JP6144543B2 - Aerosol composition - Google Patents

Description

  The present invention relates to a cleaning aerosol composition. More specifically, the present invention relates to a cleaning aerosol composition that forms a film that, when sprayed, contains an active ingredient on the surface of an injection target and that exhibits a cleaning effect by eluting the active ingredient contained by contact with water. .

  In places where water flows regularly, such as toilets and bathtubs, dirt is likely to adhere, and the attached dirt is often difficult to remove. In particular, the stool or urine stones on the inner surface of the toilet bowl are particularly likely to adhere and are difficult to remove. However, toilet bowls and bathtubs are used on a daily basis, and are always required to be kept beautiful and clean in terms of beauty and hygiene. Therefore, various drugs and methods have been proposed for the purpose of preventing the adhesion of dirt and simplifying cleaning.

  For example, a solid medicine that dissolves by contact with water is placed in or on the water tank of the flush toilet, and the water in the reservoir is given a washing effect, etc. Examples include a water-cleaning cleaner for the purpose of improving the cleaning effect and preventing dirt from adhering to the inner surface of the toilet. However, it has a flush valve type toilet that is frequently used in public toilets that are frequently used and easily contaminated, and a tankless type toilet and tank that do not have a tank to save toilet space and improve the appearance of the toilet However, there is a problem that it cannot be used for toilet bowls that cannot be equipped with flushing cleaners.

  On the other hand, as what is directly installed in the toilet bowl inner surface instead of being installed in the water storage tank, for example, those disclosed in Patent Documents 1 to 4 below can be cited.

  Patent Document 1 discloses an aerosol for preventing filth deposits in a toilet enclosing a filth deposit preventive and a liquefied gas. According to the aerosol for preventing filth deposits on the toilet bowl, a fine foam layer or a thin layer of a hydrophilic and water-soluble substance is formed on the toilet bowl surface by jetting the aerosol onto the toilet bowl face before using the toilet bowl. Even if filth is attached, the water-soluble substance layer is easily removed by water when water is passed, so that the filth thereon can also be easily removed. However, since the fine bubble layer or thin layer formed by jetting is removed by flowing water, there is a problem that the aerosol must be jetted each time it is used.

  In Patent Document 2, a flexible coating film is formed on the surface of a toilet using a coating film forming agent in which a solution containing a synthetic resin, a solvent, and a spray agent is contained in a spray container. A toilet bowl cleaning method is disclosed in which a coating film is peeled off at a predetermined time after use. Further, Patent Document 3 discloses that an aerosol propellant and a cleaning film-forming agent containing a film-forming polymer are sprayed on a dirty object and dried, and then the film formed is removed together with the dirt. A cleaning method is disclosed. However, according to the cleaning methods disclosed in Patent Documents 2 and 3, there is a sanitary problem that the film with the filth must be peeled off and processed.

  Patent Document 4 discloses a liquid composition that contains a polymer, an active ingredient, and a solvent and gels or solidifies after being released onto the inner surface of a toilet bowl or the like. It is disclosed that the gelled product or solidified product is gradually dissolved with water and the active ingredient is gradually released and washed. However, since a water-soluble polymer such as polyvinyl alcohol is used as the polymer, there is a problem that it tends to flow down with water, and a new gelled product or solidified product must be frequently formed.

JP-A-4-169624 JP-A-49-65039 JP 2006-16494 A JP 2005-187511 A

  The present invention has been made in view of the above problems, and is a film that gradually elutes an active ingredient contained by contact with water and exerts a cleaning effect on the active ingredient, and has excellent adhesion to an injection target. An object of the present invention is to provide a cleaning aerosol composition capable of forming a film excellent in the balance between the slow solubility of an active ingredient and the durability of the film on the surface of the injection target.

  The cleaning aerosol composition of the present invention is a cleaning aerosol composition comprising a stock solution containing a hydrophobic resin and an active ingredient, and a liquefied gas, and the content of the hydrophobic resin is 30% by mass. The solubility of ethanol solution dissolved in ethanol with respect to 100 g of water at 20 ° C. is 0.1 g or less, and the hydrophobic resin is contained in the stock solution in an amount of 10 to 40% by mass. The active ingredient contained by contact is eluted to form a film that exhibits its effect.

  It is preferable to contain 20 to 70% by mass of the active ingredient in the stock solution.

  The active ingredient preferably contains a solid or pasty surfactant at 25 ° C.

  The content ratio (mass ratio) between the hydrophobic resin and the active ingredient is preferably 5/95 to 60/40.

  The present invention relates to a cleaning aerosol composition comprising a stock solution containing a hydrophobic resin and an active ingredient, and a liquefied gas, wherein the hydrophobic resin is dissolved in ethanol so that the content is 30% by mass. The solubility of the ethanol solution in 100 g of water at 20 ° C. is 0.1 g or less, and the hydrophobic resin is contained in the stock solution in an amount of 10 to 40% by mass. Because it is a cleaning aerosol composition that forms a film that elutes components and exhibits its effect, it sprays a film that has excellent adhesion to the spray target and a balance between the slow dissolution of the active ingredient and the durability of the film A cleaning aerosol composition formed on the surface of an object can be provided.

  When the active ingredient is contained in the stock solution in an amount of 20 to 70% by mass, elution of the active ingredient can be sustained for a long time.

  When the active ingredient contains a solid or pasty surfactant at 25 ° C., the surfactant is easily retained in the film, and the elution persistence can be improved, and water in contact with the film is foamed. Therefore, the cleaning effect can be improved. Moreover, the active ingredient which does not melt | dissolve in water can also elute from a film | membrane, and can exhibit an effect.

  When the content ratio (mass ratio) of the hydrophobic resin and the active ingredient is 5/95 to 60/40, the balance between the slow solubility of the active ingredient and the durability of the film can be further improved.

  The cleaning aerosol composition of the present invention is a cleaning aerosol composition comprising a stock solution containing a hydrophobic resin and an active ingredient, and a liquefied gas, wherein the hydrophobic resin has a specific solubility in water. It is characterized in that a specific amount of the resin is contained in the stock solution, and when sprayed, a coating film is formed on the surface of the spray target to elute the active ingredient contained by contact with water and exert its effect.

  The hydrophobic resin has a solubility in 100 g of water at 20 ° C. of an ethanol solution dissolved in ethanol so that the content is 30% by mass, preferably 0.1 g or less. When the solubility exceeds 0.1 g, the solubility in water is too high, and the coating tends to peel off due to contact with water. The lower limit of the solubility is not particularly limited, but is preferably 0.001 g or more from the viewpoint that the active ingredient is easily eluted.

  Examples of the hydrophobic resin include cationic acrylic resins (for example, polyquatanim-99, etc.), (alkyl acrylate / diacetone acrylamide) copolymers, (hydroxyethyl acrylate / butyl acrylate / methoxyethyl acrylate) copolymers, Acrylic resin such as (octylacrylamide / acrylates / butylaminoethyl methacrylate) copolymer, (vinyl acetate / crotonic acid) copolymer, (vinyl acetate / crotonic acid / vinyl neodecanoate) copolymer, polyvinyl caprolactam, N-methacryloyloxyethyl N, N-dimethylammonium-α-N-methylcarboxybetaine / methacrylic acid alkyl ester copolymer, etc. are used, and acrylic resin is used because of its excellent adhesion and resistance to peeling. It is preferred, particularly injected in the mist, since it can be uniformly deposited by the ejection target surface without turbulence injection pattern, it is preferable to use a cationic acrylic resin.

  Content of hydrophobic resin is 10-40 mass% in stock solution, and 12-35 mass% is preferable. When the content of the hydrophobic resin in the stock solution is less than 10% by mass, the adhesion to the injection target tends to be weak and it tends to be peeled off. Moreover, when it exceeds 40 mass%, it exists in the tendency which becomes easy to clog in the channel | path of an injection hole or a valve | bulb, and there exists a tendency for the membrane | film | coat formed in the injection target surface to peel off easily.

  The hydrophobic resin can be used only in a solid content (pure content), but can also be used as a hydrophobic resin solution in which the hydrophobic resin is dissolved in a resin solvent. The hydrophobic resin solution is dissolved in the liquefied gas in the aerosol container, and after injection, the liquefied gas volatilizes and forms a film containing the active ingredient on the surface of the injection target.

  The resin solvent is a solvent that dissolves the hydrophobic resin and constitutes a hydrophobic resin solution, and is also referred to as a solvent A in order to distinguish it from the solvent B described later. Examples of the resin solvent include monohydric alcohols such as ethanol and isopropanol.

  The content of the hydrophobic resin is preferably 10 to 95% by mass in the hydrophobic resin solution, and more preferably 15 to 90% by mass. When the content of the hydrophobic resin in the hydrophobic resin solution is less than 10% by mass, it is difficult to form a film on the injection target surface, and the formed film tends to be easily peeled off. Moreover, when it exceeds 95 mass%, it tends to be difficult to handle.

  The content of the resin solvent (solvent A) is preferably 2 to 90% by mass in the hydrophobic resin solution, and more preferably 7 to 85% by mass. When the content of the resin solvent is less than 2% by mass, the amount of the solvent tends to be small and difficult to handle. Moreover, when it exceeds 90 mass%, since monohydric alcohol is amphipathic, there exists a tendency for the membrane | film | coat formed in the injection target to flow down with water easily.

  The content of the resin solvent (solvent A) is preferably 1 to 60% by mass, more preferably 5 to 50% by mass in the stock solution. When the content of the resin solvent is less than 1% by mass, the drying property is lowered, so that it tends to sag on the injection target surface. Moreover, when it exceeds 60 mass%, since monohydric alcohol is amphiphilic, there exists a tendency for the membrane | film | coat formed in the injection target to flow down with water easily. Furthermore, by making the content of the resin solvent 30% by mass or less, it is possible to easily foam the injection, and it is possible to make it difficult to sag on the injection target surface.

  The hydrophobic resin used in the present invention can contain an alkali component in addition to the hydrophobic resin and the resin solvent. By adjusting the neutralization degree of the hydrophobic resin by containing the alkali component, the solubility, viscosity, adhesiveness, and film forming property of the hydrophobic resin in water can be improved.

  Examples of the alkali component include amine compounds such as aminomethylpropanol (AMP), aminomethylpropanediol, aminoethylpropanediol, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine; potassium hydroxide, hydroxide Hydroxides such as sodium; and the like.

  In the case of containing the alkali component, the neutralization degree of the hydrophobic resin is preferably 35% or less, and more preferably 1 to 30%. When the neutralization degree of the hydrophobic resin exceeds 35%, the solubility of the hydrophobic resin in water increases, and the formed film tends to peel off easily upon contact with water. What is necessary is just to adjust suitably according to the kind of hydrophobic resin or an alkali component.

  0.05-8 mass% is preferable in a hydrophobic resin solution, and, as for content in the case of containing an alkali component, 0.1-5 mass% is more preferable. When the content of the alkali component is less than 0.05% by mass, the effect of containing the alkali component tends to be difficult to obtain. Moreover, when it exceeds 8 mass%, the solubility of the film in water tends to be high, and the film tends to be easily peeled by contact with water.

  The content of the hydrophobic resin solution is preferably 11 to 70% by mass in the stock solution, and more preferably 15 to 65% by mass. When the content of the hydrophobic resin solution is less than 11% by mass, the formed film is thin and tends to be easily peeled by contact with water. Moreover, when it exceeds 70 mass%, it tends to become clogged with an aerosol valve or an injection hole.

  The active ingredient is dissolved or dispersed in the stock solution in the aerosol container, and is retained in the film after spraying, and gradually elutes into water when the film comes into contact with water, The effect which an active ingredient has, such as a fragrance effect, is exhibited.

  Examples of the active ingredient include a surfactant, a water repellent ingredient, an antibacterial ingredient, an insect repellent ingredient, a deodorant ingredient, an aromatic ingredient, a pigment, and the like. Among these, surfactants are used because they can be dissolved and foamed by contact with water, exhibiting a high cleaning effect, and effective ingredients that do not dissolve in water can be eluted by simultaneous elution. It is preferable to contain.

  Examples of the surfactant include an anionic surfactant, an amphoteric surfactant, and a nonionic surfactant.

  Examples of the anionic surfactant include alkyl phosphates such as potassium lauryl phosphate and sodium lauryl phosphate, polyoxyethylene alkyl ether phosphates such as sodium POE lauryl ether phosphate; ammonium lauryl sulfate and potassium lauryl sulfate. Alkyl sulfates such as sodium lauryl sulfate, lauryl sulfate triethanolamine, sodium cetyl sulfate; POE sodium lauryl ether sulfate, POE lauryl ether sulfate triethanolamine, POE alkyl ether sodium sulfate, POE alkyl ether sulfate triethanolamine, etc. Polyoxyethylene alkyl ether sulfate; POE lauryl ether potassium acetate, POE lauryl ether sodium acetate, POE tridecyl ether Alkyl ether carboxylates such as potassium acid and POE tridecyl ether acetate; sodium lauryl sulfoacetate, sodium tetradecenesulfonate, dioctyl sodium sulfosuccinate, sodium dialkylsulfosuccinate, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, And sulfonic acid salts such as sodium alkanesulfonate, sodium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate; and the like. Further, N-coconut oil fatty acid acyl-L-glutamic acid triethanolamine, N-coconut oil fatty acid acyl-L-glutamic acid potassium, N-coconut oil fatty acid acyl-L-glutamic acid sodium, N-lauroyl-L-glutamic acid triethanolamine N-acyl such as potassium N-lauroyl-L-glutamate, sodium N-lauroyl-L-glutamate, potassium N-myristoyl-L-glutamate, sodium N-myristoyl-L-glutamate, sodium N-stearoyl-L-glutamate N-acylglycine salts such as glutamic acid salt; N-coconut oil fatty acid acylglycine potassium, N-coconut oil fatty acid acylglycine sodium; N-coconut oil fatty acid acyl-DL-alanine N-acylalanine such as triethanolamine ; It may be used amino acid type surfactants such as acyl alanine salts such as lauroyl methylalanine sodium.

  Examples of the amphoteric surfactant include lauryl dimethylaminoacetic acid betaine (lauryl betaine), stearyl betaine, amidopropyl betaine laurate, lauryl hydroxysulfobetaine, stearyldimethylaminoacetic acid betaine, dodecylaminomethyldimethylsulfopropylbetaine, octadecylamino Betaine types such as alkylbetaines such as methyldimethylsulfopropylbetaine, amide propylbetaine cocoate, coconut oil fatty acid amidepropyldimethylaminoacetic acid betaine (cocamidopropylbetaine), fatty acid amidepropylbetaine such as cocamidopropylhydroxysultain; 2 -Alkyl imidazole types such as alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine; Sodium glutamate, potassium lauroyl glutamate, an amino acid type, such as lauroyl methyl -β- alanine; lauryl dimethylamine N- oxide, amine oxide, such as oleyl dimethyl amine N- oxide; and the like.

  Examples of the nonionic surfactant include coconut oil fatty acid diethanolamide, lauric acid diethanolamide, myristic acid diethanolamide, stearic acid diethanolamide, oleic acid diethanolamide, coconut oil fatty acid monoethanolamide, stearic acid monoethanolamide, Fatty acid alkanolamides such as lauric acid monoisopropanolamide; pentaglyceryl monolaurate, pentaglyceryl monomyristate, pentaglyceryl monooleate, pentaglyceryl monostearate, hexaglyceryl monostearate, decaglyceryl monolaurate, decaglyceryl mono Polyglycerides such as myristate, decaglyceryl monostearate, decaglyceryl monooleate, decaglyceryl distearate Phosphorus fatty acid ester; Polyoxyethylene sorbitan fatty acid ester such as POE sorbitan monostearate and POE sorbitan tristearate; Polyoxyethylene sorbite fatty acid ester such as POE sorbit tetrastearate; Polyoxyethylene glycerin fatty acid such as POE glyceryl monostearate Esters: Polyethylene glycol fatty acid esters such as POE monostearate; Polyoxyethylene alkyl ethers such as POE lauryl ether, POE cetyl ether, POE stearyl ether and POE behenyl ether; POE / POP cetyl ether, POE / POP decyl tetradecyl ether, etc. Polyoxyethylene / polyoxypropylene alkyl ether; POE hydrogenated castor oil; It is below.

  Examples of the water-repellent component include methylpolysiloxane, decamethyltetrasiloxane, octamethylcyclotetrasiloxane, methylphenylpolysiloxane, silicone oil such as silicone emulsion, normal pentane, isopentane, kerosene, liquid paraffin, squalene, squalane, Hydrocarbons such as isoparaffin, isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, myristyl myristate, diethoxyethyl succinate, diisostearyl malate, liquid fatty acids such as oleic acid, Liquid higher alcohols such as oleyl alcohol, camellia oil, corn oil, mink oil, olive oil, rapeseed oil, sesame oil, castor oil, safflower oil, ho Ba oil, coconut oil, fats, such as balm oil, fluorocarbon resins, and silicone resins.

  Examples of the antibacterial component include benzalkonium chloride, benzethonium chloride, phenoxyethanol, chlorhexidine chloride, and parachlormetacresol.

  Examples of the insect repellent component include N, N-diethyl-m-toluamide, herbal extract, caprylic acid diethylamide and the like.

  Examples of the deodorant component include green tea extract, lauric acid methacrylate, methyl benzoate, methyl phenylacetate, geranyl crotolate, acetophenone myristate, benzyl acetate, and benzyl propionate.

  Examples of the fragrance component include synthetic fragrances and natural fragrances.

  Examples of the dye include amaranth (red No. 2), erythrosin (red No. 3), new coccin (red No. 102), phloxine (red No. 104), resorcin brown (brown no. 201), orange I (dain color) 402), Sunset Yellow (Yellow 5), Uranine (Yellow 202), Methanil Yellow (Yellow 406), Fast Green (Green 3), Alizarin Cyanine Green F (Green 201), Brilliant Blue FCF (Blue No. 1), Indigo Carmine (Blue No. 2), Patent Blue NA (Blue No. 202), Alizurol Purple (Purple No. 401), Naphthol Blue Black (Black No. 401), Rhodamine B Steer Rate (Red No. 215), Sudan III (Red No. 225), Medicinal Scarlet (Red) 01), dibromofluorescein (orange 201), orange SS (orange 403), fluorescein (yellow 201), quinoline yellow SS (yellow 204), quinizarin green SS (green 202), Stan Blue B (Blue No. 403), oil-based pigments such as Alizurin Purple SS (purple No. 201).

  The film formed by the cleaning aerosol composition of the present invention is mainly formed of a predetermined hydrophobic resin, and has excellent adhesion and sustainability to the injection target. It is preferable that it is excellent in sustainability. Although the slow solubility of the active ingredient can be improved by using a hydrophobic resin, it can be adjusted by the nature and content of the active ingredient.

  The active ingredient to be contained can be appropriately adjusted according to the purpose of use and the environment of use of the film to be formed. For example, when it is formed on the inner surface of a toilet, etc., it is possible to use a solid or pasty active ingredient at 25 ° C. because the amount of elution due to contact with water is an appropriate amount, and it can be used repeatedly while being retained appropriately in the film. preferable. Moreover, it is preferable to use a water-soluble active ingredient from the viewpoint that when the film comes into contact with water, it is easy to exert an effect together with a physical action caused by the flow of water (including hot water).

  The content of the active ingredient is preferably 20 to 70% by mass in the stock solution, and more preferably 25 to 65% by mass. When content of an active ingredient is less than 20 mass%, there exists a tendency for the effect by an active ingredient to become difficult to be exhibited. Moreover, when it exceeds 70 mass%, there exists a tendency for a membrane | film | coat to become difficult to be formed.

  Here, the content ratio (mass ratio) between the hydrophobic resin and the active ingredient in the stock solution is 5/95 to 60/40 (hydrophobic resin / active ingredient). It is preferable from the point that the balance with sustainability can be maintained, and more preferably 10/90 to 55/45. When the content ratio exceeds 60/40, the content of the hydrophobic resin is large, the durability of the coating formed by spraying is too high, and the elution of the active ingredient is finished despite the end of elution of the active ingredient. There is a tendency that the (resin component) is not removed and the film needs to be removed by other means. Moreover, when content ratio is less than 5/95, there is little content of hydrophobic resin, and there exists a tendency for the membrane | film | coat formed to peel easily by contact with water.

  The stock solution may contain solvent B, powder, hydrophilic resin, viscosity modifier and the like in addition to the hydrophobic resin and the active ingredient. Here, the solvent B is a solvent component contained separately from the resin solvent.

  In addition to the purpose of dissolving the hydrophobic resin and the active ingredient, the solvent B can be contained for the purpose of adjusting the spread of the projectile, the formation time of the film, the drying time, and the like.

  Examples of the solvent B include polyhydric alcohols such as the monohydric alcohol, water, ethylene glycol, propylene glycol, hexylene glycol, 1,3-butylene glycol, and glycerin.

  The content in the case of containing the solvent B is preferably 1 to 60% by mass, more preferably 5 to 50% by mass in the stock solution. When the content of the solvent B is less than 1% by mass, the effect of containing the solvent B tends to be difficult to obtain. Moreover, when it exceeds 60 mass%, there exists a tendency for the drying property of a film | membrane to worsen.

  10-100 mass% is preferable, as for content of the monohydric alcohol in all the solvents (solvent A + solvent B), 20-90 mass% is more preferable, and 30-80 mass% content is more preferable. When the content of the monohydric alcohol is less than 10% by mass, there is a tendency that the hydrophobic resin cannot be uniformly dissolved in the stock solution. Moreover, it is preferable that it is 100 mass% from the point that the drying property of the film | membrane in the injection object surface is excellent.

  The powder is used for the purpose of carrying an active ingredient and eluting the active ingredient gradually.

  Examples of the powder include talc, kaolin, mica, magnesium carbonate, calcium carbonate, zinc silicate, magnesium silicate, aluminum silicate, calcium silicate, silica, ceramic powder, nylon powder, and boron nitride.

  The content of the powder is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass in the stock solution. When the content of the powder is less than 0.01% by mass, the effect of containing the powder tends to be hardly exhibited. Moreover, when it exceeds 5 mass%, it tends to become clogged with an aerosol valve or an injection hole.

  The hydrophilic resin is used for the purpose of adjusting adhesiveness and film-forming property, adjusting the elution amount of active ingredients, and the like.

  Examples of the hydrophilic resin include anionic resins such as acrylic resin alkanolamine liquid; vinylpyrrolidone / N, N-dimethylaminoethylmethacrylic acid copolymer diethyl sulfate, (methylvinylvinylimidazolium chloride / vinylpyrrolidone) copolymer, methyl A cationic resin such as vinyl imidazolium / vinyl pyrrolidone copolymer methyl sulfate; an acrylic amphoteric resin such as (octylamide acrylate / hydroxypropyl acrylate / butylaminoethyl methacrylate) copolymer; polyvinyl pyrrolidone, (vinyl acetate / Vinyl pyrrolidone) copolymer, (N-vinyl pyrrolidone / methacrylamide / N-vinyl imidazole) copolymer, (diacetone acrylamide / C4-C18 aliphatic alcohol and acrylic acid or meta Esters with rillic acid / at least one acrylic acid, methacrylic acid, itaconic acid / at least one C1-C3 acrylic acid ester, methacrylic acid ester) copolymer, (dimethylacrylamide / hydroxyethyl acrylate / acrylic) Nonionic resins such as (methoxyethyl acrylate) copolymer and (hydroxyethyl acrylate / methoxyethyl acrylate) copolymer; Among these, an ionic resin is preferable from the viewpoint of excellent foamability when water is passed.

  When the hydrophilic resin is contained, the content in the stock solution is preferably 0.1 to 10% by mass, and more preferably 0.5 to 8% by mass. When the content of the hydrophilic resin is less than 0.1% by mass, the effect of containing the hydrophilic resin tends to be difficult to obtain. Moreover, when it exceeds 10 mass%, there exists a tendency for the film formed in the injection target surface to peel easily because it contacts water.

  The viscosity modifier is used for the purpose of adjusting the stickiness of the spray.

  Examples of the viscosity modifier include cellulose polysaccharides such as hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, sodium carboxymethylcellulose; carrageenan, xanthan gum, gum arabic, tragacanth gum, cationized guar gum, guar gum, gellan gum, locust bean gum Gums such as gelatin, dextran, sodium carboxymethyldextran, dextrin, pectin, starch, corn starch, wheat starch, sodium alginate, modified potato starch, hyaluronic acid, sodium hyaluronate, polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl polymer, etc. Is mentioned.

  When the viscosity modifier is contained, the content in the stock solution is preferably 0.01 to 5% by mass, and more preferably 0.05 to 3% by mass. When content of a viscosity modifier is less than 0.01 mass%, there exists a tendency for the effect containing a viscosity modifier to become difficult to be acquired. Moreover, when it exceeds 5 mass%, there exists a tendency for a viscosity to become high too much and to become difficult to handle.

  The stock solution can be prepared by mixing a hydrophobic resin, an active ingredient, and other ingredients as required.

  The content of the stock solution is preferably 30 to 95% by mass, and preferably 40 to 90% by mass in the aerosol composition. When it is less than 30% by mass, the film is thin and tends to peel off due to contact with water. Moreover, when more than 95 mass%, there exists a tendency for the drying property of a projectile to fall and to fall easily when it injects to a target.

  The liquefied gas is a liquid in the aerosol container and acts as a solvent for dissolving the hydrophobic resin, and when sprayed to the outside, it vaporizes to precipitate the hydrophobic resin, and the deposited hydrophobic resin forms a film. .

  Examples of the liquefied gas include propane, normal butane, isobutane, and mixtures thereof such as liquefied petroleum gas, dimethyl ether, hydrofluoroolefin, and mixtures thereof.

  As for content of the said liquefied gas, 5-70 mass% is preferable in an aerosol composition, and 10-60 mass% is more preferable. When it is less than 5% by mass, it tends to be difficult to eject. Moreover, when more than 70 mass%, when it injects, it tends to scatter and tends to become difficult to adhere to a target object.

  In addition to the liquefied gas, a compressed gas can be contained for the purpose of adjusting the pressure in the pressure vessel, adjusting the injection state, and the like.

  Examples of the compressed gas may include carbon dioxide gas, nitrous oxide gas, nitrogen gas, compressed air, oxygen gas, and the like.

  The cleaning aerosol composition of the present invention can be prepared by filling a pressure-resistant container with a stock solution and a liquefied gas, and fixing an aerosol valve to the opening of the pressure-resistant container. The liquefied gas may be filled with an under cup before the aerosol valve is fixed to the container body, or may be charged from the stem after the aerosol valve is fixed. Moreover, in order to adjust the pressure in a pressure vessel, you may further fill with compressed gas.

  When sprayed, the cleaning aerosol composition of the present invention adheres to the spray target and forms a film containing the active ingredient. The said film is a film which elutes the active ingredient contained by contact with water and exhibits the effect of the active ingredient, and is particularly excellent in adhesion and sustainability to the injection target. Therefore, the aerosol composition of the present invention is used as a cleaning aerosol composition. As the injection target, those in which water is regularly used are suitable, and examples include toilet bowls, washstands, bathrooms, sinks, etc. Among them, the effects of the present invention can be more exhibited by using them in toilet bowls. Further, the present invention can be applied to a glass window, a side wall, a roof, an automobile, and the like that are installed outdoors exposed to rainwater.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to these.

Examples 1-21 and Comparative Examples 1-9
A tin-made pressure-resistant container was filled with 100 g (50% by mass) of each stock solution shown in Tables 1 to 5 and 100 g (50% by mass) of dimethyl ether as a liquefied gas, and an aerosol valve was fixed to produce a test aerosol product. In addition, all the ethanol in each undiluted | stock solution is contained as a solvent for resins (solvent A).

＊１：プラスサイズＬ−５１４（商品名）、互応化学工業株式会社製
（樹脂：３０質量％、エタノール：７０質量％、３０質量％エタノール溶液の２０℃の水への溶解度：０．０１ｇ未満）
＊２：プラスサイズＬ−５３（商品名）、互応化学工業株式会社製
（樹脂：５０質量％、エタノール：５０質量％、３０質量％エタノール溶液の２０℃の水への溶解度：０．０１ｇ未満）
＊３：ＡＭＰＨＯＭＥＲ ２８−４９１０（商品名）、アクゾノーベル株式会社製
（樹脂：１００質量％、３０質量％エタノール溶液の２０℃の水への溶解度：０．０１ｇ未満）
＊４：ＲＥＳＹＮ２８−２９３０（商品名）、アクゾノーベル株式会社製
（樹脂：１００質量％、３０質量％エタノール溶液の２０℃の水への溶解度：０．０１ｇ未満）
＊５：ルビスコールＰｌｕｓ（商品名）、ＢＡＳＦジャパン株式会社製
（樹脂：４０質量％、エタノール：６０質量％、３０質量％エタノール溶液の２０℃の水への溶解度：０．０１ｇ未満）
＊６：ユカフォーマー２０２（商品名）、三菱樹脂化学株式会社製
（樹脂：３０質量％、エタノール：７０質量％、３０質量％エタノール溶液の２０℃の水への溶解度：０．０１ｇ未満）
＊７：プラスサイズＬ−２７００（商品名）、互応化学工業株式会社製
（樹脂：７０質量％、エタノール：３０質量％、３０質量％エタノール溶液の２０℃の水への溶解度：１０ｇ以上）
＊８：プラスサイズＬ−８８５０（商品名）、互応化学工業株式会社製
（樹脂：４０質量％、エタノール：６０質量％、３０質量％エタノール溶液の２０℃の水への溶解度：１０ｇ以上）
＊９：ＨＰＣ−Ｌ（商品名）、日本曹達株式会社製（粘度調整剤）
＊１０：アミゾールＣＤＥ（商品名）、川研ファインケミカル株式会社製（ノニオン性界面活性剤、２５℃で液体）

* 1: Plus size L-514 (trade name), manufactured by Kyoyo Chemical Co., Ltd. (resin: 30% by mass, ethanol: 70% by mass, 30% by mass solubility in ethanol at 20 ° C .: less than 0.01 g) )
* 2: Plus size L-53 (trade name), manufactured by Kyoyo Chemical Industry Co., Ltd. (resin: 50% by mass, ethanol: 50% by mass, solubility in ethanol solution at 20 ° C. in water of less than 0.01 g) )
* 3: AMPHOMER 28-4910 (trade name), manufactured by Akzo Nobel Co., Ltd. (resin: 100% by weight, 30% by weight ethanol solution in 20 ° C. water: less than 0.01 g)
* 4: RESYN 28-2930 (trade name), manufactured by Akzo Nobel Co., Ltd. (resin: 100% by mass, solubility of 30% by mass ethanol solution in water at 20 ° C .: less than 0.01 g)
* 5: Rubiscol Plus (trade name), manufactured by BASF Japan Ltd. (resin: 40% by mass, ethanol: 60% by mass, 30% ethanol solution in 20 ° C. water: less than 0.01 g)
* 6: Yuka Former 202 (trade name), manufactured by Mitsubishi Plastics Chemical Co., Ltd. (resin: 30% by mass, ethanol: 70% by mass, 30% ethanol solubility in water at 20 ° C .: less than 0.01 g)
* 7: Plus size L-2700 (trade name), manufactured by Kyoyo Chemical Industry Co., Ltd. (resin: 70% by mass, ethanol: 30% by mass, 30% ethanol solubility in water at 20 ° C .: 10 g or more)
* 8: Plus size L-8850 (trade name), manufactured by Kyoyo Chemical Industry Co., Ltd. (resin: 40% by mass, ethanol: 60% by mass, 30% ethanol solubility in water at 20 ° C .: 10 g or more)
* 9: HPC-L (trade name), manufactured by Nippon Soda Co., Ltd. (viscosity modifier)
* 10: Amizole CDE (trade name), manufactured by Kawaken Fine Chemical Co., Ltd. (nonionic surfactant, liquid at 25 ° C)

＊１１：アミノソープ ＡＲ−１２（商品名）、味の素ヘルシーサプライ株式会社製（２５℃で液体）
＊１２：ＮＩＫＫＯＬ ＢＬ−２１（商品名）、日光ケミカルズ株式会社製（２５℃で固形）
＊１３：ＮＩＫＫＯＬ ＰＢＣ−３４（商品名）、日光ケミカルズ株式会社製（２５℃で固形）
＊１４：ＮＩＫＫＯＬ ＨＣＯ−４０（商品名）、日光ケミカルズ株式会社製（２５℃で固形）

* 11: Amino soap AR-12 (trade name), manufactured by Ajinomoto Healthy Supply Co., Ltd. (liquid at 25 ° C)
* 12: NIKKOL BL-21 (trade name), manufactured by Nikko Chemicals Co., Ltd. (solid at 25 ° C)
* 13: NIKKOL PBC-34 (trade name), manufactured by Nikko Chemicals Co., Ltd. (solid at 25 ° C)
* 14: NIKKOL HCO-40 (trade name), manufactured by Nikko Chemicals Co., Ltd. (solid at 25 ° C)

Example 22
A test aerosol product was produced in the same manner as in Example 1 except that 80 g (40 mass%) of the stock solution and 120 g (60 mass%) of dimethyl ether were filled.

Example 23
An aerosol product for test was produced in the same manner as in Example 1 except that 140 g (70% by mass) of the stock solution and 60 g (30% by mass) of dimethyl ether were filled.

Examples 24-28
100 g (50% by mass) of each stock solution shown in Table 6 and 100 g (50% by mass) of liquefied petroleum gas (* 15) as a liquefied gas are filled in an aluminum pressure-resistant container, and an aerosol valve is fixed to test aerosol products. Manufactured. In addition, all the ethanol in each undiluted | stock solution is contained as a solvent for resins (solvent A).
* 15: A mixture of norvalbane, isobutane and propane (0.4 MPa, at 25 ° C.)

  The following evaluation was performed about each obtained aerosol product for a test. The evaluation results are shown in Tables 7-13.

1. Spraying state and adhesion The spraying state and adhesion to the coating plate were observed for 1 second toward a metallic coating plate located 10 cm away from the spraying hole, and evaluated according to the following criteria.
○ 1: Sprayed in a mist and uniformly adhered.
(Circle) 2: It injected in foamy form and adhered uniformly, without scattering.
Δ: Sprayed in the form of a mist, but the spray pattern was disturbed and a part of the spray was unevenly adhered.
X: Injected in a rod shape, dropped from the injection target surface and adhered unevenly.

2. Film persistence and slow dissolution The coating plate used for the evaluation of the sprayed state and adhesion (those with the sprayed material attached) was allowed to stand in a thermostatic chamber at 25 ° C. for 1 hour to form a film. The coating plate on which the film is formed is inclined at 45 degrees, and the process of applying 1 liter of tap water for 5 seconds is set as one time. Slow solubility was observed and evaluated according to the following criteria. The slow solubility of the active ingredient was confirmed by the presence of the eluting dye.
A: The presence of the film and the elution of the dye were confirmed from the 11th to the 20th time.
○: The presence of the film could be confirmed until the 11th to 20th times, and the elution of the dye could be confirmed until the 5th to 10th times.
(Triangle | delta): Presence of a film | membrane and the elution of a pigment | dye were confirmed until the 5th-10th time.
X1: By the 4th time, the presence of the film and the elution of the dye could not be confirmed.
× 2: The presence of the film was confirmed after the 21st time, and the film was not peeled off even when rubbed by hand while applying water. The elution of the dye was confirmed up to the fifth to tenth times.
× 3: The presence of the film could be confirmed after the 21st time, and the film was not peeled off even when rubbed by hand while applying water. Dye elution could not be confirmed by the fourth time.

Formulation Example 1 Toilet cleaner 28g (70% by mass) of the following stock solution is filled in an aluminum aerosol container (full amount 100 ml), and 12 g (30% by mass) of liquefied petroleum gas (* 15) is filled as a liquefied gas. An aerosol product for testing was manufactured with an aerosol valve attached. In addition, all the ethanol in each undiluted | stock solution is contained as a solvent for resins (solvent A).

<Undiluted solution>
Polyquaternium-99 (* 1) 35.0
Ethanol 12.6
Coconut oil fatty acid diethanolamide (* 10) 40.0
POE (40) hydrogenated castor oil (* 14) 0.5
Lauryl betaine (* 16) 5.0
Purified water 6.8
Dye (Blue No. 1) 1% ethanol solution 0.1
Total (parts by mass) 100.0
* 16: AM-301 (trade name), manufactured by Nikko Chemicals Co., Ltd.

Formulation example 2 sink cleaner 32g (80% by mass) of the following stock solution is filled in an aluminum aerosol container (full amount 100 ml), and 8 g (20% by mass) of liquefied petroleum gas (* 15) is filled as a liquefied gas.
An aerosol product for testing was manufactured with an aerosol valve attached. In addition, all the ethanol in each undiluted | stock solution is contained as a solvent for resins (solvent A).

<Undiluted solution>
(Alkyl acrylate / diacetone acrylamide) copolymer (* 2) 20.0
Ethanol 15.0
Coconut oil fatty acid diethanolamide (* 10) 40.0
POE (40) hydrogenated castor oil (* 14) 5.0
Purified water 9.9
Dimethylpolysiloxane (* 17) 10.0
Dye (Blue No. 1) 1% ethanol solution 0.1
Total (parts by mass) 100.0
* 17: SH-200 1cs (trade name), manufactured by Toray Dow Corning Co., Ltd.

Formulation Example 3 Glass Cleaner 9 g (30% by mass) of the following stock solution is filled in an aluminum aerosol container (full volume 100 ml), 21 g (70% by mass) of dimethyl ether is filled as a liquefied gas, and an aerosol valve is fixed. A test aerosol product was produced. In addition, all the ethanol in each undiluted | stock solution is contained as a solvent for resins (solvent A).

<Undiluted solution>
Polyquaternium-99 (* 1) 35.0
Ethanol 22.9
Coconut oil fatty acid diethanolamide (* 10) 40.0
POE (40) hydrogenated castor oil (* 14) 2.0
Dye (Blue No. 1) 1% ethanol solution 0.1
Total (parts by mass) 100.0

  About each obtained aerosol product for a test of prescription examples 1-3, evaluation was performed like an example and a comparative example. The evaluation results are shown in Table 14.

Claims (3)

A stock solution containing a hydrophobic resin and an active ingredient, and a cleaning aerosol composition comprising a liquefied gas,
The hydrophobic resin has a solubility in 100 g of water at 20 ° C. of an ethanol solution in which the content of the hydrophobic resin is 30% by mass is 0.1 g or less,
The hydrophobic resin is
Cationic acrylic resin, (alkyl acrylate / diacetone acrylamide) copolymer, (hydroxyethyl acrylate / butyl acrylate / methoxyethyl acrylate) copolymer, (octyl acrylamide / acrylates / butyl aminoethyl methacrylate) copolymer, (vinyl acetate / Crotonic acid) copolymer, (vinyl acetate / crotonic acid / vinyl neodecanoate) copolymer, polyvinylcaprolactam, N-methacryloyloxyethyl N, N-dimethylammonium-α-N-methylcarboxybetaine / methacrylic acid alkyl ester copolymer Including at least one selected from the group;
10 to 40% by mass contained in the stock solution,
The active ingredient is
20 to 70% by mass contained in the stock solution,
Including at least one selected from the group consisting of a surfactant, a water repellent component, an antibacterial component, an insect repellent component, a deodorant component, an aromatic component, and a pigment,
The surfactant is contained in the stock solution by 20% by mass or more,
An aerosol composition for cleaning that forms a film that, when sprayed, exhibits an effect on the surface of the spray target by eluting the active ingredient contained by contact with water. The cleaning aerosol composition according to claim 1, wherein the active ingredient contains a solid or paste surfactant at 25 ° C. The cleaning aerosol composition according to claim 1 or 2, wherein the content ratio (mass ratio) of the hydrophobic resin and the active ingredient is 5/95 to 60/40.