JP6338387B2 - Hair cosmetics - Google Patents

Description

  The present invention relates to a mist-like hair cosmetic containing an anionic polymer.

  In hair cosmetics, in order to increase the holding power of a hairstyle, it is common to increase the blending amount of a set polymer or oil. Depending on the purpose, a plurality of set polymers may be used in combination in the hair cosmetic. For example, Patent Document 1 discloses a hair cosmetic that uses a specific polyether polycarbonate and an anionic polymer in combination for the purpose of providing a hair cosmetic that has both excellent hair styling and feel. Patent Document 2 discloses a mist-like hair styling agent that uses a specific polyether polycarbonate and a specific acrylate polymer or a specific solvent in combination.

  On the other hand, a technique for masking a base odor by blending a fragrance in a hair cosmetic is well known. For example, in Patent Document 3, as a fragrance for masking the odor of a malodorous hair styling polymer, particularly a cationic hair styling polymer contained in a styling shampoo composition, 15 to 75 mass% ionone fragrance and 5 to 65 mass% An odor masking base comprising ja fragrance and 20-80% by weight of a highly volatile fragrance is disclosed. Patent Document 4 discloses an external preparation capable of masking an acrylic odor containing at least one fragrance selected from a fragrance group having an orange note and at least one fragrance selected from a fragrance group having a green note. It is disclosed. Patent Document 5 discloses that citrus essential oils such as orange essential oils and / or their constituent components are excellent in masking of off-flavors caused by resins such as acrylic resin odors. Patent Document 6 discloses a masking composition and a masking method for hair cosmetics using a blended fragrance material, and particularly discloses a masking composition containing 0.001 to 10% by weight of a surfactant. .

JP 2010-168294 A JP 2011-251918 Special table 2001-507371 JP 2001-181164 A JP 2001-220343 A Japanese Patent Laid-Open No. 2003-137758

  When the hair cosmetics of Patent Documents 1 and 2 are sprayed in a mist, the styling is improved by spraying in the mist, while the hair cosmetics become mist-like droplets around the face. In some cases, the base odor peculiar to hair cosmetics was strongly detected.

  On the other hand, the odor masking base described in Patent Document 3 contains a large amount of ionone and musk with low diffusivity and strong fragrance. The fragrance is suitable for masking, but when sprayed in the form of a mist, there is a problem that the scent is too strong and uncomfortable because the fragrance component is volatilized in the air in a larger amount than a normal washing type product. It was.

  Further, when citrus fragrance is used as in Patent Documents 4 and 5, since citrus fragrance is a fragrance excellent in diffusibility, when applied to hair cosmetics sprayed in a mist, it is more than usual. In some cases, the perfume was volatilized much faster, and it was insufficient in obtaining sufficient scent intensity to mask odor.

  In addition, when considering to perfume a refreshing floral and fruity scent that is highly acceptable to consumers as a hair cosmetic, Ionone or It was difficult to mask the polymer odor by blending a large amount of musk and citrus fragrance.

  The present invention masks the base odor peculiar to hair cosmetics that is strongly felt immediately after spraying the hair cosmetic in a mist state, and has a slight fragrance with a moderate fragrance intensity even when used around the face, and is refreshing The present invention relates to a mist-like hair cosmetic having a scent.

  The present inventors have found that an unpleasant base odor strongly felt immediately after spraying hair cosmetic in a mist is derived from a polymer containing acrylic acid and alkyl acrylate as structural units. And when analyzing the polymer, as the odor component peculiar to the polymer, in addition to alkyl acrylate such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, etc., it contains a plurality of volatile components, In the case of the dosage form sprayed in the form of a mist, it has been found that among these odor components, the influence of butyl acrylate is particularly great.

  As a result of intensive studies based on the above findings, the present inventors have found that a specific fragrance material which is solid at room temperature and has a relatively weak fragrance in a stationary state is a mist-like makeup among fruity floral fragrance materials. The present inventors have found that the unpleasant odor derived from the acrylic acid polymer when blended into the material can be masked, and the scent has a moderate strength.

That is, the present invention includes the following component (Ai) and component (Bi), and the mass ratio [Ai] / [Bi] between the content of component (Ai) and the content of component (Bi) is 1250 or more and 10,000 The following mist-like hair cosmetics are provided.
(Ai): An anionic set polymer containing a structural unit represented by the following general formula (a-1) and a structural unit represented by the following general formula (a-2) 0.05% by mass or more and 7.5% by mass or less

[Wherein, R ¹ and R ² represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to ³ carbon atoms, and R ³ represents a hydrocarbon group having 2 to 20 carbon atoms. ]
(Bi): 4- (4-Hydroxyphenyl) butan-2-one In hair cosmetics, 0.00004% by mass to 0.001% by mass

  The mist-like hair cosmetic of the present invention has a high hair set holding power by an anionic polymer, suppresses the base odor derived from an anionic polymer that is felt immediately after spraying, and is too strong when the hair cosmetic is sprayed. A refreshing and sweet scent is obtained.

[Component (Ai): Anionic set polymer containing (a-1) and (a-2) as structural units]
The anionic set polymer of the component (Ai) is a component for setting hair, and contains the structural unit (a-1) and the structural unit (a-2) in the molecule.

In the structural unit (a-1), R ¹ and R ² are a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a hydrogen atom, a methyl group, or a methoxy group is preferable. In the structural unit (a-2), R ³ is a hydrocarbon group having 2 to 20 carbon atoms, more preferably a hydrocarbon group having 2 to 10 carbon atoms, and a hydrocarbon group having 2 to 5 carbon atoms. Is more preferable.

  Specific examples of such components (Ai) include acrylic acid / ethyl acrylate / Nt-butylacrylamide copolymer (BASF Ultrahold 8, Ultrahold Strong, etc.), octylacrylamide / acrylic acid copolymer (National Starch) Anformer V-42, etc.), acrylate / methacrylate / acrylic acid / methacrylic acid copolymer (Union Carbide Amahold DR25, etc.), acrylates / diacetone acrylamide copolymer (Kyoto Chemical Co., Ltd. plus size L-9540B, L -53 etc.).

  In addition, from the viewpoint of making the hair cosmetic composition excellent in setability and re-styling, and not having a feeling of stiffness, a part or all of the carboxy group of the structural unit (a-1) is in an unneutralized acid form. Preferably it is present. In the polymer of component (Ai), the proportion of the equivalent of the base used for neutralization with respect to the carboxy group of the acid type before neutralization is 0 to 40%, further 0 to 20%, and further 0 to 10%. Is preferred.

  Among these, the anionic set polymer of component (Ai) is an unneutralized acrylates / diacetone acrylamide copolymer (also known as alkyl acrylate / methacrylic acid alkyl ester) from the viewpoint of hair cosmetic setting and re-styling. -Diacetone acrylamide / methacrylic acid copolymer) is preferable (plus size L-53, etc. from Kyoyo Chemical Industry Co., Ltd.).

  The content of the component (Ai) in the mist-like hair cosmetic of the present invention (when the mist-like hair cosmetic is an aerosol type, the content in the stock solution composed of components excluding the propellant. The same applies hereinafter) is not sticky. From the viewpoint of having good set retention and re-styling properties, it is 0.05% by mass or more in hair cosmetics, 0.08% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.5% by mass or more. Moreover, it is 7.5 mass% or less, 5 mass% or less, Furthermore, 2.5 mass% or less is preferable.

(Component (Bi): 4- (4-hydroxyphenyl) butan-2-one)
Component (Bi) is 4- (4-hydroxyphenyl) butan-2-one. 4- (4-Hydroxyphenyl) butan-2-one is also called raspberry ketone and is known as a characteristic component of raspberry scent. In addition, component (Bi) has a sweet and fruity fruit fragrance, but is a crystalline solid and weak in fragrance at room temperature. However, in the state of mist-like hair cosmetics, it is a component excellent in masking performance against the base odor derived from component (Ai). For this reason, for example, when the component (Ai) having a non-neutralized acidic group is used for the purpose of improving the setting property of the mist-like hair cosmetic, the non-neutralized acrylate / diacetone acrylamide copolymer is used. Is used, the base odor derived from the component (Ai) is remarkably increased, but the base odor can be masked even if the component (Bi) is incorporated in a small amount.

  The content of the component (Bi) in the mist-like hair cosmetic of the present invention is 0.00004% by mass or more in the hair cosmetic from the viewpoint of masking the base odor derived from the component (Ai), 0.00008% by mass or more, Furthermore, 0.0001 mass% or more, further 0.0003 mass% or more is preferable. Moreover, it is 0.001 mass% or less with respect to the total amount of hair cosmetics from a viewpoint of obtaining a refreshing and sweet fragrance with mist-like hair cosmetics, fully exhibiting a masking effect.

  The mass ratio [Ai] / [Bi] of the content of the component (Ai) and the content of the component (Bi) in the mist-like hair cosmetic of the present invention obtains a good masking effect on the odor of the acrylic acid derivative. From the viewpoint, it is 1250 or more, preferably 1500 or more, and more preferably 2000 or more. From the same viewpoint, it is 10000 or less, preferably 7500 or less, and more preferably 5000 or less.

[Component (B-ii): Lactone compound represented by formula (b-2)]
The mist-like hair cosmetic of the present invention may further contain a lactone compound represented by the general formula (b-2) as the component (B-ii).

[Wherein, R ⁴ represents an alkyl group having 5 to 8 carbon atoms. ]

  This lactone compound is a fragrance ingredient that has a fruity floral fragrance and enhances the masking effect on the acrylic acid derivative polymer without changing the intensity of the fragrance when used in combination with the ingredient (Bi).

  Component (B-ii) includes 5-octyldihydrofuran-2 (3H) -one (lactone C-12 gamma), 5-heptyldihydrofuran-2 (3H) -one (aldehyde C-14 peach), 5 -Pentyldihydrofuran-2 (3H) -one (aldehyde C-18 coconut). Any of the components (B-ii) can be used alone or in combination of two or more.

  The content of the component (B-ii) in the mist-like hair cosmetic of the present invention is from the viewpoint of obtaining a good masking effect on the odor of the acrylic acid derivative, and obtains an appropriate scent intensity when the preparation is sprayed. From this point of view, 0.00004% by mass or more, further 0.00008% by mass or more, further 0.0001% by mass or more, and further 0.0003% by mass or more in the hair cosmetic is preferable. Further, from the viewpoint of obtaining a refreshing and sweet fragrance with a slight fragrance, 0.002% by mass or less in the hair cosmetic is preferable.

  The total content of the component (Bi) and the component (B-ii) in the mist-like hair cosmetic of the present invention is from the viewpoint of obtaining a good masking effect on the odor of the acrylic acid derivative, and when the preparation is jetted. From the viewpoint of obtaining a slightly fragrant sweet scent, it is preferably 0.00008% by mass or more, more preferably 0.0001% by mass or more, further 0.0005% by mass or more, and further preferably 0.001% by mass or more in the hair cosmetic. In addition, when the hair cosmetic is sprayed in the form of a mist, the content is preferably 0.003% by mass or less, and more preferably 0.001% by mass or less from the viewpoint of obtaining a moderate fragrance intensity and a slightly fragrant sweet scent.

  In addition, since the component (Bi) strongly recalls the image of fruits derived from raspberries, from the viewpoint of obtaining a slightly fragrant sweet scent having a sweetness different from the scent characteristics of the component (Bi), the component (Bi) When the component (B-ii) is used in combination, the mass ratio [Bi] / [B-ii] of both is preferably 0.1 or more, 1 or less, more preferably 0.5 or less, and further 0.33 or less, Furthermore, 0.25 or less is preferable.

  The mass ratio of the content of component (Ai) and the total content of components (Bi) and (B-ii) is 625 or more from the viewpoint of obtaining a good masking effect on the odor of the acrylic acid derivative, and more 800 or more, more preferably 1000 or more is preferable. Further, it is preferably 7500 or less, more preferably 5000 or less, and further preferably 3750 or less.

[Component (C): Fragrance composition containing component (Ci) and not containing components (Bi) and (B-ii)]
The foggy hair cosmetic of the present invention may further contain a fragrance composition comprising a fragrance other than the components (Bi) and (B-ii). As the fragrance composition comprising the fragrance other than the components (Bi) and (B-ii), known fragrances can be used, but variations in the fragrance tone are maintained while maintaining a good masking effect on the odor of the acrylic acid derivative. From the viewpoint of expanding the above, a fragrance composition (component (C)) containing at least the following component (Ci) and not containing components (Bi) and (B-ii) is preferred.

  (C-i): an ester compound having no aromatic ring structure, represented by the following general formula (c-1)

[In the formula, R ⁵ may have a cyclic structure, and the alkyl group, alkenyl group, alkyl group or alkylalkoxy group having 2 to 10 carbon atoms in total (any one hydrogen atom of these substituents is an oxygen atom R ⁶ represents a straight-chain alkyl group or straight-chain alkenyl group having 1 to 4 carbon atoms. ]

As the ester compound having no aromatic ring structure of component (c-1), it has a fruity floral fragrance, and it is derived from component (Ai) by using in combination with component (Bi) and component (B-ii). From the viewpoint of obtaining an excellent masking effect against the base odor, butyl 2-methylbutanoate, methyl 2-cyclopentylidene acetate, ethyl 2-tert-butylcyclohexyl carbonate (Kao product name: Flora mat), ethyl tricyclo [ 5.2.1.0 ^2,6 ] Decan-2-yl carboxylate (Kao product name: Frutate), allyl cyclohexane propionate, ethyl 2-methyl-1,3-dioxolan-2-yl acetate (IFF company name: Flactone) ), Propyl propionate, and ethyl 2-methylbutyrate are preferably used.

  Ingredient (Ci) is 0.01 mass of the total amount of ingredient (Bi), ingredient (B-ii) and ingredient (C) from the viewpoint of increasing the variation of fruity floral fragrance and obtaining a fresh and sweet scent. % Or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 5% by mass or more. Further, from the viewpoint of obtaining a slightly fragrant scent, 50% by mass or less, further 40% by mass or less, further 30% by mass or less of the total amount of the component (Bi), the component (B-ii) and the component (C), Furthermore, 20 mass% or less is preferable.

  The content of the component (C-i) in the mist-like hair cosmetic of the present invention is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, and further preferably 0.001% by mass or more in the hair cosmetic. From the viewpoint of obtaining a refreshing and sweet scent without being too strong, the content of the component (C-i) in the mist-like hair cosmetic of the present invention is preferably 0.05% by mass or less, more preferably 0.03% by mass or less. Furthermore, the total content of component (Bi), component (B-ii) and component (Ci) in the mist-like hair cosmetic of the present invention is 0.00005% by mass or more in the hair cosmetic, further 0.00008% by mass or more, Further, 0.0001% by mass or more, further 0.0005% by mass or more, more preferably 0.001% by mass or more, and further preferably 0.002% by mass or more, and 0.053% by mass or less, further 0.04% by mass or less, and further 0.032% by mass or less. Is preferred.

  Furthermore, the ratio [Bi] / [Ci] of the content [Ci] (mass%) of the component (Ci) and the content [Bi] (mass%) of the component (Bi) is good for the odor of the acrylic acid derivative From the viewpoint of creating a fruity floral fragrance while exhibiting a good masking effect, 0.01 or more, 0.02 or more, further 0.025 or more, further 0.033 or more, more preferably 0.05 or more, preferably 1 or less, Further, it is preferably 0.5 or less, more preferably 0.33 or less, further 0.025 or less, and further preferably 0.2 or less.

Furthermore, the component (C) preferably contains an alcohol compound of the following component (C-ii) from the viewpoint of expanding the variation of the fragrance while maintaining a good masking effect on the odor of the acrylic acid derivative.
(C-ii): 4-Methyl-3-decen-5-ol (Givaudan, trade name: Undecabertoal), 2-methyl-4-phenylpentanol (Firmenich, trade name: Pamplefleur) , 3-methyl-1-butanol, and 2,6-dimethylheptan-2-ol (dimethol)

  These alcohol compounds are perfume ingredients having a fruity or floral fragrance, and are excellent in the masking effect of acrylic acid derivative odor, and are excellent in acrylic acid in combination with the components (Bi) and (B-ii). The masking effect of the derivative odor can be exhibited.

  Ingredient (C-ii) is 0.01 mass% or more of the total amount of ingredient (Bi), ingredient (B-ii) and ingredient (C) from the viewpoint of creating a fruity floral fragrance, and further 0.1 mass% In addition, it is preferable to add 1% by mass or more, further 3% by mass or more, and further 5% by mass or more, and the total amount of component (Bi), component (B-ii) and component (C). It is preferable to add 50% by mass or less, further 40% by mass or less, and further 30% by mass or less.

  In addition, the content of the component (C-ii) in the mist-like hair cosmetic of the present invention is 0.00001% by mass or more, more preferably 0.0001% by mass in the hair cosmetic from the viewpoint of obtaining a refreshing and sweet scent without being too strong. % Or more, preferably 0.001% by mass or more, 0.05% by mass or less, and further preferably 0.03% by mass or less.

  The total amount of component (Bi), component (B-ii) and component (C-ii) in the mist-like hair cosmetic of the present invention is 0.00005% by mass or more, more preferably 0.00008% by mass or more in the hair cosmetic. Further, 0.0001% by mass or more, further 0.0005% by mass or more, more preferably 0.001% by mass or more, and further preferably 0.002% by mass or more, and 0.053% by mass or less, further 0.04% by mass or less, and further 0.032% by mass. The following is preferred.

Furthermore, the component (C) may further contain an aldehyde compound of the following component (C-iii) from the viewpoint of expanding the variation of the fragrance while maintaining a good masking effect on the odor of the acrylic acid derivative. preferable.
(C-iii): 2,6-dimethyl-5-heptenal (meronal), isocyclocitral, and 3- (3,4-methylenedioxyphenyl) -2-methylpropanal (IFF, trade name: helional) One or more selected from

  These aldehyde compounds are fragrance ingredients having a fruity or floral fragrance, and are also excellent in the masking effect of acrylic acid derivative odor, and excellent acrylic acid in combination with the components (Bi) and (B-ii). Demonstrates masking effect of derivative odor

  Component (C-iii) is 0.01% by mass or more of the total amount of component (Bi), component (B-ii) and component (C), and further 0.1% by mass from the viewpoint of creating a fruity floral fragrance. In addition, it is preferable to add 1% by mass or more, further 3% by mass or more, and further 5% by mass or more, and the total amount of component (Bi), component (B-ii) and component (C). It is preferable to add 50% by mass or less, further 40% by mass or less, and further 30% by mass or less.

  The content of the component (C-iii) in the mist-like hair cosmetic of the present invention is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, and further preferably 0.001% by mass or more in the hair cosmetic, and is too strong. From the viewpoint of obtaining a refreshing and sweet scent, the content is preferably 0.05% by mass or less, and more preferably 0.03% by mass or less.

  The total amount of component (Bi), component (B-ii) and component (C-iii) in the mist-like hair cosmetic of the present invention is 0.00005% by mass or more, more preferably 0.00008% by mass or more in the hair cosmetic. Further, 0.0001% by mass or more, further 0.0005% by mass or more, further 0.001% by mass or more, and further 0.002% by mass or more are preferable, 0.053% by mass or less, and further 0.04% by mass or less and 0.032% by mass or less are preferable.

Furthermore, it is preferable that the component (C) further contains the following component (C-iv) from the viewpoint of expanding the variation of the fragrance while maintaining a good masking effect on the odor of the acrylic acid derivative.
(C-iv): 2-methyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol (Kao product name: Sandalmysolcore), cyclopenta Decanolide (Awata Inc., trade name: Pentalide), 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl cyclopenta-γ-2-benzopyran (IFF) Product name: Galaxolide), 4- (2,6,6-trimethyl-2-cyclohexen-1-yl) -3-methyl-3-buten-2-one (methylionone), 4- (2,6,6- Trimethyl-2-cyclohexen-1-yl) -3-buten-2-one (ionone α), 4- (2,6,6-trimethyl-1-cyclohexen-1-yl) -3-buten-2-one (Ionone β), 4- (2-methylene-6,6-dimethylcyclohexyl) -3-buten-2-one (ionone γ), 7-acetyl-1,2,3,4,5,6,7, 8-Octahydro-1,1,6,7-tetramethylnaphthalene (IFF, trade name: Iso E Super), 6-acetyl-1,1,2,4,4,7-hexa Chill tetrahydronaphthalene (PFW aroma chemicals trade name: tonalide), and one or more selected from ethylene brassylate

  Ingredient (C-iv) is a fragrance ingredient belonging to musk or woody note, and from the viewpoint of creating a fresh and sweet fruity floral fragrance, ingredient (Bi), ingredient (B-ii) and ingredient It is preferable to add 0.001% by mass or more of the total amount of (C), more preferably 0.01% by mass or more, and further preferably 0.1% by mass or more of components (Bi), (B-ii) and (C). It is preferable to add 14% by mass or less of the total amount, further 10% by mass or less, further 5% by mass or less, further 3% by mass or less, further 2% by mass or less, and further 1% by mass or less.

  The content of the component (C-iv) in the mist-like hair cosmetic of the present invention is 0.00001% by mass or more in the hair cosmetic, further 0.00005% by mass or more, further 0.0001% by mass or more, and further 0.001% by mass or more. From the viewpoint of obtaining a refreshing and sweet scent without being too strong, it is preferably 0.01% by mass or less, more preferably 0.005% by mass or less, and further preferably 0.002% by mass or less.

  Furthermore, the component (C) is one selected from the following components (Cv-1) to (Cv-7) from the viewpoint of expanding the variation of the fragrance as long as the fragrance of the fruity floral is not impaired. Or you may contain 2 or more types.

  (Cv-1): cis-3-hexenol, linalool, geraniol, nerol, tetrahydrolinalol, ethyl linalool, citronellol, 1-phenylethyl alcohol, 2-phenylethyl alcohol, benzyl alcohol, phenoxyethyl alcohol, 4-methoxybenzyl alcohol , Synamic alcohol, 3-phenylpropyl alcohol, 1-phenyl-2-methyl-2-butanol, 4-phenyl-2-methyl-3-butanol, 1-phenyl-3-methyl-3-pentanol, 3- Methyl-5-phenyl-1-pentanol, thymol, 2-methyl-5-isopropylphenol, eugenol, isoeugenol, anethole, dihydroanethole, estragole, methyl eugenol, isomethyl eugenol

(Cv-2): Citral, citronellal, rilal, perilaldehyde, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde (Givaudan trade name: Ligstral / IFF trade name: tripral), 3,5-dimethyl -3-cyclohexene-1-carboxaldehyde (Givaudan product name: Ligstral / IFF company name: tripral), 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde, 3- ( 4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde, 4- (tricyclo [5.2.1.0 ^2,6 ] decylidene-8) -butanal (Dupical), p-methylphenylacetaldehyde, phenylpropionaldehyde , Cyclamenaldehyde, p-tert-butyl-α-methyl hydrocinnamic aldehyde (Lilyal), cinnamaldehyde, α-a Arsine Na aldehyde, alpha-hexyl cinnamic aldehyde, salicylaldehyde, anisaldehyde, o-methoxybenzaldehyde, vanillin, ethyl vanillin, heliotropin

  (Cv-3): acetaldehyde diethyl acetal, 2-butyl-4,4,6-trimethyl-1,3-dioxane, 5-methyl-5-propyl-2- (1-methylbutyl) -1,3-dioxane ( Kao Product Name: Troenan)

  (Cv-4): cis-jasmon, dihydrojasmon, cycloten, α-damasenone, β-damasenone, γ-damasconone, α-damascon, β-damascon, δ-damascon, isodamascon, α-dynascon, acetyl cedrene, nootkaton , Isolongifolanone, anisylacetone

  (Cv-5): 1,8-cineole, rose oxide, nerol oxide, limetole, dodecahydro-3a, 6,6,9a-tetramethylnaphtho [2.1-b] furan (Kao product name: ambroxan), β -Naphthyl methyl ether, β-naphthyl ethyl ether

  (Cv-6): ethyl formate, propyl formate, butyl formate, amyl formate, isoamyl formate, linalyl formate, citronellyl formate, geranyl formate, afermate, benzyl formate, ethyl acetate, ethyl acetoacetate, propyl acetate, isopropyl acetate, butyl acetate , Isobutyl acetate, n-amyl acetate, isoamyl acetate, cis-3-hexenyl acetate, trans-2-hexenyl acetate, heptyl cetate, octyl acetate, 3-octyl acetate, nonyl acetate, myrenyl acetate, linalyl acetate, citro Neryl acetate, geranyl acetate, neryl acetate, ethyl linalyl acetate, terpinyl acetate, menthyl acetate, bornyl acetate, cedolyl acetate, cyclohexane Xyl acetate, menthanyl acetate, 2-tert-butylcyclohexyl acetate, tricyclodecenyl acetate, benzyl acetate, p-cresyl acetate, phenylethyl acetate, anisyl acetate, rosephenone, dimethylbenzylcarbinyl acetate, acetyleugenol , Acetylisoeugenol, ethyl acetoacetate, ethyl propionate, propyl propionate, decenyl propionate, tricyclodecenyl propionate, linalyl propionate, geranyl propionate, propyl butyrate, isopropyl butyrate, allyl butyrate, butyl Butyrate, amyl butyrate, isobutyl butyrate, isoamyl butyrate, ethyl isobutyrate, ethyl valerate, butyl valerate, isobutyl valerate, yoshi Amyl acid, cis-3-hexenyl valerate, ethyl isovalerate, propyl isovalerate, allyl isovalerate, butyl isovalerate, isobutyl isovalerate, isoamyl isovalerate, methyl hexanoate, ethyl hexanoate, hexane Allyl acid, benzyl benzoate, methyl anisate, amyl hexanoate, ethyl o-methoxybenzoate, ethyl phenylacetate, methyl salicylate, ethyl salicylate, amyl salicylate, benzyl salicylate, cis-3-hexenyl salicylate, ethyl phenylpropionate, Divescon, ethyl safranate, allyl cyclohexylpropionate, allyl cyclohexyloxy acetate (Simrise Inc .; cyclogalvanate), methylcyclooctyl carbonate (Kao; Jasma cyclat), methyl dihydrojasmonate, Chill jasmonate, methyl ATRA rate, Ok Chin carboxylate, phenylglycidic methyl, 3-methyl-3-phenyl-glycidic acid ethyl, coumarin

  (C-v-7): Limonene, osymene, p-cymene, α-pinene, β-pinene

  Ingredients (Cv-1) to (Cv-5) maintain a good masking effect on the odor of the acrylic acid derivative, and from the viewpoint of reinforcing the fragrance without disturbing the fragrance of the fruity floral, It is preferable to add 0.01% by mass or more, further 0.1% by mass or more, further 1% by mass or more, and further 5% by mass or more of the total amount of component (Bi), component (B-ii) and component (C). Further, it is preferable to add 15% by mass or less, further 14% by mass or less, further 13% by mass or less, and further 12% by mass or less.

  Ingredients (Cv-6) to (Cv-7), while maintaining a good masking effect on the odor of the acrylic acid derivative, and without impairing the fragrance of the fruity floral, It is preferable to add 0.01% by mass or more, further 0.1% by mass or more, further 1% by mass or more, and further 5% by mass or more of the component (Bi), the component (B-ii) and the component (C). It is preferable to add 20% by mass or less, more preferably 15% by mass or less.

  The total amount of the components (Cv-1) to (Cv-7) in the mist-like hair cosmetic of the present invention is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, and 0.03% by mass in the hair cosmetic. Hereinafter, it is further preferably 0.02% by mass or less, and further preferably 0.01% by mass or less. From the viewpoint of obtaining a refreshing and sweet scent without being too strong, it is desirable that the content of the component (C) in the hair cosmetic does not exceed 0.03% by mass.

  In addition, from the viewpoint of imparting a fruity floral scent, the fruits (Bi), (B-ii), (Ci), (C-ii), (C-iii) and (Cv) listed as fruity, The total amount of the floral fragrance is preferably 20 to 100% by mass of the total amount of the component (Bi), the component (B-ii) and the component (C).

[(D): Polyether polycarbonate]
The mist-like hair cosmetic composition of the present invention is characterized in that its own polymer-to-polymer adhesion (hereinafter referred to as “self-adhesion”) is high, but the adhesion to other objects (hereinafter referred to as “adhesion”) is low. From the viewpoint of imparting adhesiveness having the following (hereinafter referred to as “self-selective adhesiveness”), it is preferable to further blend a polyether polycarbonate containing the following general formula (d-1) as a structural unit.

In the general formula (d-1), A represents an alkylene group having 2 to 6 carbon atoms, and (n × p) AOs may be the same or different, but are composed of at least two alkyleneoxy groups. Is preferred. A is preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and (n × p) AOs further comprising a combination of an ethyleneoxy group and a propyleneoxy group. preferable. When (AO) _n is composed of different alkyleneoxy groups, these may be block structures or random structures, but are preferably random structures. In the general formula (1), n is a number of 5 to 1000 indicating the average number of added moles of an alkyleneoxy group, and a number of 10 to 500 is preferable. p is a number of 5 to 100 indicating the average number of repeats of the [(AO) _n COO] group, and a number of 5 to 50 is preferred.

  The polyether polycarbonate of component (D) can also contain structural units other than the general formula (d-1), but from the viewpoint of improving self-selective adhesion, the general formula (A) contained in the polymer of component (D) ( The proportion of the structural unit of d-1) is preferably 70% or more and 100% or less, preferably 80% or more and 100% or less, preferably 90% or more and 100% or less, and preferably 98% or more and 100% or less.

  The polyether polycarbonate can be produced, for example, by the method described in JP 2010-168294 A.

  The polyether polycarbonate of component (D) used in the present invention exhibits good self-selective adhesiveness in a wide molecular weight range by using in combination with the anionic polymer of component (Ai), and has high set retention and re-styling properties. Have. The weight average molecular weight of the polyether polycarbonate is preferably 50,000 or more, more preferably 70,000 or more, and even more preferably 100,000 or more, from the viewpoint of good self-selective adhesiveness. Further, from the viewpoint of ease of blending into hair cosmetics, cleanability at the time of washing, etc., 1 million or less is preferable, 700,000 or less is more preferable, and 500,000 or less is more preferable.

  In addition, the mass average molecular weight of polyether polycarbonate and the number average molecular weight of the above-mentioned polyether diol shall mean the polystyrene conversion value measured by gel permeation chromatography (GPC).

  The self-adhesiveness of the polyether polycarbonate, the property value indicating the adhesion between the same polymers to be measured is "self-adhesion", and the property value indicating the adhesion between the polymer to be measured and the others is "other adhesion" In this case, the relative ratio of the other adhesion force / self-adhesion force is desirably 0.7 or less, more preferably 0.5 or less, and still more preferably 0.3 or less. Further, it is desirable that the self-adhesion force is in a range of 200 gf or more. More preferably, the self-adhesion force is 200 gf or more, and the other adhesion force is 140 gf or less, more preferably 120 gf or less, and still more preferably 100 gf or less.

  When measuring the self-adhesion force and other adhesion force, a 20% toluene solution of the polymer to be measured is prepared, cast into a sheet at a constant thickness, the solvent is completely evaporated, and the polymer to be measured is measured. Adjust the coating. When measuring the self-adhesion force, the same polymer film as the measurement target is attached to the probe tip of the tacking tester, and the adhesion between the target film and the film attached to the probe tip is measured using the tacking tester. It is done. The other adhesion force can be obtained by attaching a polypropylene disk to the probe tip of the tacking tester and measuring the adhesive force between the target film and the disc attached to the probe tip using the tacking tester.

  The content of the polyether polycarbonate of the component (D) in the mist-like hair cosmetic of the present invention is not sticky and is 0.5% by mass or more, more preferably 1% by mass or more in the hair cosmetic from the viewpoint of good set holding power. Furthermore, 1.5 mass% or more is preferable, 20 mass% or less, further 15 mass% or less, and further 10 mass% or less is preferable.

[(A-ii): Anionic set polymer other than component (Ai)]
The hair cosmetic composition of the present invention contains, as a component (A-ii), an anionic set polymer other than the component (Ai), from the viewpoint of improving hair setting properties without increasing the problem of base odor. It is preferable to do. Examples of such component (A-ii) include xanthan gum, carrageenan, sodium alginate, pectin, farcelan, gum arabic, gatch gum, karaya gum, tragacanth gum, agar powder, carboxymethylcellulose, and the like, methyl vinyl ether / alkyl maleate Copolymer (ISP Gantrez ES-225, ES-425, SP-215, etc.), vinyl acetate / crotonic acid copolymer (National Starch resin 28-1310, etc.), vinyl acetate / crotonic acid / neodecanoic acid vinyl Copolymer (National Starch Resin 28-2930, etc.), vinyl acetate / crotonic acid / vinyl propionate copolymer (BASF Rubiset CAP, etc.), vinyl alcohol / itaconic acid copolymer (Kuraray KM-118, etc.) It is done.

  The content of the component (A-ii) in the mist-like hair cosmetic of the present invention is 0.05% by mass or more, further 0.08% by mass or more, further 0.1% by mass or more, and further 0.5% by mass or more in the hair cosmetic. Moreover, 7.5 mass% or less, Furthermore, 5 mass% or less, Furthermore, 2.5 mass% or less is preferable.

  In addition, when component (D) is contained in the mist-like hair cosmetic composition of the present invention, [D] / [A-] from the viewpoint of improving self-selective tackiness, non-stickiness, and good set holding power The mass ratio of i + A-ii] is preferably 20/80 to 80/20, more preferably 30/70 to 70/30, and particularly preferably 40/60 to 60/40.

〔solvent〕
As the solvent (supporting medium), water, lower alcohol (ethanol, isopropanol, etc.) and the like can be used, and these can be used alone or in combination. From the viewpoint of the solubility of the polymer in the composition, and from the viewpoint of achieving an appropriate fragrance and favorably expressing the effect of masking the base odor of the acrylic acid derivative with the component (Bi). The water content in the mist-like hair cosmetic is preferably 2% by mass or less, more preferably 1.7% by mass or less, further 1% by mass or less, further 0.5% by mass or less, and further preferably 0.1% by mass or less. Further, from the same viewpoint, the solvent is preferably an alcohol having 2 to 4 carbon atoms, and is preferably blended in the hair cosmetic material by 70% by mass or more, more preferably 80% by mass or more, and further 90% by mass or more.

[Surfactant]
The mist-like hair cosmetic of the present invention preferably does not contain a surfactant from the viewpoint of making the fragrance of the component (Bi) moderate and good masking property of the base odor derived from the component (Ai). Moreover, when it contains surfactant, the one where content is small is preferable, 0.00001-0.1 mass% in hair cosmetics, Furthermore, 0.00001-0.01 mass%, Furthermore, 0.00001-0.001 mass% is preferable.

[Optional ingredients]
In addition to the above-mentioned components, a cosmetic oil can be added to the mist-like hair cosmetic of the present invention within the limits that do not impede the effects of the present invention (0.1 to 10% by mass in the hair cosmetic). . Such cosmetic oils include glycerides such as castor oil, cacao oil, mink oil, avocado oil, olive oil; waxes such as beeswax, whale wax, lanolin, carnauba wax; cetyl alcohol, oleyl alcohol, hexadecyl alcohol Higher alcohols such as lauryl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol; isopropyl myristate, hexyl laurate, cetyl lactate, propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, Esters of myristic acid octyldodecyl acid; liquid oils such as liquid paraffin, petrolatum, squalane, hydrogenated polyisobutene; dimethylpolysiloxane, methylphenylpolysiloxane, polyether modified Examples include silicone derivatives such as silicone oil, epoxy-modified silicone oil, amino-modified silicone oil, and alkyl-modified silicone oil; polypropylene glycol and the like.

  Further, the mist-like hair cosmetic of the present invention can be added with a dye, a preservative and an antioxidant to prevent the daily deterioration of the hair cosmetic in order to increase commercial value, and further necessary. Add humectants such as glycerin and propylene glycol, curing agents, antistatic agents, antifoaming agents, dispersants, thickeners, UV absorbers, colored dyes, dye fixing agents, propellants, etc. You can also.

[Drug type]
The dosage form of the mist-like hair cosmetic of the present invention is not particularly limited as long as it can be sprayed in a mist form, and for example, an aerosol type, a non-aerosol type, a pump spray, an accumulator spray, and the like are possible.

  Aerosol hair cosmetics are produced by filling hair cosmetics together with a propellant in a pressure resistant container. Examples of the propellant include liquefied petroleum gas (LPG), dimethyl ether (DME), carbon dioxide gas, nitrogen gas, and mixtures thereof. Alternatively, alternative CFCs such as HFC-152a can be used. The amount of the propellant is the mass ratio of the stock solution to the propellant in order to obtain good jetting properties and good adhesive properties, and the stock solution / propellant = 5/95 to 99/1, especially 20/80 to 95/5. The range of is preferable. Moreover, in order to obtain a good injection characteristic and a good adhesive characteristic, the pressure in the pressure vessel is preferably adjusted to be 0.12 to 0.45 MPa at a temperature of 25 ° C.

Test example: Evaluation of masking performance of fragrance material against acrylic acid derivative odor (hereinafter also referred to as acrylate odor) By using the fragrance ingredients shown in Table 1, butyl acrylate, which is the main causative substance of acrylate odor derived from component (Ai) The masking performance against odor was evaluated. In order to uniformly evaluate the masking performance in the state where the set polymer of the component (Ai) and the mist-like hair cosmetic containing a fragrance were sprayed, the following model system was evaluated.
Place a circular filter paper (Advantech Qualitative Filter Paper No.2 Phi110) on the test bench, and cover it with a plastic cylinder with a height of 10 cm and an inner diameter of 9.6 cm so that the filter paper is located at the center of the bottom of the cylinder. Koganei Pharmaceutical Co., Ltd., 020-03302, Wako Special Grade) 1.8 μg and each fragrance component (100 μg) shown in Table 1 were added dropwise to the filter paper. Within 5 minutes after the addition of butyl acrylate and fragrance, the evaluator brought the face closer to the top of the cylinder, sniffed the scent that had volatilized, and evaluated the masking performance of the acrylate odor. The evaluation was carried out by three professional panelists based on the following criteria, and the evaluation result was the average value of the evaluation scores of the three persons. The evaluation results are shown in Table 1.
0: Acrylic odor is strongly felt 1: Acrylic odor can be clearly detected 2: Acrylic odor can be detected fairly 3: Acrylic odor can be detected a little 4: Acrylic odor is slightly detected 5: Acrylic odor is not felt

Synthesis Example (Synthesis of polyether polycarbonate used in Examples)
In a reaction vessel equipped with a stirrer, a fractionation condenser and a thermometer, a random copolymer of ethylene oxide and propylene oxide (number average molecular weight 5000, hydroxyl value 22.0 mg KOH / g, manufactured by ADEKA Corporation, trade name ADEKA polyether PR-5007) 27.1 g (0.005 mol), 1.15 g (0.005 mol) of diphenyl carbonate and 4 mg (0.01 mmol) of cesium carbonate were added.

  While stirring in the reaction vessel, the temperature was raised to 160 ° C., and heating was continued as it was for 2 hours. Furthermore, vacuum suction was started using a vacuum pump, and the reaction was carried out for about 4 hours while gradually raising the temperature to 180 ° C. to obtain a polyether polycarbonate. The polyether polycarbonate had a weight average molecular weight of 180,000. The other attachment strength was 106 gf, the self-adhesion strength was 233 gf, and the other attachment strength / self-adhesion strength was 0.45. The weight average molecular weight and adhesiveness were measured by the following methods.

<Measurement method of average molecular weight>
As a GPC device, the product name “HLC-8220GPC” (Tosoh Corporation) is used, and it is obtained under the following GPC measurement conditions in terms of polystyrene.
Sample concentration: 0.25% by mass (chloroform solution)
・ Sample injection volume: 100μL
・ Eluent: Chloroform ・ Flow rate: 1.0 mL / min
・ Measurement temperature: 40 ℃
Column: Trade name “KG” (1) + Trade name “K-804L” (2) (above, Shodex) connected in series for analysis.
・ Detector: Differential refractometer (attached to the GPC device trade name “HLC-8220GPC” (Tosoh Corporation))
Standard polystyrene samples: “TSKstandard POLYSTYRENE F-10” (molecular weight 102,000), F-1 (1020,000), A-1000 (870) (above, Tosoh Corporation), and “POLYSTYRENE STANDARD” (molecular weight 900,000, 3 10,000; Nishio Kogyo)

<Measurement method of adhesiveness (other adhesion and self-adhesion)>
A 20% by mass toluene solution of the polymer to be measured is prepared, cast on a PET sheet to a thickness of 500 μm with a bar coater, heated at 60 ° C. for 12 hours, and then left at 25 ° C. and 50% RH for 1 day. Using a tacking tester (Resca, TACIIUC-2006), the adhesive strength between the sheet and various materials attached to the probe of the tacking tester is measured.
The measurement conditions were a probe lowering speed of 600 mm / sec, a probe pressing load of 200 gf, and a pressing time of 0.5 sec. A polypropylene disk (engineering test service test piece: Mitsubishi Chemical Noblen NH-8) with an indenter area of 8 mm ² was attached to the tip of the probe, and the adhesive strength was measured. The obtained value was defined as “other adhesion”. On the other hand, the polymer to be measured was dissolved in a solution, cast and dried in the same manner as described above to obtain a PET disc having an indenter area of 8 mm ² , and this was attached to the probe tip to measure the adhesive force. The value was “self-adhesion”.

Examples 1-16, Comparative Examples 1-8
According to a conventional method, a stock solution of a mist-like hair cosmetic composition having the composition shown in Tables 2, 3, and 5 is prepared, and the following valve is used together with a propellant (30:70 mixture of liquefied petroleum gas (LPG) and dimethyl ether (DME)). An aerosol-type mist-like hair cosmetic was prepared by filling an aerosol spray can equipped with a button. The moisture content in the hair cosmetic was adjusted by using ethanol with different alcohol content. In addition, the fragrance | flavor composition shown in Table 4 was mix | blended with the stock solution shown in Table 5.
About the obtained hair cosmetics, the masking effect, incense tone, and the intensity of fragrance were evaluated according to the following evaluation.

Valve: Stem diameter φ0.4mm, housing diameter φ0.6mm x vapor tap diameter φ0.4mm
Button: Diameter 0.60mm (with mechanical breakup) (Mitani Valve)

1. Evaluation of masking performance The obtained aerosol-type mist-like hair cosmetic is made of polystyrene cup (opening diameter 64mm, capacity 215m
The composition was sprayed into L), and the masking property against the acrylate odor of hair cosmetics within 3 minutes from the spraying was evaluated according to the following evaluation criteria. Evaluation was carried out by three professional panelists, and the evaluation result was the average of the evaluation scores of the three persons.
0: Strong acrylate odor (not masked at all)
1: Acrylate odor can be clearly detected (masking is insufficient)
2: The acrylate odor can be sensed considerably (masking is slightly insufficient)
3: Slightly perceived acrylate odor (substantially masked)
4: The acrylate odor can be slightly detected (almost masked)
5: No acrylate odor is felt (completely masked)

2. Evaluation of incense tone The evaluation of incense tone was carried out by three expert panelists, and the evaluation results were determined by consultation of three people.

3. Evaluation of fragrance strength The obtained aerosol-type mist-like hair cosmetic was made into a polystyrene cup (opening diameter 64 mm, capacity 215 m
L), and the fragrance strength of the hair cosmetics within 3 minutes from the injection was evaluated according to the following evaluation criteria. Evaluation was carried out by three professional panelists, and the evaluation result was the average of the evaluation scores of the three persons.
0: The scent is not felt 1: The scent is hardly felt 2: The scent is felt to the extent that it is understandable 3: The scent intensity is just right 4: The scent is slightly too strong 5: The scent is too strong

  When the fragrance compositions 10 to 14 shown in Table 6 were blended in place of the fragrance composition 1 of Example 8 and the obtained hair cosmetic was evaluated for the masking effect, fragrance tone, and fragrance strength, The hair cosmetics of No. 1 were sufficiently masked with an acrylate odor within 3 minutes after spraying. In addition, the scent was fresh fruity floral, and even when sprayed in the form of a mist, the scent was not too strong and had a moderate scent intensity.

Claims (6)

Misty hair comprising the following component (Ai) and component (Bi), wherein the mass ratio [Ai] / [Bi] of the content of component (Ai) to the content of component (Bi) is 1250 or more and 10,000 or less Cosmetics.
(Ai): An anionic set polymer containing a structural unit represented by the following general formula (a-1) and a structural unit represented by the following general formula (a-2) Mass% or less

[Wherein, R ¹ and R ² represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to ³ carbon atoms, and R ³ represents a hydrocarbon group having 2 to 20 carbon atoms. ]
(Bi): 4- (4-Hydroxyphenyl) butan-2-one In hair cosmetics, 0.00004% by mass to 0.001% by mass The composition further comprises a component (B-ii), wherein the mass ratio [Bi] / [B-ii] of the content of the component (Bi) to the content of the component (B-ii) is 0.1 or more and 1 or less, 2. The mist according to claim 1, wherein the mass ratio [Ai] / [Bi + B-ii] of the content of Ai) and the total content of component (Bi) and component (B-ii) is 625 or more and 7500 or less. Hair cosmetics.
(B-ii): Lactone compound represented by the following general formula (b-2) 0.00004% by mass or more and 0.002% by mass or less in hair cosmetics

[Wherein, R ⁴ represents an alkyl group having 5 to 8 carbon atoms. ] The mist-like hair cosmetic according to claim 1 or 2, wherein the water content is 1.7% by mass or less. The mist-like hair cosmetic according to any one of claims 1 to 3, wherein the anionic set polymer of component (Ai) has a non-neutralizing acidic group. Furthermore, the following component (C) is contained, and the content of the component (Ci) with respect to the total amount of the component (Bi), the component (B-ii) and the component (C) is 0.01% by mass or more and 50% by mass or less. Item 5. An atomized hair cosmetic according to any one of Items 1 to 4.
(C): A perfume composition containing at least component (Ci) and not containing components (Bi) or (B-ii)
(Ci): an ester compound having no aromatic ring structure, represented by the following general formula (c-1)

[In the formula, R ⁵ may have a cyclic structure, and the alkyl group, alkenyl group, alkyl group or alkylalkoxy group having 2 to 10 carbon atoms in total (any one hydrogen atom of these substituents is an oxygen atom R ⁶ represents a straight-chain alkyl group or straight-chain alkenyl group having 1 to 4 carbon atoms. ] The ester compound of component (Ci) is butyl 2-methylbutanoate, methyl 2-cyclopentylidene acetate, ethyl 2-tert-butylcyclohexyl carbonate, ethyl tricyclo [5.2.1.0 ^2,6 ] decan-2-yl It is one or more selected from the group consisting of carboxylate, allyl cyclohexanepropionate, ethyl 2-methyl-1,3-dioxolan-2-yl acetate, propyl propionate and ethyl 2-methylbutyrate. 5. The mist-like hair cosmetic according to 5.