JPH0366933B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a foaming aid that significantly improves the foaming properties and foam stability of aqueous foam systems, and to a fire extinguishing agent containing the same. "Industrial Application Fields" There are a wide variety of industrial fields where foams are applied. For example, foam extinguishing agents must be applied in the form of foam to extinguish fires, and the stability and appropriate foaming ratio (foaming ability) of the foam are among the most important factors in terms of performance. In addition, there are technical fields that utilize the properties of foam, such as foam cleaners in the field of detergents, foaming processing of silicone softeners in the field of textile processing, foaming backing processing of urethane emulsions, and flotation. There is a need for technology to control stability and appropriate foaming ratio. The present invention is applied to these foam technology fields. "Prior Art" Foaming properties are generally greatly influenced by the type or amount of surfactant added. Foaming properties are better when a combination of several types of surfactants are used than when using a single type of surfactant, and the ionicity of the surfactants used is also a combination of surfactants rather than a single type, such as anionic and nonionic, anionic and amphoteric, etc. It is known that high-quality foam can be easily obtained by combining these surfactants. Additionally, there is a cosurf actant as an additive that has a significant effect on foamability. Although this substance has almost no water solubility when used alone, it significantly improves foaming properties when mixed with a surfactant. A well-known example from ancient times is lauryl alcohol, which has almost no water solubility, but dissolves well in an aqueous solution of sodium lauryl sulfate, and can form an aqueous solution by adding 10% to 0.1% of sodium lauryl sulfate. Significantly improves foaming properties. Further, the optimum foam system is determined from the balance with other physical properties such as fire extinguishing performance, permeability, surface tension, and emulsifying properties. Therefore, the allowable selection range for surfactants, which are the basic components of foam, is usually quite narrow, and when investigating the improvement of foaming properties, additives other than surfactants are often used for adjustment. Viscosity improvers are known as such additives. The aim is to stabilize the foam by increasing the viscosity of the aqueous solution to reduce the rate of liquid drainage from the foam. Water-soluble polymers are known as such polymers, such as polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, partially hydrolyzed protein, and sodium alginate. These additives considerably increase the viscosity of the bulk aqueous solution, but apart from these, ethylene glycol alkyl ether type additives are known as additives that contribute to foam stabilization without significantly affecting the bulk viscosity. There is. Typical examples include butyl cellosolve and butyl carbitol. These are often added as a solvent that also serves as a solubilizer for surfactants that have poor water solubility. ``Problems to be Solved by the Invention'' In actual foam systems, efforts are made to find the optimal formulation by combining these additives, but the reality is that the desired foaming level cannot be achieved.
In general, increasing the foaming ratio lowers the stability, and improving the stability lowers the foaming ratio. Although technology to improve both expansion ratio and stability is extremely important, the search for such additives is currently difficult. For example, if the amount of water-soluble polymer added is increased with the intention of improving foam stability, the viscosity of the system increases and the foaming ratio decreases. Furthermore, the ethylene glycol alkyl ether type is a water-soluble solvent, and if it is added in a large amount, it will affect the solubility and physical properties of the entire system. Therefore, due to restrictions on the amount added, the effect of improving foamability cannot reach the expected level. Furthermore, even if a sufficient amount is added, sufficient foamability cannot be obtained in many cases. This is because this type of additive functions as a solvent and is neither a surfactant nor a so-called co-surfactant, and therefore has little effect on foaming performance. If it is difficult to improve the foaming properties with additives, the addition of other types of surfactants or co-surfactants is considered, but this often causes a large change in the surface chemical properties of the system and is not practical. "Means for Solving the Problems" In view of the above circumstances, the present inventors have developed a method that does not particularly affect the surface and interfacial chemical properties of the foam system, but has a significant impact on the solubility and physical properties of the entire system. As a result of intensive research focused on the development of additives that can improve the foaming properties of the system and also improve foam stability without affecting the The present invention was achieved based on the discovery that this material exhibits unique characteristics. That is, the present invention provides H1:C ₆ H ₁₃ O(CH ₂ CH ₂ O) _l H
(However, l is an integer from 1 to 5) and H2: R ₁ O (R ₂ C) _n
H (where R ₁ is an alkyl group having 1 to 5 carbon atoms, R ₂ is an alkylene group having 2 to 3 carbon atoms, m is an integer of 0 to 20),
or HO(R ₃ O) _o H (where R ₃ is an alkylene group having 2 to 6 carbon atoms, and n is an integer of 1 or more), and has excellent foaming properties and foam stability. It can be summarized as an auxiliary agent and a foam fire extinguishing agent containing the same. Essential component H1 in the present invention, namely C ₆ H ₁₃ O
In (CH ₂ CH ₂ C) ₁ , 1 is an integer of 1 to 5, and when 1 is 0, that is, C ₆ H ₁₃ OH, the hydrophobicity is too strong and no synergistic effect is exhibited. Moreover, when l is 6 or more, hydrophilicity becomes strong and a sufficient synergistic effect is similarly not expressed. The effects of the present invention are first manifested in the range where l is 1 to 5. The combination component H2 in the present invention is R ₁ O(R ₂ O) _n H
(However, R ₁ is an alkyl group having 1 to 5 carbon atoms, R ₂ is an alkylene group having 2 to 3 carbon atoms, and m is an integer of 0 to 20.)
It is poly(n:1-20) alkylene (C:2-3) glycol monoalkyl (C:1-5) ether. Specific examples of such things are as follows. CH ₃ O (CH ₂ CH ₂ O) ₂ H, C ₂ H ₅ O
(CH ₂ CH ₂ O) ₂ H, C ₃ H ₇ O (CH ₂ CH ₂ O) ₂ H, C ₄ H ₉ OCH ₂ CH ₂ OH, C ₄ H ₉ O (CH ₂ CH ₂ O) ₂ H, C ₄ H ₉ O
(CH ₂ CH ₂ O) ₂₀ H, C ₅ H ₁₁ O (CH ₂ CH ₂ O) ₃ H, C ₃ H ₇ OH, C ₄ H ₉ OH, C ₅ H ₁₁ OH, C ₂ H ₅ OCH ₂ CH (OH) _CH3 , _{C4H9OCH2CH (} OH) _{CH3 ,}
C ₂ H ₅ OCH ₂ CH ₂ OCH ₂ CH (OH) CH ₃ , C ₄ H ₉ OCH ₂ OCH ₂ CH (OH) CH ₃ , C ₂ H ₅ O (CH ₂ CH ₂ OCH ₂ CH (CH ₃ ) O ) − ₁₀ H, C ₄ H ₉ O (CH ₂ CH ₂ OCH ₂ CH (CH ₃ ) O) − ₁₀ H, and H2 is HO (R ₃ O) _o H (however, R ₃ has 2 to 2 carbon atoms)
6 alkylene group, n is an integer of 1 or more, preferably 2 to 300) (C: 2
~6) It is a glycol. Specific examples of this include the following. HOCH ₂ CH ₂ OH, HOCH ₂ CH ₂ CH ₂ OH,
HOCH ₂ CH (CH ₃ ) OH, HO (CH ₂ ) ₄ OH, HO (CH ₂ ) ₅ OH,

[Formula] HO (CH ₂ ) ₆ OH, HO (CH ₂ CH ₂ O) ₁₀ H, HO (CH ₂ CH ₂ O) ₅₀ H, HO (CH ₂ CH (CH ₃ ) O) ₂ H,

[Effect]

As mentioned above, it is a well-known fact in the industry that monoalkyl ethers of (poly)alkylene glycols are used as foam stabilizers and foaming aids. (For example, in the fire extinguishing foam industry,
48-23161, JP-A-55-76664, JP-A-59-18389
In addition to improving and stabilizing foaming, this product also functions as a solubilizer for poorly water-soluble substances or as a pour point depressant, and is particularly used in the fire extinguishing foam industry. It is something that exists. However, it is still recognized that the foaming ratio improving effect and the stabilizing effect are insufficient, and in order to compensate for this, the use of various foam stabilizers in combination is also being considered. The inventors have developed the general formula (H1) C ₆ H ₁₃ O
When monohexyl ether of ethylene glycol represented by (CH ₂ CH ₂ O) _l H (where l is an integer from 1 to 5) is used in combination with the above-mentioned ordinary foam stabilizers, it has an extremely remarkable synergistic effect. In other words, it has been discovered that the foaming ratio can be improved and the foam can be stabilized. Even if H1 is used alone in place of a conventional foam stabilizer, it cannot exhibit sufficient effects in improving solubility and foaming properties. However, it is only when used in combination with the conventional regular foam stabilizer represented by H2 that a synergistic foaming property improvement effect is realized, and it has little effect on the compatibility, physical properties, fire extinguishing properties, etc. of the system. confirmed. When the foaming aid is used in a fire extinguishing foam, any commonly used surfactant may be used as the surfactant. Such surfactants include fluorine-based, silicon-based, and hydrocarbon-based active agents, including anionic, cationic, nonionic, and amphoteric surfactants. Among these, fluorine-based surfactants are particularly preferred. In addition, other additives such as rust preventive agents, pour point depressants, viscosity modifiers, and PH modifiers can be used in this fire extinguishing agent. EXAMPLES Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Note that "middle" in Examples and Comparative Examples represents parts by weight. Examples 1 to 5, Comparative Examples 1 to 5 The formulation of the synthetic surfactant foam fire extinguishing agent is shown below. Among these, conventional foaming aids (Comparative Examples 1 to 5) and compositions of the present invention (Examples 1 to 5) were used as foaming aids that also served as solvents, and their foaming properties were compared and examined. The pH of the stock solution below was adjusted to 7.5. [Composition A] Synthetic surfactant component Higher alcohol (average carbon number 12) Sulfate ester ammonium salt 7 parts Higher alcohol (average carbon number 16) Sulfate ester triethanolamine salt 3 parts Polyoxy with an average of 3 moles of oxyethylene groups Ethylene nonyl phenyl ether sulfate ammonium salt 8 parts Polyoxyethylene nonyl phenyl ether sulfate ester triethanolamine salt having an average of 3 moles of oxyethylene groups
3 parts Cosurfactant Higher alcohol (average carbon number 12) 3 parts Foaming aid 26
Mechanical foam 3 for low foaming by diluting 3% with
It was filled into a small fire extinguisher and the entire amount was emitted at an initial nitrogen pressure of 9.0Kg/cm ² . The entire amount of foam was collected in a drum with an inner diameter of 40 cm and a depth of 50 cm, which had a graduated window at the bottom of the side wall to measure the amount of reduction. Measure the foaming ratio from the foam height and measure it by 1/4 from the pre-calibrated scale window.
The reduction time (time taken until 1/4 part by weight of the foam becomes liquid due to foam breakage) was measured. The results are shown in Table-1. Examples 6 to 10, Comparative Examples 6 to 10 The formulation of the water-forming foam fire extinguishing agent is shown below. Among these, the conventional foaming aids (Comparative Examples 6 to 10) and the compositions of the present invention (Examples 6 to 10) were used as foaming aids that also served as solvents, and their foaming properties were compared and examined. The pH of the stock solution below was adjusted to 7.5. [Composition B] Surfactant component Perfluorohexylsulfonamide Aminosulfonate sodium salt 7 parts Higher alcohol (average carbon number 12) Sulfate ester ammonium salt 7 parts Foaming aid X (compounds listed in Table 1) 25 parts Water 61 Total : 100 parts These stock solutions were diluted to 3% with tap water and synthetic seawater and filled into a small mechanical foam 3 fire extinguisher for water film forming foam.
The entire amount was irradiated at an initial nitrogen pressure of 9.0 Kg/cm ² . The foam was collected in the same container as in the previous example, and the magnification and 1/4 reduction time were measured. The results are shown in Table-1. Comparison with comparative examples shows the excellent foaming improvement and foam stabilizing effects of the foaming aid of the present invention.

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Claims (1)

[Claims] 1 H1: C ₆ H ₁₃ O (CH ₂ CH ₂ O) _l H (where l is 1 to
5 integer) and H2: R ₁ O (R ₂ O) _n H (where R ₁ is an alkyl group having 1 to 5 carbon atoms, R ₂ is an alkylene group having 2 to 3 carbon atoms,
m is an integer of 0 to 20) or HO(R ₃ O) _o H (where R ₃ is an alkylene group having 2 to 6 carbon atoms, and n is an integer of 1 or more); Foaming aid with excellent foam stability improvement effect. 2. The foaming aid according to claim 1, wherein the weight ratio of H1 to H2 is 1/100 to 100/1. 3 H1: C ₆ H ₁₃ O (CH ₂ CH ₂ O) _l H (however, l is from 1 to
5 integer) and H2: R ₁ O (R ₂ O) _n H (where R ₁ is an alkyl group having 1 to 5 carbon atoms, R ₂ is an alkylene group having 2 to 3 carbon atoms,
HO( _R3O ) _oH (wherein _R3 is an alkylene group having 2 to 6 carbon atoms, and n is an integer of 1 or more).