JP2002201464A - High pressure aerosol product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high pressure aerosol product having high safety for fire and a human body, and excellent spray characteristics. SOLUTION: The high pressure aerosol product comprises an aerosol product charged with an aerosol composition comprising a liquid composition having a critical temperature of >=90 deg.C and being a liquid under pressure conditions, and a pressurizing agent having a critical temperature of <=50 deg.C, and a pressure of the product at 25 deg.C being 1-5 MPa.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aerosol product, and more particularly to a high-pressure aerosol product having high safety against fire, high safety against human body, and excellent spray characteristics.

[0002]

2. Description of the Related Art In an aerosol product using a compressed gas, since the compressed gas exists in a gaseous state in a gas phase in a container, a pressure change due to a temperature change is small and a change in a spray state is small. However, aerosol products using conventional compressed gas have a product pressure of 0.1 to
1.0 MPa, and the weight ratio between the stock solution and the compressed gas is 9
Since the ratio was 9.9: 0.1 to 95: 5, the dissolved amount of the compressed gas in the undiluted solution was small, and the volume of the compressed gas expanded by vaporization when injected into the atmosphere like a liquefied gas. Because there is no spray button, the size of the spray particles is reduced only by the structure of the spray button, so the size of the spray particles (spray particle diameter) is larger than aerosol products using liquefied gas, and the diffusivity in space is poor. was there. In addition, a conventional aerosol product using compressed gas has a problem that the volume of the gas phase increases with each injection, and the product pressure decreases accordingly, so that the injection form changes depending on the remaining amount of the aerosol composition. there were.

On the other hand, an aerosol product using a liquefied gas is instantaneously vaporized when the liquefied gas, which was present in a liquid state inside the container, is sprayed into the atmosphere. It has excellent spraying properties such as excellent diffusion in space and cooling effect by heat of vaporization. However, since a flammable gas such as liquefied petroleum gas or dimethyl ether is used as the liquefied gas, safety against fire is low.In particular, when a flammable undiluted solution such as ethanol or kerosene and the liquefied gas are used, spraying is performed. There is a danger of ignition if there is a fire source while the particles are diffusing into the space, which is dangerous. In addition, in the spray aerosol composition using a liquefied gas, the weight ratio of the stock solution and the liquefied gas is generally 60:40 to 20:80, and the product pressure is 0.3 to 0.8M.
Pa.

On the other hand, the spray composition Ru with carbon dioxide in a liquid state (liquefied carbon dioxide) is, JP-B 60-38977
JP, JP-A-7-241498, JP-A-8-1
88506 and JP-A-7-309704. However, in these documents,
Carbon dioxide gas is used in a liquid state, and a pressure around the saturated vapor pressure of carbon dioxide gas is required for the presence of the carbon dioxide gas as a liquid, and the saturated vapor pressure at 25 ° C. is 6.4 MPa. Further, in order to obtain the above pressure, it is necessary to reduce the amount of the solvent or the active ingredient to less than 50% by weight, for example, 0.01 to 10% by weight in the composition. Further, since the carbon dioxide gas exists in a liquid state, the product temperature becomes critical temperature Tc (in the case of carbon dioxide gas, the temperature is 3c).
At around 1.1 ° C.), the carbon dioxide gas cannot exist as a liquid, and the carbon dioxide gas is entirely vaporized. As a result, the pressure rise accompanying the temperature rise from around room temperature (25 ° C.) is large, and especially the pressure rise around 30 ° C. is large. Furthermore, when this composition is sprayed in a large amount, the concentration of carbon dioxide in the space rapidly increases, which is not preferable in terms of safety to the human body. The Occupational Safety and Health Regulations set an upper limit on the concentration of carbon dioxide in the air. However, in the case of aerosol products, the concentration of carbon dioxide is locally high immediately after injection, and it is dangerous for users to easily inhale.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aerosol product, in particular, high safety against fire, high safety against the human body, excellent spray characteristics, and a temperature rise above normal temperature. Another object of the present invention is to provide a high-pressure aerosol product in which the product pressure hardly rises sharply.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a method for forming a critical temperature (T
An aerosol product filled with an aerosol composition comprising a liquid composition wherein c) is 90 ° C. or higher and which is liquid under pressure and a pressurizing agent having a Tc of 50 ° C. or lower, wherein the product pressure at 25 ° C. It relates to a high-pressure aerosol product of 1-5 MPa.

For example, the critical temperature of a liquid composition is 170
When the temperature is not lower than ° C, the content of the liquid composition in the aerosol composition is preferably not less than 50% by weight.

For example, the critical temperature of the liquid composition is 90 to
When the temperature is 170 ° C., it is preferable that the liquid composition is composed of a hydrocarbon.

Preferably, the pressurizing agent is carbon dioxide gas or nitrogen suboxide gas.

The amount of the pressurizing agent in the aerosol composition is preferably 5 to 50% by weight.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The aerosol product of the present invention has a Tc
And a pressurizing agent having a Tc of 50 ° C. or less, wherein the product pressure at 25 ° C. is 1 to 5 MPa. Using a liquid composition having a specific Tc and a pressurizing agent, the pressurizing agent is dissolved in the liquid composition under pressure to reduce the product pressure to 1 to 5
By adjusting to MPa, the pressurizing agent dissolves in a specific amount in the liquid composition, excellent spray properties are obtained, and safety against fire is increased. The pressure dissolution means that a pressurizing agent is filled in a pressure-resistant container filled with a liquid composition, and the gaseous pressurizing agent in the gas phase inside the pressure-resistant container changes over time with the liquid composition. It means that it dissolves in and becomes equilibrium, and the state of the pressurizing agent when filling the pressure-resistant container is not particularly limited. If the product pressure is less than 1 MPa, the amount of the pressurizing agent dissolved in the liquid composition is small, so that the spray particles are not sufficiently finely divided and the safety against fire is low. On the other hand, if the pressure exceeds 5 MPa, the pressure agent exists in a liquid state depending on the temperature condition, and the pressure rise accompanying the temperature rise becomes large, which is dangerous.

The liquid composition has a Tc of 90 ° C. or higher,
In an airtight container (pressurized state), it exists as a liquid and contains an active ingredient. When the Tc of the liquid composition is lower than 90 ° C., the product pressure of the liquid composition exceeds 1 MPa,
Since the amount of the pressurizing agent and the amount of the pressurizing agent dissolved in the liquid composition are small, the effect of the pressurizing agent cannot be sufficiently obtained. Further, the liquid composition has a Tc of 90 to 170 ° C. and is a liquid in an airtight container, but a liquefied gas which becomes a gas when released into the atmosphere, and a Tc of 170 ° C. or higher and a pressure of less than atmospheric pressure. However, they can be classified as liquid components that are liquids.

The liquid composition is preferably contained in the aerosol composition in an amount of 15 to 95% by weight, more preferably 20 to 90% by weight, and still more preferably 50 to 90% by weight.
In particular, when a liquid component having a Tc of 170 ° C. or higher is used as the main solvent of the liquid composition, specifically, in the case of a lower alcohol described below, preferably 35 to 90% in the aerosol composition.
% By weight, more preferably 50 to 90% by weight, still more preferably 60 to 85% by weight. When the main solvent is a hydrocarbon, preferably 50 to 93% by weight, more preferably 60 to 90% by weight, and the main solvent is water. Is preferably 60 to 95% by weight, more preferably 65 to 90% by weight, and when the main solvent is a polyhydric alcohol, preferably 55 to 95% by weight, more preferably 65 to 90% by weight. . When a liquefied gas having a Tc of 90 to 170 ° C. is used as the main solvent of the liquid composition, 15 to 95% in the aerosol composition.
% By weight, preferably 30 to 90% by weight, more preferably 50 to 90% by weight. The liquid composition may be mixed with the aforementioned liquid components having a Tc of 170 ° C. or higher, or may be further mixed with a liquefied gas having a Tc of 90 to 170 ° C.

When the amount of the liquid composition is less than 15% by weight, the amount of the pressurizing agent increases, so that the pressurizing agent is hardly dissolved in the liquid composition depending on the combination of the liquid composition and the pressurizing agent. In some cases, the two are separated from each other and the pressure is increased, so that the pressurizing agent may be present as a liquid. Further, even if the pressurizing agent is dissolved in the liquid composition, the pressurizing agent is present in a liquid state depending on the temperature condition, and the pressure rise is drastically increased as the temperature rises, which is dangerous. In addition, when carbon dioxide gas or nitrogen suboxide gas is used as the pressurizing agent, the gas concentration becomes too high when the whole or large amount is injected, which may adversely affect the human body. On the other hand, when the compounding amount of the liquid composition exceeds 95% by weight, the compounding amount of the pressurizing agent is reduced, so that the product pressure is low, the amount of the pressurizing agent dissolved in the liquid composition is reduced, and fine They cannot be sprayed with fog and tend to have poor diffusivity. Also, safety against fire is reduced.

Examples of the liquid component having a Tc of 170 ° C. or higher include water (Tc = 374.0 ° C.), lower alcohols, hydrocarbons, polyhydric alcohols, ketones, ester oils, silicone oils, and mixtures thereof. And so on.

The water includes purified water, distilled water, ion-exchanged water and the like.

The lower alcohols include ethanol (Tc = 243.1 ° C.) and propanol (Tc = 26
3.6 ° C.), isopropanol (Tc = 235.2)
° C), isobutyl alcohol (Tc = 262.8 ° C),
An alcohol having 2 to 5 carbon atoms such as t-butyl alcohol (Tc = 233.0 ° C.) is exemplified.

The hydrocarbons include normal pentane (Tc = 196.5 ° C.) and isopentane (Tc = 18
7.2 ° C.), normal hexane (Tc = 234.2)
° C), isohexane (Tc = 224.3 ° C), kerosene, liquid paraffin, isoparaffin, squalane, squalene and the like.

As the polyhydric alcohol, for example,
Ethylene glycol, propylene glycol, 1,3-
Butylene glycol, glycerin, xylitol, sorbitol, diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, diglycerin, polyethylene glycol, triglycerin, ethylene glycol monoethyl ether, ethylene glycol monophenyl ether, diethylene glycol monoethyl ether, dipropylene Glycol ethyl ether, ethylene glycol monoethyl ether acetate and the like can be mentioned.

As ketones, acetone (Tc = 23)
5.0 ° C.), methyl ethyl ketone and the like.

Examples of the silicone oil include methylpolysiloxane, decamethyltetrasiloxane, octamethylcyclotetrasiloxane, and methylphenylpolysiloxane.

Examples of the ester oil include isopropyl myristate, cetyl octoate, octyl dodecyl myristate, isopropyl palmitate, cetyl lactate, ethyl acetate, diethyl phthalate, diethoxyethyl phthalate, diethoxyethyl succinate and the like. Is raised.

The Tc of the liquid component is preferably 170 ° C. or higher, more preferably 180 ° C. or higher. If the Tc of the liquid component is lower than 170 ° C., volatilization under atmospheric pressure is rapid, and Precise dispensing requires special equipment and is time-consuming.

On the other hand, as the liquefied gas having a Tc of 90 to 170 ° C., a liquefied gas having a Tc of preferably 90 ° C. or higher, more preferably 95 to 170 ° C., can be used. For example, propane (Tc
= 96.7 ° C.), normal butane (Tc = 152.0)
C.), isobutane (Tc = 135.0.degree. C.), dimethyl ether (Tc = 126.9.degree. C.) and mixtures thereof. The liquefied gas has a Tc of 90.
If the temperature is lower than 0 ° C., the product pressure of the liquid composition exceeds 1 MPa and the filling amount of the pressurizing agent decreases, so that the effect of the pressurizing agent tends not to be sufficiently obtained. When a pressurizing agent is dissolved in a liquefied gas having a Tc of 90 to 170 ° C., the liquefied gas is pressurized to a liquid component having a Tc of 170 ° C. or more, despite having a vapor pressure itself. The product pressure tends to be lower than when the agent is dissolved.

The liquid component having a Tc of 170 ° C. or higher or a liquefied gas having a Tc of 90 to 170 ° C. is used not only as a medium for dissolving or dispersing an active ingredient, but also for dissolving a pressurizing agent and forming a spray particle size or It is a component that greatly affects the spray state, such as product pressure, and is selected according to the desired spray form and product purpose. Further, it is used for the purpose of reducing the rise in pressure when the temperature rises.

The active ingredient is selected depending on the purpose and use of the product. Examples of the active ingredient include a deodorant, a bactericidal / preservative, a cooling agent, a pest repellent, an insecticidal ingredient, an insecticidal efficacy enhancer, a fragrance, and a set for hair. Agents, moisturizers, ultraviolet absorbers, amino acids, vitamins, hormones, antioxidants, various extracts, antiphlogistic analgesics, astringents, anti-inflammatory agents, local anesthetics, antihistamines, whitening agents, resins, plasticizers, Pigments, dispersants, desiccants, anti-skinning agents and the like are used.

Examples of the deodorant include methacrylate laurate, methyl benzoate, methyl phenylacetate, geranyl crotrate, acetophenone myristate, benzyl acetate, benzyl propionate and the like.

Examples of the disinfectant / preservative include paraoxybenzoate, sodium benzoate, potassium sorbate, phenoxyethanol, benzalkonium chloride, benzethonium chloride, chlorhexidine chloride, photosensitizer, parachlorometacresol and the like. .

Examples of the cooling agent include l-menthol, camphor and the like.

Examples of the insect repellent include N,
N-diethyl-m-toluamide (diet), caprylic acid diethylamide and the like can be mentioned.

Examples of the insecticidal component include phthalthrine, allethrin, permethrin, imiprothrin,
Cismethrin, propulsrin, resmethrin, d-phenothrin, benfluthrin, neopinamine forte,
Chrislon Forte and the like.

Examples of the insecticidal efficacy enhancer and flavor include sinepirin, piperonyl butoxide, octachlorodipropyl ether and the like.

Examples of the hair setting agent include:
Dialkylaminoethyl (meth) acrylate / alkyl (meth) acrylate copolymer, octylamide acrylate / hydroxypropyl acrylate / butylaminoethyl methacrylate copolymer, vinylpyrrolidone / vinyl acetate copolymer, hydroxy acrylate Examples include an ethyl-butyl acrylate-methoxyethyl acrylate copolymer, an alkanolamine acrylate, an alkyl acrylate copolymer emulsion, and an alkyl acrylate-styrene copolymer emulsion.

Examples of the humectant include propylene glycol, glycerin, 1,3-butylene glycol, collagen, xylitol, sorbitol, hyaluronic acid, caronic acid, sodium lactate, d, l-pyrrolidone carboxylate, keratin, casein , Lecithin and the like.

Examples of the ultraviolet absorber include para-aminobenzoic acid, monoglycerin monoester of para-aminobenzoic acid, octyl salicylate, phenyl salicylate,
Isopropyl paramethoxycinnamate, octyl paramethoxycinnamate and the like.

Examples of the amino acids include glycine, alanine, leucine, serine, tryptophan, cystine, cysteine, methionine, aspartic acid, glutamic acid, arginine and the like.

Examples of the vitamins include vitamin A oil, retinol, retinol palmitate, pyridoxine hydrochloride, benzyl nicotinate, nicotinamide, d, l-α-tocopherol nicotinate, vitamin D2 (ergocasiferol), d, l-α-tocopherol, d, l-α-tocopherol acetate, pantothenic acid, biotin and the like.

Examples of the hormones include elastradiol, ethinylestradiol and the like.

Examples of the antioxidant include ascorbic acid, α-tocopherol, dibutylhydroxytoluene, butylhydroxyanisole and the like.

Examples of the various extracts include peonies extract, loofah extract, rose extract, lemon extract, aloe extract, shobu root extract, eucalyptus extract, sage extract, tea extract, seaweed extract, placenta extract, silk extract and the like. can give.

Examples of the antiphlogistic analgesic include methyl salicylate, camphor, diphenhydramine, indomethacin, piroxicam, felbinac, ketoprofen, crotamiton and the like.

Examples of the astringent include zinc oxide, allantoin hydroxyaluminum, tannic acid, citric acid, lactic acid and the like.

Examples of the anti-inflammatory agent include allantoin, glycyrrhetinic acid and azulene.

Examples of the local anesthetic include dibucaine hydrochloride, tetracaine hydrochloride, lidocaine hydrochloride and the like.

The antihistamines include, for example,
Examples include diphenhydramine hydrochloride and chlorpheniramine maleate.

Examples of the whitening agent include arbutin and kojic acid.

Examples of the resin include cellulose resins such as nitrocellulose, ethylcellulose, acetylcellulose, benzylcellulose and butylcellulose, methacrylates (methyl methacrylate, ethyl methacrylate, n-butyl methacrylate) and acrylates (Methyl acrylate, ethyl acrylate,
Acrylic resins such as (n-butyl acrylate), epoxy resins, silicone resins, vinyl resins such as polyvinyl butyl ether and polyvinyl ethyl ether, and polyester resins such as polyethylene terephthalate.

Examples of the plasticizer include citrate esters such as acetyltrimethyl citrate and acetyltributyl citrate; phthalate esters such as diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diamyl phthalate and diethylhexyl phthalate; Tributyl phosphate,
Phosphates such as tricresyl phosphate, adipic esters such as diethyl adipate and dibutyl adipate, isobutyric acid / sucrose acetate, methylphthalylmethyl glycolate, ethylphthalylethyl glycolate, chlorinated paraffin, chlorinated biphenyl, etc. Is raised.

Examples of the pigment include inorganic pigments such as titanium dioxide, zinc white, carbon black, zinc, red iron oxide, graphite, lead chromate, aluminum, copper, and cobalt; and organic pigments such as phthalocyanine, quinoclamin, and toluidine. And so on.

Examples of the dispersant include polyaminoamide,
Modified acrylic block copolymers, alkyl ammonium salts, polycarboxylates, polyoxyethylene alkyl ethers, polyethylene glycol esters, sorbitan alkylates and the like can be mentioned.

Examples of the drying agent include lead naphthenate, cobalt naphthenate, manganese naphthenate, lead octylate,
Cobalt octylate, manganese octylate and the like can be mentioned.

Examples of the anti-skinning agent include methyl ethyl ketone oxime, butyl dioxime, ionol, eugenol, ditenpen, turpentine oil and the like.

The active ingredient is preferably contained in the liquid composition in an amount of 0.1 to 30% by weight, more preferably 0.5 to 20% by weight. If the active ingredient is less than 0.1% by weight,
The effect of the active ingredient tends not to be sufficiently exerted. On the other hand, if it exceeds 30% by weight, the concentration of the active ingredient is too high, and depending on the active ingredient, there is a case that the human body is adversely affected.

It should be noted that the active ingredient is preferably dissolved in a liquefied gas when no liquid component is blended or when the solubility in a liquefied gas is excellent.

Incidentally, as an auxiliary component of the liquid composition, an oil component, a surfactant, a powder and the like can be blended.

The oil component is a component for improving the feeling of use and imparting effects such as water repellency, and examples thereof include higher fatty acids, waxes, oils and fats.

The higher fatty acids include, for example, lauric acid, myristic acid, palmitic acid, stearic acid,
Oleic acid and the like.

As the wax, for example, beeswax,
Lanolin, lanolin acetate, candelilla wax and the like.

The fats and oils include, for example, camellia oil,
Corn oil, olive oil, rapeseed oil, sesame oil, castor oil, linseed oil, safflower oil, jojoba oil, coconut oil and the like.

The above-mentioned surfactants are used for solubilizers, dispersants, fatliquors and the like, and include, for example, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants. Surfactants, polymer surfactants, and silicon surfactants.

Examples of the nonionic surfactant include sorbitan fatty acid ester, glycerin fatty acid ester, decaglycerin fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbite fatty acid ester, and polyoxyethylene. Glycerin fatty acid ester,
Examples include polyethylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene castor oil and hydrogenated castor oil derivatives.

Examples of the anionic surfactant include alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, and fatty acid soaps. Examples of the cationic surfactant include an alkyl ammonium salt and an alkyl benzyl ammonium salt. Examples of the amphoteric surfactant include betaine acetate and lecithin.

Examples of the high molecular surfactant include polyalkylvinylpyridinium, alkylphenol polymer derivatives, styrene / maleic acid polymer derivatives, and the like.

Examples of the silicone surfactant include polyoxyethylene / methylpolysiloxane copolymer, polyoxypropylene / methylpolysiloxane copolymer, poly (oxyethylene / oxypropylene).
Methyl polysiloxane copolymer and the like can be mentioned.

The above-mentioned powder is used as a carrier, a protective agent, an adhering agent, a solid lubricant or the like, which itself acts as an active ingredient, or carries another active ingredient. For example, talc, zinc oxide, kaolin, Examples include mica, magnesium carbonate, calcium carbonate, zinc silicate, magnesium silicate, aluminum silicate, calcium silicate, silica, zeolite, ceramic powder, and boron nitride.

The pressurizing agent is a component for spraying the liquid composition in the form of a mist, and has a Tc of 50 ° C. or lower, preferably 0 to 40 ° C. If the Tc of the pressurizing agent is less than 0 ° C., the product pressure becomes too high when the desired filling amount is reached, and if it exceeds 50 ° C., it exists as a liquid depending on the conditions of the temperature and the product pressure. There is a tendency that the effect cannot be obtained.

As the pressurizing agent, nitrogen gas (Tc =
-147.0 ° C.), carbon dioxide gas (Tc = 31.0 ° C.), nitrogen suboxide gas (Tc = 36.4 ° C.), compressed air, and mixtures thereof. Carbon dioxide gas and nitrogen suboxide gas, which have high solubility in substances, are preferable. In addition, when Tc is close to room temperature and carbon dioxide gas and nitrogen suboxide gas are present as liquids,
Although the product pressure greatly changes with a slight temperature change, by dissolving under pressure into a liquid composition having a specific Tc, there is no sharp pressure increase even when the product temperature exceeds Tc.
High security is obtained.

The pressurizing agent is incorporated in the aerosol composition preferably in an amount of 5 to 85% by weight, more preferably 10 to 80% by weight, and still more preferably 10 to 50% by weight. When the amount of the pressurizing agent is less than 5% by weight, the product pressure tends to be low, the amount of dissolution in the liquid composition tends to be small, it cannot be sprayed with a fine mist, and the diffusivity tends to be poor. . Also,
Fire safety is reduced. On the other hand, when the content is 85% by weight or more, depending on the combination with the liquid composition, the pressurizing agent is separated without being dissolved in the liquid composition, and the pressurizing agent is easily present as a liquid. In addition, the product pressure increases, and the pressurizing agent exists in a liquid state depending on the temperature conditions. Therefore, the pressure increase due to the temperature increase increases, which is dangerous. In addition, when carbon dioxide gas or nitrous oxide gas is used as the pressurizing agent, if the total amount or large amount is injected, the gas concentration becomes too high, which may adversely affect the human body.

The solubility of the pressurizing agent in the liquid composition is 2
At 5 ° C. and product pressure, the weight ratio is preferably 2% or more, more preferably 3% or more. If the solubility is less than 2%, the spray particle size tends to be large and the diffusivity tends to be poor. In particular, when a combustible liquid component or liquefied gas is used, the solubility of the pressurizing agent in the liquid composition is, for example, 6% or more, preferably 7% when a lower alcohol such as ethanol is used as a main solvent. That's it,
When using a hydrocarbon such as kerosene as the main solvent, 3
%, Preferably 4% or more. If the solubility is less than the above range, the flammability of the sprayed particles cannot be lowered, and the safety against fire decreases.

The solubility is determined by the following method. A predetermined amount of a pressurizing agent is filled in a gas phase portion of a pressure-resistant container filled with a liquid composition, and the pressure when the pressurizing agent dissolves in the liquid composition under pressure and equilibrates is measured. Next, the gas phase obtained using the ideal gas equation of state PV = nRT (where P is the product pressure in an equilibrium state, V is the volume occupied by the gas phase, T is the temperature, and R is the gas constant) From the number of moles n of the pressurizing agent present in the gas phase part, the weight of the pressurizing agent present in the gas phase part is determined. Next, the weight of the pressurizing agent dissolved in the liquid composition is determined by subtracting the weight of the pressurizing agent present in the gas phase from the weight of the filled pressurizing agent. The weight of the pressurizing agent dissolved in the liquid composition, 25 ℃,
The solubility is determined as a ratio to the weight of the liquid composition in which the pressurizing agent is dissolved under product pressure.

In the method for producing an aerosol product of the present invention, first, an effective component and, if necessary, an auxiliary component are dissolved or dispersed in a liquid component or a liquefied gas to prepare a liquid composition, and the liquid composition is filled into a pressure-resistant container. Then, the pressure-sensitive agent is obtained by filling the gaseous phase portion of the container with the pressure-sensitive agent and dissolving the pressure-sensitive agent under pressure in the liquid composition. Pressurizing agent can be filled in any state of gas, liquid, and solid.
Preferably, it is dissolved in a liquid composition.

The pressure-resistant container is preferably made of a metal such as aluminum, tinplate, stainless steel or the like, or made of high pressure-resistant glass. The container size is preferably 100 ml or less, and if it exceeds 100 ml, Containers are regulated by the High Pressure Gas Safety Law. Further, the filling rate of the liquid composition is preferably 60% by volume or less, more preferably 50% by volume or less. If the filling rate of the liquid composition exceeds 60% by volume, the gas phase portion (head space) filled with the pressurizing agent becomes too small, and immediately after filling the pressurizing agent (the pressurizing agent dissolves in the liquid composition). In the case where the container is not used, the pressure becomes too high and may exceed the pressure resistance of the container.

The pressure at 25 ° C. of the aerosol product obtained by the aerosol composition and the filling method described above is 1
-5 MPa, preferably 1.5-4 MPa. As described above, by applying a specific pressure to the product using a pressurizing agent, the pressurizing agent dissolves in a specific amount in the liquid composition, has excellent diffusibility of spray particles, and has high safety against fire. The effect of is obtained. Also, even when the product temperature rises above the Tc of the pressurizing agent, the pressure does not rise sharply, and the safety is excellent.

FIGS. 1 to 4 show a stainless steel pressure vessel (full filling 98 ml), a filling ratio of the liquid composition of 30% and a filling rate of 25%.
Liquid compositions in ℃ and the mixing ratio of carbonate (CO ₂₎ gas (weight ratio) is a diagram showing the relationship between the product pressure. 1 shows an example using a mixed solvent of ethanol and kerosene, FIG. 2 shows an example using a mixed solvent of ethanol and water, FIG. 3 shows an example using a mixed solvent of ethanol and glycerin, and FIG. 4 shows an example using a mixed solvent of ethanol and isobutane.

According to FIG. 2, for example, in order to obtain a product pressure of 5 MPa, carbon dioxide gas was supplied by using 65.0% by weight when the solvent was ethanol alone, and 40.0% by weight when using water alone. 48. In the case of a mixed solvent of ethanol and water,
It can be seen that 0% by weight may be filled. The hatched portion in FIG. 2 indicates a region where the carbon dioxide gas is not completely dissolved and becomes cloudy and separated.

A comparison between the aerosol product of the present invention in which a pressurizing agent such as carbon dioxide is dissolved in a solvent and a conventional aerosol product in which a liquefied gas such as liquefied petroleum gas or dimethyl ether is dissolved in a solvent shows that the pressurizing agent is dissolved. The product you let me
Due to the high energy stored, the spray particles can reach farther away. As a result, an aerosol product can be obtained in which the amount of propellant can be reduced as compared with the case of using only a liquefied gas to form a spray product, and which is excellent in safety against fire. As a result, in addition to home and car applications such as human body products such as hair and skin, indoor insecticides and deodorants, disinfectants, and paint, it can be applied to large spaces such as buildings and condominiums, and even outdoors. it can.

The following is an example of the formulation of the high-pressure aerosol product of the present invention.

As the container, a stainless steel pressure-resistant container (full filling 98 ml) was used, and the filling rate of the liquid composition was 3
0%.

Formulation Example 1 (Insecticide for space) As an active ingredient, 0.3% by weight of permethrin and 0.05% by weight of sinepiline were dissolved in 99.65% by weight of kerosene to prepare a stock solution. The obtained stock solution (85.0% by weight) was filled with carbon dioxide gas (15.0% by weight), and the product pressure was 1.7 MPa.
(25 ° C.) high pressure aerosol product was obtained. The dissolved amount of carbon dioxide was 7.7%.

Formulation Example 2 (Fumigant) 0.3% by weight of d-phenothrin and 0.1% by weight of resmethrin as active ingredients, 80.0% by weight of ethanol
And purified water in a mixed solvent of 19.6% by weight to prepare a stock solution. Carbon dioxide gas was added to 85.0% by weight of the obtained stock solution.
5.0% by weight and a product pressure of 1.6 MPa (25
C.). The dissolved amount of carbon dioxide was 8.9%.

Formulation Example 3 (Space Deodorant) As active ingredients, 0.5% by weight of lauryl methacrylate and 0.1% by weight of a tea extract were dissolved in 99.4% by weight of ethanol to prepare a stock solution. 75.0 of undiluted solution obtained
The high-pressure aerosol product having a product pressure of 2.0 MPa (25 ° C.) was obtained by charging 25.0% by weight of carbon dioxide gas to the weight%.
The solubility of carbon dioxide in the liquid composition was 18.4%.

Formulation Example 4 (Horticultural insecticide) 0.2% by weight of allethrin and 0.3% by weight of permethrin as active ingredients are dissolved in a mixed solvent of 20.0% by weight of ethanol and 79.5% by weight of purified water. Then, a stock solution was prepared. 90.0% by weight of the obtained stock solution was filled with 10.0% by weight of carbon dioxide to obtain a high-pressure aerosol product having a product pressure of 1.5 MPa (25 ° C.). The solubility of carbon dioxide was 4.4%.

Formulation Example 5 (Pest repellent) N, N-diethyl-m-toluamide 1 as an active ingredient
0.0% by weight and 1,3-butylene glycol 2.0
By weight, sorbitan monooleate (0.5% by weight as a surfactant) and 4.0% by weight of silicic anhydride as a powder were dissolved and dispersed in 83.5% by weight of ethanol to prepare a stock solution. Carbon dioxide gas was added to 85.0% by weight of the obtained stock solution.
5.0% by weight and a product pressure of 1.3 MPa (25
C.). The solubility of carbon dioxide was 9.6%.

Formulation Example 6 (Hair setting agent) 5.0% by weight of a dialkylaminoethyl (meth) acrylate / alkyl (meth) acrylate copolymer as an active ingredient, 0.2% by weight of a fragrance, and methyl as an oil component 0.5% by weight of polysiloxane, 0.5% by weight of sorbitan monooleate as a surfactant,
It was dissolved in 3.8% by weight to prepare a stock solution. Liquefied petroleum gas (25 ° C.) was used as a propellant in 60.0% by weight of the obtained stock solution.
0.3 MPa) 20.0% by weight, carbon dioxide 2
0.0% by weight and a product pressure of 1.7 MPa (25
C.). The solubility of carbon dioxide was 13.5%.

Formulation Example 7 (Matte spray for hair) 8.0% by weight of vinylpyrrolidone / vinyl acetate copolymer as active ingredient, 1.0% by weight of octamethylcyclotetrasiloxane as surfactant, silica 2 as powder .0
The weight% was dissolved and dispersed in 89.0% by weight of ethanol to prepare a stock solution. 80.0% by weight of the obtained stock solution was filled with 20.0% by weight of carbon dioxide gas, and the product pressure was 1.6 MPa.
(25 ° C.) high pressure aerosol product was obtained. The solubility of carbon dioxide was 14.1%.

Formulation Example 8 (Instant Cooling Agent) 0.5% by weight of 1-menthol as an active ingredient was dissolved in a mixed solvent of 10.0% by weight of isopentane and 89.5% by weight of ethanol to prepare a stock solution. Stock solution 7 obtained
A high pressure aerosol product having a product pressure of 2.4 MPa (25 ° C.) was obtained by filling 0.0 wt% of carbon dioxide gas with 30.0 wt%. The solubility of carbon dioxide was 23.0%.

Formulation Example 9 (Anti-inflammatory analgesic) 1.0% by weight of indomethacin, 0.5% by weight of l-menthol and 3.0 of propylene glycol as active ingredients
% By weight of 30.0% by weight of isopentane and 6% by weight of ethanol.
It was dissolved in a mixed solvent of 5.5% by weight to prepare a stock solution.
15.0% by weight of carbon dioxide gas was added to 85.0% by weight of the obtained stock solution.
To obtain a high-pressure aerosol product having a product pressure of 1.3 MPa (25 ° C.). The solubility of carbon dioxide was 9.4%.

Formulation Example 10 (Disinfectant) A mixed solvent of 0.5% by weight of benzalkonium chloride and 5.0% by weight of glycerin as active ingredients, and 70.0% by weight of ethanol and 24.5% by weight of purified water And a stock solution was prepared. Carbon dioxide gas was added to 85.0% by weight of the obtained stock solution.
5.0% by weight and a product pressure of 1.6 MPa (25
C.). The solubility of carbon dioxide was 9.0%.

[0089]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

Examples 1 to 12 and Comparative Examples 1 to 3 High-pressure aerosol products were prepared by filling 30 ml of a liquid composition shown in Table 1 and carbon dioxide gas as a pressurizing agent in a pressure-resistant stainless steel container having a full injection volume of 80 ml. The following evaluation was performed using the obtained high-pressure aerosol product. In addition, a straight injection hole and an injection button having an injection hole diameter of 0.5 mm were used.

Examples 13 to 24 and Comparative Examples 4 to 6 High-pressure aerosol products were prepared by filling 30 ml of a liquid composition shown in Table 2 and carbon dioxide gas as a pressurizing agent in a pressure-filled stainless steel container having a full injection volume of 98 ml. The following evaluation was performed using the obtained high-pressure aerosol product. In addition, a straight injection hole and an injection button having an injection hole diameter of 0.5 mm were used.

<Evaluation Method> Product Pressure The obtained high-pressure aerosol product was kept in a constant temperature water bath at 25 ° C. for 30 minutes, and then the pressure was measured.

Diffusion The obtained high-pressure aerosol product is placed in a water bath at 25 ° C. for 3 hours.
After holding for 0 minutes, the height of 150c in the windless space
The diffusivity of the spray particles when sprayed horizontally from the position of m was determined based on the following criteria. A: The diffusion time is long and the diffusion range is very wide (the reach of the spray particles is 4 m or more). ：: The diffusion time is long and the diffusion range is wide (the reach of the spray particles is 2 to 4 m). Δ: The diffusion time was rather short, and the diffusion range was rather narrow (the range of the spray particles was 1.5 to 2 m). X: Spray particles fall quickly and do not spread widely in space (the reach of the spray particles is less than 1.5 m).

Average particle size The obtained high-pressure aerosol product was placed in a water bath at 25 ° C. for 30 minutes.
It was measured for three minutes using a particle size distribution analyzer (LDSA-3400A) manufactured by Tohnichi Computer Applications Co., Ltd. with a laser light scattering method at a spray distance of 15 cm, and averaged. The average particle size of the spray particles was determined using the Rosin-Rammler distribution function.

Flame length test The obtained high-pressure aerosol product was placed in a 25 ° C. constant temperature water bath.
Hold for 0 minutes, and place a flame (length 5 cm) at a distance of 15 cm.
cm) so as to pass through the upper third of the flame.

Injection Amount Test A high-pressure aerosol product held in a constant temperature water bath at 25 ° C. for 30 minutes was injected for 5 seconds, and the injection amount per second was measured.

The results are shown in Tables 1 and 2.

[0098]

[Table 1]

[0099]

[Table 2]

As shown in Tables 1 and 2, Examples 1 to 24 were conducted in which the product pressure was 1 to 5 MPa using carbon dioxide gas.
Has a higher diffusibility of spray particles as compared with Comparative Examples 1 to 6 in which the product pressure is less than 1 MPa, and the average particle diameter is 15 to 55 μm.
It can be seen that the user can be prevented from inhaling the spray particles and has excellent diffusivity in space.

In the flame length test, when a flammable liquid was used (Examples 1 to 8, 13 to 20), the flame length was shorter than in the conventional examples (Comparative Examples 1, 2, 4 and 5). Has become. Furthermore, Examples 2, 6 and 13 to 20 are superior in safety to fire because the flame length is shorter in spite of a larger injection amount than Comparative Examples 1, 2 and 4. I understand.

Examples 25 to 29 and Comparative Example 7 A high-pressure aerosol product was prepared by filling 30 ml of a liquid composition shown in Table 3 and carbon dioxide as a pressurizing agent in a pressure-resistant stainless steel container having a full injection volume of 98 ml. After keeping the obtained high-pressure aerosol product in a constant temperature water bath at a predetermined temperature for 30 minutes, the pressure at each temperature was measured. Table 3 shows the results. As a reference example, a result (pressure) at each temperature when only carbon dioxide gas is charged is shown.

[0103]

[Table 3]

In Examples 25 to 29, the product pressure at 25 ° C. was less than 5 MPa. Even when these products were heated to a temperature equal to or higher than Tc of carbon dioxide gas, no rapid pressure increase was observed. On the other hand, in Comparative Example 7, as shown in FIG. 5, the product pressure at 25 ° C. exceeds 5 MPa, and it can be seen that the pressure rapidly increases from 30 ° C.

[0105]

According to the high pressure aerosol product of the present invention, since the product pressure is in the range of 1 to 5 MPa, the amount of the pressurizing agent dissolved in the liquid composition is large, and it becomes very fine particles when injected. Excellent diffusibility. Further, the safety of the jet against fire is high, and the pressure rise due to the temperature rise is small, so that the safety in storage is high. Furthermore, in the case of an aerosol product sprayed with a fine mist using a conventional liquefied gas, the amount of the liquefied gas is required to be 50% by weight or more in the aerosol composition. In the case of (1), only a small amount needs to be used, and the adverse effect on the human body is small.

[Brief description of the drawings]

FIG. 1 is a graph showing a relationship between a mixing ratio of ethanol, kerosene, and carbon dioxide and a product pressure.

FIG. 2 is a graph showing a relationship between a mixture ratio of ethanol, water, and carbon dioxide and a product pressure.

FIG. 3 is a graph showing the relationship between the mixing ratio of ethanol, glycerin and carbon dioxide and the product pressure.

FIG. 4 is a graph showing the relationship between the mixing ratio of ethanol, isobutane and carbon dioxide and the product pressure.

FIG. 5 is a graph showing the relationship between temperature and product pressure of an aerosol product composed of ethanol and carbon dioxide.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B65D 83/36

Claims (7)

[Claims] 1. An aerosol product filled with an aerosol composition comprising a liquid composition having a critical temperature of 90 ° C. or higher and being liquid under pressure and a pressurizing agent having a critical temperature of 50 ° C. or lower, Product pressure at 25 ° C is 1-5MPa
Is a high pressure aerosol product. 2. The aerosol product according to claim 1, wherein the critical temperature of the liquid composition is 170 ° C. or higher. 3. The liquid composition has a critical temperature of 90 to 170 ° C.
The aerosol product according to claim 1, which is: 4. The liquid composition according to claim 3, wherein the liquid composition comprises a hydrocarbon.
The aerosol product as described. 5. The high-pressure aerosol product according to claim 1, wherein the pressurizing agent is carbon dioxide gas or nitrogen suboxide gas. 6. The aerosol product according to claim 1, wherein the content of the liquid composition in the aerosol composition is 50% by weight or more. 7. An aerosol product according to claim 1, wherein the amount of the pressurizing agent in the aerosol composition is 5 to 50% by weight.