JPH11246382A - Perfume composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a perfume composition which has an excellent durability of aroma, does not cause lowering of its viscosity, and is liquid or gel by including a specific cationic thickener, hydroxypropylcellulose, and so on, at a specific ratio. SOLUTION: This composition is obtained by including (A) a cationic thickener obtained by polymerizing a monomer composition, for a thickener, containing (i) an aminecontaining (meth)acryl-based monomer shown by formula I (R<1> is H or methyl; R<2> and R<3> are each H, τ-butyl, or the like; A is O or NH; B is a 1-4C alkylene) at 15.0-85.0 wt.%, (ii) a vinyl monomer shown by formula II [R<4> is a group shown by formula III ((p) is 3 or 4) or formula VI] at 0-80.0 wt.%, (iii) a (meth)acryloyl group-containing monomer shown by formula V [R<5> is a 1-17C alkylene or a group shown by formula VI ((n) is 1-4; (q) is 1-25; R<6> is H or methyl] at 1.0-60.0 wt.%, and (iv) a crosslinking vinyl monomer at 0.1-20.0 wt.%, at 0.01-10.0 wt.% and (B) hydroxypropylcellulose and so on at 0.01-10.0 wt.%, an aroma component at 0.2-30.0 wt.%, ethanol at 0.1-79.0 wt.%, and water at 10.0-99.0 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fragrance product which is applied on the skin and enjoys a fragrance. More particularly, the present invention relates to a fragrance product which is excellent in scent persistence, does not cause a decrease in viscosity over time, and has good skin treatment effects The present invention relates to a liquid or gel-like skin fragrance composition having an excellent touch.

[0002]

2. Description of the Related Art Flavor materials generally include natural flavors obtained from animals or plants and synthetic flavors produced by chemical synthesis means. In order to create a superior fragrance, Pahumer combines these fragrance materials with years of experience, sense and inspiration,
For example, in the case of various flower scents, the natural flower scent itself is reproduced, or in the case of an oriental scent,
Oriental images are expressed in fragrance. All of these fragrance materials are dissolved in ethyl alcohol to become fragrance products that enjoy fragrance.

[0003] Liquid- or gel-like bases of the type widely applied to the skin which have been widely used in the past often contain a water-soluble polymer. When these polymers are blended in a specific amount, the system thickens and stabilizes the system. It is characterized in that the degree of thickening changes depending on the compounding amount, and the spread when the base is applied changes accordingly. These polymers are frequently compounded in body products such as whole body or partial use massage preparations, and skin care products such as packs. When used as a base for whole body massage, before and after bathing, apply an appropriate amount to the whole body, spread while spreading, and use massage together. By blending an appropriate amount of the polymer in the base, a viscosity suitable for massage can be created, and the system is also stabilized. While having these great features,
It is also a disadvantage of polymers that stickiness is felt in the process of applying the base to the skin and drying it.

[0004] In response to these drawbacks, the present applicant has first
Developed a system in which an alcohol-based base is thickened with a specific cationic polymer, and has a refreshing feeling of use against stickiness that was a problem with the conventional feeling of use, and moderate alcohol volatility A fragrance composition having a viscosity matching that of a gel is obtained (Japanese Patent Laid-Open No. 9-67239).

[0005]

However, this fragrance composition has a disadvantage that the viscosity tends to decrease with time and it is difficult to maintain an appropriate viscosity for a long period of time.

On the other hand, when the blending amount of alcohol is reduced to make it water-based, the perfume is solubilized with an activator or the like, and when a thickener such as a carboxyvinyl polymer is blended with a cationic polymer, the viscosity decreases. Even if it can be suppressed, stickiness occurs in usability, while on the other hand, if a carboxyvinyl polymer is blended with the blending amount of the alcohol as it is, it does not dissolve and becomes cloudy, and in any case, the viscosity decreases while maintaining preferable characteristics It was difficult to prevent. When the amount of the specific cationic polymer was increased, an increase in viscosity was observed, but the situation in which the viscosity decreased with time was not improved.

[0007]

The inventors of the present invention have conducted intensive studies, and as a result, have found that the viscosity of an alcohol-based liquid or gel base using a specific cationic thickener decreases with the lapse of time. It has been found that the use of one or more thickeners selected from propylcellulose, xanthan gum, hydroxyethylcellulose, and methylcellulose in combination has a remarkable effect of reducing the viscosity over time, thus completing the present invention.

That is, in the present invention, the following component (A) is contained in an amount of 0.01 to 10.0% by weight, and (B) is contained in an amount of 0.01 to 10.0.
0% by weight, 0.2 to 30.0% by weight of a fragrance component, 0.1 to 79.0% by weight of ethanol, and 10.0 to 99.
A liquid or gel-like skin fragrance composition containing 0% by weight. Here, the term “for skin” means that those directly applied to the skin by spraying, application or the like are included in the scope of the present invention, and those that are not directly applied to the skin such as Loom Colon are excluded.

(A) A cationic thickener obtained by polymerizing a monomer composition for a thickener containing: General formula (I):

[0010]

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(Wherein R ¹ is a hydrogen atom or a methyl group,
R ² and R ³ each independently represent a hydrogen atom, a methyl group,
Ethyl group or t-butyl group, A represents an oxygen atom or -N
H-group and B represent a linear or branched alkylene group having 1 to 4 carbon atoms. Amine-containing (meta) represented by)
Acrylic monomer 15.0 to 85.0% by weight, General formula (II):

[0012]

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(Wherein R ¹ has the same meaning as described above, and R ⁴ is a general formula:

[0014]

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(Wherein p represents 3 or 4) or a group represented by the formula:

[0016]

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The group represented by 0 to 80.0% by weight of a vinyl monomer represented by the following general formula (III):

[0018]

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(Wherein, R ¹ and A have the same meanings as described above;
R ⁵ is a linear or branched alkylene group having 1 to 17 carbon atoms or a general formula (IV):

[0020]

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Wherein n is an integer of 1 to 4, and q is 1 to 25.
Indicates an integer. ), R ⁶ represents a hydrogen atom or a methyl group. (Meth) acryloyl group-containing monomer represented by 1.0 to 60.0% by weight, crosslinkable vinyl monomer 0.1 to 20.0% by weight

(B) One or more selected from hydroxypropylcellulose, xanthan gum, hydroxyethylcellulose and methylcellulose.

Next, the configuration of the present invention will be described. (Component (A)) The cationic thickener of the component (A) is obtained by polymerizing the monomer composition for a thickener containing the above-mentioned. Hereinafter, each component constituting the cationic thickener will be described in detail.

The amine-containing (meth) acrylic monomer represented by the general formula (I) is obtained by neutralizing a copolymer obtained by copolymerizing a monomer composition for a thickener with an appropriate acid. Occasionally, it is a component having a role of giving the property of a cationic ion to the copolymer.

Representative examples of the amine-containing (meth) acrylic monomer include, for example, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (Meth) acrylamide and the like,
The present invention is not limited to only such examples. In the present invention, the amine-containing (meth) acrylic monomers are used alone or in combination of two or more.

The ratio of the amine-containing (meth) acrylic monomer in the monomer composition for a thickener is 15.0.
To 85.0% by weight, preferably 25.0 to 75.0% by weight, more preferably 35.0 to 65.0% by weight. When the proportion of the amine-containing (meth) acrylic monomer is less than the above range, the amount of neutralization of the amine-containing (meth) acrylic monomer by the acid in the obtained copolymer is too small. If the viscosity exceeds the above range, the resulting cationic thickener loses the flexibility of the film formed after drying.

The vinyl monomer represented by the general formula (II) is a component that imparts flexibility, gloss and smoothness to a film formed after the cationic thickener is dried.

Representative examples of the vinyl monomer include, for example, N-vinylpyrrolidone, N-vinylpiperidone,
Examples thereof include acrylamide and methacrylamide, but the present invention is not limited only to such examples. In the present invention, the vinyl monomers are used alone or in combination of two or more.

The proportion of the vinyl monomer in the monomer composition for a thickener is 80.0% by weight or less, preferably 7% by weight.
It is prepared so as to be 5.0% by weight or less, more preferably 60.0% by weight or less. When the proportion of such a vinyl monomer exceeds the above upper limit, the gel viscosity of the resulting cationic thickener is significantly reduced. In addition, effects achieved by blending the vinyl monomer,
That is, in order to sufficiently impart flexibility, gloss, and smoothness to a film formed after the cationic thickener is dried, the ratio of the vinyl monomer in the thickener monomer composition is 3.0. % By weight or more, preferably 5.0% by weight or more, more preferably 20.0% by weight
It is desirable that it is above.

The (meth) acryloyl group-containing monomer represented by the general formula (III) is used for improving the gloss of a film formed after the cationic thickener is dried, improving the gel viscosity, and various settings. It is a component for improving compatibility with the polymer.

Specific examples of the (meth) acryloyl group-containing monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. Acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, Stearyl (meth) acrylate, cyclohexyl (meth) acrylate, Nt-butyl (meth) acrylamide, Nt-octyl (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) (T) acrylate, hydroxybutyl (meth) acrylate, polyoxyethylene (in the general formula (IV), n is 2 and q is an integer of 2 to 9)
(Meth) acrylate, methoxypolyethylene glycol (in the general formula (IV), n is 3 and q is an integer of 2 to 23)
Examples thereof include (meth) acrylates, but the present invention is not limited to only such examples. In the present invention, the (meth) acryloyl group-containing monomers are used alone or in combination of two or more.

The ratio of the (meth) acryloyl group-containing monomer in the monomer composition for a thickener is 1.0 to 6
It is adjusted to be 0.0% by weight, preferably 1.0 to 55.0% by weight, more preferably 2.0 to 30.0% by weight. When the proportion of the (meth) acryloyl group-containing monomer exceeds the above range, the proportion of the hydrophobic group in the obtained copolymer becomes large, and the solubility in water becomes small even after neutralization, It is difficult to obtain a smooth gel, and if the amount is less than the above range, the gel viscosity is reduced, so it is necessary to increase the amount of the cationic thickener used. The gloss of the film formed after the cationic thickener has dried is reduced.

The crosslinkable vinyl monomer is a compound having two or more carbon-carbon unsaturated double bonds in one molecule, and has a property of crosslinking with another monomer.

Representative examples of the crosslinkable vinyl monomer include, for example, ethylene glycol di (meth) acrylate, polyoxyethylene di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and polypropylene. (Meth) having two or more carbon-carbon unsaturated double bonds in one molecule such as glycol di (meth) acrylate
Acrylic monomers; methylenebis (meth) acrylamide, 1,2-bis (meth) acrylamideethane,
1, such as 1,5-bis (meth) acrylamidopentane
(Meth) acrylamide monomers having two or more carbon-carbon unsaturated double bonds in the molecule; vinyl monomers having two or more carbon-carbon unsaturated double bonds in one molecule such as divinylbenzene; However, the present invention is not limited only to such an example. In the present invention, the crosslinkable vinyl monomers are used singly or as a mixture of two or more.

The proportion of the crosslinkable vinyl monomer in the monomer composition for a thickener is 0.1 to 20.0% by weight,
It is preferably prepared to be 1.0 to 10.0% by weight, more preferably 2.0 to 8.0% by weight. When the proportion of the crosslinkable vinyl monomer is less than the above range, the crosslink density of the obtained cationic thickener becomes too small, so that the viscosity of the cationic thickener cannot be increased, and If the above range is exceeded,
Although the viscosity of the cationic thickener increases, fine aggregates are formed in the gel, and it becomes difficult to obtain a uniform gel.

The polymerization reaction of the monomer composition for a thickener containing the amine-containing (meth) acrylic monomer, vinyl monomer, (meth) acryloyl group-containing monomer and crosslinkable vinyl monomer is carried out by a general solution polymerization method or the like. The polymerization can be performed by a bulk polymerization method, for example, by a precipitation polymerization method that is a polymerization method for obtaining a powder, and is usually performed by heating in a nonaqueous solvent under an inert gas atmosphere such as nitrogen gas. It is done while. Thus, the polymerization reaction is carried out in a non-aqueous solvent under an inert gas atmosphere,
This is for preventing the ester group present in the monomer or the formed copolymer from being hydrolyzed.

In the present invention, a good solvent alone or a mixed solvent of a good solvent and a poor solvent is used as the non-aqueous solvent.

In the present invention, the good solvent is used
This is because the formation of a homopolymer due to the difference in reactivity of each monomer is suppressed, and a uniform copolymer is obtained. In the present specification, the good solvent means the good solvent 1 at 25 ° C.
A solvent in which a copolymer having a molecular weight of 10,000 or more is dissolved in an amount of 20 g or more per 00 ml and no turbidity is observed. Specific examples of the good solvent include, for example, methanol, ethanol, isopropanol, acetone,
Examples include ethyl acetate, benzene, toluene, xylene and the like. Among these good solvents, ethanol, isopropanol and benzene are particularly preferable since they can obtain a copolymer having a relatively high molecular weight. Since benzene and the like are harmful, ethanol and isopropanol are most preferable.

The reason why the poor solvent is used in the present invention is that the produced copolymer is easily precipitated from the polymerization solution. The poor solvent means a solvent which dissolves a copolymer having a molecular weight of 10,000 or more in 5 g or less in 100 ml of the poor solvent at 25 ° C. Specific examples of the poor solvent include linear, branched or cyclic aliphatic hydrocarbons having 15 or less carbon atoms, such as n-pentane, n-hexane, and cyclohexane. Among these poor solvents, linear, branched or cyclic aliphatic hydrocarbons having a relatively high boiling point and 7 or less carbon atoms are preferred. Among them, straight-chain, branched-chain or cyclic aliphatic hydrocarbons having 6 or 7 carbon atoms are particularly preferable because of their high boiling points. Further, n-hexane, cyclohexane, and the like are preferable because they are inexpensive and industrially easy to handle.

In order to synthesize a cationic thickener without impairing the properties of the resulting cationic thickener, it is preferable to mix the good solvent and the poor solvent in appropriate ratios. If the proportion of the poor solvent is too large, the polymerization proceeds promptly, and a cationic thickener having desired physical properties tends to be obtained in a short time because the powder is precipitated in a short time. The ratio of the poor solvent to the mixed solvent of the good solvent and the poor solvent is 98% by weight or less, preferably 97% by weight or less, and the ratio of the good solvent is 2% by weight or more, preferably 3% by weight or more. It is desirable.

In order to efficiently obtain the cationic thickener from the reaction solution, it is preferable to use a reaction device for improving the stirring during the polymerization. When using a stirrer for solution polymerization generally used as such a reactor,
It is preferable to dilute with the solvent such that the concentration of the monomer composition for a thickener is 30% by weight or less. In addition,
At the time of the reaction, it is preferable to sufficiently stir using a stirrer or the like in order to prevent the reaction solution from stagnating. The polymerization reaction is preferably performed under heating at 50 to 100 ° C., and is generally performed at the reflux temperature of the solvent used in the reaction. The time required for the polymerization reaction is usually 1
0 hours or more. The polymerization reaction can be arbitrarily terminated when the amount of the remaining monomer becomes 10% by weight or less. In addition, the amount of the remaining monomer can be determined by, for example, adding sulfur to the double bond by a known method such as the PSDB method and measuring the double bond content.

Thus, a reaction solution containing a precipitate of the cationic thickener is obtained. The mixed solvent can be removed, for example, by filtering the obtained precipitate of the cationic thickener,
It can be carried out by performing vacuum drying or distilling off under normal pressure or reduced pressure.

In the polymerization reaction, a polymerization catalyst may be used. Such polymerization catalysts include, for example, 2,2'-
Azobisisobutyronitrile, 2,2'-azobis (4
-Methoxy-2,4-dimethylvaleronitrile), azo compounds such as dimethyl-2,2'-azobisisobutyrate, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, and di-t-butylperoxide There are peroxides represented by dialkyl peroxides such as oxides, peroxycarbonates such as diisopropylperoxydicarbonate, and peroxyesters such as t-butylperoxypivalate. These catalysts are used alone or in combination of two or more. These are used in combination. In addition, the present invention is not limited only to such an example. When a large amount of an amine-based monomer is used in the monomer composition for a thickener, an excessive use of a peroxide catalyst may cause undesired side reactions such as an oxidation reaction at the same time, and may hinder polymerization. Be careful when using.
In general, it is preferable to mainly use an azo-based catalyst, but it depends on the boiling point of the solvent used. For example, when ethanol or benzene is used, 2,2′-azobisisobutyronitrile is not easily handled. Most preferred because it is good. The amount of the polymerization catalyst used is preferably 0.05 to 3.0% by weight, more preferably 0.1 to 1.0% by weight, based on the total weight of the monomers of the monomer composition for a thickener.

In the course of the polymerization of the monomers,
Various aspects are exhibited. For example, when only the above-mentioned good solvent is used, the appearance is similar to that in the case where general solution polymerization is performed in the initial stage of the polymerization reaction, but the crosslinking reaction proceeds with the progress of the reaction, and the gel-like state is obtained. And a grease-like product without a precipitate is obtained as the reaction further proceeds.

Further, when a mixed solution of the above-mentioned good solvent and poor solvent is used, at the initial stage of polymerization, the same aspect as when a general solution polymerization method is employed is exhibited, but the reaction proceeds. As the reaction proceeds, the crosslinking reaction progresses and the mixture becomes gel-like. As the reaction further progresses, the obtained polymer can no longer be dissolved in the mixed solvent, becomes insoluble, and precipitates as a precipitate.

Thus, a cationic thickener is obtained,
The cationic thickener is described, for example, in JP-A-5-140531.
And Japanese Patent Application No. Hei 5-298659.
The cationic thickener itself is non-greasy and has a gel-forming ability, and is incorporated in the entire composition in an amount of 0.01 to 10.0% by weight, preferably 0.1 to 5.0% by weight. 0.
If it is less than 01% by weight, the thickening effect cannot be obtained, and if it exceeds 10.0% by weight, stickiness is felt when applied to the skin, which is not preferable.

(Component (B)) The component (B) used to reduce the decrease in viscosity due to the cationic thickener is one or more selected from hydroxypropylcellulose, xanthan gum, hydroxyethylcellulose and methylcellulose. is there. Regarding any thickener, it thickens sufficiently even in the region where the alcohol content is high,
The component (A) has a function of reducing the decrease in viscosity of the cationic thickener, and among them, hydroxypropyl cellulose is particularly preferred. .

The component (B) is contained in an amount of 0.01 to 1 in the total composition.
0.0% by weight, preferably 0.5 to 3.0% by weight. If the amount is less than 0.01% by weight, the effect of improving the decrease in viscosity over time is small.

(Fragrance) As the flavor, any of animal, plant, and mineral natural flavors and synthetic flavors can be used.
The amount of the fragrance is such that a sufficient fragrance can be obtained as a fragrance product, but is generally 0.5 to 30.0% by weight, preferably 1.0 to 10.0% by weight.

(Powder) Specific examples of the powder include talc,
Kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, phlogopite, biotite, lithia mica, vermiculite, magnesium carbonate, calcium carbonate, aluminum silicate, barium silicate, calcium silicate, silica Magnesium silicate, strontium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (baked gypsum), calcium phosphate, fluoroapatite, hydroxyapatite,
Ceramic powder, metal soap (zinc myristate, calcium palmitate, aluminum stearate),
Inorganic powder such as boron nitride, polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, polystyrene powder, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose Powder, organic powders such as starch, inorganic white pigments such as titanium dioxide and zinc oxide, inorganic red pigments such as iron oxide (iron oxide) and iron titanate, inorganic brown pigments such as γ-iron oxide, yellow iron oxide, Inorganic yellow pigments such as loess black Inorganic black pigments such as black iron oxide, carbon black and lower titanium oxide, inorganic purple pigments such as mango violet and cobalt violet, and inorganic such as chromium oxide, chromium hydroxide, and cobalt titanate Green pigments, inorganic blue pigments such as ultramarine and navy blue, titanium oxide coated mica, titanium oxide coated Bismuth oxychloride, titanium oxide coated talc, colored titanium oxide coated mica, bismuth oxychloride, pearl pigments such as fish scale foil, aluminum powder, metal powder pigments such as copper powder, red 201, red 202, red 204, red 205
No. 220, Red No. 226, Red No. 228, Red No. 405, Orange No. 203, Orange No. 204, Yellow No. 205
Organic pigments such as No. 401, Yellow No. 401 and Blue No. 404, Red No. 3, Red No. 104, Red No. 106, Red No. 227,
Red 230, Red 401, Red 505, Orange 20
No. 5, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203
No. 3, organic pigments such as zirconium, barium or aluminum lake such as green No. 3 and blue No. 1, chlorophyll,
and natural pigments such as β-carotene. Among these powders, polyamide resin powder, silica, polyethylene powder and starch are particularly preferred.

In the present invention, by further blending a powder, a smooth feel is imparted, and a fragrance composition having a better use feeling can be obtained. When compounding powder,
The compounding amount is 0.01 to 20.0% by weight, preferably 0.1 to 10.0% by weight.

(Water, Ethanol) In the present invention, the amount of water is 10.0 to 99.0% by weight. If it is less than 10.0% by weight, the amount of ethanol will increase as a result, and the skin treatment effect and the scent persistence will be insufficient. The amount of ethanol is 0.1 to 79.0% by weight, preferably 10.0 to 60.0% by weight. The smaller the amount of ethanol, the less irritating the skin becomes, and the resulting fragrance composition has an excellent skin treatment effect.

(Optional Components) In addition to the above essential components, other optional components can be added to the fragrance composition of the present invention as long as the quality is not impaired. Such optional components include:
For example, there is the following.

Acids such as lactic acid, phosphoric acid, citric acid, maleic acid, and succinic acid for adjusting the viscosity and gel strength are exemplified.

Examples of liquid oils and fats include avocado oil, camellia oil, evening primrose oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, sasanqua oil,
Castor oil, linseed oil, safflower oil, cottonseed oil, eno oil,
Soybean oil, peanut oil, teaseed oil, kaya oil, rice bran oil, cinnamon oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin, trioctanoic acid glycerin, triisopalmitic acid glycerin, etc. Fat, coconut oil, horse fat, hardened coconut oil, palm oil, tallow, sheep butter, hardened beef tallow, palm kernel oil, lard, beef tallow, moku kernel oil, hardened oil, beef tallow, mokuro, hardened castor oil Examples of waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibotaro wax, whale wax, montan wax, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, hexyl laurate, reduced lanolin , Jojoba wax, hard lanolin, shellac wax, POE lanolin alcohol ether Examples of POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, etc., and hydrocarbon oils such as liquid paraffin, ozokerite, squalene, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax, etc. Oils.

The higher fatty acids include, for example, lauric acid, myristic acid, palmitic acid, stearic acid, behenic (beheninic) acid, oleic acid, 12-hydroxystearic acid, undecylenic acid, tallic acid, isostearic acid, linoleic acid, and linoleic acid. Acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA) and the like.

The higher alcohols include, for example, linear alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, and cetostearyl alcohol, monostearyl glycerin ether (bacyl alcohol), and 2-decyltetradecyl alcohol. And branched-chain alcohols such as knol, lanolin alcohol, cholesterol, phytosterol, hexyldecanol, isostearyl alcohol and octyldodecanol.

Examples of synthetic ester oils include isopropyl myristate, cetyl octoate, octyl dodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyl octanoate, Cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexylate, fatty acid ester of dipentaerythritol, N-alkyl glycol monoisostearate, neodicaprate Pentyl glycol, diisostearyl malate, glycerin di-2-heptylundecanoate, trimethylol tri-2-ethylhexylate Bread, trimethylolpropane triisostearate, pentaneerythritol tetra-2-ethylhexylate, glycerin tri-2-ethylhexylate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, trimyristate Glycerin, tri-2-heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, oleic acid oil, cetostearyl alcohol, acetoglyceride, palmitic acid 2-
Heptylundecyl, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate, triethyl citrate and the like.

Examples of the silicone include linear polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane and methylhydrogenpolysiloxane, and cyclic polysiloxanes such as decamethylpolysiloxane, dodecamethylpolysiloxane and tetramethyltetrahydrogenpolysiloxane. Examples include polysiloxane, silicone resin and silicone rubber forming a three-dimensional network structure.

Examples of the vitamins include vitamin A such as vitamin oil, retinol and retinol acetate; vitamin B ₂ such as riboflavin, riboflavin butyrate and flavin adenine nucleotide; and vitamin B ₆ such as pyridoxine hydrochloride and pyridoxine dioctanoate. , L-ascorbic acid, L-ascorbic acid dipalmitate,
L-ascorbic acid-2-sodium sulfate, L-ascorbic acid phosphate, DL-α-tocopherol-
Vitamin Cs such as dipotassium L-ascorbic acid diester phosphate, pantothenic acids such as calcium pantothenate, D-pantothenyl alcohol, pantothenyl ethyl ether, acetyl pantothenyl ethyl ether, and vitamin D such as ergocalciferol and cholecalciferol , Nicotinic acids such as nicotinic acid, nicotinamide, benzyl nicotinate, α-tocopherol, tocopherol acetate, DL-α-tocopherol nicotinate,
Vitamin Es such as DL-α-tocopherol succinate,
Vitamin P, biotin and the like.

Examples of the ultraviolet absorber include paraaminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester, N,
Benzoic acid-based ultraviolet absorbers such as N-dimethyl PABA ethyl ester and N, N-dimethyl PABA butyl ester; anthranilic acid-based ultraviolet absorbers such as homomenthyl-N-acetylanthranilate; amyl salicylate;
Salicylic acid UV absorbers such as menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl-2,5-diisopropyl cinnamate , Ethyl-2,
4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, octyl-p-methoxycinnamate (2- Ethylhexyl-p
-Methoxycinnamate), 2-ethoxyethyl-p-
Methoxy cinnamate, cyclohexyl-p-methoxy cinnamate, ethyl-α-cyano-β-phenyl cinnamate, 2-ethylhexyl-α-cyano-β-phenyl cinnamate, glyceryl mono-2-ethylhexanoyl-diparamethoxy Cinnamic acid-based ultraviolet absorbers such as cinnamate, 3,4,5-trimethoxycinnamic acid 3-methyl-4- [methylbis (trimethylsiloxy) silyl] butyl, 2,4-dihydroxybenzophenone, 2,2 ′
-Dihydroxy-4-methoxybenzophenone, 2,
2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4′-methylbenzophenone, 2-hydroxy-4methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone,
Benzophenone ultraviolet absorbers such as 2-ethylhexyl-4'-phenyl-benzophenone-2-carboxylate, hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone, 3
-(4'-methylbenzylidene) -d, l-camphor, 3-benzylidene-d, l-camphor, urocanic acid, urocanic acid ethyl ester, 2-phenyl-5
-Methylbenzoxazole, 2,2'-hydroxy-5
-Methylphenylbenzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenylbenzotriazole, dibenzarazine, dianisoylmethane, 4-methoxy -4'-t-butyldibenzoylmethane, 5- (3,3-dimethyl-2-norbornylidene) -3-pentan-2-one and the like.

Examples of the humectant include polyethylene glycol, propylene glycol, glycerin, 1,3-butylene glycol, hexylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl- 12-hydroxystearate, sodium lactate, bile salts, dl-pyrrolidone carboxylate, short-chain soluble collagen, diglycerin (E
O) PO adducts, Izayobara extract, Achillea millefolium extract, melilot extract and the like.

Other examples include plant extracts, drugs, stabilizers, and high molecular compounds.

[0064]

The present invention will be further described with reference to the following examples.
In addition, the compounding amount is weight%. Prior to the examples, a method for producing the cationic thickener used in the examples will be described.

(1) Preparation of cationic thickener A three-necked flask equipped with a thermometer, a reflux tube and a nitrogen inlet tube was charged with 50 g of N, N-dimethylaminoethyl methacrylate as monomer and N-vinylpyrrolidone 47 as a monomer. .5
g, 2.5 g of stearyl acrylate and 1.9 g of tripropylene glycol diacrylate, and a mixed solvent (mixing ratio (weight ratio) of 4:96) of 23.1 g of ethanol and 554.3 g of cyclohexane were added. While refluxing, the mixture was stirred for 2 hours under a nitrogen stream to degas.

Next, 0.41 g of 2,2'-azobisisobutyronitrile was added to a three-necked flask, and polymerization was started at 80 ° C. After a lapse of 45 minutes from the start of the polymerization, 1.9 g of tripropylene glycol diacrylate was added, and after a lapse of 45 minutes, 1.9 g of tripropylene glycol diacrylate was added. After performing a polymerization reaction for about 10 hours while stirring under a nitrogen stream, the obtained polymer slurry solution was filtered under reduced pressure, and the solid component was dried under reduced pressure. The obtained dried polymer was pulverized with a pulverizer to obtain a white powdered cationic thickener.

(Test on Viscosity Stability of Cationic Thickener) 0.7% by weight of the cationic thickener obtained above
An aqueous solution was prepared, and the viscosity change with time at 50 ° C., 37 ° C., room temperature, and 0 ° C. for 1 to 4 weeks was measured. Table 1 shows the results.

[0068]

[Table 1] ℃ 50 ℃ 37 ℃ Room temperature 0 ℃ ──────────── １ 1w viscosity (cps) 1900 1900 2100 2000 2w viscosity (cps) 1700 1750 2100 2400 3w viscosity (cps) 1400 1800 1750 1800 4w viscosity (cps) 1200 1800 1800 1900 ───────────────────────────

Table 1 shows that the viscosity of the cationic thickener alone decreases with time, particularly on the high temperature side.

Comparative Examples 1 to 3 (Test on Viscosity Stability of Cationic Thickener) In the formulation shown in Table 2, 0.7% by weight of the cationic thickener,
0.75% by weight and 0.8% by weight of the fragrance composition were prepared, and the viscosity change with time from immediately after preparation at 50 ° C. to 4 weeks was measured. Table 2 also shows the results.

[0071]

[Table 2] 比較 Comparative Example No. 1 2 3 ──────────── ─────────────── (1) Deionized water 20.0 20.0 20.0 (2) Ethanol residue Residual residue (3) Fragrance 3.0 3.0 3.0 (4) Menthol 0.5 0.5 0.5 (5) Cationic Thickener 0.7 0.75 0.8 (6) Lactic acid 0.21 0.225 0.24 ─────────────────────────── Immediate viscosity (cps) 2200 3200 5300 1w viscosity (cps) 1900 2400 4150 2w viscosity (cps) 1700 2150 3650 3w viscosity (cps) 1380 1960 3300 4w viscosity (cps) 1200 1960 2500 ──────────────────── ───────

From Table 2, it can be seen that when the viscosity is increased by increasing the concentration of the cationic thickener, the viscosity immediately increases, but the rate of decrease in viscosity over time tends to increase.

Examples 1 to 4 (Test on Viscosity Stability of Cationic Thickener + Hydroxypropylcellulose) Perfume compositions were prepared according to the formulations shown in Table 3, and their viscosity stability was tested. Table 3 also shows the results.

[0074]

[Table 3] {Example No. 1 2 3 4} ──────────────────── (1) Deionized water 20.0 20.0 20.0 20.0 (2) Ethanol residue Residue Residual residue (3) Fragrance 3.0 3.0 3.0 3.0 (4) Menthol 0.5 0.5 0.5 0.5 (5) Cationic thickener 0.7 0.7 0.7 0.7 (6) Hydroxypropyl cellulose 0.06 0.08 0.1 0.12 (7) Lactic acid 0.21 0.21 0.21 0.21 ────────────────直 後 Immediately after viscosity (cps) 5200 5580 6920 6800 1w viscosity (cps) 4460 4300 6840 7210 2w viscosity (cps) 4450 4190 6400 7110 3w viscosity (cps) 3890 4020 6300 6800 4w Viscosity (cps) 3100 3620 5700 6260 ─────────────────────────────

Table 3 shows that the combined use of the cationic thickener and hydroxypropylcellulose reduces the decrease in viscosity as compared with Comparative Examples 1 to 3 in which only the cationic thickener was blended.

Examples 5 to 8 and Comparative Examples 4 to 7 Perfume compositions having the compositions shown in Table 4 were produced and evaluated for viscosity stability and stickiness. Table 4 also shows the results.

[Evaluation Method] (1) Evaluation of stickiness The usability evaluation monitor applied 10 perfume compositions of Examples and Comparative Examples to the skin and evaluated the stickiness. The evaluation results are shown in the following display. ◎: Eight or more out of ten answered that there was no sticky feeling. ；: Out of 10 persons, 6 or more persons answered that there was no sticky feeling. Δ: 4 or more out of 10 answered that there was no sticky feeling. ×: Less than 4 out of 10 persons answered that there was no stickiness.

[0078]

[Table 4] ─────────────────────────────────── Example Comparative Example ─────── ───── ５ 5 6 7 8 4 5 6 7 ────────────────────────── ───────── (1) Ion-exchange water 20.0 20.0 20.0 20.0 20.0 40.0 30.0 20.0 (2) Ethanol residue residue residue residue residue residue residue residue residue (3) fragrance 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 (4) Cationic thickener 0.7 0.7 0.7 0.7 0.7 − − − (5) Methyl cellulose 0.1 − − − − 1.0 − − (6) Human peroxyethyl cellulose − 0.1 − − − − − 1.0 (7) Xanthan gum − − 0.1 − − − − − (8) Human peroxyfluorocellulose − − − 0.1 − − 1.0 − (9) Lactic acid 0.3 0.3 0.3 0.3 0.3 − − − ──────────────────────── ─────直 後 Immediately after viscosity (cps) 5780 3300 3900 6520 5900 increase 12050 increase 1w viscosity (cps) 5140 3150 2870 6150 4570 viscosity 8480 viscosity 2w viscosity (cps) 6300 4810 4120 6300 4570 increase 8620 increase 3w viscosity (cps) 4790 3010 3350 5150 4420 N 7760 N 4W viscosity (cps) 5250 3230 2900 6390 4560 N 6800 N ───── Stickiness ○ ○ ○ ○ ○ × △ △ ───────────────────────────────────

From the results shown in Table 4, the fragrance composition of the present invention was
It has been found that the composition has less tackiness and a lower rate of viscosity decrease as compared with a composition containing a conventionally used polymer thickener.

Examples 9 to 14 Perfume compositions having the compositions shown in Table 5 were produced and evaluated for stickiness and dryness. Table 5 shows the results.

[Production Method] (1) Production of Cationic Thickener The same one as produced in Example 1 was used.

(2) Production of fragrance composition (6) and (7) are added to a solution of (1) to (5) described in Table 5, and further (8) is added.

[Evaluation Method] (1) Evaluation of Stickiness The evaluation was performed in the same manner as in Example 1.

(2) Evaluation of dry feeling 10 usability evaluation monitors applied appropriate amounts of the fragrance compositions of Examples and Comparative Examples to the skin, and evaluated the dry feeling after drying. The evaluation result will be represented by the following display. ◎; 8 or more out of 10 responded that there was a feeling of smoothness. ；: 6 or more out of 10 responded that there was a feeling of smoothness. Δ: Four or more out of ten responded that there was a feeling of smoothness. ×: Less than 4 out of 10 respondents felt smooth.

[0085]

[Table 5] Example No. 9 10 11 12 13 14 ───────────────────────────── (1) Deionized water 30.0 30.0 30.0 30.0 30.0 30.0 (2) Ethanol residue residue residue residue residue residue Residual (3) Fragrance 2.0 2.0 2.0 2.0 2.0 2.0 (4) Cationic thickener 1.0 1.0 1.0 1.0 1.0 1.0 (5) Human peroxyfluorocellulose 0.1 0.1 0.1 0.1 0.1 0.1 (6) Polyamide resin powder 1.0 3.0 5.0 7.0 − − ( 7) Starch − − − − 7.0 − (8) Lactic acid 0.3 0.3 0.3 0.3 0.3 0.3 ─────────────────────────────── ── Evaluation A. Stickiness ◎ ◎ ◎ ◎ ◎ ◎ B. Smoothness △ △ ○ ◎ ◎ × ─────────────────────────── ──────

As is evident from the results in Table 5, by blending the powder, not only a non-sticky feeling but also a good dry feeling were obtained. In addition, the decrease in viscosity over time was small.

Example 15 (1) Dipropylene glycol 6.0% by weight (2) 1,3-butylene glycol 5.0 (3) Polyoxyethylene (20) Oleyl alcohol ether 0.5 (4) Cationic increase Viscosity 0.7 (5) hydroxypropylcellulose 0.1 (6) lactic acid 0.1 (7) ethanol 60.0 (8) citric acid 0.1 (9) sodium citrate 0.05 (10) hydroxymethoxy Benzophenone sodium sulfonate qs (11) Flavor 1.0 (12) methyl paraben qs (13) trisodium edetate qs (14) ion-exchanged water balance

[Production method] Citric acid, sodium citrate, trisodium edetate, sodium hydroxymethoxybenzophenone sulfonate, dipropylene glycol, 1,3-butylene glycol, cationic thickener, hydroxypropyl cellulose, Dissolves lactic acid (aqueous phase). Separately polyoxyethylene in ethanol
(20) Oleyl alcohol ether, fragrance, and methyl paraben were dissolved and added to the above-mentioned aqueous phase to solubilize to obtain a liquid colon.

Example 16 (1) Squalane 3.0% by weight (2) Polyoxyethylene (60) Glyceryl monoisostearate 3.0 (3) Ethyl paraben (4) Perfume 2.0 (5) Polyamide resin Powder 5.0 (6) Ethanol 15.0 (7) 1,3-butylene glycol 7.0 (8) Trisodium edetate 0.05 (9) Cationic thickener 1.0 (10) Hydroxypropyl cellulose 0.1 (11) Xanthan gum 0.05 (12) Lactic acid 0.3 (13) Deionized water residue

[Production method] (1) to (5) were heated and dissolved,
(6) to (13), which have been warmed, are added with stirring. After homogenizing the mixture to make the emulsified particles fine, the mixture was rapidly cooled with stirring to obtain a colon.

Example 17 (1) Liquid paraffin 3.0% by weight (2) Polyoxyethylene (40) hydrogenated castor oil 4.0 (3) Proper amount of ethyl paraben (4) Fragrance 4.0 (5) Silica 0 (6) Ethanol 30.0 (7) 1,3-butylene glycol 5.0 (8) Trisodium edetate 0.05 (9) Cationic thickener 3.0 (10) Hydroxypropyl cellulose 0.1 (11) Xanthan gum 0.05 (12) Phosphoric acid 0.3 (13) Deionized water residue

[Production method] (1) to (4) were dissolved by heating,
(5) to (13), which had been warmed, were added with stirring. After homogenizing the mixture to make the emulsified particles fine, the mixture was rapidly cooled with stirring to obtain a colon.

Example 18 (1) Glycerin 20.0% by weight (2) Ethanol 25.0 (3) Cationic thickener 3.0 (4) Hydroxypropylcellulose 0.1 (5) Xanthan gum 0.05 ( 6) Citric acid 1.0 (7) Polyethylene powder 3.0 (8) Starch 10.0 (9) Polyoxyethylene (10) methylpolysiloxane copolymer 2.0 (10) Isopropyl myristate 2.0 ( 11) Squalane 1.0 (12) Fragrance 5.0 (13) Deionized water residue

[Production method] (1) to (4) are dissolved in purified water.
A mixture obtained by mixing and dissolving other components was added to obtain a slightly viscous colon.

Comparative Examples 8 to 11 Perfume compositions were prepared in the same manner as in Examples 15 to 18, except that ethanol was used instead of ion-exchanged water. I got

[Effect test] Using Examples 15 to 18 and Comparative examples 8 to 11, 10 panelists specialized in scent persistence after 3 hours of application and skin treatment effects typified by skin moistness and smoothness Was used for comparative evaluation. The results are shown in Tables 6 and 7. The evaluation criteria for odor persistence and skin treatment effect are as follows.

[0097]

[0099]

[Table 6] (1) Persistence of fragrance ─────────────────────────── Score 4 3 2 1 ─────── Example 15 0 4 4 2 Example 16 6 3 1 0 Example 17 8 2 0 0 Example 18 10 0 0 0比較 Comparative Example 8 0 0 1 9 Comparative Example 9 0 0 2 8 Comparative Example 10 0 1 3 6 Comparative Example 11 0 2 4 4

[0100]

[Table 7] (2) Skin treatment effect ─────────────────────────── Score 4 3 2 1 ────── ───────────────────── Example 15 0 4 5 1 Example 16 10 0 0 0 Example 17 9 10 0 0 Example 18 10 0 0 0比較 Comparative Example 8 0 0 1 9 Comparative Example 9 0 0 2 8 Comparative Example 10 0 0 2 8 Comparative Example 11 0 1 1 8

Examples 15 to 18 and Comparative Examples 8 to 1
In each case, the viscosity stability over time was good.

[0102]

As described above, the fragrance composition of the present invention is excellent in scent persistence, has a small rate of decrease in viscosity over time, and is not sticky even when dried after application to the skin.
And it has excellent treatment effect. In addition, by blending the powder, a fragrance composition for skin having a smooth feel can be obtained.

Claims (5)

[Claims] 1. The following component (A): 0.01 to 10.0% by weight, (B): 0.01 to 10.0% by weight, fragrance component: 0.2 to 30.0% by weight, ethanol From 0.1 to 79.
A liquid or gel-like skin fragrance composition comprising 0% by weight and 10.0 to 99.0% by weight of water. (A) A cationic thickener obtained by polymerizing a monomer composition for a thickener containing: General formula (I): (Wherein R ¹ is a hydrogen atom or a methyl group, R ² and R ³
Each independently represents a hydrogen atom, a methyl group, an ethyl group or a t-butyl group, A represents an oxygen atom or a -NH- group, and B represents a linear or branched alkylene group having 1 to 4 carbon atoms. 15.0 to 85.0% by weight of an amine-containing (meth) acrylic monomer represented by the following formula (II): (Wherein, R ¹ has the same meaning as described above, and R ⁴ has the general formula: (Wherein p represents 3 or 4) or a group represented by the following formula: Represents a group represented by ) Vinyl monomer 0
~ 80.0% by weight, General formula (III): (Wherein, R ¹ and A have the same meanings as described above, and R ⁵ is a linear or branched alkylene group having 1 to 17 carbon atoms or a general formula (IV): (Wherein, n represents an integer of 1 to 4 and q represents an integer of 1 to 25), and R ⁶ represents a hydrogen atom or a methyl group. (Meth) acryloyl group-containing monomer represented by the formula: 1.0 to 60.0% by weight, crosslinkable vinyl monomer 0.1 to 20.0% by weight (B) selected from hydroxypropylcellulose, xanthan gum, hydroxyethylcellulose and methylcellulose One or more. 2. The fragrance composition according to claim 1, wherein (B) is hydroxypropylcellulose. 3. The fragrance composition according to claim 1, which is of a type to be applied. 4. The fragrance composition according to claim 1, further comprising a powder. 5. The fragrance composition according to claim 4, wherein the powder is one or more selected from polyamide resin powder, silica, polyethylene powder and starch.