JP4807945B2 - Aerosol-type antistatic agent in a container - Google Patents

Description

  The present invention relates to an aerosol type antistatic agent for clothing. More specifically, the present invention relates to an aerosol-type antistatic agent in a container that is excellent in antistatic properties and excellent in safety and jetting characteristics during use.

  In recent years, with the diversification of fashion, clothing using various new materials has appeared. Most of these new materials try to produce a new texture by making the cross section of the fiber irregular. As these new materials, synthetic fibers such as polyester and nylon are inevitably used for ease of processing. In addition, as clothing has become more casual, new forms of clothing such as fleece have also appeared. Polyester is also used here for ease of processing. One of the disadvantages of clothing using synthetic fibers such as polyester is ease of charging. As means for preventing the charging of clothes, as described in Japanese Patent Laid-Open No. 56-120788, Japanese Patent Laid-Open No. 10-88113, Japanese Patent No. 1323069, Japanese Patent No. 2838229, etc. Antistatic agent compositions based on quaternary ammonium salts are known. Furthermore, as described in JP-A-2-202977, a method using a special phosphate compound is also known.

  Furthermore, the increase in the amount of brushed clothing such as the fleece described above is a recent trend, and such clothing is easy to ignite with a small amount of fire, and there is a risk that it may lead to a major accident. In particular, when used in the form of an aerosol in a dry atmosphere in winter, there is a case where static electricity accumulated in clothing sparks toward a metal can, which becomes a fire and ignites the propellant gas, causing a fire accident. . As a method for solving this problem, as described in Japanese Patent No. 2838229, there is a method using a specific ammonium salt and a specific amide compound, and using ethanol containing water appropriately as a solvent.

  On the other hand, when considering a method of using an aerosol type antistatic agent, if the spraying is performed while wearing clothes, a use scene in which the can is turned upside-down appears. As an aerosol valve that can be used upside down, an aerosol valve equipped with a vapor tap is known, but this valve also has a loss of propellant from the gas phase at the same time as the spraying of the content liquid, so the propellant and the inner solution are mixed uniformly If the mixing is not uniform, there is a problem that the spraying characteristics are deteriorated and spraying is poor (a large amount of liquid content remains in the can without being sprayed). This phenomenon is particularly likely to occur when standing upright using a vapor tap valve that can be used upside down, and when using water-containing ethanol as a solvent, it tends to cause spray defects, especially when ignited. It was impossible to add a sufficient amount of water to prevent accidents.

JP-A 56-120788 JP-A-2-202977 JP-A-10-88113 Japanese Patent No. 1323069 Japanese Patent No. 2838229

  The problem to be solved by the present invention is to reduce the risk of accidents due to accidental ignition during use, and by using an aerosol valve equipped with a vapor tap that can be used upside down, it is possible to achieve good spraying even when used upright. It is to provide an aerosol type antistatic agent having characteristics.

  As a result of intensive studies to overcome the above problems, the present inventors have combined an antistatic agent composition in which an antistatic base is dissolved in ethanol containing a specific amount of water and a specific propellant. Aerosol-type antistatic agent that reduces the risk of accidents due to accidental ignition during use and has good spray characteristics even when used upright using an aerosol valve with a vapor tap that can be used upside down I came to find.

That is, the present invention is an aerosol-type antistatic agent in a container filled with an aerosol container in which an aerosol valve for injection is provided with a vapor tap, and the aerosol-type antistatic agent in a container is
An antistatic agent composition comprising an ethanol solution containing 25 to 40% by weight of water and an antistatic base;
As a propellant, containing a mixed gas of (A) dimethyl ether and (B) liquefied petroleum gas in a mass ratio of (A) :( B) = 65: 35 to 100: 0,
The above-mentioned aerosol-type antistatic agent in a container is provided, wherein the antistatic agent composition and the propellant are contained in a mass ratio of 75:25 to 60:40.

  The aerosol type antistatic agent composition of the present invention not only has excellent antistatic properties, but also reduces the risk of accidents due to accidental ignition during use, and uses an aerosol valve equipped with a vapor tap that can be used upside down. Thus, it has good spray characteristics even when used upright.

  In the present invention, an ethanol solution containing 25 to 40% by mass of water is used as the solvent. The amount of water is preferably 26% by mass or more, more preferably 30% by mass or more, and preferably 37% by mass or less, more preferably 35% by mass or less. If the water content is less than 25% by mass, sufficient flammability prevention function cannot be exhibited, and if it exceeds 40% by mass, spray failure may occur even if the propellant is selected sufficiently, and the remaining amount of injection is large. This is not preferable.

The antistatic base used in the present invention is not particularly limited as long as it has an antistatic function. Hereinafter, specific examples of the antistatic base are given.
[Solvent type antistatic base]
Examples include polyethylene glycol, polypropylene glycol, glycerin, and polyglycerin. Among these, polyethylene glycol is preferable, polyethylene glycol having a weight average molecular weight of 200 to 1000 is more preferable, and polyethylene glycol having a weight average molecular weight of ethylene oxide of 70 mol is more preferable. Polyethylene glycol having an added mole number of ethylene oxide of 4 to 23 mol is particularly preferable.

[Cationic antistatic base]
Mono long-chain alkyl or alkenyl quaternary ammonium salts having an alkyl or alkenyl group having 8 to 22 carbon atoms, di-long chain alkyl or alkenyl quaternary ammonium salts having an alkyl or alkenyl group having 8 to 22 carbon atoms, etc. It is done. Of these, di-long-chain alkyl quaternary ammonium salts having a long-chain alkyl group having 8 to 12 carbon atoms and a short-chain alkyl group having 1 to 3 carbon atoms are preferable. Preferred examples of the cationic antistatic base include beef tallow alkyltrimethylammonium chloride, beef tallow alkyltrimethylammonium bromide, beef tallow alkyltrimethylammonium methyl sulfate, tallow alkylethyldimethylammonium ethyl sulfate, stearyltrimethylammonium chloride, stearyltrimethylammonium bromide. , Stearyl trimethyl ammonium methyl sulfate, stearyl ethyl dimethyl ammonium ethyl sulfate, oleyl trimethyl ammonium chloride, oleyl trimethyl ammonium bromide, oleyl trimethyl ammonium methyl sulfate, oleyl ethyl dimethyl ammonium ethyl sulfate, palmityl oleyl trimethyl Ammonium chloride, palmityl trimethyl ammonium bromide, palmityl oleyl trimethyl ammonium methyl sulfate, palmityl ethyl dimethyl ammonium ethyl sulfate, didecyl dimethyl ammonium chloride, didecyl dimethyl ammonium bromide, didecyl dimethyl ammonium methyl sulfate, didecyl methyl ethyl ammonium ethyl Sulfate, didodecyldimethylammonium chloride, didodecyldimethylammonium methyl sulfate, didodecylethylmethylammonium ethyl sulfate, dioctyldimethylammonium chloride, dioctyldimethylammonium methyl sulfate, dioctylethylmethylammonium ethyl sulfate, decyldede Le dimethyl ammonium chloride, decyl dodecyl dimethyl ammonium methyl sulfate, decyl dodecyl methyl ammonium ethylsulfate, decyl octyl dimethyl ammonium chloride, decyl octyl dimethyl ammonium methyl sulfate, decyl octyl methyl ammonium ethylsulfate and the like. Of these, didecyldimethylammonium chloride, didecyldimethylammonium methylsulfate and didecylmethylethylammonium ethylsulfate are preferable, and didecyldimethylammonium chloride is particularly preferable.

[Amine-type antistatic base]
Mono long chain alkyl or alkenylamine salt having an alkyl or alkenyl group having 8 to 22 carbon atoms, dilong chain alkyl or alkenylamine salt having an alkyl or alkenyl group having 8 to 22 carbon atoms, 8 to 22 carbon atoms And long-chain alkyl or alkenylamine ethylene oxide adducts having an alkyl or alkenyl group, and dilong-chain alkyl or alkenylamine ethylene oxide adducts having an alkyl or alkenyl group having 8 to 22 carbon atoms.
[Silicone-type antistatic base]
Examples include amino-modified silicone, polyether-modified silicone, and alkyl polyether-modified silicone. Of these, polyether-modified silicone is preferred. As such a polyether-modified silicone, those which can be produced by a known method can be used, and commercially available products can also be used. As a commercially available product, for example, one sold by Toray Dow Corning Silicone Co., Ltd. under the trade name SH3775M can be used.
[Amide-type antistatic base]
Examples thereof include fatty acid alkanol amides having an alkyl or alkenyl group having 7 to 18 carbon atoms and ethylene oxide adducts thereof.
[Phosphate ester antistatic base]
Examples thereof include monoalkyl or alkenyl phosphate ester salts having an alkyl or alkenyl group having 7 to 18 carbon atoms, and dialkyl or alkenyl phosphate ester salts having an alkyl or alkenyl group having 7 to 18 carbon atoms.

Among the above antistatic bases, polyethylene glycol and water-soluble cationic charging are possible because they can be uniformly dissolved in an ethanol solution containing 25 to 40% by mass of water and exhibit good antistatic performance. It is preferable to use a combination of prevention bases, and further selected from polyethylene glycol having 3 to 70 moles of added ethylene oxide, didecyldimethylammonium chloride, didecyldimethylammonium methylsulfate, and didecylmethylethylammonium ethylsulfate. It is preferable to use a combination of one or more cationic antistatic bases.
In the present invention, the antistatic base is preferably added in an amount of 0.1 to 5% by mass, more preferably 0.2 to 3% by mass in the antistatic agent composition.
The antistatic agent composition used in the present invention can be produced by stirring and mixing an ethanol solution containing a specific amount of water and an antistatic base until the antistatic base is dissolved in the solution. I can do it.

In the aerosol type antistatic agent of the present invention, the above-mentioned antistatic agent composition is filled in an aerosol container in which an aerosol valve for injection is provided with a vapor tap, and (A) dimethyl ether and (B) liquefied petroleum gas as a propellant. (A) :( B) = 65: 35 to 100: 0, a mixture of gas and antistatic agent composition and propellant in a mass ratio of composition: propellant = 75: 25 to 60:40 It is used by filling to become.
Referring to FIG. 1, an aerosol valve having a vapor tap that can be used in the present invention is a valve that uses a housing having a horizontal hole (vapor tap hole) for taking in gas phase gas, and is a vaporized propellant. Is taken through the side hole of the housing, mixed with the contents passing through the dip tube, and sprayed. If this valve is used, it can be used not only in the normal upright state but also in an inverted state, and if it is used for stockings, skirts, etc., very good usability can be obtained.

As the propellant used in the present invention, a mixed gas of dimethyl ether (DME) and liquefied petroleum gas (LPG) is used.
The liquefied petroleum gas is a hydrocarbon mixture which is gaseous at normal temperature and pressure and mainly contains propane and butane, and preferably has a vapor pressure at 20 ° C. of 0.15 to 0.4 MPa.
Dimethyl ether and liquefied petroleum gas are mixed at a mass ratio of 65:35 to 100: 0, preferably 65:35 to 90:10, more preferably 67:33 to 80:20. If the blending ratio of liquefied petroleum gas exceeds this range, uniform liquidity cannot be maintained, and there is a problem that the loss of propellant from the gas phase becomes large when spraying the content liquid, resulting in an increase in the remaining amount of injection, which is preferable. Absent.
In the present invention, the stock solution and the propellant in which the antistatic base is dissolved are in a mass ratio of stock solution: propellant = 75: 25-60: 40, preferably the ratio of stock solution: propellant = 72: 28-65: 45. To fill the aerosol container. Even if the amount of the propellant exceeds the upper limit of this range or less than the lower limit, it is preferable because the injection balance of the gas phase and the internal solution during spraying is lost, causing a decrease in internal pressure and increasing the remaining amount of injection. Absent.

The antistatic agent composition of the present invention can be blended with the following optional components in addition to the essential components in the previous period as long as the effects of the present invention are not impaired.
1) Antioxidants such as 2,6-di-tert-butyl-4-methylphenol (BHT) 2) Preservatives such as methylparaben, benzoic acid or salts thereof 3) Fragrances 4) pH adjusters such as acids and alkalis The target fiber to be used for the antistatic agent composition of the present invention is not particularly limited, and synthetic fibers such as polyester, nylon, and acrylic, semi-synthetic fibers such as acetate, regenerated fibers such as rayon, tencel, and polynosic, It can be used for a wide range of applications such as natural fibers such as cotton, wool and silk, and blended products, blended fabrics and blended products of these various fibers.

The components used in Examples and Comparative Examples are shown below.

The container used by the Example and the comparative example is shown below.
Can: Aluminum JIS A-3004P inner surface coated can (Toyo Seikan Co., Ltd.)
100mL button: GDE-button (Kitano Manufacturing Co., Ltd.)
Valve A: DY02-H04222 × C92R (manufactured by Toyo Aerosol Co., Ltd.)
Vapor tap type valve)
Valve B: A80W1 (F) 13.157 (0.48) x C91R (Maruichi Co., Ltd.)
Vapor tap type valve)

[Flammability test]
An electronic lighter is placed at a position 20 cm away from the aerosol-type antistatic agent, fire is ignited, and the aerosol-type antistatic agent is sprayed toward the fire to determine the presence or absence of ignition.
Judgment criteria ○: No ignition
×: Ignition

[Injection remaining amount test]
After thoroughly shaking the aerosol-type antistatic agent adjusted to 25 ° C., the content liquid is ejected in an upright state until it is no longer ejected, and then the mass is measured. Thereafter, the can is opened, the remaining content liquid is taken out, and the remaining amount of injection is obtained by the following equation.
Remaining injection quantity (g) = mass after injection (g) −mass of empty can (g)
Judgment criteria ○: The remaining amount of injection is less than 5 g (a level at which almost no liquid remains)
Δ: The remaining amount of injection is 5 g or more and less than 8 g (level at which the remaining liquid is a little worrisome)
X: Remaining injection amount is 8g or more

[Antistatic evaluation method A: half-life measurement (ability to remove static electricity)]
A commercially available polyester tropical was used as a test cloth. 4 g of the prepared aerosol type antistatic agent was uniformly sprayed on the test cloth cut into 30 cm × 30 cm, and the humidity was adjusted at 20 ° C. and 45% RH for 24 hours. Then, the half life was measured according to JIS-L-1094 and the A method using STATIC HONESTEMETER TYPES-5109 (made by Ashito Shokai).
Judgment criteria ○: Less than 5 seconds
Δ: Half-life 5 seconds or more and less than 30 seconds
×: Half-life 30 seconds or more

[Antistatic Evaluation Method B: Friction Voltage (Ability to Prevent Static Electricity)]
A commercially available polyester tropical was used as a test cloth. 4 g of the prepared aerosol type antistatic agent was uniformly sprayed on the test cloth cut into 30 cm × 30 cm, and the humidity was adjusted at 20 ° C. and 45% RH for 24 hours. Thereafter, the frictional voltage was measured according to JIS-L-1094, Method B, using ROTARY STATIC TESTER (manufactured by Koa Shokai). In addition, as the friction cloth, a cotton gold no. 3 was used.
Judgment criteria ○: Less than 500V
Δ: Friction voltage 500V or more and less than 1000V
X: Friction band voltage 1000V or more

(Adjustment of antistatic agent composition)
Evaluation by aerosol is converted to a total volume of 75 mL of the injection gas with an antistatic agent composition adjusted by stirring and mixing at room temperature according to Tables 2 to 4, and after filling, clinch (canned), Evaluation was performed by filling a predetermined amount of the injection gas.

FIG. 1 shows a cross-sectional view of a vapor tap valve.

Claims (5)

An aerosol-type antistatic agent contained in an aerosol container in which an aerosol valve for injection is provided with a vapor tap, the aerosol-type antistatic agent contained in the container,
An ethanol solution containing 25-40% by weight of water;
One or more cationic antistatic groups selected from the group consisting of polyethylene glycol having an addition mole number of ethylene oxide of 3 to 70 moles, didecyldimethylammonium chloride, didecyldimethylammonium methylsulfate and didecylmethylethylammonium ethylsulfate. An antistatic agent composition comprising an antistatic base that is a mixture with the agent ;
Containing a mixed gas of (A) dimethyl ether and (B) liquefied petroleum gas as a propellant in a mass ratio of (A) :( B) = 65: 35 to 100: 0,
The aerosol-containing antistatic agent in a container, wherein the antistatic agent composition and the propellant are contained in a mass ratio of 75:25 to 60:40. The aerosol-type antistatic agent according to claim 1, wherein the antistatic base is a mixture of polyethylene glycol having 4 to 23 moles of added ethylene oxide and didecyldimethylammonium chloride . The aerosol type antistatic agent according to claim 1 or 2, wherein the antistatic agent is an antistatic agent for polyester . An aerosol-type antistatic agent for garments with a container in which an aerosol container for injection is filled with an aerosol container provided with a vapor tap, the aerosol-type antistatic agent for garments with a container,
An ethanol solution containing 25-40% by weight of water;
An antistatic agent composition comprising a polyethylene glycol having an addition mole number of ethylene oxide of 3 to 70 mol and an antistatic base which is a mixture of a cationic antistatic base;
Containing a mixed gas of (A) dimethyl ether and (B) liquefied petroleum gas as a propellant in a mass ratio of (A) :( B) = 65: 35 to 100: 0,
The aerosol-type antistatic agent for garments in a container, wherein the antistatic agent composition and the propellant are contained in a mass ratio of 75:25 to 60:40 . 5. The cationic antistatic base is one or more cationic antistatic bases selected from the group consisting of didecyldimethylammonium chloride, didecyldimethylammonium methyl sulfate and didecylmethylethylammonium ethyl sulfate. The aerosol-type antistatic agent for clothes as described in container.

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