JP6058950B2 - Aerosol type foamy hair dye composition - Google Patents

Description

  The present invention relates to an aerosol-type foamy oxidative hair dye composition, and more specifically, each agent including a first agent containing an alkaline agent selected from ammonia or an ammonium salt and a second agent containing an oxidizing agent. The present invention relates to an aerosol-type foamy oxidative hair dye composition that is discharged and mixed from an aerosol container at the time of use.

〔Definition of terms〕
1) “Oxidative hair dye” means a dye comprising an alkaline agent and a first agent containing a dye component (an intermediate of an oxidized dye and further a coupler) and a second agent containing an oxidizing agent. Refers to hair.

  2) In an oxidative hair dye, hair is swollen with an alkaline agent, melanin of hair is decomposed (hair is decolored) with an oxidant, and in parallel, a dye component is oxidatively polymerized (hair dyed) inside the hair. Therefore, the term “hair dyeing power”, “hair dyeing”, etc., for an oxidative hair dye means the above-mentioned hair dyeing.

  3) “Oxidative hair dye” or “oxidative hair dye composition” refers to the state before being discharged in the form of foam, and the first and second agents in this state are referred to as “stock solutions”. There is. The term “foam oxidative hair dye” or “foam oxidative hair dye composition” refers to a state of being discharged in a foam form using an aerosol container.

  4) “Hair” is not particularly limited, but preferably hair on the head including the face, particularly preferably hair on the head including the human face, particularly preferably a portion other than the face on the human head. Say no hair.

  5) About the foamy first agent and the second agent of the foamed oxidative hair dye, “discharge and mix” means that these agents are “mixed uniformly using fingers after discharging” "Means. The aerosol container is a type in which the foamed first agent and the second agent are discharged from separate discharge ports and a type in which the first agent and the second agent are discharged together from a single discharge port. Some are already mixed to some extent at the time of discharge, but the above “discharge” includes discharge by both types of aerosol containers.

  2. Description of the Related Art Conventionally, aerosol-type foam-like oxidative hair dye compositions are known in which an oxidative hair-dyeing composition is discharged in the form of foam using a propellant such as LPG. Such an aerosol foam hair dye composition is used by discharging each agent of the composition together with a propellant from an aerosol container in a foam shape.

In the aerosol type foam hair dye composition, each agent is mixed with a propellant as a stock solution and stored in an aerosol container, or in an aerosol container having an inner bag, each agent is contained in the inner bag. And a propellant (for foaming) and a propellant (for extrusion) outside the inner bag.

  In general, aerosol foam hair dyes can be discharged in a foam form by simply pressing a button on an aerosol container, compared to liquid or cream forms. Convenient. There is also an advantage that the required amount can be divided into a plurality of times.

  The aerosol-type oxidized hair dye composition includes an alkaline agent and a first agent containing a dye component, and a second agent containing an oxidizing agent. And each agent containing a 1st agent and a 2nd agent is separately accommodated in an aerosol container, and is discharged and mixed in foam form at the time of use. Examples of the alkali agent include ammonia and ammonium salts, and examples of the oxidant include hydrogen peroxide.

  With regard to such an aerosol foam oxidation hair dye composition, in Patent Document 1 below, a nonionic surfactant exhibiting a specific HLB value is further blended to realize a good foam state and hair dyeing power. An aerosol foam oxidative hair dye composition is disclosed. Patent Document 2 below discloses a two-component foamy hair dye composition in which the amount of ammonia in the first agent is reduced, or for example, an alkanolamine other than ammonia is contained in the first agent as an alkaline agent. ing. On the other hand, in the following Patent Document 3, a linear higher alcohol, a branched higher alcohol, a hydrocarbon having a branched chain, a surfactant and the like are further contained, and the foam specific gravity at 25 ° C. is 0.02 to 0.30. The foam-like hair dye composition set up so that it may become is indicated.

JP-A-11-139945 JP 2002-284655 A JP 2003-073240 A

  By the way, ammonia or ammonium salt is an alkaline agent suitable for realizing excellent hair dyeing power with an oxidative hair dye, but has a disadvantage that it has an unpleasant pungent odor due to the volatility of ammonia. And when the oxidative hair dye is an aerosol type foam oxidative hair dye, such an irritating odor is particularly strong.

  For example, the aerosol foam oxidation hair dye composition according to Patent Document 1 achieves a good foam state and hair dyeing power as described above, but contains ammonia as an alkaline agent and has an irritating odor. There is room for improvement in terms of reduction. In the two-component foam hair dye composition according to Patent Document 2, the irritating odor can be reduced by reducing the amount of ammonia blended or by blending as an alkaline agent other than ammonia. There is room for improvement in terms of possible decline. In the foam-like hair dye composition according to Patent Document 3, ammonia or the like is used as an alkaline agent to ensure hair decolorization (hair brightness improvement) effect, and the foam specific gravity is specified, but this foam specific gravity is It is regulated from the viewpoint of dripping prevention, and its relationship with the reduction of irritating odors has not been studied.

  An object of the present invention is to suppress an irritating odor of ammonia while maintaining good hair dyeing properties in an aerosol type foamed hair dye. In addition, the aerosol foam hair dye that discharges and mixes the first agent and the second agent in a foam state at the time of use may have good mixing properties between the foamed first agent and the second agent. Is very important for good hair dyeing.

  Therefore, the present invention comprises an aerosol foam hair oxidative hair dye composition comprising a first agent containing an alkali agent selected from ammonia or an ammonium salt, which is discharged and mixed with the second agent in the form of foam during use. Solves the problem of suppressing the pungent odor of ammonia and maintaining good hair dyeing by ensuring good mixing in the first agent and the second agent mixed by discharging in a foam state during use. It should be a technical issue to be done.

  Conventionally, in solving the technical problem of suppressing the pungent odor of ammonia, as in Patent Document 2, it is common to reduce the amount of ammonia blended or to use an alkali agent such as alkanolamine instead of ammonia. However, in those cases, there is a problem that the hair coloring power and the lightness of the hair are sacrificed.

  The inventor of the present application says that in the process of pursuing the means for solving the above technical problem, the relationship between the foam specific gravity (bubble size) and the ammonia-stimulated odor during the discharge of the first agent and the second agent is considered. I came to get a very innovative look. In the process of pursuing this focus, the following new findings were obtained. The present invention has been completed based on these novel findings.

  (Premise) In general technical common sense, a foam-like discharge is easy to break if the foam specific gravity is small (the foam is large). Therefore, in the foamed oxidative hair dye, when the foam of the foamed first agent containing ammonia is large, it is considered that ammonia is released by bubble breaking and the ammonia-stimulated odor becomes strong.

  (Knowledge 1) However, according to the experiment of the present inventor, when the foam specific gravity of the foamed first agent is made smaller (larger foam) than that of the foamed second agent, the ammonia-stimulated odor can be effectively suppressed. In addition, as shown in Comparative Example 1 in Table 5 at the end, when the foam specific gravity of the foamed first agent is made larger (smaller foam) than the foamed second agent, the ammonia-stimulated odor cannot be suppressed. The results were unpredictable from conventional technical common sense.

  (Knowledge 2) In Comparative Example 1 above, the absolute value of the foam specific gravity is set to be slightly smaller (foam slightly larger) for both the foamed first agent and the foamed second agent. “In short, since the absolute value of the foam specific gravity of the foamed first agent is small (the foam is large), it is not possible to suppress the ammonia-stimulated odor according to conventional technical common sense. It is possible to give a reason that “the difference in specific gravity (bubble size) does not matter”. Therefore, although it is a comparative example which is not included in the table at the end, “the foam specific gravity of the foamed first agent is larger (the foam is smaller) than the foamed second agent, and the foamed first agent, foamy When a comparative example of “the absolute value of the foam specific gravity is large (the foam is small) for both the second agent” was verified, the ammonia-stimulated odor could not be suppressed.

  (Knowledge 3) The reason why the above experimental results have been obtained is not yet fully understood, but rational assumptions such as the following guess 1 and guess 2 are possible.

  Presumption 1: First, in the experiment according to the example, the foam of the foamed first agent having a small foam specific gravity (large foam) is easy to break up and release ammonia, but a part of the foam that actually breaks up is partly. In most bubbles that are not broken, the effect of enclosing and enclosing ammonia is large due to the size of the bubbles. And the ammonia released from some broken foam is absorbed quickly into the foam of the foamed second agent that has a large foam specific gravity (small foam) and is hard to break, resulting in an ammonia-stimulating odor. Can be effectively suppressed.

  Guess 2: On the other hand, in the experiment related to the comparative example, the foam of the foamed first agent having a large foam specific gravity (small foam) is difficult to break, whereas the foam is small so that it contains and encloses ammonia well. Ammonia is volatilized for reasons that are different from guess 1, which is difficult. This volatilization effect of ammonia is unavoidable in all bubbles of the first agent regardless of the presence or absence of bubbles. Even if the ammonia volatilized from the entire foam of the first agent is absorbed in the foam of the second foam agent, the foam of the second agent is relatively large and easily broken in this case. Eventually, ammonia is released, and as a result, the ammonia stimulating odor cannot be effectively suppressed.

  (Knowledge 4) In addition, if the foamed hair dye has a small foam, the elongation at the time of application to the hair is poor, so uniform application becomes difficult, and the operability deteriorates such that it is easy to slip off from fingers and hair. Is seen. However, if the foam of the first agent is large, as a result, the foam becomes larger as a whole even after mixing with the foam of the second agent, so the merit that the operability is improved cannot be ignored.

  (Knowledge 5) Furthermore, if the foam specific gravity (bubble size) of the first agent and the second agent is excessively different, it is difficult to uniformly mix them, and the hair dyeing power of the oxidative hair dye is reduced.

(First invention)
The configuration of the first invention of the present application for solving the above problem is that each agent including a first agent containing an alkali agent selected from ammonia or an ammonium salt and a second agent containing an oxidant are used in foaming. An aerosol foam oxidation hair dye composition that is discharged and mixed in the form of a foam, and the ratio of the foam specific gravity (f1) of the first agent and the foam specific gravity (f2) of the second agent at the time of discharge, f2 / f1 Is an aerosol-type foamy oxidative hair dye composition in which is in the range of 1.1 to 3.

  In the present invention, “foam specific gravity” refers to the weight (gram) at a constant temperature (preferably 25 ° C.) in terms of the volume (ml) of the first agent or the second agent discharged in the form of foam. Say the divided value. The method for measuring the foam specific gravity is not limited as long as it can be accurately measured. For example, if an aerosol container of a type in which the first agent and the second agent are discharged in foam from different discharge ports, the first agent or the second agent discharged in a foam at a certain temperature can be easily separated. Can be taken. Then, if these foam-like first agent or second agent is immediately weighed (before defoaming begins) so that it fills a wide-mouthed container of known volume and weight, the volume value of the foam (Ml) is obtained. Next, if the weight of the container is measured and then the known weight of the container itself is subtracted, the foam weight value (grams) is obtained. Therefore, the foam specific gravity can be accurately calculated. If there is a hydrometer that can directly measure the specific gravity and can be applied to the measurement of the foam specific gravity, it may be used.

(Second invention)
In order to solve the above-mentioned problem, the second invention of the present application is the aerosol foamed hair dye composition according to the first invention, wherein the first agent and the second agent further contain a higher alcohol, Aerosol-type foamy oxidative hair, in which the ratio a2 / a1 of the higher alcohol content (a1) in the agent to the higher alcohol content (a2) in the second agent is in the range of 0.5 to 2.0 Agent composition.

  In the first invention, the ratio f2 / f1 between the foam specific gravity (f1) of the first agent and the foam specific gravity (f2) of the second agent at the time of discharge is in the range of 1.1 to 3. That is, the foam specific gravity of the foamed first agent is relatively small (the foam is large), and the foam specific gravity of the foamy second agent is relatively large (the foam is small). For this reason, the ammonia-stimulated odor can be satisfactorily suppressed for the reason described in the above “knowledge”. Further, since the foam of the first agent is large, as described in the above “knowledge”, the foam becomes larger overall even after mixing with the foam of the second agent, and an important advantage is obtained that the operability is improved. It is done. If the foam specific gravity ratio f2 / f1 is less than 1.1, the ammonia-stimulated odor cannot be satisfactorily suppressed.

  On the other hand, the foam specific gravity (f2) of the second agent does not exceed 3 times the foam specific gravity (f1) of the first agent, and the foam specific gravity (bubble size) of the two agents is not excessively different. Accordingly, the mixing property between the foamed first agent and the second agent is ensured, and therefore, the hair dyeing power is not deteriorated due to the poor mixing property. When the foam specific gravity ratio f2 / f1 exceeds 3, the hair dyeing power of the foamy oxidative hair dye deteriorates.

  Therefore, according to the first invention, an objective index that the ratio f2 / f1 between the foam specific gravity (f1) of the first agent and the foam specific gravity (f2) of the second agent is in the range of 1.1 to 3 is used. By preparing an aerosol foam hair oxidative hair dye composition that satisfies the above requirements, “suppressing the pungent odor of ammonia and ensuring good mixing of the first agent and the second agent discharged in foam during use. Thus, the problem of the present invention that “maintains good hair dyeability” can be solved.

  In other words, the first invention is an aerosol in which each agent including a first agent containing an alkali agent selected from ammonia or an ammonium salt and a second agent containing an oxidant are discharged and mixed in the form of foam during use. On the premise that the composition is a foam-type oxidized hair dye composition, the index “f2 / f1 is in the range of 1.1 to 3” is set as a specific, objective, and new component, It is invention which provides the aerosol type foamy hair dye composition which can solve the subject of the present invention by composition.

  The composition of the first agent and the second agent that can easily satisfy or actually satisfy the above-mentioned index is supported by the “Best Mode for Carrying Out the Invention” column and the “Example” column described later. . However, the essence of the first invention is not an example of each of these specific compositions, but an aerosol-type foamy oxidative hair dye that satisfies the index “f2 / f1 is in the range of 1.1 to 3” “Composition”. A person skilled in the art can determine whether or not an aerosol-type foamy oxidative hair dye composition that satisfies such an index has been prepared by discharging the foam-like first agent and the foam-like second agent separately. Since it can be confirmed by simply checking the specific gravity of the bubbles, this is easily possible.

  According to the second invention, the first agent and the second agent further contain a higher alcohol, and the ratio of the higher alcohol content (a1) in the first agent to the higher alcohol content (a2) in the second agent. a2 / a1 is in the range of 0.5 to 2.0. The higher alcohol itself can generally be expected to have effects such as adjustment of the viscosity in the oxidative hair dye composition and foam hardness based on the adjustment of the viscosity, but a2 / a1 is 0.5 to 2.0. In other words, the content of the higher alcohol in the first agent and the second agent does not exceed two times each other, so that the mixing property of the foam-like first agent and the second agent becomes foam. The hair dyeing power of the oxidative hair dye is further improved.

  Hereinafter, embodiments of the present invention will be described including the best embodiment. The technical scope of the present invention is not limited by the following embodiments.

[Aerosol type foam hair dye composition]
(Configuration and use form of oxidative hair dye composition)
The oxidative hair dye composition of the present invention is as described in the "Definition of terms" column at the beginning of the specification. The stock solution of the oxidative hair dye composition is usually configured in a two-part system comprising a first agent containing an alkali agent and a dye component and a second agent containing an oxidant.

  In the following, only the two-component oxidative hair dye composition will be described. Each agent constituting the oxidative hair dye composition is accommodated in different spaces in the aerosol container.

  Moreover, the dosage form of the undiluted | stock solution of each agent which comprises an oxidative hair dye composition is not limited, However, The dosage form which is easy to foam based on water is preferable.

  An appropriate amount of LPG (liquefied petroleum gas), dimethyl ether, nitrogen, carbon dioxide and other known propellants is blended in each agent constituting the oxidative hair dye composition. These propellants are contained in an aerosol container having an inner bag, in addition to the case where they are blended into the undiluted solution of each agent. The propellant and propellant (for foaming) are accommodated inside the inner bag, and the propellant is disposed outside the inner bag. It can also be configured to accommodate (for extrusion). Although the quantity of the propellant used in this way is not limited, For example, the quantity of the propellant in the undiluted | stock solution of each agent containing a propellant can be made into the range of 2-10 mass%.

  In addition, the propellant amount of the first agent in the oxidative hair dye composition can be made larger than that of the second agent. For example, the amount of the propellant in the stock solution of the first agent can be increased by about 1 to 2% by mass than the propellant in the stock solution of the second agent.

  The mixing ratio of the foamed first agent and the second agent is not particularly limited, and may be, for example, a first agent: second agent = 1: 1 mass mixing ratio, or the first agent: You may set suitably in the range of the mass mixing ratio of about 2nd agent = 1: 2 to 2: 1.

  The two-component oxidative hair dye composition as described above is used in a form in which the first agent and the second agent are discharged and mixed in the form of foam when used and applied to the hair. Specifically, usage forms such as the following (1) to (3) can be exemplified. At that time, it is preferable that the foamed discharges of each agent are mixed well with fingers after discharge and applied to the hair after being taken by hand, brush, comb, etc. It can also be applied directly to the hair and mixed on the hair. The application target may be the entire hair such as head hair, or a part thereof.

  (1) Each agent is separately ejected from the aerosol container in the form of foam, mixed and applied to the hair.

(2) Each agent is separately discharged from the aerosol container in the form of foam, applied to the hair, and mixed on the hair.
(3) After each agent is discharged from a single discharge port of the aerosol container, these are further uniformly mixed and then applied to the hair.

(Foam specific gravity of foamy hair dye composition)
The ratio f2 of the foam specific gravity (f1) of the first agent and the foam specific gravity (f2) of the second agent when the first agent and the second agent of the oxidative hair dye composition are discharged in a foam form from the aerosol container. / F1 is in the range of 1.1-3. On the premise of this point, the foam specific gravity (f1) of the first agent is preferably in the range of 0.03 to 0.2, and the foam specific gravity (f2) of the second agent is 0.06 to 0.4. It is preferable to be within the range.

(Configuration example of oxidative hair dye composition)
(1) Specific constitutional examples of the oxidative hair dye composition of the present invention include a first agent containing an alkali agent selected from ammonia or an ammonium salt and a second agent containing an oxidant. An aerosol foam hair dye composition that discharges and mixes each agent in the form of foam when in use, the foam specific gravity (f1) of the first agent and the foam specific gravity (f2) of the second agent at the time of discharge An oxidative hair dye composition having a ratio f2 / f1 within the range of 1.1 to 3 is exemplified. The foam specific gravity ratio f2 / f1 is more preferably in the range of 1.3 to 2.8.

  (2) As another specific structural example of the oxidative hair dye composition of the present invention, a first agent containing an alkali agent selected from ammonia or an ammonium salt and a second agent containing an oxidant An aerosol foam oxidation hair dye composition in which each of the included agents is discharged and mixed in a foam state at the time of use, further comprising water, a surfactant, and a propellant, An oxidative hair dye composition in which the ratio f2 / f1 between the foam specific gravity (f1) of the first agent and the foam specific gravity (f2) of the second agent is in the range of 1.1 to 3 is exemplified. The foam specific gravity ratio f2 / f1 is more preferably in the range of 1.3 to 2.8.

  (3) As still another specific configuration example of the oxidative hair dye composition of the present invention, a first agent containing an alkali agent selected from ammonia or an ammonium salt, and a second agent containing an oxidant An aerosol foam oxidation hair dye composition that is discharged and mixed in the form of foam at the time of use, and further contains water, a surfactant, a propellant, and a higher alcohol, An oxidative hair dye composition in which the ratio f2 / f1 between the foam specific gravity (f1) of the first agent and the foam specific gravity (f2) of the second agent at the time of discharge is within the range of 1.1 to 3 is exemplified. The The foam specific gravity ratio f2 / f1 is more preferably in the range of 1.3 to 2.8.

  (4) In the above configuration example (3), the first agent and the second agent contain a higher alcohol, the content of the higher alcohol in the first agent (a1) and the content of the higher alcohol in the second agent (a2) And the ratio a2 / a1 is particularly preferably in the range of 0.5 to 2.0.

  (5) Furthermore, in the structural example (3), as the surfactant, a nonionic surfactant, particularly a polyoxyethylene (hereinafter referred to as “POE”) alkyl ether having an alkyl group with 14 or less carbon atoms is used. Certain nonionic surfactants (p14) are preferred. Further, it is more preferable to contain such a nonionic surfactant and a nonionic surfactant (p16) which is a POE alkyl ether having an alkyl group having 16 or more carbon atoms. Further, the content of the nonionic surfactant in the first agent is preferably 1.1 times or more, and preferably 1.5 to 4 times the content in the second agent. More preferable.

  (6) Furthermore, in the structural example (3), in addition to the nonionic surfactant, the surfactant is a cationic surfactant, in particular, a cation that is an alkyltrimethylammonium whose alkyl group has 12 or more carbon atoms. It is further preferable to contain a surfactant.

[Essential component of oxidative hair dye composition]
In the oxidative hair dye, an alkali agent and a dye component are essential in the first agent, and an oxidant is essential in the second agent. Moreover, water is essentially essential in each agent of the oxidative hair dye composition.

(Alkaline agent)
In the oxidative hair dye composition of the present invention, it is premised that the first agent contains one or more alkali agents selected from ammonia and ammonium salts. Although content of these alkali agents in a 1st agent is not specifically limited, Preferably it exists in the range of 0.5-20 mass%.

  Examples of ammonium salts include ammonium salts of inorganic acids such as ammonium carbonate, ammonium bicarbonate, ammonium bicarbonate, ammonium sulfate, ammonium phosphate, and ammonium nitrate, or organic acids such as ammonium citrate, ammonium acetate, ammonium oxalate, and ammonium tartrate. The ammonium salt is preferably exemplified.

  Examples of the first agent include alkali agents other than the above, for example, alkanolamines, organic amines (2-amino-2-methyl-1,3-propanediol, guanidine, etc.), inorganic alkalis (sodium hydroxide, hydroxide) Potassium, etc.), carbonates (sodium carbonate, potassium carbonate, ammonium carbonate, ammonium hydrogen carbonate, etc.), basic amino acids (arginine, lysine, etc.) and their salts, etc., in an appropriate content You may use together. Specific examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, isopropanolamine, dipropanolamine, tripropanolamine, 2-amino-2-methyl-1,3-propanediol, 2- Examples include amino-2-methyl-1-propanol and 2-amino-2-hydroxymethyl-1,3-propanediol.

(Dye component)
In the narrowly-defined oxidative hair dye, the first agent contains a dye component as an essential component. The content of the dye component in the first agent can be appropriately set. The dye component comprises an oxidative dye and / or a direct dye, and the oxidative dye comprises an oxidative dye intermediate or an oxidative dye intermediate and a coupler. The dye component may further contain a melanin precursor and the like.

  An oxidative dye is a compound that can develop color by oxidative polymerization with an oxidizing agent. More specifically, as oxidation dyes, phenylenediamine and derivatives thereof, phenol derivatives, aminophenol and derivatives thereof, diphenylamine and derivatives thereof, pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, pyrrolidine derivatives, toluene derivatives, indole derivatives, pyrrole derivatives. And imidazole derivatives.

  More specifically, for example, oxidative dye intermediates include phenylenediamines (excluding metaphenylenediamine), aminophenols (provided, however, metaaminophenol, 2,4-diaminophenol, and paramethylaminophenol). ), Toluylenediamine (excluding toluene-3,4-diamine and toluene-2,4-diamine), diphenylamines, diaminophenylamines, N-phenylphenylenediamines, diaminopyridines (However, 2,6-diaminopyridine is excluded).

  As couplers, resorcin, pyrogallol, catechol, metaaminophenol, metaphenylenediamine, 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, paramethylaminophenol, 2,4-diaminophenoxyethanol, gallic acid, tannic acid, ethyl gallate, gallic acid Examples include methyl, propyl gallate, pentaploid, 5- (2-hydroxyethylamino) -2-methylphenol, and the like.

  The above-mentioned oxidation dye is a concept including a salt of a compound capable of color development by oxidative polymerization using an oxidizing agent. For example, acid addition salts of the above-mentioned compounds can be mentioned. Preferably, an addition salt of an organic acid, an addition salt of an inorganic acid, or the like is used.

  These oxidation dyes may be blended alone or in combination.

  Examples of direct dyes include acid dyes, basic dyes, natural dyes, nitro dyes, and disperse dyes. These direct dyes may be blended alone or in combination.

  Examples of the acid dye include Red No. 2, Red No. 3, Red No. 102, Red No. 104 (1), Red No. 105 (1), Red No. 106, Red No. 227, Red No. 230 (1), Yellow No. 4, Yellow No. 5, Yellow No. 202 (1), Yellow No. 202 (2), Yellow No. 203, Dai No. 205, Dai No. 207, Dai No. 402, Green No. 3, Green No. 204 Green 401, purple 401, blue 1, blue 2, blue 202, brown 201, black 401 and the like.

  The basic dyes include Basic Blue 3, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 41, Basic Blue 47, Basic Blue 99, Basic Brown 4, Basic Brown 16, Basic Brown 17 , Basic Green 1, Basic Green 4, Basic Orange 1, Basic Orange 2, Basic Orange 31, Basic Red 1, Basic Red 2, Basic Red 22, Basic Red 46, Basic Red 51, Basic Red 76, Basic Red 118, Basic Examples include Violet 1, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet 11: 1, Basic Violet 14, Basic Violet 16, Basic Yellow 11, Basic Yellow 28, Basic Yellow 57, Basic Yellow 87, and the like.

  Examples of the natural dye include gardenia pigments, turmeric pigments, anato pigments, copper chlorophyllin sodium, paprika pigments, and rack pigments.

  Examples of the nitro dye include 4-nitro-o-phenylenediamine, 2-nitro-p-phenylenediamine, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, picramic acid, picric acid, and the like. HC Blue No.2, HC Blue No.5, HC Blue No.6, HC Blue No.9, HC Blue No.10, HC Blue No.11, HC Blue No.12, HC Blue No.13 , HC Orange No.1, HC Orange No.2, HC Orange No.3, HC Red No.1, HC Red No.3, HC Red No.7, HC Red No.10, HC Red No.11, HC Red No.13, HC Red No.14, HC Violet No.1, HC Violet No.2, HC Yellow No.2, HC Yellow No.4, HC Yellow No.5, HC Yellow No.6, HC Yellow No .9, HC Yellow No. 10, HC Yellow No. 11, HC Yellow No. 12, HC Yellow No. 13, HC Yellow No. 14, HC Yellow No. 15 and the like.

  Disperse Black 9, Disperse Blue 1, Disperse Blue 3, Disperse Blue 7, Disperse Brown 4, Disperse Orange 3, Disperse Red 11, Disperse Red 15, Disperse Red 17, Disperse Violet 1, Disperse Violet 4, Disperse Violet 15 etc. can be illustrated.

(Oxidant)
Specific examples of the oxidizing agent include, for example, hydrogen peroxide, urea peroxide, melamine peroxide, sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, sodium peroxide, potassium peroxide, peroxide. Examples thereof include magnesium, barium peroxide, calcium peroxide, strontium peroxide, sulfate hydrogen peroxide adduct, phosphate hydrogen peroxide adduct, pyrophosphate hydrogen peroxide adduct, and the like. These oxidizing agents may be blended singly or in combination of two or more. Among these oxidizing agents, hydrogen peroxide is preferred because of its excellent melanin decolorizing power.

  The content of the oxidizing agent in the second agent is preferably in the range of 0.1 to 15% by mass.

(Surfactant)
Each agent of the oxidative hair dye composition of the present invention contains one or more surfactants. Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. In particular, nonionic surfactants and cationic surfactants are used. It is preferable to contain, and it is preferable to use a nonionic surfactant and an ionic surfactant together.

  Although it does not limit as a cationic surfactant, C16 (carbon number 16) or less alkyltrimethylammonium and its salt are preferable from a viewpoint of foamability improvement. Specific examples include stearyl trimethyl ammonium, lauryl trimethyl ammonium, cetyl trimethyl ammonium, and salts thereof. In addition, the C16 or lower alkyl group in the cationic surfactant is preferably saturated, and is preferably linear, and may be modified with a halogen element or a hydroxyl group. The content of the cationic surfactant in the oxidative hair dye composition is not limited, but is preferably in the range of 0.01 to 6% by mass in the first agent, and 0.01 to 6% by mass in the second agent. Within the range of is preferable.

  Although it does not limit as a nonionic surfactant, from a viewpoint of foaming improvement, C14 or less POE alkyl ether is preferable, Specifically, POE (10) lauryl ether, POE (30) lauryl ether, etc. POE lauryl ether, POE myristyl ether, and the like. C16 or more POE alkyl ethers are also preferable, and specific examples include POE cetyl ethers such as POE (10) cetyl ether and POE (30) cetyl ether, POE stearyl ether, POE behenyl ether and the like. The number of polyoxyethylenes described above is preferably in the range of 2-50. The C14 or lower alkyl group in the nonionic surfactant is preferably saturated and is preferably linear.

  The content of the nonionic surfactant in the oxidative hair dye composition is not limited, but is preferably in the range of 0.5 to 10% by mass in the first agent, and 0.3 to 5% by mass in the second agent. % Is preferable.

  Although the total content of the surfactant in each agent constituting the oxidative hair dye composition is not particularly limited, the first agent is about 0.5 to 10% by mass, and the second agent is 0.3 to 5% by mass. Can be about. When the amount of the surfactant of the first agent is made larger than the amount of the surfactant of the second agent, the foam specific gravity of the first agent can be made relatively small.

  In addition, anionic surfactant is preferable at the point of foamability, and specifically, POE sodium lauryl sulfate etc. can be illustrated. Examples of amphoteric surfactants include lauryldimethylaminoacetic acid betaine.

(water)
Water is a base material for dispersing each other component in each agent constituting the oxidative hair dye composition, and is necessary for making each agent foamy. It is preferable that the compounding quantity of the water in each agent exists in the range of 30-90 mass%.

[Preferred component of oxidative hair dye composition]
Each agent of the oxidative hair dye composition of the present invention preferably contains several kinds of higher alcohols, solvents and the like.

(Higher alcohol)
In the present invention, “higher alcohol” refers to an alcohol having C6 (having 6 carbon atoms) or more. In the oxidative hair dye composition, it is preferable to contain a higher alcohol from the viewpoint of improving the hair dyeing performance and improving the foam quality, and in particular, a higher alcohol having 16 or more carbon atoms (C16 or more) and 14 or less carbon atoms. A combination of higher alcohols (C14 or lower) is preferred.

  As the C16 or higher alcohol and 14 or lower alcohol, monovalent higher alcohols are particularly preferable. These higher alcohols include straight-chain and branched-chain higher alcohols, more preferably straight-chain higher alcohols. Saturated and unsaturated higher alcohols are also included, and saturated higher alcohols are more preferable.

  C16 or higher alcohols include cetyl alcohol (cetanol), 2-hexyldecanol, cetostearyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, aralkyl alcohol, 2-octyldodecanol, behenyl alcohol, decyltetradecanol, lanolin Alcohol etc. can be illustrated. Of these, higher alcohols that are solid at 25 ° C. and 1 atm are preferred, and cetanol, stearyl alcohol, cetostearyl alcohol, aralkyl alcohol, behenyl alcohol, and the like are more preferred.

  Although the compounding quantity of the C16 or higher alcohol in the first agent is not limited, it is preferably in the range of 0.1 to 7% by mass, particularly preferably in the range of 0.2 to 4% by mass. The blending amount of the higher alcohol of C16 or higher in the second agent is not limited, but is preferably in the range of 0.1 to 7% by mass, particularly preferably in the range of 0.2 to 4% by mass.

  Examples of the C14 or higher alcohol include lauryl alcohol, myristyl alcohol, capryl alcohol and the like. More preferred is myristyl alcohol.

  Although the compounding quantity of 14 or less higher alcohol in a 1st agent is not limited, Preferably it exists in the range of 0.1-5 mass%, Most preferably, it exists in the range of 0.2-4 mass%. Although the compounding quantity of 14 or less higher alcohol in a 2nd agent is not limited, Preferably it exists in the range of 0.1-5 mass%, Most preferably, it exists in the range of 0.2-4 mass%.

  In the first agent or the second agent, when a higher alcohol of C16 or higher and a higher alcohol of C14 or lower are blended together, the content (a16) of the higher alcohol of C16 or higher and the content of the higher alcohol of C14 or lower in those cases The mass ratio a16 / a14 with respect to the amount (a14) is preferably in the range of 0.1 to 150, particularly 1 to 20 from the viewpoints of improving foam quality and improving hair dyeing properties. More preferably, it is within the range.

  Furthermore, regarding the above-mentioned various higher alcohols contained in the first agent and the second agent, the ratio of the higher alcohol content (a1) in the first agent to the higher alcohol content (a2) in the second agent a2 / a1 Is preferably in the range of 0.5 to 2.0, and more preferably in the range of 0.8 to 1.7.

(solvent)
Each agent constituting the oxidative hair dye composition may contain a solvent. These contents are preferably 10% by mass or less from the viewpoint of improving hair dyeing properties and from the viewpoint of facilitating emulsification of each agent.

  Examples of the solvent include lower alcohols such as ethanol, n-propanol, and isopropanol, polyols, and lower alkyl ethers thereof. Examples of polyols include glycerin, propylene glycol, dipropylene glycol, 1,3-butylene glycol, ethylene glycol, diethylene glycol, polyethylene glycol (PEG), isoprene glycol, sorbitol, and the like. Examples of the lower alkyl ethers of the polyol include mono-lower alkyl ethers and poly-lower alkyl ethers (for example, di-lower alkyl ethers) of the aforementioned polyols.

[Other components of oxidative hair dye composition]
In addition to the components described above, each agent constituting the oxidative hair dye composition includes, for example, fatty acids, thickeners, amino acids, water-soluble polymers such as hydroxyethyl cellulose, oils, waxes, silicones, hydrocarbons. Sugars such as sorbitol and maltose, antiseptic ingredients such as paraben and sodium benzoate, chelating ingredients such as EDTA-2Na, hydroxyethanediphosphonic acid and its salts, phenoxyethanol, phenacetin, 8-hydroxyquinoline, acetanilide, sodium pyrophosphate, Stabilizing components such as barbituric acid, uric acid and tannic acid, pH adjusting components, plant or herbal extracts, vitamins including ascorbic acids, fragrances and the like may be optionally blended. In addition, for example, at least one selected from those listed in “Quasi-drug raw material standards 2006” (Pharmaceutical Daily) may be blended.

[Aerosol container]
As an aerosol container, each agent of the oxidative hair dye composition is accommodated in a separate space, and a foam-like agent is discharged together from a single discharge port of the head portion, or a plurality of head portions. Various well-known aerosol containers can be used that discharge each foam-like agent separately from the discharge port.

  In these discharge methods, the first agent containing an alkali agent selected from ammonia or ammonium salt is discharged in the form of bubbles from the lower discharge port, and the second agent is covered with the first agent. An aerosol container which is set to be discharged in a foam form from the upper discharge port is particularly preferable. More preferably, it is an aerosol container which is set to be discharged in a foam form from the discharge port so that the second agent covers the periphery of the first agent.

  As an example of a standard aerosol container, an aerosol container disclosed in JP-A-2002-284655 can be given. This aerosol container is provided with two cans in a body portion, and one can is filled with a first agent and a propellant, and the other can is filled with a second agent and a propellant at a predetermined mass ratio. The stem extending from each can communicates with the mixing passage of the head portion through the communication hole, and this mixing passage communicates with the discharge portion that is conducted to the outside only when the discharge lever is pushed. Therefore, when the discharge lever is pressed, the first agent and the second agent are mixed in the mixing passage while being foamed, and discharged from the discharge port of the discharge portion.

  As another example of the aerosol container, an aerosol container disclosed in JP-A-2005-231644 can be exemplified. This aerosol container corresponds to a two-component oxidative hair dye composition, and contains two stock solution containing pouches and a member connecting these pouches in one can, and the first agent and the second agent. The mixture of agents is discharged in the form of foam.

  The material and internal pressure of the aerosol container can be appropriately determined in accordance with the types of alkali agent, oxidizing agent, propellant, and the method for containing each agent.

  Examples of the present invention and comparative examples are described below. The technical scope of the present invention is not limited by these examples and comparative examples.

[First Example Group]
(Preparation of oxidative hair dye composition)
It consists of the 1st agent and 2nd agent which show a composition as "1 agent" and "2 agents", respectively at the last Table 1-Table 5, and it concerns on Example 1- Example 38 and Comparative Example 1- Comparative Example 2. A two-component oxidative hair dye composition (stock solution) was prepared according to a conventional method. In these examples and comparative examples, the unit of the numerical value indicating the blending amount of each component of the first agent and the second agent is “mass%” in the stock solution of the first agent or the second agent. Regarding the component display of the first agent and the second agent, for example, “cetanol (16)”, the number appended in parentheses to the component name of the higher alcohol indicates the carbon number of the higher alcohol. The “remaining amount” described in the column of “purified water” for the first agent and the second agent is so-called Quantum Sufficit, and the total content of all components other than purified water in the stock solution is X (mass% ) Means a numerical value represented by “100-X” (mass%).

  In the column of “2 agents OH / 1 agent OH” in the “2 agents” section of each table, the content of higher alcohol in the second agent (2 agents OH for each example and each comparative example) That is, the mass ratio between the a2) and the content of the higher alcohol in the first agent (one agent OH, ie, the a1) is shown.

(Preparation of aerosol foam hair dye composition)
Next, the first and second agents of the two-component oxidative hair dye composition (stock solution) according to Examples 1 to 38 and Comparative Examples 1 to 2, respectively, are commercially available aerosol-type discharges. Add a propellant (LPG) to a container (aerosol container described in JP-A No. 2002-284655) and fill it to 50 g, and use the propellant (LPG) separately prepared in the container to create an aerosol foam. As the first agent and the second agent of the oxidative hair dye composition, they were discharged in the form of foam.

  As the above-mentioned aerosol-type discharge container, the first agent and the second agent are accommodated in different cans, and the foam-like first agent and the second agent are respectively discharged from the two outlets of the head portion by the action of the propellant. Were used separately, and a system that can increase or decrease the amount of propellant used for foaming the first agent or the second agent was used. This aerosol-type discharge container is a can container having a diameter of 2.7 cm and a length from the top to the bottom (excluding the stem length) of 15 cm. The mass ratio of the stock solution and the propellant in the first agent and the second agent according to each Example and Comparative Example is a column of “stock solution: propellant ratio” in the sections of “1 agent” and “2 agents” in each table. It was shown to.

  By the way, as shown in each table, the mass ratio of the stock solution and the propellant in the first agent and the second agent according to each example and each comparative example is basically unified as “95: 5”. In the case of the first agent according to Examples 35 and 36 in FIG. 5 and the second agent according to Examples 37 and 38, this mass ratio is somewhat changed. Nevertheless, the foam specific gravity of the foamed first agent and second agent to be described later does not change much compared to other examples. Therefore, it can be seen that the mass ratio of the stock solution and the propellant in the first agent and the second agent does not affect the foam specific gravity of the foamed first agent and the second agent so much.

(Measurement of foam specific gravity)
After about 15 g of the foamy first agent and the second agent according to each Example and each Comparative Example were discharged in register, this was completely filled into a cylindrical measuring cup having a known weight (A gram) capacity of 30 ml. Put in the excess foam, and measure the weight (B grams) of the measuring cup in this state. Calculate “(BA) / 30” using “(BA) grams” and “30 ml”. Thus, the foam specific gravity (f1) of the foamy first agent and the foam specific gravity (f2) of the foamy second agent were measured. The measured foam specific gravity (f1) of the first agent is shown in the column of “one agent specific gravity” in the table, and the measured foam specific gravity (f2) of the second agent is shown in the “two agent specific gravity” column of the table. Show. The unit of foam specific gravity is g / ml. In addition, the aerosol type | formula foaming oxidation hair dye composition used for the measurement used the thing of the next day after filling, and used what was discharged for the first time after filling after shaking.

(Evaluation of odor)
The odor was evaluated about the 1st agent and the 2nd agent which concern on each Example and each comparative example which were discharged in foam shape similarly to the said "measurement of foam specific gravity". That is, 10 panelists evaluated whether or not there was an ammonia-stimulating odor while stirring and mixing the foamed first agent and the foamed second agent immediately after discharge as in normal hair dyeing.

  The evaluation criteria are rank “5” when “I do not feel ammonia-stimulated odor”, rank “4” when “I feel ammonia-stimulated odor that I hardly care about”, and “I am a little concerned about ammonia-stimulated odor” "Rank" 3 "," Ammonia stimulated odor is slightly strong "rank" 2 "," Ammonia stimulated odor "is rank" 1 ".

  The average score of the evaluation ranks of the 10 panelists for each evaluation target obtained in this way is calculated. If the average score has a numerical value less than the decimal point, the first numerical value after the decimal point is rounded off. The evaluation rank was determined. The results are shown in the “odor” column at the bottom of each table.

(Mixability evaluation)
In advance, the appropriate amount of Yellow No. 203 was blended into the stock solution of the first agent according to each Example and each Comparative Example, the first agent was colored, and this was combined with the second agent prepared as usual as described above. The aerosol type foamed hair dye composition is discharged as foam as the first agent and second agent, and then the foamy first agent and second agent are used for 10 persons as in normal hair dyeing. The panel was stirred and mixed by hand, and the mixing property at that time was evaluated. The manual operation procedure, the operation speed and the number of operations of the hand in the agitation and mixing were strictly made manual, and each panel was protected. The mixing property was evaluated on the basis of whether or not the colored foam part of the first agent and the uncolored second agent foam part were mixed so uniformly as to be indistinguishable.

  Specifically, the foam part of the first agent and the foam part of the second agent are ranked “5” when “not at all distinguishable”, ranked “4” when “mostly indistinguishable”, “slightly distinguishable” "Rank" is ranked "3", "somewhat clearly distinguishable" is ranked "2", and "clearly distinguishable" is ranked "1".

  The average score of the evaluation ranks of the 10 panelists for each evaluation target obtained in this way is calculated. If the average score has a numerical value less than the decimal point, the first numerical value after the decimal point is rounded off. The evaluation rank was determined. The results are listed in the “mixability” column at the bottom of each table.

(Evaluation of hair dyeing power)
As described above, about 1.5 g each of the foamy first agent and the foamy second agent according to each of the examples and the comparative examples is discharged from the aerosol-type discharge container, and these are the points during normal use. After stirring and mixing in step 1, each hand was applied to 1 g of a white hair bundle sample having a length of 10 cm, and the hair bundle samples were left in a thermostatic bath (30 ° C.) for 30 minutes. Washed with water. Thereafter, the hair bundle samples were each treated once with shampoo and rinse (conditioner) and then dried with warm air.

Ten panelists visually observed the above-mentioned hair bundle sample, and sensory evaluation was performed whether or not the hair dyeing power was good. Specifically, in comparison with the hair dyeing power of a normal foamy oxidative hair dye, the rank “5” indicates that “the hair dyeing power is excellent”, and “the hair dyeing power is somewhat superior”. Rank "4", rank "3" when "hair dyeing power is normal", rank "2" when "hair dyeing power is slightly inferior", rank "1" when "hair dyeing power is inferior" It was. The average score of 10 panelists for each evaluation target obtained in this way is calculated, and if the average score has a numerical value below the decimal point, round the first numerical value below the decimal point. Evaluation rank was determined. The results are shown in the column of “hair dyeing power” at the bottom of each table.
(Evaluation of operability)
In the hair dyeing treatment using the foamed oxidative hair dye composition according to each example and each comparative example, in the application operation, the foam lump drop suppression, the bubble scatter suppression, and the viewpoint of good foam elongation Then, 10 panelists visually observed and evaluated (sensory evaluation) whether or not the operability was good as a comprehensive evaluation of the above three points. Although the evaluation results are not shown in the table, there was a tendency that good results were obtained when the foam specific gravity was small (bubbles were large).

[Second Example Group]
Nonionicity in the composition of Example 1 of the 1st Example group which made foamy 1st agent relatively low foam specific gravity (large foam) rather than foamed 2nd agent, and the stock solution of the foamy 1st agent By reducing the content of the surfactant, the foam specific gravity of the foamed first agent is 0.5 higher than that of Example 34, so that the foam has a higher specific gravity (smaller bubbles) than the foamed second agent. In Comparative Example 3 set to 1), the foamed first agent and the second agent were each discharged and stirred and mixed in an aerosol-type discharge container. "Sex" was evaluated.

  As a result, in the case of Example 1, the elongation at the time of application to hair was good, uniform application was easy, and good operability such that it was difficult to slide off from fingers and hair was seen. However, in the case of the comparative example 3, since the elongation at the time of application to hair was poor, uniform application was difficult, and it was easy to slip off fingers and hair.

[Third Example Group]
Regarding Example 28 in the first example group, the content of cetanol in the first agent was increased to 1.5% by mass, and the content of behenyl alcohol was increased to 0.6% by mass, respectively. The total alcohol content (a1) is changed to 2.1% by mass, so that the ratio a2 / a1 to the total alcohol content (a2) in the second agent is within the range of 0.5 to 2.0. An oxidative hair dye according to Example 28a, which would come off, was prepared.

  On the other hand, conversely to Example 28a, the content of cetanol in the second agent of Example 28 of the first example group was 1.8% by mass, and the content of myristyl alcohol in the second agent was 0.3%. The total content (a2) of the higher alcohol in the second agent was changed to 2.1% by mass by increasing the amount to 2% by mass, respectively, and the ratio a2 with the total content (a1) of the higher alcohol in the first agent An oxidative hair dye was prepared according to Example 28b, where / a1 would fall outside the range of 0.5 to 2.0.

  About the oxidative hair dye which concerns on these Examples 28a and 28b, each foamy 1st agent and 2nd agent are discharged and stirred and mixed with an aerosol-type discharge container, About these foamy mixtures, as above-mentioned When “Mixability” and “Hair-dyeing power” were evaluated, both of the evaluation ranks of “Mixability” and “Hair-dyeing power” were “4” in both Examples 28a and 28b. The evaluation rank of “5” was inferior.

  According to the present invention, there is provided an aerosol-type foam oxidative hair dye composition that suppresses an irritating odor and can maintain good hair dyeing properties by securing the mixing ability of the first agent and the second agent discharged in the form of foam during use Provided.

Claims (1)

Each agent including a first agent containing an alkali agent selected from ammonia or an ammonium salt (excluding those containing a phosphate ) and a second agent containing an oxidizer is discharged in the form of foam during use. Aerosol type foamy hair dye composition to be mixed,
The first agent and the second agent further contain a higher alcohol,
Aerosol-type foam oxidation characterized in that the ratio f2 / f1 of the foam specific gravity (f1) of the first agent and the foam specific gravity (f2) of the second agent during discharge is in the range of 1.1 to 3 Hair dye composition.