JP2009179624A - Multi-layer hair cosmetics - Google Patents

Abstract

To provide an acidic hair cosmetic that is excellent in odor stability and does not wash away.
The wash layer contains an oil layer and an aqueous layer, the aqueous layer has a pH (diluted 20 times by mass, 25 ° C.) of 2 to 5.5, and the oil layer contains a fragrance component selected from the following (a) to (e): No multi-layer hair cosmetics.
(A) an ester having a total number of 3 to 18 carbon atoms represented by the formula R ¹ —COOR ² [R ¹ is an H atom, or C _{1− in} which an O or N atom may be inserted between C—C bonds; ₁₂ hydrocarbon group; R ² is a C _1-15 hydrocarbon group in which an O atom may be inserted between C—C bonds]
(B) Acetal having 4 to 18 carbon atoms (c) Macrocyclic lactone or macrocyclic ether lactone having 15 to 17 carbon atoms (d) Macrocyclic diester having 14 to 15 carbon atoms (e) Phenylacetaldehyde, indole and Compound selected from 4 (3)-(4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde [Selection] None

Description

  The present invention relates to a multilayer hair cosmetic that does not wash away.

  In recent years, due to the chemical treatment with hair color and the physical treatment with blow, etc., peeling of the cuticle on the hair surface and hollowing out of the hair due to the outflow of lipid inside the hair, etc., as a result, the hair becomes dry. It is said that bad fingering, loose hair, and loss of luster may occur.

  As one of means for solving these problems, aqueous hair cosmetics using specific organic acids and organic solvents, which have attempted to modify the hair by acting on the inside of the hair, are known (for example, Patent Documents 1 to 3). However, there is a problem in that the stability of a specific perfume is poor under acidic conditions where these aqueous hair cosmetics are effective.

JP-A-6-172131 JP-A-62-298625 Japanese Unexamined Patent Publication No.7-112921

  An object of the present invention is to provide an acidic hair cosmetic that is excellent in odor stability and does not wash away.

  The present inventors have found that a fragrance component can be stably blended by making a hair cosmetic into a multi-layered dosage form and blending a specific fragrance into the oil layer.

That is, the present invention includes at least an oil layer and an aqueous layer, the pH at 25 ° C when the aqueous layer is diluted 20 times by mass with water is 2 to 5.5, and the oil layer is selected from the following (a) to (e) The present invention provides a multi-layer hair cosmetic that does not wash away and contains one or more fragrance ingredients.
(A) Ester having 3 to 18 carbon atoms represented by general formula (1) R ¹ -COOR ² (1)
[Wherein, R ¹ represents a hydrogen atom or a linear, branched, or cyclic hydrocarbon group having 1 to 12 carbon atoms in which an oxygen atom or a nitrogen atom may be inserted between carbon-carbon bonds; R ² represents a linear, branched or cyclic hydrocarbon group having 1 to 15 carbon atoms in which an oxygen atom may be inserted between carbon-carbon bonds. ]
(B) Acetal having 4 to 18 carbon atoms (c) Macrocyclic lactone or macrocyclic ether lactone having 15 to 17 carbon atoms (d) Macrocyclic diester having 14 to 15 carbon atoms (e) Phenylacetaldehyde , Indole and 4 (3)-(4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde

  The non-washing-out type hair cosmetic of the present invention is excellent in odor stability, has a good scent when applied to the hair, has a moderately strong scent, and further has an oily odor, acid odor and organic High masking effect against solvent odor.

(Oil layer)
-Fragrance | flavor component The fragrance | flavor component (a)-(e) is mix | blended with the oil layer of the multilayer hair cosmetics of this invention.

  Examples of the ester having 3 to 18 carbon atoms represented by the general formula (1) of the fragrance component (a) include terpene esters, aliphatic esters, and aromatic esters.

Among (a), terpene esters include citronellyl formate, geranyl formate, linalyl formate, neryl formate, citronellyl acetate, geranyl acetate, isobornyl acetate, linalyl acetate, ethyl linalyl acetate, tetrahydrolinalyl acetate, neryl acetate, tarpinyl acetate, acetic acid Tetrahydrogeranyl, nopyru acetate, cedolyl acetate, vetiberyl acetate, citronellyl propionate, geranyl propionate, linalyl propionate, neryl propionate, terpinyl propionate and the like.
Particularly preferred are citronellyl acetate, geranyl acetate, isobornyl acetate, linalyl acetate, neryl acetate, terpinyl acetate, cedolyl acetate, and vetiberyl acetate.

Among (a), the aliphatic esters include cis-3-hexenyl formate, α, 3,3-trimethylcyclohexanemethyl formate (IFF trade name Aphalmate), oxyoctaline formate, prenyl acetate, cis-3-hexenyl acetate , Dihydrotricyclodecenyl acetate, ethyl acetate, hexyl acetate, isoamyl acetate, amyl acetate, ot-butylcyclohexyl acetate, pt-butylcyclohexyl acetate, trans-2-hexenyl acetate, tricyclodecenyl acetate, isononyl acetate, Cis-3-hexenyl propionate, tricyclodecenyl propionate, ethyl acetoacetate, ethyl isobutyrate, ethyl butyrate, ethyl 2-methylbutyrate, methyl 2-noninoate (methyloctyne carbonate), cis-3-hexenylmethyl carbonate (IFF product name Rifalome), 2,2-dimethylpropionate 3-methyl-3-buteni (Kao brand name Lomirat), 2-methylpentanoic acid ethyl (dibodan brand name manzanate), allyl caproate, 2-methyl-1,3-dioxolane-2-ethyl acetate (IFF brand name flactone), 2-methylvaleric acid 2-methylvaleryl (Kao brand name Peranat), allyl enanthate, allyl cyclohexyl glycolate, ethyl 2-ethylcaproate (Kao brand name Irotyl), allyl cyclohexanepropionate, methylcyclooctyl carbonate (Kao brand name Jasmasi CRAT), ethyl 3,5,5-trimethylcaproate (Kao brand name Mersat), ethyl 2-cyclohexylpropionate (Kao brand name Polenate), ethyl 2-t-butylcyclohexyl carbonate (Kao brand name Flora mat), ethyltri cyclo [5.2.1.0 ^{2, 6]} decan-2-yl-carboxylate (Kao tradename off Tate), methyl dihydro jasmonate, and the like methyl jasmonate.
Especially cis-3-hexenyl acetate, ethyl acetate, hexyl acetate, isoamyl acetate, amyl acetate, ot-butylcyclohexyl acetate, pt-butylcyclohexyl acetate, trans-2-hexenyl acetate, tricyclodecenyl acetate, tricyclopropionate Decenyl, ethyl acetoacetate, ethyl isobutyrate, ethyl butyrate, ethyl 2-methylbutyrate, ethyl 2-methylpentanoate (dibodan trade name manzanate), allyl caproate, 2-methyl-1,3-dioxolane-2- Ethyl acetate (IFF trade name: flactone), 2-methylvaleryl 2-methylvalerate (Kao trade name: Peranat), allyl enanthate, allylcyclohexyl glycolate, allyl cyclohexanepropionate, ethyl 3,5,5-trimethylcaproate (Kao brand name Mersat), ethyl 2-cyclohexylpropionate (Kao brand name Poare Over g), ethyl 2-t-butylcyclohexyl carbonate (Kao tradename Furoramatto) ethyl tricyclo [5.2.1.0 ^{2, 6]} decan-2-yl-carboxylate (Kao tradename Furuteto), methyl dihydro jasmonate is preferably .

Among the aromatic esters in (a), benzyl formate, phenylethyl formate, benzyl acetate, cinnamyl acetate, dimethylbenzyl carvinyl acetate, paracresyl acetate, phenylethyl acetate, styryl acetate, phenylethyl propionate, styryl propionate, propionate Benzyl acid, dimethylbenzyl carvinyl butyrate, phenylethyl isobutyrate, phenoxyethyl isobutyrate, amyl salicylate, cis-3-hexenyl salicylate, cyclohexyl salicylate, hexyl salicylate, isoamyl salicylate, methyl salicylate, phenylethyl salicylate, benzyl salicylate, benzoic acid Benzyl, methyl benzoate, methyl anthranilate, methyl methyl anthranilate, methyl phenylacetate, phenylethyl phenylacetate, methyl cinnamate, Examples include ethyl enylglycidate, methyl dihydroxydimethylbenzoate (IFF brand name Veramos), and ethyl methylphenylglycidate (aldehyde C-16).
Especially benzyl acetate, cinnamyl acetate, dimethylbenzyl carvinyl acetate, phenylethyl acetate, styrylyl acetate, phenylethyl isobutyrate, phenoxyethyl isobutyrate, amyl salicylate, cis-3-hexenyl salicylate, cyclohexyl salicylate, hexyl salicylate, isoamyl salicylate, salicylic acid Benzyl, benzyl benzoate, methyl anthranilate, methyl methyl anthranilate, methyl cinnamate, methyl dihydroxydimethyl benzoate (IFF brand name Veramos), ethyl methylphenylglycidate (aldehyde C-16) and the like are preferred.

The acetal having 4 to 18 carbon atoms in the fragrance component (b) includes acetaldehyde diethyl acetal, acetaldehyde ethyl linalyl acetal, acetaldehyde ethyl cis-3-hexenyl acetal, acetaldehyde ethyl phenyl ethyl acetal, acetaldehyde phenyl ethyl propyl acetal, octyl aldehyde Glycol acetal, octanal dimethyl acetal, heptanal ethylene glycol acetal, citral dimethyl acetal, citral diethyl acetal, hydroxycitronellal diethyl acetal, hydroxy citronellal dimethyl acetal, phenylacetaldehyde dimethyl acetal, phenylacetaldehyde glyceryl acetal, phenylacetaldehyde ethyleneglycol Acetal, phenylpropyl aldehyde propylene glycol acetal, hydrotropic aldehyde methyl acetal, 4,4,6-trimethyl-2-benzyl-1,3-dioxane, 2-butyl-4,4,6-trimethyl-1,3-dioxane , Tetrahydroindeno-m-dioxane (Simrise trade name Indoflor), dimethyltetrahydroindeno-m-dioxin (Simrise trade name Magnolan), 2- (2,4-dimethyl-3-cyclohexenyl) -5-methyl- 5- (1-methylpropyl) -1,3-dioxane (dibodan trade name Caranal), 5-methyl-5-propyl-2- (1-methylbutyl) -1,3-dioxane (Kao trade name Troenan), 2 4,6-trimethyl-2-phenyl-1,3-dioxane (Simrise trade name Fluoropearl).
In particular, acetaldehyde diethyl acetal, acetaldehyde ethyl linalyl acetal, acetaldehyde ethyl cis-3-hexenyl acetal, acetaldehyde ethyl phenyl ethyl acetal, acetaldehyde phenyl ethyl propyl acetal, phenyl acetaldehyde dimethyl acetal, phenyl acetaldehyde glyceryl acetal, phenyl acetaldehyde ethylene glycol acetal, phenyl propyl Aldehyde propylene glycol acetal, hydrotropic aldehyde dimethyl acetal, tetrahydroindeno-m-dioxane (Simrise trade name Indoflor), dimethyltetrahydroindeno-m-dioxin (Simrise trade name Magnolan), 2- (2,4-dimethyl- 3-Cyclohexenyl) -5-methyl-5- (1-mes Rupropyl) -1,3-dioxane (dibodan trade name caranal), 5-methyl-5-propyl-2- (1-methylbutyl) -1,3-dioxane (Kao trade name Troenan), 2,4,6-trimethyl -2-Phenyl-1,3-dioxane (Simrise trade name Fluoropearl) is preferred.

Examples of macrocyclic lactones or macrocyclic ether lactones having a total carbon number of 15 to 17 in the perfume component (c) include cyclopentadecanolide (Iwata perfume trade name pentaride), hexadecanolide, cis-9-cyclohexadecenolide (Centride), 7-cyclohexadecenolide (ambretride), oxacyclohexadecen-2-one (Filmenich trade name Havanolide), 10-oxahexadecanolide (Takasago International Corporation trade name oxalide), 11-oxa Hexadecanolide (dibodan brand name musk R1), 12-oxahexadecanolide (dibodan brand name cerboride) and the like can be mentioned.
In particular, 7-cyclohexadecenolide (ambretride), oxacyclohexadecen-2-one (Filmenich trade name Havanolide), and cyclopentadecanolide (Iwata Fragrance trade name pentaride) are preferable.

  Examples of the macrocyclic diester having a total carbon number of 14 to 15 in the fragrance component (d) include ethylene brushate and ethylene dodecanedioate (trade name Musk C-14, Takasago Fragrance Industry Co., Ltd.), and ethylene brushate is particularly preferable. .

  The perfume component (e) is selected from phenylacetaldehyde, indole and 4 (3)-(4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde (Lilal).

  These fragrance | flavor components (a)-(e) can be used individually or in combination of 2 or more types. The blending amount of the fragrance components (a) to (e) is preferably 0.001 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, particularly 0.05 to 0.5% by mass, based on the intensity of the fragrance. % Is preferred.

  In addition to the fragrance components (a) to (e), the hair cosmetic composition of the present invention further includes other fragrance components, such as “Fundamental knowledge of fragrance and fragrance” (edited by Motoki Nakajima, Sangyo Tosho Co., Ltd., 1995) Synthetic fragrances, natural fragrances, blended bases and the like described in the first edition of June 21) can be blended as flavoring agents.

  Synthetic perfumes include hydrocarbons such as limonene, α-pinene, β-pinene; alcohols such as linalool, citronellol, geraniol, menthol, phenylethyl alcohol; ethoxymethylcyclododecyl ether (Kao brand name Boazin Brenforte), 3α, Ethers such as 6,6,9α-tetramethyldodecahydronaphtho [2,1-b] furan (Kao brand name ambroxan); decylaldehyde, citral, α-hexylcinnamic aldehyde pt-butyl-α-methylhydroxycin Aldehydes such as Namic Aldehyde (IFF trade name Liliar); methylionone, β-ionone, 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl Naphthalene (IFF trade name IsoE Super), ketones such as Damasenone; 6-acetylhexatetralin (PFW trade name Tonalide), Such Kisa methyl hexahydrocyclopenta benzopyran (IFF tradename Garakusorido) are exemplified.

  Examples of natural fragrances include essential oils such as orange, lemon, lime, bergamot, lavender, lavandine, peppermint, spearmint, mint, patchouli, and resinoids such as olivanum, elemi, benzoin, perubalsum, and troutsum. .

-Highly polymerized silicone It is preferable to mix highly polymerized silicone in the oil layer. Examples of the highly polymerized silicone include dimethicone (dimethylpolysiloxane), dimethiconol (dimethylpolysiloxane having a hydroxy end group), and amino-modified silicone.

  The number average degree of polymerization of the highly polymerized silicone is 1000 to 20000, preferably 2000 to 15000. The blending amount of the highly polymerized silicone is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass with respect to the entire hair cosmetic composition of the present invention, from the viewpoint of ease of extension to the hair, smoothness and unity. Is preferably 2 to 8% by mass, particularly 3 to 7% by mass. Moreover, the compounding quantity with respect to the oil layer of highly polymerized silicone is 3-80 mass% from the same viewpoint, Furthermore, 5-65 mass%, Especially 9-50 mass% is preferable.

  Specific examples of commercially available highly polymerized silicone products include SH200-1,000,000cs (Toray Dow Corning; High Polymerization Dimethicone), TSF451-100MA (Momentive Performance Materials; High Polymerization Dimethicone), BY11-026 (Toray・ Dow Corning: Diluted solution of highly polymerized dimethicone with low viscosity silicone), KF9008 (Shin-Etsu Chemical; diluted solution of highly polymerized dimethicone with cyclic silicone), BY22-050A (Toray Dow Corning: anion of highly polymerized dimethicone) Emulsion), BY22-060 (Toray Dow Corning Co .; Cationic emulsion of a solution obtained by diluting highly polymerized dimethicone with low-viscosity silicone), BY22-020 (Toray Dow Corning Co., Ltd .; Solution obtained by diluting highly polymerized dimethicone with light liquid isoparaffin) Cation emulsion), KM904 (Shin-Etsu Chemical Co., Ltd .; low viscosity of highly polymerized dimethicone) Cationic emulsion of solution diluted with silicone), DC1501 Fluid (Toray Dow Corning; diluted solution of highly polymerized dimethiconol with cyclic silicone), DC1503 Fluid (Toray Dow Corning: diluted solution of highly polymerized dimethiconol with low viscosity dimethicone) , X-21-5849 (Shin-Etsu Chemical Co., Ltd .; highly polymerized dimethiconol) X-21-5666 (Shin-Etsu Chemical Co., Ltd .; dilute solution of highly polymerized dimethiconol with cyclic silicone), X-21-5613 (Shin-Etsu Chemical Co., Ltd .; high Diluted solution of polymerized dimethiconol with low viscosity dimethicone), TSF4705 (Momentive Performance Materials; highly polymerized amino-modified silicone).

-Volatile oil In order to lower the viscosity of the oil layer and dissolve the highly polymerized silicone, it is preferable to add volatile oil to the oil layer. Volatile oils include volatile silicones and hydrocarbons. Among these, it is preferable to use a low boiling chain silicone oil, a low boiling cyclic silicone oil, a low boiling isoparaffinic hydrocarbon, or the like. Here, the low boiling point means that the boiling point is 260 ° C. or less at normal pressure.

  The low-boiling chain silicone is represented by the following general formula. Specific examples thereof include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, hexadecamethylheptasiloxane, and the like, such as KF-96A- 5cs, KF-96L-2cs (Shin-Etsu Chemical Co., Ltd.), etc.

[In formula, a shows the integer of 0-5. ]

  Cyclic silicones are represented by the following general formula, and specific examples include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetradecamethylcycloheptasiloxane, and the like, such as KF994, KF995 (Shin-Etsu Chemical Co., Ltd.)

[Wherein, b represents an integer of 3 to 7. ]

  Examples of the low-boiling isoparaffinic hydrocarbon include light liquid isoparaffin having a boiling point of 260 ° C. or less at normal pressure, a purified product of isododecane, a mixture of aliphatic hydrocarbons having various chain lengths, and the like. Commercially available products include IP Solvent (Idemitsu Petrochemical), Marukasol (Company), and the like.

  Of these, volatile silicones, especially cyclic silicones, are preferred to obtain a refreshing feel and finish without stickiness. Among these, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane are used in airtight containers. It is preferably used because it exists relatively stably. In order to obtain a moist feeling of use and a finished feeling, volatile hydrocarbons, particularly low-boiling isoparaffinic hydrocarbons are preferred. Among these, light liquid isoparaffin, particularly isododecane is preferable. These volatile oils enhance the drying of the aqueous hair cosmetic and form a strong cosmetic coating film of highly polymerized silicone on the hair by volatilization.

  Volatile oils can be used alone or in combination of two or more, and the total blending amount is preferably from 5 to 69.5% by mass, more preferably from 20 to 60% by mass, especially with respect to the entire hair cosmetic of the present invention. 30-50 mass% is preferable. Furthermore, the mass ratio of highly polymerized silicone to volatile oil is highly polymerized silicone: volatile from the viewpoints of optimizing the mixing and separating properties of the oil layer and aqueous layer, ease of extension to the hair, smoothness, and cohesion. Oil = 1: 30 to 3: 1, more preferably 1:20 to 2: 1, particularly 1:10 to 1: 1. In addition to the above components, lower alcohols such as ethanol and isopropyl alcohol may be added.

-Other silicones In the oil layer, silicones other than highly polymerized silicones and volatile silicones can be further blended in order to improve the conditioning effect.

-Oil agent An oil agent can be further mix | blended with an oil layer for the improvement of the unity feeling of the hair after drying. Oils include squalene, squalane, liquid isoparaffin, heavy liquid isoparaffin, α-olefin oligomer, liquid paraffin, cycloparaffin and other hydrocarbons; castor oil, cocoa oil, mink oil, avocado oil, olive oil and other glycerides; beeswax, Waxes such as whale wax, lanolin, microcrystalline wax, ceresin wax, carnauba wax; higher alcohols such as cetyl alcohol, oleyl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol; octyldodecyl myristate, hexyl laurate, lactic acid Cetyl, propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, isononyl isononanoate, tridecyl isononanoate, isoprotyl palmitate Esters such as pills; capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, coconut oil fatty acid, isostearyl acid, isopalmitic acid and other higher fatty acids; other isostearyl glyceryl ethers, polyoxy Examples include propylene butyl ether. Among these, branched hydrocarbons such as squalene, squalane, liquid isoparaffin, heavy liquid isoparaffin, and α-olefin oligomer are particularly preferable.

  The blending amount of the oil agent is preferably 0.1 to 10% by mass, more preferably 0.5 to 4% by mass, particularly 1 to 3% by mass with respect to the entire hair cosmetic composition of the present invention from the viewpoint of good unity and no stickiness. Mass% is preferred.

[Water layer]
It is preferable to mix | blend C2-C8 organic carboxylic acid or its salt with a water layer. Examples of the organic carboxylic acid include glycolic acid, lactic acid, citric acid, tartaric acid, malic acid, levulinic acid, acetic acid, maleic acid, and fumaric acid. Of these, α-hydroxy acids are preferable, and glycolic acid, citric acid, malic acid, and lactic acid, particularly malic acid, lactic acid, and citric acid are preferable. Examples of these salts include salts with alkali metals, alkaline earth metals, ammonia, organic amine compounds and the like.

  Two or more organic carboxylic acids or salts thereof may be used in combination, and at least malic acid or a salt thereof is preferably used. The blending amount of the organic carboxylic acid or its salt is a free acid equivalent amount for the entire hair cosmetic composition of the present invention in terms of the effect of internal modification (such as cavity repair) of hair, the effect of improving set retention, and the effect of improving unity. 0.5 to 10% by mass is preferable, further 1 to 8% by mass, and particularly 2 to 6% by mass is preferable.

・ Hydrophilic organic solvent The water layer contains a hydrophilic organic solvent selected from the group consisting of aromatic alcohol, N-alkylpyrrolidone, alkylene carbonate, polypropylene glycol, lactone and cyclic ketone, and ClogP of −2 to 3. It is preferable to do.

  Examples of such hydrophilic organic solvents include the following (a) to (e).

  (A) Aromatic alcohol represented by general formula (2)

[Wherein R ³ represents a group R ⁴ —Ph—R ⁵ — (R ⁴ ; a hydrogen atom, a methyl group or a methoxy group, R ⁵ ; a bond or a saturated or unsaturated divalent carbon atom having 1 to 3 carbon atoms. Hydrogen group, Ph; paraphenylene group), Y and Z each represent a hydrogen atom or a hydroxyl group, and p, q, and r each represent an integer of 0 to 5. However, when p = q = 0, Z is not a hydrogen atom and R ³ is not a group R ⁴ -Ph-. ]

  (B) N-alkylpyrrolidone having a C 1-18 alkyl group bonded to a nitrogen atom

  (C) C3-C4 alkylene carbonate

  (D) Polypropylene glycol having a number average molecular weight of 100 to 1000

  (E) Lactone or cyclic ketone represented by general formula (3), (4) or (5)

[Wherein, X represents a methylene group or an oxygen atom, R ⁶ and R ⁷ represent different substituents, and s and t represent 0 or 1. ]

Among these hydrophilic organic solvents, (a) includes benzyl alcohol, cinnamyl alcohol, phenethyl alcohol, p-anisyl alcohol, p-methylbenzyl alcohol, phenoxyethanol, 2-benzyloxyethanol and the like. Examples of (b) include N-methylpyrrolidone, N-octylpyrrolidone, N-laurylpyrrolidone and the like. Examples of (c) include ethylene carbonate and propylene carbonate. As (d) polypropylene glycol having a number average molecular weight of 100 to 1000, those having a number average molecular weight of 100 to 500, particularly those having a polymerization degree of 2 to 5 are preferred. In (e), R ⁶ and R ⁷ in the general formulas (3) to (5) are linear, branched or cyclic alkyl groups, hydroxyl groups, sulfonic acid groups, phosphoric acid groups, carboxy groups, phenyl groups. , A sulfoalkyl group, an alkyl phosphate group, a carboxyalkyl group, etc. are preferable. In particular, in the case of γ-lactone, the γ-position is substituted, and in the case of δ-lactone, the δ-position (that is, the methylene adjacent to the hetero oxygen atom) is substituted. C1-C6 linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl and butyl groups are preferred. When it is desired to increase the water solubility of the compounds (3) to (5), R ⁶ or R ⁷ has an acidic group such as a sulfonic acid group, a phosphoric acid group or a carboxy group, or an alkyl group substituted with these. Is preferred. Among (e), examples of the lactone include γ-butyrolactone, γ-caprolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, δ-heptanolactone, and the like, from the viewpoint of lactone stability. Γ-lactone, particularly γ-butyrolactone and γ-caprolactone are preferred. Among (e), examples of the cyclic ketone include cyclopentanone, cyclohexanone, cycloheptanone, 4-methylcycloheptanone, and the like.

  Particularly preferred hydrophilic organic solvents include benzyl alcohol, benzyloxyethanol, propylene carbonate and polypropylene glycol (number average molecular weight 300 to 500, particularly 400).

  The hydrophilic organic solvent used in the present invention is preferably a liquid at 25 ° C., and ClogP is preferably −2 to 3, particularly preferably −1 to 2 from the viewpoint of promoting penetration. Here, ClogP is a calculated value of the octanol-water-partition coefficient (logP) defined by the following formula, which is a scale representing the distribution of substances between the octanol phase and the water phase. An example is described in Vol. 71, No. 6 (1971).

logP = log ([Substance] _Octanol / [Substance] _Water )

[In the formula, [Substance] _Octanol represents the molar concentration of the substance in the 1-octanol phase, and [Substance] _Water represents the molar concentration of the substance in the aqueous phase. ]

  Specifically, ClogP, the main hydrophilic organic solvent, is benzyl alcohol (1.1), 2-benzyloxyethanol (1.2), 2-phenylethanol (1.2), 1-phenoxy-2-propanol (1.1), polypropylene Glycol 400 (0.9), propylene carbonate (-0.41), and γ-butyrolactone (-0.64).

  Two or more types of hydrophilic organic solvents may be used in combination. The amount of the hydrophilic organic solvent is optimized for the mixing and separating properties of the oil layer and the aqueous layer, the feeling of use, the gloss of hair and the promotion of the modification effect (elasticity) Of the hair cosmetic composition of the present invention is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, further 0.5 to 4% by mass, particularly 1 to 5%. 3 mass% is preferable.

  The mass ratio of the organic carboxylic acid or a salt thereof and the hydrophilic organic solvent is used to effectively exhibit the effect of improving internal hair (such as cavity repair), the improvement of set retention, and the improvement of unity. Salt: hydrophilic organic solvent = 10: 1 to 1: 7, particularly preferably 4: 1 to 1: 3.

-Water The content of water in the water layer is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, and particularly preferably 30 to 50% by mass with respect to the entire hair cosmetic composition of the present invention.

-Ethanol In the water layer, ethanol can be further blended. Ethanol contributes to solubilization or stable dispersion of the hydrophilic organic solvent (ClogP = −2 to 3). The blending amount of ethanol is preferably 0.5 to 20% by mass, particularly 1 to 15% by mass, based on the entire hair cosmetic composition of the present invention. The mass ratio of ethanol to the hydrophilic organic solvent is ethanol: hydrophilic organic solvent = 40: 1 to 2: 1, particularly from the viewpoint of promoting penetration of the organic carboxylic acid or salt thereof and the hydrophilic organic solvent into the hair. The range of 20: 1 to 3: 1 is preferable.

-Set polymer You may mix | blend a set polymer with a water layer from a viewpoint of the improvement of hair-styling property, stability, the improvement of the adhesiveness at the time of hair application | coating, touch improvement, and the hair modification effect early expression. Such polymers include polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymer, vinylpyrrolidone / vinyl acetate / vinyl propionate terpolymer, vinylpyrrolidone / alkylaminoacrylate (quaternary chloride) copolymer, vinyl Polyvinyl pyrrolidone polymer compounds such as pyrrolidone / acrylate / (meth) acrylic acid copolymer, vinyl pyrrolidone / alkyl amino acrylate / vinyl caprolactam copolymer; acidic vinyl ether such as methyl vinyl ether / alkyl maleic anhydride alkyl half ester copolymer Polymer compounds; acidic polyvinyl acetate polymer compounds such as vinyl acetate / crotonic acid copolymer, vinyl acetate / crotonic acid / vinyl neodecanoate copolymer, vinyl acetate / crotonic acid / vinyl propionate copolymer; Acid acrylic polymer such as (meth) acrylic acid / (meth) acrylic acid ester copolymer, acrylic acid / acrylic acid alkyl ester / alkylacrylamide copolymer; N-methacryloylethyl-N, N-dimethylammonium α Amphoteric acrylic polymer compounds such as -N-methylcarboxybetaine / butyl methacrylate copolymer, hydroxypropyl acrylate / butylaminoethyl methacrylate / octylamide acrylate copolymer; acrylamide / acrylic ester quaternary copolymer Examples include basic acrylic polymer compounds such as coalescence; chitin / chitosan derivatives such as hydroxypropyl chitosan, carboxymethyl chitin, and carboxymethyl chitosan.

  These set polymers can be used singly or in combination of two or more, and the content thereof is 0.1 to 10% by mass, particularly 0.5 to 5% by mass with respect to the entire hair cosmetic composition of the present invention. preferable.

Surfactant A surfactant can be added to the aqueous layer from the viewpoints of system stability including solubilization and dispersibility of the solvent and improvement in feel. As the surfactant, any of a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and an anionic surfactant can be used.

  Examples of the cationic surfactant include quaternary ammonium salts represented by the following general formula (6).

[In the formula, R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 28 carbon atoms or a benzyl group, and simultaneously a hydrogen atom or a benzyl group; Except when it becomes an alkyl group. Z ⁻ represents an anion. ]

Here, one of R ⁸ and R ⁹ is preferably an alkyl group having 16 to 24 carbon atoms, more preferably 16 to 18 carbon atoms, particularly a linear alkyl group, and the other is a lower alkyl group having 1 to 3 carbon atoms. In particular, a methyl group is preferable. Examples of the anion Z ⁻ include halide ions such as chloride ions and bromide ions; organic anions such as ethyl sulfate ions and methyl carbonate ions, and halide ions, particularly chloride ions are preferable.

  As the cationic surfactant, mono long-chain alkyl quaternary ammonium salts are preferable, and specific examples include cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, aralkyltrimethylammonium chloride, and behenyltrimethylammonium chloride. Stearyl trimethyl ammonium and behenyl trimethyl ammonium chloride are preferable.

  Nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, higher fatty acid sucrose ester, polyglycerin fatty acid ester, higher fatty acid mono- or diethanolamide, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid Examples thereof include esters, polyoxyethylene sorbite fatty acid esters, alkyl saccharide surfactants, alkyl amine oxides, and alkyl amido amine oxides. Of these, polyoxyalkylene alkyl ether and polyoxyethylene hydrogenated castor oil are preferable, and polyoxyethylene alkyl ether is particularly preferable.

  Examples of amphoteric surfactants include imidazoline series, carbobetaine series, amide betaine series, sulfobetaine series, hydroxysulfobetaine series, and amide sulfobetaine series.

  Anionic surfactants include alkyl benzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, Examples include α-sulfone fatty acid salts, N-acyl amino acid type surfactants, phosphate mono- or diester type surfactants, and sulfosuccinate esters.

  Counter ions of the anionic residue of the surfactant include alkali metal ions such as sodium ion and potassium ion; alkaline earth metal ions such as calcium ion and magnesium ion; ammonium ion; alkanol group having 2 or 3 carbon atoms Alkanolamine having 1 to 3 (for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.).

  Examples of the counter ion of the cationic residue of the surfactant include halide ions such as chloride ion, bromide ion and iodide ion, methosulphate ion and saccharinate ion.

  Of these, cationic surfactants are preferred from the viewpoint of feel. Surfactants can be used alone or in combination of two or more. From the viewpoint of system stability including solubilization of solvent, emulsification of oil agent, suspension stability during mixing, etc. 0.01-5 mass% with respect to the whole hair cosmetics of this invention, Furthermore, 0.05-3 mass%, Especially 0.1-1 mass% is preferable. From the viewpoint of optimizing the mixing / separating properties of the oil layer and the water layer, imparting smoothness to the hair, and easiness of elongation to the hair, the mass ratio of hydrophilic organic solvent: surfactant is 500: 1 to 1. : 10, more preferably 100: 1 to 1: 5, and particularly preferably 10: 1 to 1: 2.

-Water-soluble polymer thickener It is preferable to mix a water-soluble polymer thickener in the water layer. Examples of the water-soluble polymer thickener include polysaccharides, acrylic acid polymer compounds, carboxyvinyl polymers, polyvinyl alcohol, polyvinyl pyrrolidone, and derivatives thereof. In particular, polysaccharides and acrylic acid polymer compounds, and derivatives thereof are preferable.

  Examples of the polysaccharide include cellulose, guar gum, cellulose gum, and starch. As the polysaccharide derivative, those substituted with one or more of the substituents shown below are preferred.

  Examples of the substituent include a lower alkyl group such as a methyl group, an ethyl group, and a propyl group that may be substituted by a hydroxy group; a linear or branched group having 8 to 40 carbon atoms that may be substituted by a hydroxy group. Alkyl group, alkenyl group, arylalkyl group, alkylaryl group, alkoxy group, alkoxyalkyl group, alkenyloxy group, alkenyloxyalkyl group, arylalkyloxy group, arylalkyloxyalkyl group, alkylaryloxy group, alkylaryloxyalkyl Group: alkyl glyceryl ether group having a linear or branched alkyl group having 10 to 40 carbon atoms, alkenyl glyceryl ether group having a linear or branched alkenyl group having 10 to 40 carbon atoms; polyoxyethylene group, polyglycerin group , Sulfoalkyl group, trimethylammonium And a trimethylammonium alkyl group. In addition, when these substituents have a hydroxy group, the hydroxy group may be further substituted with another substituent described above.

  Specific examples of polysaccharide derivatives include hydroxyethyl cellulose, hydroxyethyl guar gum, hydroxyethyl starch, methyl cellulose, methyl guar gum, methyl starch, ethyl cellulose, ethyl guar gum, ethyl starch, hydroxypropyl cellulose, hydroxypropyl guar gum, hydroxypropyl starch, hydroxy Ethyl methyl cellulose, hydroxyethyl methyl guar gum, hydroxyethyl methyl starch, hydroxypropyl methyl cellulose, sodium stearoxy PG hydroxyethyl cellulose sulfonate, laureth-13PG hydroxyethyl cellulose, stearoxy PG hydroxyethyl cellulose, cationized hydroxyethyl cellulose (polyquaternium-10), hydroxypropylmethy Examples include lugua gum and hydroxypropylmethyl starch.

  Specific examples of the acrylic acid polymer compound or derivative thereof include polyacrylic acid, polymethacrylic acid, acrylic acid methacrylic acid copolymer, acrylic acid-alkyl methacrylate copolymer, alkyl acrylate copolymer, polyacrylic acid. Acid, sodium polyacrylate, polyacrylamide, cationized diethyl methacrylate / cationized acrylic amide / dimethacrylic acid polyethylene glycol copolymer (polyquaternium-52), cationized methacryloylethyl polymer (polyquaternium-37) ) And the like.

  Among these, polymers having emulsifying ability are preferable, and specifically, stearoxy PG hydroxyethyl cellulose sodium sulfonate, laureth-13PG hydroxyethyl cellulose, stearoxy PG hydroxyethyl cellulose, cationized hydroxyethyl cellulose (polyquaternium-10), (acrylic acid / acrylic) An alkyl acid (C10-30)) copolymer, a (hydroxyethyl acrylate / acryloyldimethyltaurine Na) copolymer, and the like are preferable.

  The blending amount of the water-soluble polymer thickener is 0.005 to 5% by mass based on the total amount of the hair cosmetic composition of the present invention from the viewpoint of improving the mixing state immediately after mixing and also improving the separation state after standing. More preferably, it is 0.01 to 2% by mass, particularly 0.05 to 1% by mass.

-Polyhydric alcohol Furthermore, a polyhydric alcohol can be mix | blended with an aqueous layer. The polyhydric alcohol contributes to solubilization and stable dispersion of the hydrophilic organic solvent, and works synergistically with the hydrophilic organic solvent to promote improvement of the gloss and hair modifying effects. Examples of the polyhydric alcohol include ethylene glycol, glycerin, sorbitol, propylene glycol, 1,3-butylene glycol, dipropylene glycol and the like, and glycerin, propylene glycol, 1,3-butylene glycol and dipropylene glycol are particularly preferable. A polyhydric alcohol can be used individually or in combination of 2 or more types, and the compounding quantity is 0.5-5 mass% with respect to the whole hair cosmetics of this invention, Especially 1-3 mass% is preferable.

・ PH
The aqueous layer is adjusted to a pH of 2 to 5.5 at 25 ° C when diluted 20-fold with water from the viewpoint of performance such as hair elasticity, gloss improvement, flexibility, cohesion, and suppleness. Furthermore, it is preferable to adjust the pH to 2.5 to 5, particularly pH 3 to 4.5. In order to adjust the pH within the above range, it is preferable to use sodium hydroxide, potassium hydroxide or the like in addition to the organic carboxylic acid described above.

  The water layer suppresses changes in pH during hair application, promotes the penetration of organic carboxylic acids and organic solvents into the hair, provides a buffering capacity for the early manifestation of hair-modifying effects and further improvement of the effect. Is 0.001 gram equivalent / L or more and less than 0.2 gram equivalent / L, preferably 0.003 gram equivalent / L or more and less than 0.1 gram equivalent / L, more preferably 0.005 gram equivalent / L or more and 0.05 gram equivalent / L. Less than L. Here, the buffer capacity in the present invention refers to a value obtained by the following equation using the concentration of a base required to raise the pH of a 5 mass% aqueous solution at 25 ° C. by 1 from the initial value.

Buffer capacity = | dC _B / dpH |

Wherein, C _B represents an ion concentration of the base (gram equivalent / L). ]

  Such buffering ability can be imparted by adding a pH buffer or the like to the hair cosmetic. As the pH buffering agent, a combination of an organic acid or an inorganic acid having a buffering action in the range of pH 2 to 5.5 and a salt thereof can be used. As the organic acid, the aforementioned organic carboxylic acid is used, and as the inorganic acid, for example, phosphoric acid, sulfuric acid, nitric acid and the like can be mentioned. Examples of these acid salts include alkali metal salts such as sodium salts and potassium salts; ammonium salts; alkanolamine salts such as triethanolamine salts. The blending amount of the pH buffering agent is not particularly defined, and varies depending on the type of compound that provides the buffering capacity. For example, when sodium citrate is used as a compound that mainly provides buffering capacity, it is blended at a concentration of about 1% by mass or more.

[Other components (common to oil layer and water layer)]
In addition to the above-described components, the hair cosmetic of the present invention can be appropriately mixed with components used in normal hair cosmetics depending on the purpose. Examples of such components include anti-dandruff agents, vitamin agents, bactericides, anti-inflammatory agents, antiseptics, chelating agents, moisturizers such as panthenol, coloring agents such as dyes and pigments, plant extracts, pearlizing agents, and the like. Ultraviolet absorbers; antioxidants; and other components described in ENCYCLOPEDIA OF SHAMPOO INGREDIENTS (MICELLE PRESS).

  In the hair cosmetic composition of the present invention, the mass ratio of the oil layer to the water layer is 15:85 from the viewpoint of achieving smoothness, gloss, and cohesion of the hair with the modification of the hair, and ease of mixing. It is preferable to be -70: 30, especially 30: 70-60: 40.

  The hair cosmetic composition of the present invention may be a three-layer type or more having an oil layer, an emulsified layer, a powder layer, or the like that does not dissolve in the oil layer and the water layer, in addition to the two-layer type composed of the oil layer and the water layer. . The hair cosmetic composition of the present invention is preferably used as a hair styling agent, a hair conditioning agent that does not wash away, and the like.

  Since the effect of the hair cosmetic of the present invention is the highest immediately after mixing, in order to clarify the period when the high effect is exhibited, one of the oil layer and the water layer is colored, or both are colored with different colors, It is preferable to fill a transparent or translucent container. Thereby, it becomes possible to judge the degree of mixing visually, and it is easy to draw out the effect of hair cosmetics.

  A dye is used for coloring, and an acid dye and a basic dye are preferable, and an acid dye is particularly preferable. More specifically, examples of acidic dyes include blue No. 1, purple No. 401, black No. 401, orange No. 205, red No. 227, red No. 106, yellow No. 203, Acid Orange 3, and the like. Basic Blue 99, Basic Brown 16, Basic Brown 17, Basic Red 76, Basic Red 51, Basic Yellow 57, Basic Yellow 87, Basic Orange 31 and the like.

[Filling into containers]
The oil layer and the water layer of the hair cosmetic composition of the present invention are preferably prepared separately and filled into a container with a filling machine equipped with two nozzles. In the filling procedure into the container, it is preferable to fill the upper oil layer after filling the lower water layer.

〔how to use〕
Further, the hair cosmetic composition of the present invention is shaken well before use, taken out by hand before separation into an oil layer and an aqueous layer, and well stretched with a palm before being applied to hair. After application, the penetration of the organic carboxylic acid and the hydrophilic organic solvent into the hair can be promoted by heating or natural drying. Heating is particularly preferred, and a dryer, heater, iron, or the like can be used for heating. The temperature is preferably 50 ° C. or higher, particularly 70 ° C. or higher.

Examples and Comparative Examples (Production Methods)
Examples (double-layer hair cosmetics; formulation 1 or 2)
After each fragrance | flavor of Tables 2-6 is diluted with solvent DPG (dipropylene glycol) according to the intensity | strength of the fragrance, a final density | concentration is set to the unscented oil layer in the prescription 1 or prescription 2 of Table 1. It added so that it might become 0.1 mass% of double layer type hair cosmetics.
Moreover, the compounding fragrance | flavor (fruit tone fragrance | flavor HC) of Table 8 was added to the unscented oil layer in the prescription 1 of Table 1 so that a final concentration might be 0.1 mass% of a two-layer type hair cosmetic.
9 g of the oil layer was weighed into a 50 mL standard bottle (transparent), and two each of which 11 g of the aqueous layer of the formulation 1 in Table 1 was added were prepared.

・ Comparative example (single-layer hair cosmetics; formulation 3)
Each of the fragrances listed in Tables 2 to 6 is diluted with a solvent DPG (dipropylene glycol) according to the strength of the scent, and then the final concentration is applied to the unscented composition in Formula 3 of Table 1 for hair makeup. It added so that it might become 0.1 mass% of a material. Two hair cosmetics were prepared by weighing 20 g each in a 50 mL standard bottle (transparent).
Also, two preparations were prepared by adding the blended fragrances (fruit fragrance HC) listed in Table 8 to the unscented composition in Formula 3 of Table 1 so that the final concentration was 0.1% by mass of the hair cosmetic. did.

(Evaluation methods)
Each hair cosmetic was stored in a constant temperature layer at 5 ° C. and 60 ° C. for 10 days, and then the odor was evaluated. The evaluation was based on products stored at 5 ° C., and the odor of products stored at 60 ° C. was evaluated by a specialist panel according to the following evaluation criteria.
In Tables 2-7, the result of the said evaluation is shown together with the name and the compounding quantity of each fragrance | flavor raw material, and a DPG compounding quantity.

・ Odor stability evaluation criteria A: Equivalent odor compared to products stored at 5 ℃, very stable B: Slightly different odor compared to products stored at 5 ℃, but almost stable C: Products stored at 5 ℃ Compared with odor, slightly stable, but quite stable D: Slightly different odor compared with 5 ° C storage product, but stable E: Compared with 5 ° C storage product, smell different, unstable F: Stored at 5 ° C Compared to products, smell is clearly different and very unstable

Claims (7)

1 or more types of fragrance | flavors in which pH in 25 degreeC when including an oil layer and an aqueous layer at least when diluted 20 mass times with water is 2-5.5, and an oil layer is chosen from following (a)-(e) A multi-layered hair cosmetic that contains ingredients and does not wash away.
(A) Ester having 3 to 18 carbon atoms represented by general formula (1) R ¹ -COOR ² (1)
[Wherein, R ¹ represents a hydrogen atom or a linear, branched, or cyclic hydrocarbon group having 1 to 12 carbon atoms in which an oxygen atom or a nitrogen atom may be inserted between carbon-carbon bonds; R ² represents a linear, branched or cyclic hydrocarbon group having 1 to 15 carbon atoms in which an oxygen atom may be inserted between carbon-carbon bonds. ]
(B) Acetal having 4 to 18 carbon atoms (c) Macrocyclic lactone or macrocyclic ether lactone having 15 to 17 carbon atoms (d) Macrocyclic diester having 14 to 15 carbon atoms (e) Phenylacetaldehyde , Indole and 4 (3)-(4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde   The multilayer hair cosmetic according to claim 1, wherein the mass ratio of the oil layer to the water layer is 15:85 to 70:30.   The multilayer hair cosmetic according to claim 1 or 2, wherein the oil layer contains a highly polymerized silicone having a number average polymerization degree of 1000 to 20000.   The multilayer hair cosmetic composition according to any one of claims 1 to 3, wherein the oil layer contains volatile oil.   The multilayer hair cosmetic composition according to any one of claims 1 to 4, wherein the aqueous layer contains an organic carboxylic acid having 2 to 8 carbon atoms or a salt thereof.   The multilayer hair cosmetic composition according to any one of claims 1 to 5, wherein the aqueous layer contains a surfactant.   The multilayer hair cosmetic composition according to any one of claims 1 to 6, wherein the aqueous layer contains a water-soluble polymer thickener.