JPH0142988B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to fire prevention or combustion suppression in a flammable liquid storage tank, or to a combustion suppressant that can be added to a fire extinguisher to further improve its fire extinguishing ability. In the field of extinguishing agents, for example, they have high extinguishing ability regardless of whether it is a conventional wood fire or oil fire, the capacity of the fire extinguisher can be made small, and it extinguishes quickly regardless of the target of the fire. Dry powder extinguishing agents are widely and commonly used due to their advantages. In addition to fire extinguishers, low boiling point gasoline and heavy oil,
In order to suppress the evaporation of liquid hydrocarbon compounds such as benzene and xylene, it is also known from JP-A-49-13088 that fine powder particles coated with a fluorocarbon compound to make them oil-repellent can be sprinkled on the surface of the liquid. It is being However, dry powder extinguishing agents have the disadvantage of lacking the ability to prevent re-ignition, especially for oil fires. In other words, powder extinguishing agents do not have the ability to accumulate on combustible materials and block air like foam does, and for this reason, if the flammable parts are not extinguished instantly, the once extinguished parts will not be able to spread to other parts. This is based on the fact that if there is a fire source, it will re-ignite and burst into flames. In addition, some powder fire extinguishers contain silicone added to improve the fluidity and moisture resistance of the agent, but silicone itself is not oil repellent, so it is particularly effective against low boiling point oil fires such as gasoline. No effect, and also
Even in the invention of No. 49-13088, in order to impart oil repellency to the fine powder particles, it is necessary to add a considerable amount of fluoride, resulting in high cost and impractical. In view of the current situation, the present inventors have finally solved the above-mentioned problems after many years of experimentation and research, and have combined the unique effects of fluorine compounds with the unique effects of silicone compounds. By doing so, a more synergistic effect than imagined can be obtained. Specifically, silicone oil, silane cup, etc. The present invention relates to a combustion suppressant characterized in that 0.01 to 10% by weight of a mixture of a silicone compound such as a ring agent, a silane monomer, etc. and a fluorine compound is added. The present invention also relates to a combustion suppressant characterized in that a fluorine compound is added to a main agent or an auxiliary agent of a fire extinguisher, or a mixture of a main agent and an auxiliary agent of a fire extinguisher that has been previously treated with silicone. The base agent referred to herein may be any compound that thermally decomposes in a fire in a fire extinguisher to generate nonflammable gas such as carbon dioxide gas or ammonia gas, or exhibits a negative catalytic effect on combustion. Specifically, the following compounds are mentioned as examples. Sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate, ammonium sulfate, ammonium dihydrogen phosphate, potassium chloride, sodium chloride, calcium carbonate, barite, diammonium hydrogen phosphate, or these with aluminum sulfate and/or aluminum chloro Mixtures with hydrates are mentioned. Two or more of these may be used in combination. The auxiliary agent is a powder that is mixed with the main agent in a fire extinguisher in order to improve its extinguishing performance, workability, flow characteristics, economic efficiency, etc. Examples of such auxiliaries include white carbon, mica, talc, etc. to improve fluidity, silicone resin, metal soap, wax, etc. to improve moisture resistance, and epoxy resins to improve foam buildup. , polyester, various plastics such as melamine resin, urea, borax, thiourea, sodium polyacrylate, carboxymethyl cellulose, perlite, vermiculite, hollow glass, and glass balloons. It goes without saying that the above-mentioned combustion suppressant consisting of the main agent and auxiliary agent has been treated with silicone to give it fluidity and water repellency, but it has no ability to float on oil. Because it does not have the effect of suppressing evaporation of combustibles like foam fire extinguishing agent, which accumulates on combustibles and blocks air, it does not prevent re-ignition after extinguishing if there is another ignition source. Therefore, research by the present inventors has recently led to the development of a method of treating the main agent and auxiliary agent of the dry powder fire extinguisher with an organic fluorine compound that can float on oil. As a result, it has become possible to obtain a powder extinguishing agent that has extremely effective extinguishing ability against not only water but also oil fires such as methanol or solvents. Furthermore, it has not been possible to add silicone compounds to improve water repellency by eliminating moisture absorption and preventing caking. This is because silicone compounds themselves do not float on oil, so if they were added to the organic fluorine compounds mentioned above, it would definitely significantly reduce the ability of the organic fluorine compounds themselves to float on oil. This was based on the common sense notion among those skilled in the art that this would be the case. However, according to subsequent experimental results by the present inventors, the above-mentioned silicone compound did not reduce the floating ability on oil when combined with an organic fluorine compound, but on the contrary improved the floating ability, resulting in a reduction in the amount of fluorine added. It has become clear that it can be done. If the contents of the above-mentioned organic fluorine compounds are shown, 3~
It has 20 fluorinated aliphatic groups, preferably 6 to 12 carbon atoms, is water insoluble (less than 1% by weight at 25°C) and has a major transition temperature, i.e. melting point, glass transition point or softening point, above 20°C. Molecular weight is about 700 to about 200000
It is a non-stick compound. Examples of such organic fluorine compounds are as follows. (1) A homopolymer of a vinyl monomer having a fluoroalkyl group having 3 to 20 carbon atoms or a copolymer with a vinyl monomer that does not contain fluorine. Examples of vinyl monomers having a fluoroalkyl group include the following. C ₇ F ₁₅ CH ₂ OCOCH=CH ₂ C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCH=CH ₂ C ₈ F ₁₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ C ₂ F ₅ CFCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ SO ₂ NCH ₃ CH ₂ = CHCOOH ₂ CH ₂ C ₇ F ₁₅ CON(C ₂ H ₅ ) CH ₂ CH ₂ OCOC( CH ₃ )=CH ₂ CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OCOCH=CH ₂ CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ OCH=CH ₂ C ₈ F ₁₇ (CH ₂ ) ₁₁ OCOC(CH ₃ ) ＝ _CH2 (CH ₃ ) ₂ CFO (CH ₂ ) ₅ OCOCH=CH ₂ C ₈ F ₁₇ SO ₂ N (CH ₂ CH ₂ OCOCH=CH ₂ ) ₂ C ₈ F ₁₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₁₀ COOCH ₂ CH=CH ₂ C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) CH ₂ CH ₂ OCOCH=CHCOOC ₄ H ₉ C ₆ F ₁₃ SO ₂ N(CH ₃ )CH ₂ CH ₂ OCOCH=CH ₂ C ₈ F ₁₇ SO ₂ NHCH ₂ CH ₂ SO ₂ CH=CH ₂ Fluorine Examples of vinyl monomers that do not include ethylene, propylene, butylene, butadiene, isoprene, chloroprene, vinyl chloride, vinylidene chloride, styrene, alcohols or alkyl amines of (meth)acrylic acid (all with 20 carbon atoms or less) Examples include esters or amides of , diacetone acrylamide, N-methylolacrylamide, acrylonitrile, acrylamide, vinyl acetate, and vinyl compounds having a siloxane bond. Any of the monomers can be used in combination. Vinyl polymerization of these homopolymers or copolymers can be carried out by known methods, but
For example, solution polymerization using a radical initiator or emulsion polymerization is common. The molecular weight of the polymer can be adjusted within a preferred range depending on the concentration of the initiator and the type and concentration of the chain transfer agent, but is generally preferably 3000 or more. (2) (Poly)ester of a monohydric or polyhydric alcohol containing a fluoroalkyl group having 3 to 20 carbon atoms and a monohydric or polyhydric carboxylic acid which may be fluorinated. A (poly)ester of an optionally fluorinated monohydric or polyhydric alcohol and a monohydric or polyhydric carboxylic acid having a fluoroalkyl group having 3 to 20 carbon atoms. Examples of ingredients used in this case are listed below. C ₉ F ₁₉ CH ₂ CH ₂ OH C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OH C ₈ F ₁₇ SO ₂ N (CH ₂ CH ₂ OH) ₂ C ₈ F ₁₇ SO ₂ N ( C ₃ H ₅ ) CH ₂ CH ₂ (OH) CH ₂ OH C ₇ H ₁₅ COOH C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ COOH Benzoic acid, adipic acid, sebacic acid, phthalic acid, maleic acid, trimellitic acid, ethylene glycol monomethyl ether, ethylene glycol, propylene glycol, diethylene glycol, glycerin, polypropylene glycol,
2-ethylhexanol, stearyl alcohol. The (poly)ester preferably has a molecular weight of 1000 or more. (3) A monohydric or polyhydric alcohol having a fluoroalkyl group having 3 to 20 carbon atoms (in some cases, a fluorine-free monohydric or polyhydric alcohol may be mixed) and a monohydric or polyhydric isocyanate, e.g. (Poly)urethanes with phenyl hesocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenyl isocyanate. The (poly)urethane preferably has a molecular weight of 700 or more. (4) Epoxy compounds having a fluoroalkyl group having 3 to 20 carbon atoms, e.g.

A homopolymer of the formula and preferably a copolymer with a fluorine-free epoxy compound such as propylene oxide or epichlorohydrin. The molecular weight of such a polymer is preferably 3000 or more. The organic fluorine compound used in the present invention must have 5% by weight or more of fluorine atoms in its molecule, and must also have a hydrophilic functional group or structure in its molecular structure, such as gasoline or alcohol to extinguish the fire. Preferably, it does not have a functional group or structure that provides easy solubility in organic solvents. However, the organic fluorine compound used in the present invention is a diluted liquid (solution or dispersion) with a concentration of 0.5% by weight.
Soak a 100% polyester processed yarn fabric in this, wet, weight, pick up 50%
Squeeze until the diluent has adhered to the same weight as the fabric.
Post-treated fabrics dried at 170℃ for 3 minutes are AATCC
When measured by Test Method 118-1966 method, it should have oil repellency of 4 or more, that is, n-tetradecane should not penetrate into the fabric, and the organic fluorine compound should have an AATCC
It should exhibit water repellency of 50 or higher when measured by Test Method 22-1971 spray method, that is, water does not ooze out to the back side of the fabric. On the other hand, silicone compounds to be mixed with this include silicone oils such as methylhydrogenpolysiloxane, dimethylpolysiloxane, and methylmethoxysilicone, silane coupling agents such as methyltriethoxysilane and methylhydrogenpolysiloxane, and silane This includes monomers, etc. Although the mixing ratio of the fluorine compound and the silicone compound is not necessarily constant as shown in the examples described later, the amount of the mixture of both added to the fire extinguishing agent may be as long as it shows the effect. Needless to say, as shown in the examples, too much is not only uneconomical, but also reduces fire extinguishing performance, so it is generally not recommended.
A preferable range is 0.01 to 10% by weight. The method of treating the main agent or auxiliary agent of the extinguishing agent in the above mixture of combustion suppressants, or the addition of an auxiliary agent to the main agent of the extinguishing agent, is important in order to achieve the effects of the present invention or to pursue economic efficiency. It is. Generally, after immersing the main agent or auxiliary powder of a fire extinguisher in an organic solvent solution, water dispersion, or organic solvent dispersion of the above mixture, the water and solvent are evaporated,
In some cases, a method of subsequently pulverizing is used. However, when the main agent and auxiliary agent of the extinguishing agent are porous powders, the organic fluorine compounds contained in the above method tend to adhere in more than the desired amount compared to when they are non-porous. Considering that it is economically expensive, it is not only uneconomical, but it has also been found that there is no difference in effectiveness even if the mixture is applied only to the surface of the porous main agent or auxiliary agent powder particles. Ta. Therefore, the present invention also provides the organic fluorine compound only on the surface of the porous base agent or porous auxiliary powder particles of the fire extinguisher in a combustion suppressant, or the powder particles obtained by adding a porous auxiliary agent to the porous base agent of the fire extinguisher. A method of making a flame suppressant according to the present invention is provided by treating it with a mixture with a silicone compound. An example of this improved manufacturing method is a method in which a diluted solution of the mixture is sprayed with a spray nozzle while stirring the main ingredient or auxiliary agent of the powder fire extinguisher, or a method in which the mixture is dried after spraying. However, the most preferred method is to saturate the porous base extinguishing agent or auxiliary agent, or the porous base extinguishing agent with an auxiliary agent, in advance with an inert solvent or water, and then immerse it in a dilute solution of the mixture. This method involves processing, then drying, and optionally further pulverizing. The invention therefore also relates to a process for the preparation of such combustion suppressants. In addition, in the present invention, a mixture of a silicone compound and a fluorine compound may be added to the main agent or auxiliary agent of a fire extinguisher, or a mixture of a silicone compound and a fluorine compound to the main agent or auxiliary agent of a fire extinguisher, or a mixture of a silicone compound and a fluorine compound. The addition of fluorine compounds to a fire extinguisher that has been treated with silicone by adding an auxiliary agent to the main ingredient should be broadly understood, and is not limited to just adding them; This naturally includes cases where powder particles are subjected to surface treatment, and the present invention is not necessarily limited thereto. Furthermore, the present invention prevents fires by spraying combustible substances that are likely to cause a fire in advance, and further sprays them on the liquid level in an oil storage tank of gasoline, phenol, alcohol, etc. It also relates to agents that are effective in inhibiting evaporation under certain conditions and also in preventing ignition. In addition, when treating the main agent and auxiliary agent of a fire extinguisher, it is not always necessary to coat the powder particle surface with the mixture; if the amount of the mixture is particularly large, just pulverizing it and mixing the powders together can be quite effective. You can see the effect. Furthermore, both the main agent and the auxiliary agent may be treated as a mixture, or only one of them may be treated. During the treatment, there is no problem in using a combination of two types of the main agent, the auxiliary agent, and a mixture, or a combination of several types or more. The combustion suppressant according to the present invention is particularly suitable as a fire extinguisher for extinguishing flammable liquids such as gasoline, heavy oil, light oil n-heptane, alcohol, ketone, and ester. This combustion suppressant, especially when it is a porous powder, encloses air and does not allow it to escape, and because it is light, it easily floats on the surface of flammable liquids, whether water or oil, and its floating time is long and it is difficult to sink, so it accumulates. Highly effective. For this reason, when extinguishing a fire, powder residue from thermal decomposition or excess powder applied forms a thick layer on the surface of the flammable liquid, which prevents evaporation of the flammable liquid and at the same time blocks air and liquid to prevent re-ignition. , even if a part of it ignites, the flame will not spread easily. Furthermore, since the combustion suppressant of the present invention is a mixture of a fluorine compound and a silicone compound, its oil repellency is significantly improved, so even if it is left for a long period of time, the powder particles will agglomerate, for example at the nozzle of a fire extinguisher. There is no such thing as blocking. In addition, since the fluidity is significantly improved, there is no need to add a separate flow aid, and fire extinguishing properties are also good. As mentioned above, the combustion suppressant of the present invention is highly effective against not only general fires but also oil fires, and is also effective against ordinary wood fires, electrical fires, and organic metal fires such as silane compounds and alkyl aluminum fires. In addition to being effective, it is also highly effective in preventing fires if it is sprayed on the surface of a liquid that is at risk of catching fire. Furthermore, when used as a powdered digestive agent,
On the other hand, when a mixture of a fluorine compound and a silicone compound is added as in the present invention, the addition ratio of fluorine is reduced compared to when a single fluorine compound is added. Therefore, the economic effect is also significant. The above description mainly refers to the case where a mixture of a silicone compound and a fluorine compound is added to the main agent or auxiliary agent of a powder fire extinguisher, or to the main agent and an auxiliary agent, but this does not necessarily apply. Although not limited to this, the same effect can be obtained by adding a fluorine compound to the base agent or auxiliary agent of a powder fire extinguisher, or to a mixture of the base agent and an auxiliary agent that has been previously treated with silicone. It is possible to obtain a fire extinguishing agent having the following properties, and by spraying it on combustible materials in advance, it can also have a preventive effect against fires. Example ₁ 90 parts of _C8F17SO2N ( _CH3 ) _CH2CH2OCOCH = _CH2 , 10 parts of β _{- hydroxyethyl} methacrylate and 1 part of azobisisobutyronitrile are dissolved in 1000 parts of benzotrifluoride, This was stirred at 80° C. for 4 hours to obtain a copolymer solution with a molecular weight of about 30,000. After further diluting this solution with 1,1,1-trichloroethane, methylhydrodiene polysiloxane belonging to silicone oil was added, and this was further mixed with a mixture of 100 parts of ammonium dihydrogen phosphate powder and 4 parts of auxiliary agent (white carbon). mixed with.
Further, this was heated and dried at 80° C. for 2 hours so as to uniformly adhere to the surface of the powder particles of the above mixture, then ground in a mortar and sieved through a 30-mesh sieve to obtain the treated powder of the present invention. Next, 30 ml of flammable liquid was placed in multiple sample bottles each having a diameter of 30 mm, and 1 g of the treated powder was sprinkled onto each sample bottle, and the degree of floating was measured after 30 minutes. The results are shown in Table 1 below, and the ○ marks indicate that no ignition occurred even when an open flame was brought close to 1 cm above the liquid surface. Next, the lower end of a glass funnel (70φ) was held down with thick paper, 60 g of the processing agent was added, and the paper was removed to measure the degree of flow. Finally, the fire extinguisher was filled with 1.2 kg of treatment agent and left at room temperature for one month, after which the solidification status was observed. All of the above results are shown in Table 1.

[Table] ×: Bad △: Incomplete ○: Good
(These marks have the same meaning in the examples below)
Example 2 When dimethylpolysiloxane, which belongs to silicone oil, was used in the same process as in Example 1, the effects shown in Table 2 were confirmed.

[Table] Example 3 In the same process as in Example 1, methyltriethoxysilane, a silane coupling agent, was used instead of silicone oil, and the effects shown in Table 3 were confirmed.

【table】

[Table] Example 4 When a mixed solution of methylhydrodiene polysiloxane and methyltriethoxysilane was used in the same process as in Example 1, the effects shown in Table 4 were confirmed.

【table】

Claims (1)

[Scope of Claims] 1. A combination of a silicone compound such as a silicone oil, a silane coupling agent, a silane monomer, etc. and a fluorine compound, as opposed to the main agent or auxiliary agent of a fire extinguisher, or a mixture of an auxiliary agent added to the main agent of a fire extinguisher. mixture
A combustion inhibitor characterized by adding 0.01 to 10% by weight. 2. A combustion suppressant characterized by adding a fluorine compound to the main agent or auxiliary agent of a fire extinguisher, or a mixture of the main agent and an auxiliary agent that has been previously treated with silicone.