, a polyfluorocyclohexyl group, a polyfluorocyclohexylalkyl group or a polyfluorocyclohexyl-alkenyl group, Z represents a divalent linking group selected from the group consisting of ##STR27## in which R.sub.1 represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group, a monovalent group containing an aromatic ring, or --CH.sub.2 CH.sub.2 --.sub.j R.sub.2, in which R.sub.2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and j represents an integer of 1 to 6, and i represents an integer of 1 to 3, Q represents --(CH.sub.2)--.sub.l, ##STR28## --CH.sub.2 --.sub.m O--CH.sub.2 --.sub.m or --CH.sub.2 --.sub.p O--CH.sub.2 --.sub.2 O--CH.sub.2 --q, in which l is an integer of 1 to 6, m and n are integers of 2 to 6, and p and q are 2 or 3, and each of Q.sub.1 and Q.sub.2 represents a divalent linking group --CH.sub.2 --.sub.r or --CH.sub.2 --.sub.s in which r and s are integers of 1 to 3 and each of M.sub.1 and M.sub.2 represents a hydrogen atom or an inorganic or organic cation,

and (B) a cationic water-soluble polymeric substance which is a polyamine-type polymeric substance having a primary amino group, a secondary amino group, a tertiary amino group, an ammonium group, a pyridinium group or a quaternary ammonium group in the main chain or side chain, the weight ratio of the component (B) to the component (A), B/A being from 0.05 to 50.

4. An aqueous foam fire-extinguisher comprising (A) a fluorine-containing aminocarboxylate-type surface-active agent of formula (A-2) ##STR29## wherein Rf represents a polyfluoroalkyl group having 3 to 20 carbon atoms which may contain an oxygen atom, a polyfluoroalkenyl group, a polyfluorocyclohexyl group, a polyfluorocyclohexylalkyl group or a polyfluorocyclohexylalkenyl group, Z represents a divalent linking group selected from the group consisting of ##STR30## in which R.sub.1 represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group, a monovalent group containing an aromatic ring, or --CH.sub.2 CH.sub.2 --.sub.j R.sub.2, in which R.sub.2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and j represents an integer of 1 to 6, and i represents an integer of 1 to 3, Q represents --CH.sub.2 --.sub.l, ##STR31## --CH.sub.2 --.sub.m O--CH.sub.2 --.sub.m or --CH.sub.2 --.sub.p O--CH.sub.2 --.sub.2 O--CH.sub.2 --.sub.q, in which l is a integer of 1 to 6, m and n are integers of 2 to 6, and p and q are 2 or 3, and each of M.sub.1 and M.sub.2 represents a hydrogen atom or an inorganic or organic cation,

(B) a cationic water-soluble polymeric substance which is a polyamine-type polymeric substance having a primary amino group, a secondary amino group, a tertiary amino group, an ammonium group, a pyridinium group or a quaternary ammonium group in the main chain or side chain, and (C) a polybasic acid compound which is an aromatic aliphatic, alicyclic or heterocyclic dibasic, tribasic, tetrabasic, pentabasic or hexabasic acid having carboxylic, sulfonic or phosphoric acid groups, the weight ratio of the component (B) to the component (A), B/A being from 0.05 to 50, the weight ratio of the component (A) to the component (B) plus the component (C), A/B+C being from 0.01 to 10, and the weight ratio of the component (B) to the component (C), B/C being from 5 to one-third.

5. An aqueous foam fire-extinguisher comprising (A) a fluorine-containing surface-active agent selected from the group consisting of ##STR32## C.sub.11 H.sub.23 CONHCH.sub.2 CH.sub.2 N(CH.sub.2 COONa).sub.2, C.sub.17 H.sub.35 CONH(CH.sub.2).sub.3 N.sup..sym. [(CH.sub.2).sub.3 SO.sub.3 Na].sub.3 Cl.sup..beta. ##STR33## C.sub.8 F.sub.17 SO.sub.2 N(C.sub.3 H.sub.7)CH.sub.2 COOK, C.sub.8 F.sub.17 SO.sub.2 N(C.sub.3 H.sub.7)CH.sub.2 CH.sub.2 OSO.sub.3 Na and

C.sub.7 F.sub.15 CON(C.sub.3 H.sub.7)(CH.sub.2).sub.3 SO.sub.3 Na,

and (B) a cationic water-soluble polymeric substance which is a polyamine-type polymeric substance having a primary amino group, a secondary amino group, a tertiary amino group, an ammonium group, a pyridinium group or a quaternary ammonium group in the main chain or side chain, the weight ratio of the component (B) to the component (A), B/A being from 0.05 to 50.

6. An aqueous foam fire-extinguisher comprising (A) a fluorine-containing surface-active agent (A) is a compound selected from the group consisting of ##STR34## C.sub.11 H.sub.23 CONHCH.sub.2 CH.sub.2 N(CH.sub.2 COONa).sub.2, C.sub.17 H.sub.35 CONH(CH.sub.2).sub.3 N.sup..sym. [(CH.sub.2).sub.3 SO.sub.3 Na].sub.3 Cl.sup..crclbar. ##STR35## C.sub.8 F.sub.17 SO.sub.2 N(C.sub.3 H.sub.7)CH.sub.2 COOK, C.sub.8 F.sub.17 SO.sub.2 N(C.sub.3 H.sub.7)CH.sub.2 CH.sub.2 OSO.sub.3 Na and

C.sub.7 F.sub.15 CON(C.sub.3 H.sub.7)(CH.sub.2).sub.3 SO.sub.3 Na,

(B) a cationic water-soluble polymeric substance which is a polyamine-type polymeric substance having a primary amino group, a secondary amino group, a tertiary amino group, an ammonium group, a pyridinium group or a quaternary ammonium group in the main chain or side chain, and (C) a polybasic acid compound which is an aromatic, aliphatic, alicyclic or heterocyclic dibasic, tribasic, tetrabasic, pentabasic or hexabasic acid having carboxylic, sulfonic or phosphoric acid groups, the weight ratio of the component (B) to the component (A), B/A being from 0.05 to 50, the weight ratio of the component (A) to the component (B) plus the component (C), A/B+C being from 0.01 to 10, and the weight ratio of the component (B) to the component (C), B/C being from 5 to one-third.

7. An aqueous foam fire extinguisher comprising (A) a surface-active agent containing an anionic hydrophilic group selected from the group consisting of --COO--, --SO.sub.3 --, --OSO.sub.3 -- and --OPO(OH)O--, or containing a combination of the anionic hydrophilic group and a cationic hydrophilic group, and (B) a cationic water-soluble polymeric substance selected from the group consisting of polyethyleneimine, polymer of ##STR36## wherein R' is --C.sub.n H.sub.2n+1, --COC.sub.n H.sub.2n+1, or --CH.sub.2 CH.sub.2 O).sub.n H in which n is an integer of 1 to 6, ##STR37## polyamide polyamine epichlorohydrin, and guanidineformaldehyde polycondensate.

the weight ratio of the component (B) to the component (A), B/A being from 0.05 to 50.

8. An aqueous foam fire extinguisher comprising (A) hydrophilic group selected from the group consisting of --COO--, --SO.sub.3 --, --OSO.sub.3 -- and --OPO(OH)O--, or containing a combination of the anionic hydrophilic group and a cationic hydrophilic group, (B) a cationic water-soluble polymeric substance selected from the group consisting of polyethylenimine, polymer of ##STR38## wherein R' is --C.sub.n H.sub.2n+1, --COC.sub.n H.sub.2n+1, or --CH.sub.2 CH.sub.2 O).sub.n H in which n is a integer of 1 to 6, ##STR39## polyamide polyamine epichlorohydrin, and guanidineformaldehyde polycondensate,

and (C) a polybasic acid compound which is an aromatic, aliphatic, alicyclic or heterocyclic dibasic, tribasic, tetrabasic, pentabasic or hexabasic acid having carboxylic, sulfonic or phosphoric acid groups, the weight ratio of the component (B) to the component (A), B/A being from 0.05 to 50, the weight ratio of the component (A) to the component (B) plus the component (C), A/B+C being from 0.01 to 10, and the weight ratio of the component (B) to the component (C), B/C being from 5 to one-third.

9. The fire extinguisher of any one of claims 2, 4, 6 or 8 wherein the polybasic acid compound (C) is a dibasic acid compound having 3 to 24 carbon atoms and having carboxylic acid groups.

10. The fire extinguisher of claim 7 or 8 wherein the surface-active agent is an amphoteric surface-active agent of the following formula (A-1) ##STR40## wherein Rf represents a fluorinated aliphatic group having 3 to 20 carbon atoms, Y represents --SO.sub.2 -- or --CO--, Q.sub.1 and Q.sub.2 each represent an organic divalent linking group selected from the group consisting of aliphatic hydrocarbon groups, hydroxyl-substituted aliphatic hydrocarbon groups, aromatic hydrocarbon groups and substituted aromatic hydrocarbon groups, R.sub.1 and R.sub.2 represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an aliphatic hydrocarbon group substituted by a hydrophilic group, or R.sub.1 and R.sub.2 are linked to each other to form a ring together with the adjacent nitrogen atom, A represents said anionic hydrophilic group and M represents a hydrogen atom, an alkali metal, an alkaline earth metal, or ammonium group or an organic cationic group.

11. The fire extinguisher of claim 10 wherein in the formula (A-1), Q.sub.1 and Q.sub.2 represent --CH.sub.2 --.sub.j in which j is an integer of 1 to 6, or ##STR41## in which R.sub.3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

12. A method for extinguishing fires of water-soluble solvents which comprises applying to the site of the fire a foam of the aqueous foam fire extinguisher of any one of claims 1, 2, 3, 4, 5, 6, 7, and 8.