JPH0244351B2 - EAZOORUSEIHIN - Google Patents

Description

[Detailed description of the invention]

The present invention relates to aerosol products. When considering the safety of aerosol products, the following three points are important. (1) Toxicity of active ingredients and other ingredients Since aerosol products are usually intended to disperse the contents into the air, it is important to not only use substances that are safe for the active ingredients, but also to use safe solvents and propellants. need to use something. (2) Flammability of concentrates in aerosol products The flammability of concentrates in aerosol products is related to the safety of aerosol products during storage. In other words, the lower the flash point of the stock solution is, the more likely it is to catch fire and cause a fire or explosion. It is desirable that there is no flash point. (3) Flammability when using aerosol products Flammability when using aerosol products is related to safety when using aerosol products, and both the flame length determined by flammability tests and the explosive concentration determined by explosiveness tests must be considered. It is desirable that the flame length is less than 45 cm and the explosive concentration is 0.13 g/or more. Regarding the safety of chlorinated fluorocarbon gases and chlorinated fluorocarbon solvents, which are currently used in large quantities in aerosol products, there is a hypothesis that although they are not generally toxic, they may cause environmental problems.In other words, they destroy ozone in the stratosphere. There has been a hypothesis that this is the case, and it is preferable not to use it as much as possible. On the other hand, when a fire extinguisher is made using halon in an aerosol product, it has a greater extinguishing capacity and can be stored for a longer period of time than when using water, reinforced liquid, powdered foam, powder, carbon dioxide, etc. as the extinguishing agent. Because of its various advantages, it is used as a fire extinguisher or fire extinguishing equipment in aircraft, factories, computer rooms, etc. It is also used as an aerosol type fire extinguisher for initial fire extinguishing in homes. be. Halon can also be used to dissolve flammable ingredients into a non-flammable aerosol product stock solution, and can be used as an inexpensive injection agent such as dimethyl ether (hereinafter referred to as DME), liquefied petroleum gas, or a mixture of DME and liquefied petroleum gas. If a propellant with good flammability and little problems is mixed with halon and used as a propellant, the flame length will be less than 45 cm and the explosive concentration will be 0.13 g/
You can do more than that. The toxicity of halons is very low, for example, UL group number 5A for dibromotetrafluoroethane and UL group number 6 for bromotrifluoromethane. Halon has the above-mentioned characteristics, and while halon itself is very safe, it is a substance that is extremely sensitive to moisture, and the saturated amount (approximately
If water of 80ppm or more is mixed in, it will decompose,
It has the disadvantage that it produces a highly corrosive substance, which causes corrosion of the container. The reason why moisture gets mixed into aerosol products containing halon is that moisture from the equipment or the atmosphere is always absorbed during the manufacturing process, especially when the contents are mixed and/or filled. Even if the aerosol product is manufactured with a water content below the water saturation level, water may pass through the joints of the container and get mixed in. If water gets mixed in, the stability of the aerosol product during storage can be significantly reduced. The present inventors have attempted to improve the sealing method of containers in order to prevent the stability of aerosol products containing halon from decreasing due to moisture during storage. It has been found that it is technically very difficult to prevent the particles from penetrating through the sealing material and resin material of the machine and getting mixed into the interior, and it is also uneconomical. In view of the current situation, the present inventors have conducted intensive research to create an aerosol product containing halon, which is sufficiently stable against small amounts of moisture. The flammability of aerosol products containing halon can be reduced by adding liquid polyhydric alcohol, preferably glycol (or 0.01 to 12 parts of ethylene glycol) as a stabilizer to halon-containing aerosol products. The present inventors have discovered the remarkable effect that it is possible to obtain an aerosol product that is sufficiently stable even when a small amount of water is mixed in, while maintaining the characteristics of low toxicity, and has led to the completion of the present invention.Used in the present invention Examples of halon include dibromotetrafluoroethane, bromotrifluoromethane, bromochlorodifluoromethane, etc. These compounds may be used alone,
Two or more types may be mixed and used. The content containing halon used in the present invention is one that usually contains about 5 to 100% halon, and other components of the content include halon, such as those used in normal aerosol products. Ingredients other than propellants, diluents, insecticidal active ingredients, deodorizing active ingredients, powders, resins, silicones, etc. may be mentioned, but are not particularly limited. The liquid polyhydric alcohol used in the present invention functions as follows. In other words, when moisture is mixed into halon, it reacts, especially when water in excess of the saturation amount is mixed in, and when metals such as aluminum and iron are present, it reacts explosively and generates corrosive gas, but liquid polyhydric alcohol, For example, glycerin and ethylene glycol inhibit this reaction and stabilize the halon-containing contents used in aerosol products. The liquid polyhydric alcohol contains halon.
It is preferable to use about 0.01 to 12 parts per 100 parts. If the amount used is less than about 0.01 part, the effect of suppressing the reaction between the content containing halon and moisture and stabilizing it will not be achieved, If the amount exceeds about 12 parts, the content of the aerosol becomes viscous, causing the problem that the content is difficult to form into fine particles. In the present invention, the liquid polyhydric alcohol used is preferably glycerin and/or ethylene glycol, but is not limited thereto. For example, propylene glycol, diethylene glycol, etc. are also used as well as glycerin and ethylene glycol. Can be used. However, when using propylene glycol etc.
It will not be effective unless it is 0.5 parts or more. Liquid polyhydric alcohols, such as glycerin and ethylene glycol, have low reactivity under normal conditions and low toxicity ( _LD50 , oral administration).
According to Merck Index, propylene oxide 1.14g/kg (rat), nitroethane 1.10g/kg
Kg (rat), hydrazine 0.057g/Kg (mouse),
Thiosemicarbazide is 0.013g/Kg (adult Norway rat), while glycerin is 31.5g/Kg (mouse) and ethylene glycol is 8.54g/Kg (rat), which are low and improve the safety of aerosol products. The aerosol product of the present invention is obtained by filling a commonly used aerosol container made of aluminum or tin with a content containing halon and a predetermined amount of glycerin and/or ethylene glycol by a conventional method. Next, the aerosol products of the present invention will be explained using Examples and Comparative Examples. Examples 1 to 31 and Comparative Examples 1 to 17 The compounds shown in Table 1 are shown in Table 1. 525 in percentage
480g was sealed and filled into a ml aerosol can. The resulting 10 samples were stored in a thermostat at 45°C and 90% humidity for 8 hours a day for 3 months, and outdoors for the rest of the day.
The number of holes out of 10 was measured. The result is the first
Shown in the table. In Table 1, DBTFE is dibromotetrafluoroethane, BTFM is bromotrifluoromethane, BCDFM is bromochlorodifluoromethane,
G is glycerin, EG is ethylene glycol, PO
indicates propylene oxide, A indicates an aluminum aerosol can, and S indicates a tinplate aerosol can. Examples 32 to 34 and Comparative Examples 18 to 20 0.25 parts of neopinamine (manufactured by Sumitomo Chemical Industries, Ltd.) and 0.03 parts of Cryslon Forte (manufactured by Sumitomo Chemical Industries, Ltd.), which are active ingredients of insecticides, were mixed with a flammable solvent. When dissolved in 44.72 parts of IP Solvent 2028 (manufactured by Idemitsu Petrochemical Co., Ltd.), a flammable composition with a flash point of 83°C was obtained. The above composition was dissolved in 5 parts of dibromotetrafluoroethane to give a non-flammable stock solution with no flash point. Add the obtained non-flammable stock solution and the stabilizer shown in Table 1 in the amount shown in Table 1 to a 260 ml aerosol can with a stopper valve, and add 25 parts of DME and liquefied petroleum gas (n-butane/iso-butane weight ratio). 70/30 mixture) to prepare an insecticide aerosol containing 150 g. The flame length of the resulting pesticide aerosol was less than 45 cm in flammability tests, and the explosive concentration in explosive tests was
It was 0.13g/or more. Further, in the same manner as in Example 1, the stability was determined by measuring the corrosion state inside the container and the number of holes among 10 containers. The results are shown in Table 1. Examples 35 to 38 and Comparative Examples 21 to 23 0.25 parts of neopinamine and Crylonfuorte
0.03 part of IR Solvent 1620 (manufactured by Idemitsu Petrochemical Co., Ltd.)
When dissolved in 48.72 parts, a flammable composition with a flash point of 50°C was obtained. The above composition was dissolved in 6 parts of dibromotetrafluoroethane to give a non-flammable stock solution with no flash point. The obtained non-flammable stock solution and the stabilizer shown in Table 1 were added to a 260 ml aerosol can in the amount shown in Table 1 with a stopper valve, and liquefied petroleum gas (n-butane/iso-butane/propane weight ratio) was added.
Add 45 parts of 39/17/44 mixture, content 140g
An insecticide aerosol was created. The flame length of the resulting pesticide aerosol was less than 45 cm in flammability tests, and the explosive concentration in explosive tests was
It was 0.13g/or more. Further, in the same manner as in Example 1, the stabilizer was determined by measuring the corrosion state inside the container and the number of holes among 10 containers. The results are shown in Table 1.

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[Table] As is clear from the results shown in Table 1, liquid polyhydric alcohols are very effective in stabilizing aerosol products containing halon, whether used alone or in combination. . The aging conditions described above correspond to about 5 years or more under normal use or storage conditions, which indicates that the stabilizer has sufficient effects.

Claims (1)

[Scope of Claims] 1. A stabilized aerosol product characterized in that 0.01 to 12 parts by weight of a liquid polyhydric alcohol is added as a stabilizer to 100 parts by weight of a content containing halon. 2. The aerosol product according to claim 1, wherein the stabilizer is glycerin and/or ethylene glycol.