JP5841722B2 - 2-component foamable aerosol products - Google Patents

Description

  The present invention relates to a two-component foamable aerosol product characterized in that the foam specific gravity of the first content and / or the second content decreases with time from immediately after discharge.

  Conventionally, a two-component hair dye comprising a first agent containing an oxidative dye and a second agent containing an oxidizer has been widely known. Such a two-component hair dye can obtain a higher hair dyeing effect by one hair dyeing operation than a one-component hair dye. On the other hand, it is necessary for the two-component hair dye to prepare an oxidative hair dye by mixing the first agent and the second agent.

  In a two-component hair dye, a two-component foamable aerosol product that can simultaneously discharge the first agent and the second agent with foam in order to simplify the preparation operation of mixing the first agent and the second agent. Has been proposed. This aerosol product is not only excellent in operability because it can easily discharge and prepare hair dyes, but also has no contact with the outside air, so there is no deterioration of the hair dye, and it can be used in multiple times. Therefore, it is easy to apply to hair as compared with liquid or cream hair dyes because it is discharged as foam. However, when a two-component hair dye is used as a foamable aerosol product, the state of the foam becomes unstable depending on the type and amount of the oxidative dye contained, and when the first and second agents are mixed and It may be easy to defoam during the reaction.

  Therefore, an aerosol product of a two-component hair dye that has improved the state of foam of the discharged substance has been proposed. For example, Patent Document 1 discloses a two-component foam oxidation hair dye composition in which a first container and a second container are filled in separate containers and mixed and used immediately before use, and is included in this composition. In order to improve the state of foam that changes depending on the type and blending amount of the oxidized dye, a surfactant having a specific hydrophilic-lipophilic balance value is contained in the first agent of the oxidized hair dye containing the oxidized dye. Disclosed is a two-component foam oxidation hair dye composition.

JP-A-11-139945

  However, Patent Document 1 discloses that the first oxidation dye containing an oxidation dye contains a surfactant having a specific hydrophilic-lipophilic balance value in the first oxidation hair dye containing an oxidation dye. Although there is a description of improving the foamyness of the discharged product by discharging the agent alone, the foam in the step of mixing the oxidation dye first agent containing the oxidation dye and the oxidation dye second agent containing the oxidation agent The problem of defoaming and defoaming and liquefaction when applied to hair after mixing are not considered. Moreover, when the 1st agent and the 2nd agent are stable foams, since a foam contains gas inside, even if foams are mixed, liquids are hard to contact, and an active ingredient does not react easily.

  The present invention is an invention made in view of such a problem, and the process of mixing the discharged contents of the first contents and the second contents is easy, and bubbles are applied when the mixture is applied to the object. The purpose of the present invention is to provide a two-component foamable aerosol product that is easy to spread, can visually check the applied portion, and is difficult to spill.

  The two-component foamable aerosol product of the present invention has a first container filled with a first content and a second container filled with a second content, and the first content and the second content are mixed. The two-component foamable aerosol product used in the above-described manner is a two-component foamable aerosol product in which the foam specific gravity of the first content and / or the second content decreases with time immediately after discharge.

  It is preferable that the rate of change of the bubble specific gravity is −0.1 to −0.0005 (g / ml · min).

  Preferably, the first content and the second content contain a propellant, and the vapor pressure of each propellant is different.

  In the propellant, one propellant contains a low pressure propellant having a vapor pressure of 0.01 to 0.2 MPa at 20 ° C., and the other propellant has a vapor pressure of 0.3 to 0 at 20 ° C. It is preferable to contain a high-pressure propellant that is 0.7 MPa.

  It is preferable that the first content or the second content containing the low-pressure propellant further contains a pressurizing agent.

  Further, the two-component oxidative hair dye, wherein the first contents and the second contents are composed of a first agent for hair dye containing an oxidative dye and a second agent for hair dye containing an oxidant. It is preferable that

  According to the two-component foamable aerosol product of the present invention, the foam specific gravity of the first content and / or the second content decreases with time from immediately after discharge, so that the foam is not completely foamed immediately after discharge. Liquid or partially foamed state, easy to mix with the other discharge, and since foaming continues after mixing, even if the reacted active ingredient has a defoaming effect, it is easy to spread on the coated surface, Since the state of the foam can be maintained, it is possible to provide a two-part foamable aerosol product in which the applied part can be visually confirmed and the liquid does not easily drip.

It is a graph which shows a time-dependent change of the foam specific gravity of some 1st agent aerosol products in this invention. It is a graph which shows a time-dependent change of the foam specific gravity of some 2nd agent aerosol products in this invention. It is a graph which shows a time-dependent change of the bubble specific gravity of the discharge material of the one Example and comparative example in this invention.

  The two-component foamable aerosol product of the present invention has a first container filled with a first content and a second container filled with a second content, and the first content and the second content are mixed. The foam specific gravity of the first content and / or the second content decreases with time from immediately after discharge.

  In the present invention, “the foam specific gravity decreases with time from immediately after discharge” means that the discharged material immediately after discharge is in a state where most of the foam, such as cream, gel or liquid, is not foamed or partly foamed. This means that the discharged material foams over time, the foam increases, and the foam specific gravity decreases.

  Also, in the present invention, it is preferable that the first content and the second content have different foaming properties. When the contents have different foaming properties, the first content and the second content are discharged independently. When the foaming state immediately after discharge is different, when the foaming behavior is different over time after discharge, the foaming state immediately after discharge and the foaming behavior after discharge are different.

  When the foamed state immediately after discharge is different, almost all of the discharged material is foamed immediately after discharge (foaming completion type), and part of the discharged material is foamed immediately after discharge (partially foamed type) There is a state (non-foamed type) in which the discharged material is hardly foamed immediately after the discharge.

  When the foaming behavior is different after discharge, the foaming is completed immediately after the ejection, and when the foam is broken and then liquefied, the foam is almost not foamed or partly foamed immediately after the ejection. It is in a state of being foamed and then foaming to increase foam. In the former, the bubble specific gravity increases with time, and the latter decreases with time.

  In the present invention, at least one of the first content and the second content is easy to mix the two discharges, easy to apply when applying the mixture to the object, and easy to confirm the place where the mixture is applied, The ejected material immediately after ejection is in a liquid state or in a partially foamed state, and the ejected material is foamed over time to increase the foam and the foam specific gravity is decreased.

  As a method of reducing the foam specific gravity of the discharged material over time immediately after discharge, for example, an aqueous stock solution containing a surfactant or an active ingredient and a propellant are used, and the propellant has a vapor pressure of 0. The case where the low pressure propellant which is 01-0.2 MPa is used is mentioned.

  Examples of the low-pressure propellant include normal butane (vapor pressure: 0.1 MPa), isobutane (vapor pressure: 0.2 MPa), normal pentane (vapor pressure: 0.05 MPa), and isopentane (vapor pressure: 0.07 MPa). Hydrofluoroethers such as aliphatic hydrocarbons having 4 to 5 carbon atoms such as methyl perfluorobutyl ether (vapor pressure: 0.02 MPa), ethyl perfluorobutyl ether (vapor pressure: 0.01 MPa), etc. These are used alone or mixed to adjust the vapor pressure range. In particular, it is preferable to use one having a vapor pressure of 0.05 to 0.15 MPa from the point of slow foaming after mixing two discharged products.

  When the vapor pressure of the low-pressure propellant is lower than 0.01 MPa, the discharged product tends not to foam even when mixed, and when it is higher than 0.2 MPa, almost all of the foam is foamed at the time of discharge (foaming) The foam specific gravity tends not to decrease with time. Further, in order to reduce the influence on the foaming property due to the temperature during use, and further to adjust the discharge amount with other contents, a compressed gas such as nitrogen gas, carbon dioxide gas, compressed air or the like is used. It is preferable to adjust to the same vapor pressure as 3 to 0.7 MPa, and other contents.

  The low-pressure propellant is preferably blended in an amount of 3 to 40% by mass, more preferably 5 to 30% by mass. When the blending amount of the low-pressure propellant is less than 3% by mass, the foamability is insufficient, the foam after discharge is hardly increased, and the foam specific gravity tends not to decrease with time. On the other hand, when it is more than 40% by mass, it tends to scatter during ejection, and the foam disappears after application.

  As the discharged product whose bubble specific gravity decreases with time from immediately after discharge, those having a change rate of bubble specific gravity of −0.1 to −0.0005 (g / ml · min) are preferable. The foam specific gravity is determined by immersing an aerosol product filled with the contents in a constant temperature water bath at 25 ° C. for 1 hour, adjusting the temperature of the contents to 25 ° C., and discharging it to a glass cup having a predetermined volume. The mass when a glass cup is filled with bubbles for a predetermined time, for example, 2 minutes, is measured, and the foam specific gravity that changes in 1 minute is calculated.

  When the rate of change in the specific gravity of the bubbles is greater than −0.1 (g / ml · min), the increase in bubbles is too fast and it becomes difficult to apply. On the other hand, when it is smaller than −0.0005 (g / ml · min), there is a tendency that the increase in bubbles is small and the effect of the present invention is hardly obtained.

  On the other hand, as the other contents, the above-mentioned foam specific gravity may decrease with time from immediately after discharge, but almost all of the discharge foams at the time of discharge (foaming completion type), and after discharge, When the liquid is broken and liquefied, or when it is discharged, it is in a non-foaming state such as cream, gel, or liquid (non-foaming type), and the state hardly changes over time. can give.

  The former foam-completed contents include, for example, an aqueous stock solution containing a surfactant and an active ingredient and a propellant, and the propellant has a vapor pressure of 0.3 to 0.7 MPa at 20 ° C. The case where a propellant is used is mentioned.

  Examples of the high-pressure propellant include fats having 3 to 4 carbon atoms such as propane (vapor pressure: 0.85 MPa), isobutane (vapor pressure: 0.2 MPa), and normal butane (vapor pressure: 0.1 MPa). Group hydrocarbons, ethers such as dimethyl ether (vapor pressure: 0.41 MPa), hydrofluoroolefins such as 1,3,3,3-tetrafluoroprop-1-ene (vapor pressure: 0.4 MPa), and the like. These are used alone or mixed to adjust the vapor pressure range. In particular, it is preferable to use one having a vapor pressure of 0.35 to 0.6 MPa from the viewpoint that almost all the foam can be discharged.

  The high-pressure propellant is preferably blended in an amount of 3 to 40% by mass, more preferably 5 to 30% by mass. When the blending amount of the high-pressure propellant is less than 3% by mass, the foaming property is insufficient, and there is a tendency that almost all of the foamed state is hardly foamed at the time of discharge. On the other hand, when it is more than 40% by mass, it tends to scatter during ejection, and the foam disappears after application.

  When this content is discharged, almost all of the discharged material becomes foamed foam at the time of discharging, and breaks with time to increase the specific gravity of the foam. By doing so, the active ingredients contained in the contents are easily brought into contact with each other due to the increase of bubbles due to the discharged material, and the effects of the active ingredients are easily obtained. Furthermore, since the foamed state continues for a certain period of time even during application, it is easy to spread, and the applied portion can be visually confirmed. Further, since the liquid is not liquefied during application, dripping can be suppressed.

  Examples of the latter non-foamed contents include contents composed of a stock solution containing an active ingredient and a pressurizing agent that pressurizes the stock solution.

  The stock solution is not particularly limited, for example, cream, gel or liquid. Examples of the pressurizing agent include compressed gases such as carbon dioxide gas, nitrogen gas, compressed air, oxygen gas, and nitrous oxide gas.

  In addition, as a preferable filling form into the aerosol container of the contents composed of the stock solution and the pressurizing agent, a double aerosol container equipped with a flexible inner container is used, the stock solution is filled into the inner container, and the pressurizing agent is filled inside. What filled the space between a container and an external container is mentioned. In this case, since the undiluted solution is filled in the inner container, almost the entire amount can be discharged even with a highly concentrated undiluted solution, and the outer container is not corroded even with a highly corrosive undiluted solution such as a hair dye. To preferred.

  This content is discharged in almost the same state as the stock solution, such as cream, gel, liquid, etc., and hardly changes over time, but by mixing with the discharged material, the foam specific gravity decreases with time from immediately after discharge, The active ingredients contained in the contents are easily brought into contact with each other due to the increase of bubbles due to the discharged material, and the effects of the active ingredients are easily obtained. Furthermore, since the foamed state continues for a certain period of time even during application, it is easy to spread, and the applied portion can be visually confirmed. Further, since the liquid is not liquefied during application, dripping can be suppressed.

  Examples of the contents include a two-component oxidative hair dye, a two-component exothermic preparation, and a two-component food. In particular, in the case of a two-component oxidative hair dye, an oxidation reaction between the oxidative dye contained in the first hair dye agent and the oxidant contained in the second hair dye agent when the discharged product is mixed. It is possible to start or accelerate foaming of the discharge containing the low-pressure propellant by the reaction heat generated by this oxidation reaction. Also in the case of a two-component exothermic preparation, foaming of the discharge containing the low-pressure propellant is caused by the heat of hydration of polyol and water and the heat of dissolution of inorganic salt such as magnesium chloride and water when the discharge is mixed. Can be started or promoted.

  The case where a two-component foamable aerosol composition is used as a two-component oxidative hair dye will be described.

  As the first agent for hair dyes containing the oxidation dye, oxidation dyes, hair dyeing auxiliary components, alkali agents, stabilizers, viscosity modifiers, other active ingredients that exhibit effects other than the hair dyeing effect, interfaces Examples thereof include a first agent stock solution for a hair dye containing an activator, an oily component and the like in a solvent, and a propellant.

  The oxidation dye is not particularly limited as long as it is a normal oxidation dye used for oxidation hair dyes. For example, paraphenylenediamine, paraphenylenediamine sulfate, paratoluylenediamine, N, N-bis (2-hydroxy) 1) or 2 of ethyl) -paraphenylenediamine, N-phenyl-paraphenylenediamine, diaminodiphenylamine, 2-chloroparaphenylenediamine, N, N-dimethylparaphenylenediamine, paraaminophenol, metaaminophenol, orthoaminophenol More than seeds can be used. In particular, paraphenylenediamine, paraphenylenediamine sulfate, paraaminophenol, metaaminophenol and the like are preferable from the viewpoint of good hair dyeing effect.

  The content of the oxidation dye is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass in the first agent stock solution for hair dye. When the content of the oxidative dye is less than the lower limit, there is a tendency that a sufficient hair dyeing effect is difficult to be obtained. Even when the content is more than the upper limit, the hair dyeing effect does not change, and when mixed with the second agent for hair dye The bubbles tend to liquefy in a short time and tend to sag.

  The hair dyeing auxiliary component is not particularly limited as long as it is a normal hair dyeing auxiliary component used in oxidation hair dyes. For example, one or two or more of acid dyes, direct dyes, other auxiliary components, and the like are used. Can be used.

  Examples of the acid dye include amaranth (red No. 2), erythrosine (red No. 3), new coccin (red No. 102), rose bengal (red No. 105), acid red (red No. 106), and tartrazine (yellow). 4), Sunset Yellow (Yellow 5), Fast Green (Green 3), Brilliant Blue FCF (Blue 1), Indigo Carmine (Blue 2), Rose Bencal K (Red 232), Orange II (Daidai) Color No. 205), Uranine (Yellow No. 202), Quinoline Yellow WS (Yellow No. 203), Alizanin Cyanine Green F (Green No. 201), Pyranine Conch (Green No. 204), Patent Blue (Blue No. 203), Resorcin Brown (Brown 201), Violamine R (Red 401), Orange I (Dai 40) No.) naphth - Ruero S (403 Yellow No.), naphthol green B (No. green 401), Arizu roll purple (No. 401 purple), and the like Naphthol Blue Black (No. 401 black). This content is preferably 0.0001 to 0.3% by mass, more preferably 0.001 to 0.2% by mass. When the content of the acid dye is less than the lower limit, the blending effect tends to be difficult to obtain. When the content is more than the upper limit, the foam easily liquefies in a short time when mixed with the second agent for hair dye. , Tends to sag.

  Examples of the direct dye include 4-nitro-O-phenylenediamine, 2-nitro-p-phenylenediamine, 1-amino-4-methylanthraquinone, 1,4-diaminoanthraquinone, 2-amino-4-nitrophenol, Examples include 2-amino-5-nitrophenol and picric acid. This content is preferably 0.0001 to 0.3% by mass, more preferably 0.001 to 0.2% by mass. When the content of the direct dye is less than the lower limit, the blending effect tends to be difficult to obtain. When the content is more than the upper limit, the foam is liquified in a short time when mixed with the second agent for hair dye. , Tends to sag.

  Examples of the other auxiliary components include resorcin, pyrogallol, catechol, metaaminophenol, metaphenylenediamine, orthoaminophenol, 2,4-diaminophenol, 1,2,4-benzenetriol, toluene-3,4- Diamine, toluene-2,4-diamine, hydroquinone, α-naphthol, 2,6-diaminopyridine, 1,5-dihydroxynaphthalene, 5-aminoorthocresol, diphenylamine, paramethylaminophenol, phloroglucin, 2,4-diamino Phenoxyethanol, gallic acid, tannic acid, ethyl gallate, methyl gallate, propyl gallate, 5- (2-hydroxyethylamino) -2-methylphenol and their salts, aromatic alcohols such as benzyl alcohol, E phenethyl alcohol, benzyloxy ethanol, N- methylpyrrolidone, alkyl pyrrolidones such as N- ethyl-pyrrolidone, ethylene carbonate, such as a lower alkylene carbonates such as propylene carbonate. This content is preferably 0.01 to 15% by mass, more preferably 0.1 to 10% by mass. If the content of the auxiliary component is less than the lower limit, a sufficient blending effect tends to be difficult to obtain, and even if it is contained in excess of the upper limit, the blending effect does not change, which is not economical.

  The alkali agent is not particularly limited as long as it is a normal alkali agent used for oxidative hair dyes. For example, 2-amino-2-methyl-1-propanol, monoethanolamine, triethanolamine, isopropanolamine, An alkanolamine such as triisopropanolamine, or one or more of ammonia, potassium hydroxide, potassium carbonate, calcium carbonate, potassium bicarbonate, ammonium bicarbonate, etc. can be used. It is preferable from the viewpoint of hair dyeing / bleaching effect and skin irritation to adjust the pH to a range of 6 to 13, preferably 7 to 12.

  The stabilizer is not particularly limited as long as it is a normal stabilizer used for oxidative hair dyes. For example, anhydrous sodium sulfite, L-sodium ascorbate, pentetate, disodium hydrogen phosphate, etidronate , Phenacetin, EDTA, 8-hydroxyquinoline, acetanilide, sodium pyrophosphate, barbituric acid, uric acid, tannic acid, paraben and the like can be used.

  0.001-10 mass% in the 1st agent stock solution for hair dyes in the case of containing the said stabilizer, Furthermore, 0.01-5 mass% is preferable. If the content of the stabilizer is less than the lower limit, the effect tends to be difficult to obtain, and even if it is contained in excess of the upper limit, the effect does not change and is not economical.

  The viscosity modifier is not particularly limited as long as it is a normal viscosity modifier used for oxidative hair dyes. For example, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose ethyl ether, carboxy 1 type (s) or 2 or more types, such as sodium methylcellulose, a quaternary nitrogen containing cellulose ether, a carboxy vinyl polymer, a xanthan gum, can be used.

  When the said viscosity modifier is contained, 0.01-10 mass% in the 1st agent stock solution for hair dyes, Furthermore, 0.1-5 mass% is preferable. When the content of the viscosity modifier is less than the lower limit, the viscosity adjustment effect tends to be difficult to obtain, and when it is more than the upper limit, the viscosity becomes too high, and preparation and filling tend to be difficult.

  Other active ingredients that exhibit an effect other than the hair dyeing effect are not particularly limited as long as they are ordinary active ingredients used in oxidative hair dyes. For example, propylene glycol, glycerin, 1,3-butylene glycol, Moisturizers such as collagen, hyaluronic acid, sodium lactate, urea, paraoxybenzoic acid ester, sodium benzoate, phenoxyethanol, benzalkonium chloride, benzethonium chloride, chlorhexidine chloride, silver and other antibacterial / preservatives, paraaminobenzoic acid, paraaminobenzoic acid UV absorbers such as acid monoglycerin ester, octyl salicylate, phenyl salicylate, isopropyl paramethoxycinnamate, octyl paramethoxycinnamate, glycine, alanine, leucine, serine, tryptophan, cystine, cysteine, methioni Amino acids such as aspartic acid, glutamic acid and arginine, retinol, retinol palmitate, pyridoxine hydrochloride, benzyl nicotinate, nicotinamide, nicotinic acid dl-α-tocopherol, vitamin D2, dl-α-tocopherol, dl-α-acetic acid Vitamins such as tocopherol and pantothenic acid, hormones such as elastradiol and ethinylestradiol, antioxidants such as ascorbic acid, dibutylhydroxytoluene and butylhydroxyanisole, peony extract, loofah extract, rose extract, lemon extract, aloe extract, Eucalyptus extract, sage extract, tea extract, seaweed extract, placenta extract, various extracts such as silk extract, polyoctanium 6, polyoctanium 7, polyoctanium 2 Conditioning agents such as, can be used one or two or more of such perfumes.

  The surfactant is not particularly limited as long as it is a normal surfactant used for oxidative hair dyes. For example, sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene oleyl ether, polyoxy Polyoxyethylene alkyl ether such as ethylene cetyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene castor oil / hardened castor oil, poly Oxyethylene lanolin alcohol, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkylolamide, alkyl polyglucoside, poly Xylethylene / methylpolysiloxane copolymer, polyoxypropylene / methylpolysiloxane copolymer, poly (oxyethylene / oxypropylene) / methylpolysiloxane copolymer, fatty acid soap, N-acyl glutamate, N-acyl glutamic acid, N-acylglycine salt, N-acylalanine salt, behentrimonium methosulfate / cetanol / isoalkyl (C10-40) amidopropylethyldimonium methosulfate, polyoxyethylene lauryl ether sodium sulfate, sodium lauryl sulfate and the like or Two or more kinds can be used.

  When the surfactant is contained, 0.01 to 20% by mass, and further 0.1 to 15% by mass is preferable in the first agent stock solution for hair dye. When the content of the surfactant is less than the lower limit, the discharged product tends to be difficult to foam, and when it is more than the upper limit, it tends to be sticky and the feeling of use tends to decrease.

  The oil component is not particularly limited as long as it is a normal oil component used for oxidative hair dyes. For example, methylpolysiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, octamethylcyclotetrasiloxane, methylphenylpolysiloxane. Silicone oils such as siloxane, ester oils such as isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, diethoxyethyl succinate, hydrocarbons such as squalane, squalene, isoparaffin, liquid paraffin, camellia oil, corn Oils, olive oil, rapeseed oil, sesame oil, castor oil, jojoba oil, coconut oil and other oils, higher fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, myristyl Call, cetyl alcohol, stearyl alcohol, can be used behenyl alcohol, higher alcohols, such as lanolin alcohol, beeswax, lanolin, candelilla wax, one or more of such waxes such as microcrystalline wax (wax).

  When the oil component is contained, 0.01 to 15% by mass, and further 0.1 to 10% by mass is preferable in the first agent stock solution for hair dye. When the content of the oil component is less than the lower limit, the blending effect tends to be difficult to obtain, and when it is contained more than the upper limit, it tends to be difficult to foam.

  Examples of the solvent include water, alcohols, and mixtures thereof. Examples of the water include purified water, ion exchange water, and physiological saline. Examples of the alcohols include monovalent lower alcohols such as ethanol and isopropanol, ethylene glycol, propylene glycol, 1,3-butylene glycol, glycerin, diglycerin, diethylene glycol, dipropylene glycol, triethylene glycol, and polyethylene glycol. And polyhydric alcohols such as polypropylene glycol.

  The second agent for hair dye containing the oxidizing agent includes an oxidizing agent, a pH adjuster, a stabilizer, a viscosity adjuster, other active ingredients that exhibit effects other than the hair dyeing effect, a surfactant, and an oily agent. Examples thereof include a second agent stock solution for hair dye containing components and the like in a solvent, and a propellant.

  The oxidizing agent is not particularly limited as long as it is a normal oxidizing agent used for oxidative hair dyes. For example, hydrogen peroxide, oxidase, and the like can be used.

  When hydrogen peroxide is contained as the oxidizing agent, it is preferably 0.1 to 10% by mass, and more preferably 1 to 6% by mass in terms of pure content in the second agent stock solution for hair dye. If the oxidizer content is less than the lower limit, the oxidizing power is insufficient and a good hair dyeing effect tends to be difficult to obtain.If it exceeds the upper limit, damage to the hair and scalp and corrosion or pressure on the aerosol container Tend to rise.

  The oxidase is not particularly limited as long as it is a normal oxidase used for oxidative hair dyes. For example, one or more of laccase, peroxidase, uritase, catalase, tyrosinase, etc. can be used. .

  When oxidase is contained as the oxidizing agent, it is preferably 0.001 to 20% by mass, and more preferably 0.01 to 15% by mass in the second agent stock solution for hair dye. When the content of the oxidase is less than the lower limit, the oxidizing power is insufficient and a good hair dyeing effect tends to be difficult to obtain.

  The pH adjuster is not particularly limited as long as it is a normal pH adjuster used for an oxidative hair dye, and for example, one or more of phosphoric acid, citric acid, sulfuric acid, acetic acid, lactic acid, tartaric acid and the like. It is preferable to adjust the pH of the second agent stock solution for the hair dye to a range of 1 to 6, and more preferably 2 to 5.

  In addition, the said stabilizer, a viscosity modifier, surfactant, an oil-based component, and a solvent can use the same component as what was illustrated by the above-mentioned 1st agent for hair dyes.

  In the two-component foamable aerosol product, the first agent stock solution and the propellant are filled in a first container, the second agent stock solution and the propellant are filled in a second container, and the first container and the second container are filled. It can manufacture by attaching and attaching the discharge member which can operate a 1st container and a 2nd container simultaneously.

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

1) Foaming property (foaming property after mixing two kinds of discharged materials)
The test aerosol product was kept in a constant temperature water bath at 25 ° C. for 1 hour, the first content and the second content were discharged simultaneously, and the foamability when the discharged materials were mixed was evaluated. Evaluation is based on the following criteria.
○: Partially foamed at the time of discharge, foamed slowly when mixed, foam increased × 1: Almost foamed at the time of discharge, gradually defoamed when mixed × 2: Foam and liquid at the time of discharge Yes, defoamed as soon as mixed

2) Mixability The test aerosol product was kept in a constant temperature water bath at 25 ° C. for 1 hour, the first content and the second content were discharged simultaneously, and the mixability when the discharged materials were mixed was evaluated. Evaluation is based on the following criteria.
○: The first contents and the second contents reacted evenly, and the entire discharged material changed color. X: A part of the discharged material changed color.

3) Ease of application (difficulty of dripping)
The test aerosol product is kept in a constant temperature water bath at 25 ° C. for 1 hour, the first content and the second content are discharged at the same time, the discharged materials are mixed, and the ease of spreading when the mixture is applied to the hair is improved. evaluated. Evaluation is based on the following criteria.
○: Smoothly spread without dripping due to micro-foaming Δ: Dipping during application X: Dipping immediately after application

4) Confirmation of application | coating part The state after apply | coating a mixture to hair was evaluated visually. Evaluation is based on the following criteria.
○: Foam remained in the applied part, and the applied part could be visually confirmed. ×: No foam remained in the applied part, and the applied part could not be visually confirmed.

5) Foam specific gravity Hold the test aerosol product in a constant temperature water bath at 25 ° C. for 1 hour, and discharge it into a hemispherical glass container with a volume of 25 ml. Calculated.

<Preparation of first agent stock solution for hair dye>
The 1st agent stock solution for hair dyes shown in Table 1 was prepared.

＊１：キレスト ＰＡ−ＳＤ（商品名）、キレスト株式会社製
＊２：ＰＧ（商品名）、株式会社ＡＤＥＫＡ製
＊３：ソルビトール（商品名）、花王株式会社製
＊４：マーコート ２８０（商品名）、ＮＡＬＣＯ社製
＊５：マーコート ５５０（商品名）、ＮＡＬＣＯ社製
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＊７：エマール Ｅ−２７Ｃ（商品名）、花王株式会社製
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＊９：アミゾール ＣＤＥ（商品名）、川研ファインケミカル研株式会社製
＊１０：ステアリン酸 ５５０Ｖ（商品名）、花王株式会社製
＊１１：ルナック ＭＹ−９８（商品名）、花王株式会社製
＊１２：ルナック ＳＯ−９０Ｌ（商品名）、花王株式会社製

* 1: Kyrest PA-SD (trade name), manufactured by Kyrest Co., Ltd. * 2: PG (trade name), manufactured by ADEKA Co., Ltd. * 3: Sorbitol (trade name), manufactured by Kao Corporation * 4: Marcoat 280 (trade name) ), NALCO * 5: Marcote 550 (trade name), NALCO * 6: NIKKOL BC-2 (trade name), Nikko Chemicals Co., Ltd. * 7: Emar E-27C (trade name), Kao Corporation * 8: Mydoll 12 (trade name), Kao Corporation * 9: Amizole CDE (trade name), Kawaken Fine Chemicals Laboratories * 10: Stearic acid 550V (trade name), Kao Corporation * 11 : LUNAC MY-98 (trade name), manufactured by Kao Corporation * 12: LUNAC SO-90L (trade name), manufactured by Kao Corporation

<Preparation of second agent stock solution for hair dye>
Second stock solutions for hair dyes shown in Table 2 were prepared.

＊１３：キレスト ＰＨ−２１０ＳＤ（商品名）、キレスト株式会社製
＊１４：エマール １０ＰＴ（商品名）、花王株式会社製
＊１５：ラノリンアルコール Ａ（商品名）、日本精化株式会社製
＊１６：カルコール ６８５０（商品名）、花王株式会社製

* 13: Kirest PH-210SD (trade name), manufactured by Kirest Co., Ltd. * 14: Emar 10PT (trade name), manufactured by Kao Corporation * 15: Lanolin alcohol A (trade name), manufactured by Nippon Seika Co., Ltd. * 16: Calcoal 6850 (trade name), manufactured by Kao Corporation

<Manufacture of first agent aerosol products>
Manufacture of 1st agent aerosol product A 47.5g (95 mass%) 1st agent stock solutions a for hair dyes of Table 1 were filled into the 1st container, and the aerosol valve was fixed to this container. Next, 2.5 g (5% by mass) of low-pressure propellant 1 (* 17) was filled and pressurized to 0.6 MPa with nitrogen gas. Further, a discharge member was attached to the aerosol valve to produce a first agent aerosol product A. Foam specific gravity was evaluated about the obtained aerosol product. The foam specific gravity was measured every 30 seconds, and the change with time was evaluated. The results are shown in Table 3.

Manufacture of first-agent aerosol product B The filling amount of the first agent stock solution a for hair dye is 42.5 g (85 mass%), and the filling amount of the low-pressure propellant 1 (* 17) is 7.5 g (15 mass%). Except for the above, an aerosol product was produced in the same manner as the first agent aerosol product A and evaluated in the same manner.

Production of first agent aerosol products C to F Aerosol in the same manner as the first agent aerosol product B except that the first agent stock solutions b to e for hair dyes were used instead of the first agent stock solution a for hair dyes, respectively. The product was manufactured and evaluated.

Manufacture of First Agent Aerosol Product G An aerosol product was manufactured and evaluated in the same manner as the first agent aerosol product A except that the low pressure propellant 2 (* 18) was used.

Manufacture of First Agent Aerosol Product H An aerosol product was manufactured and evaluated in the same manner as the first agent aerosol product B except that the low pressure propellant 2 (* 18) was used.

Manufacture of first agent aerosol product I 35.0g (70% by mass) of the first agent stock solution a for hair dye, and 15.0g (30% by mass) of the low pressure propellant 2 (* 18) An aerosol product was produced and evaluated in the same manner as the first agent aerosol product H except that it was filled.

Production of first agent aerosol product J An aerosol product was produced and evaluated in the same manner as the first agent aerosol product A except that the propellant was low pressure propellant 3 (* 19).

Manufacture of first agent aerosol product K Manufacture an aerosol product in the same manner as the first agent aerosol product A except that high pressure propellant 1 (* 20) was used and nitrogen gas was not pressurized. evaluated.

Production of First Agent Aerosol Product L An aerosol product was produced and evaluated in the same manner as the first agent aerosol product K except that the propellant was high pressure propellant 2 (* 21).

Manufacture of First Agent Aerosol Product M An aerosol product was manufactured and evaluated in the same manner as the first agent aerosol product A except that the low pressure propellant 1 (* 17) was not used.

＊１７ イソペンタン ２０℃における蒸気圧 ０．０５ＭＰａ
＊１８ イソペンタン／ノルマルブタン （４４／５６）質量比 ２０℃における蒸気圧 ０．０７ＭＰａ
＊１９ ノルマルブタン ２０℃における蒸気圧 ０．１ＭＰａ
＊２０ ブタン／プロパン （８０／２０）質量比 ２０℃における蒸気圧 ０．４０ＭＰａ
＊２１ ブタン／プロパン （４４／５６）質量比 ２０℃における蒸気圧 ０．５０ＭＰａ

* 17 Isopentane vapor pressure at 20 ° C 0.05 MPa
* 18 Isopentane / normal butane (44/56) mass ratio Vapor pressure at 20 ° C 0.07 MPa
* 19 Normal butane Vapor pressure at 20 ° C 0.1 MPa
* 20 Butane / propane (80/20) mass ratio Vapor pressure at 20 ° C 0.40 MPa
* 21 Butane / propane (44/56) mass ratio Vapor pressure at 20 ° C 0.50 MPa

  From the results shown in Table 3, the first agent aerosol products A to J are ejected products that are partially foamed immediately after ejection and further foamed with time, and the difference depends on the type of propellant and the mixing ratio of the stock solution and the propellant. That is, the specific gravity of bubbles is decreasing with the passage of time after discharge. That is, it turns out that foaming is advancing. In addition, the first agent aerosol products K and L completed foaming immediately after discharge, and the foam specific gravity increased with the passage of time. That is, it can be seen that bubbles are broken. Furthermore, although the 1st agent aerosol product M foamed slightly after discharge, it turns out that it bubbles after that and becomes liquid state.

  FIG. 1 is a graph showing the change over time in the foam specific gravity from 120 seconds after immediately after discharging the first agent aerosol products C, G, J and K, which are a part of the first agent aerosol products shown in Table 3. . It can be seen that the foam specific gravity of the first agent aerosol products C, G and J decreases with the passage of time after discharge. Moreover, about the 1st agent aerosol product K, it turns out that foam specific gravity becomes large with progress of the time after discharge.

<Manufacture of second-agent aerosol products>
Manufacture of 2nd agent aerosol product A 50.0g (100 mass%) of 2nd agent stock solutions a for hair dyes of Table 2 were filled into the 2nd container, and the aerosol valve was fixed to this container. Next, nitrogen gas was pressurized to 0.6 MPa. Further, an injection member was attached to the aerosol valve to produce a second agent aerosol product A. Foam specific gravity was evaluated about the obtained aerosol product. The foam specific gravity was measured every 30 seconds and the change with time was evaluated. The results are shown in Table 4.

Manufacture of 2nd agent aerosol product B After filling 47.5g (95 mass%) of 2nd agent stock solutions a for hair dyes of Table 2 in the 2nd container, the aerosol valve was fixed to this container. Next, 2.5 g (5% by mass) of low-pressure propellant 2 (* 18) was charged, and an aerosol product was produced and evaluated in the same manner as the second agent aerosol product A.

Manufacture of second-agent aerosol product C Produces an aerosol product in the same manner as second-agent aerosol product B except that high-pressure propellant 1 (* 20) was used and nitrogen gas was not pressurized. evaluated.

Manufacture of Second Agent Aerosol Product D An aerosol product was manufactured and evaluated in the same manner as the second agent aerosol product C except that the second stock solution b for hair dye was used.

Production of second agent aerosol product E An aerosol product was produced and evaluated in the same manner as the second agent aerosol product B except that the second stock solution b for hair dye was used.

  From the results shown in Table 4, it can be seen that the second agent aerosol product A foamed slightly after discharge, but then bubbled and became liquid. Further, the second agent aerosol products B and E are ejected products that partially foam immediately after ejection and further foam with time, and the foam specific gravity decreases with the passage of time after ejection. That is, it turns out that foaming is advancing. Furthermore, it turns out that foaming of the 2nd agent aerosol products C and D is completed immediately after discharge, and foam specific gravity becomes large with progress of time, that is, foam breaks.

  FIG. 2 is a graph showing the change over time in the specific gravity of foam from immediately after discharge of the second agent aerosol products A to C, which is a part of the second agent aerosol product shown in Table 4, to 120 seconds later. As for the second agent aerosol product A, it can be seen that the discharged product foamed slightly, but then it was broken to become liquid. Regarding the second agent aerosol product B, it can be seen that the foam specific gravity decreases with the passage of time after discharge. Moreover, about 2nd agent aerosol product C, it turns out that foam specific gravity becomes large with progress of the time after discharge.

<Examples 1 to 15 and Comparative Examples 1 and 2>
Using the first agent aerosol products A to M and the second agent aerosol products A to E, two-component foamable aerosol products were produced in the combinations shown in Table 5. The first contents A to M are filled with the contents of the first agent aerosol products A to M in Table 3, and the second contents A to E are filled with the contents of the second agent aerosol products A to E of Table 4. It represents what has been done. The resulting two-pack foamable aerosol product was evaluated for foamability, mixability, ease of application, confirmation of the application area, and foam specific gravity. Moreover, the change rate (g / ml * min) of the foam specific gravity from immediately after discharge to 2 minutes after was measured. The results are shown in Table 5.

  From the results shown in Table 5, Examples 1 to 12 are two-component foamable aerosol products in which the foam specific gravity of the first contents decreases with time immediately after discharge, and Examples 13 and 14 are examples of the second contents. This is a two-component foamable aerosol product in which the foam specific gravity decreases with time immediately after ejection, and Example 15 is a two-component foaming in which the foam specific gravity of the first content and the second content decreases with time from immediately after ejection. It can be seen that this is a two-part foamable aerosol product that is excellent in the foaming property, mixing property, ease of application, and the result of confirming the application part.

  Of the examples shown in Table 5, the foam specific gravity immediately after discharge of Examples 1, 8, 12, and 15 and Comparative Examples 1 and 2, 1 minute and 2 minutes later are shown in a graph in FIG. In Examples 1, 8, 12 and 15, it can be seen that the foam specific gravity decreases with the passage of time after discharge. Moreover, about Comparative Examples 1 and 2, it turns out that foam specific gravity becomes large with progress of the time after discharge.

Claims (4)

A first container filled with a first content;
A second container filled with a second content,
A two-component foamable aerosol product that uses a mixture of a first content and a second content,
The first content contains a low-pressure propellant having a propellant vapor pressure of 0.01 to 0.2 MPa at 20 ° C,
The second content contains a high-pressure propellant having a vapor pressure of 0.3 to 0.7 MPa at 20 ° C,
At least, Ri of time small just after the foam density of the discharge of the first contents are discharged,
The foam specific gravity is a two-component foamable aerosol product, which is a foam specific gravity that changes in 1 minute by measuring the mass when two minutes have passed since the two-component foamable aerosol product is discharged and immediately after the discharge . The two-component foamable aerosol product according to claim 1, wherein a change rate of the foam specific gravity is −0.1 to −0.0005 (g / ml · min). The two-component foamable aerosol product according to claim 1, wherein the first content or the second content containing the low-pressure propellant further contains a pressurizing agent. The first content and the second content are a two-component oxidative hair dye comprising a first agent for a hair dye containing an oxidative dye and a second agent for a hair dye containing an oxidant. The two-component foamable aerosol product according to any one of claims 1 to 3.

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