JPH0967239A - Perfume composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid or jelly-like perfume composition for skin having excellent persistence of perfume and combinedly having a skin treatment effect and excellent in touch feeling. SOLUTION: This perfume composition includes 0.05-10wt.% of a cationic thickener obtained by polymerizing a monomer composition for a thickener, 0.5-30wt.% of a perfume component, 20-99wt.% water and 0.1-79wt.% ethanol as active components. The cationic thickener is obtained by polymerizing 15-85wt.% of an amine-containing (meth)acrylic monomer of formula I (R<1> is H or methyl; R<2> and R<3> are each H, methyl, ethyl or t-butyl; A is O or NH; B is a 1-4C alkylene) with 0-80wt.% of a vinyl monomer of formula II (R<4> is formula III, etc.; (p) is 3 or 4), 1-60wt.% of a (meth)acryloyl group-containing monomer of formula IV (R<5> is a 1-17C alkylene, etc.; R<6> is H or methyl) and 0.1-20wt.% of a crosslinkable vinyl monomer. Furthermore, by mixing powder (e.g; polyamide resin powder), dry feeling is imparted to obtain the objective composition having excellent use feeling.

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 to enjoy a fragrance, and more specifically, it is a liquid or gel form having an excellent fragrance durability, a skin treatment effect and a good feel. Perfume composition for skin.

[0002]

BACKGROUND OF THE INVENTION Perfume materials generally include natural flavors obtained from animals or plants and synthetic flavors produced by chemical synthesis means. In order to create an excellent scent, Perfumer combines years of experience, sense and inspiration to combine these fragrance materials,
For example, in the case of various flower scents, the natural flower scent itself is reproduced, or in the case of an oriental scent,
The oriental image is expressed as a scent. All of these fragrance materials are dissolved in ethyl alcohol to become fragrance products that enjoy the scent. In addition, there are many liquid or gel bases of the type applied to the skin which have hitherto been widely used, in which a water-soluble polymer is blended. These polymers are mixed in a certain amount to thicken and stabilize the system. The feature is that the degree of thickening changes depending on the blending amount, and the spread when the base is applied changes accordingly. These polymers are frequently compounded in body products such as whole body or partially used massage preparations and skin care products such as packs. When using it as a base for whole body massage, apply an appropriate amount on the whole body before and after bathing, and spread while applying,
Use with massage. By adding an appropriate amount of the polymer to the base, it is possible to create a viscosity suitable for massage and also stabilize the system. While having such an excellent function, the polymer is also disadvantageous in that it feels sticky during the process of applying the base to the skin and then drying.

[0003]

[Problems to be Solved by the Invention] The fragrance composition for skin, which is composed of an alcohol, is not sticky and is characterized by a refreshing sensation by alcohol and a refreshing sensation. However, in rare cases, when a fragrance containing alcohol is used, some people may have rough skin, and there is a layer in which a product with a high alcohol content cannot or cannot be used. Therefore, it is expected that the fragrance product for the skin will contain the alcohol as little as possible or contain no alcohol. However, fragrances generally contain a wide variety of substances, from highly polar to non-polar ones, and on a water base, even if a surfactant is used, it is 0.5% or more. It was almost impossible to dissolve a fragrance and to obtain a stable product which does not separate over time even with an emulsion system.

On the other hand, the applicant of the present invention has already developed a fragrance composition of a type using a liquid or gel base, which is applied to the skin (patent application filed on February 22, 1995). Although this fragrance composition has a low alcohol content and is excellent in skin treatment effects, it uses the liquid or gel base that has been widely used as described above, and thus has the drawback of becoming sticky after drying. was there. Therefore, it has been expected to develop a liquid or gel-like fragrance composition for skin, which can be appropriately massaged immediately after application and is not sticky after drying.

[0005]

Therefore, as a result of intensive studies, the present inventor has found that by adding a fragrance to a specific cationic thickener, a stable liquid or gel can be obtained even when the amount of ethanol is small. It was found that there is obtained a fragrance composition having a long-lasting fragrance, an excellent skin treatment effect, and an extremely low stickiness after drying, which is applied to the skin. Furthermore, by adding powder to this, it will be even less sticky.
The present invention has been completed by finding that a fragrance composition having an extremely good usability can be obtained.

That is, according to the present invention, the following component (A) is added to
It is characterized by containing 05 to 10.0% by weight, a fragrance component of 0.5 to 30.0% by weight, water of 20.0 to 99.0% by weight, and ethanol of 0.1 to 79.0% by weight. It is a liquid or gel-like fragrance composition for skin. The term "for skin" as used herein means that those which are directly applied to the skin by a method such as spraying or coating are the objects of the present invention, and those which are not directly applied to the skin such as room colon are excluded.

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

[0008]

[Chemical 7]

(Wherein R ¹ is a hydrogen atom or a methyl group,
R ² and R ³ are each independently a hydrogen atom, a methyl group,
Ethyl group or t-butyl group, A is an oxygen atom or -N
H-group and B represent a linear or side chain 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):

[0010]

Embedded image

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

[0012]

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

[0014]

Embedded image

A group represented by: ) Vinyl monomer represented by the formula: 0-80.0% by weight, general formula (III):

[0016]

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

[0018]

[Chemical 12]

(In the formula, 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 1.0 to 60.0% by weight, crosslinkable vinyl monomer 0.1 to 20.0% by weight

Next, the structure of the present invention will be described. First, the cationic thickener of the component (A) is as described above.
It is obtained by polymerizing a monomer composition for thickeners containing. 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 copolymerizing a monomer composition for a thickener and neutralizing a copolymer obtained 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 proportion of the amine-containing (meth) acrylic monomer in the monomer composition for a thickener is 15.0.
-85.0% by weight, preferably 25.0-75.0% by weight, more preferably 35.0-65.0% 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 which imparts flexibility, gloss and smoothness to a film formed after the cationic thickener is dried.

Typical examples of the vinyl monomer include, for example, N-vinylpyrrolidone, N-vinylpiperidone,
Examples include acrylamide and methacrylamide, but the present invention is not limited to these examples. In addition, in this invention, the said vinyl monomer is used individually or in mixture of 2 or more types.

The ratio of the vinyl monomer in the monomer composition for a thickener is 80.0% by weight or less, preferably 7% by weight.
The content is adjusted to 5.0% by weight or less, more preferably 60.0% by weight or less. If the proportion of the vinyl monomer exceeds the above upper limit, the gel viscosity of the obtained cationic thickener is remarkably lowered. In addition, effects achieved by blending the vinyl monomer,
That is, in order to sufficiently impart flexibility, gloss and smoothness to the 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
The above is desirable.

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, 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) A) 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) acrylate, but the present invention is not limited to these examples. In addition, in this invention, the said (meth) acryloyl group containing monomer is used individually or in mixture of 2 or more types.

The ratio of the (meth) acryloyl group-containing monomer in the monomer composition for a thickener is 1.0 to 6
The content is adjusted to 0.0% by weight, preferably 1.0 to 55.0% by weight, and more preferably 2.0 to 30.0% by weight. When the ratio of the (meth) acryloyl group-containing monomer exceeds the above range, the ratio of the hydrophobic group in the obtained copolymer becomes large, and the solubility in water becomes small even after neutralization, It becomes difficult to obtain a smooth gel, and when the amount is less than the above range, the gel viscosity decreases, so it is necessary to increase the amount of the cationic thickener used, and at the same time, the compoundable amount of various setting resins decreases. The gloss of the film formed after the cationic thickener is 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 monomer; methylenebis (meth) acrylamide, 1,2-bis (meth) acrylamideethane,
1 such as 1,5-bis (meth) acrylamide pentane
(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 to such examples. In addition, in this invention, the said crosslinkable vinyl monomer is used 1 type or in mixture of 2 or more types.

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 adjusted to 1.0 to 10.0% by weight, more preferably 2.0 to 8.0% by weight. When the ratio 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 it exceeds the above range,
Although the viscosity of the cationic thickener increases, fine agglomerates are generated 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 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 to prevent 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 to suppress the formation of a homopolymer due to the difference in reactivity of each monomer and to obtain a uniform copolymer. 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 a volume of 20 g or more with respect to 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. It should be noted that ethanol and isopropanol are most preferable because they are harmful to benzene and the like.

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 refers to a solvent capable of dissolving a copolymer having a molecular weight of 10,000 or more in an amount of 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 having 7 or less carbon atoms are preferable. Of these, straight-chain, branched-chain or cyclic aliphatic hydrocarbons having 6 or 7 carbon atoms are particularly preferable because they have a high boiling point. In addition, n-hexane, cyclohexane and the like are preferable from the viewpoints of being 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 solution polymerization stirrer commonly used as such a reaction device,
It is preferable to dilute the monomer composition for a thickener with the solvent so that the concentration thereof is 30% by weight or less. In addition,
During the reaction, it is preferable to sufficiently stir the reaction solution using a stirrer or the like in order to prevent the reaction solution from being stagnant. The polymerization reaction is preferably carried out under heating at 50 to 100 ° C., and is generally carried out 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 optionally terminated when the amount of the remaining monomer is 10% by weight or less. The amount of the remaining monomer can be determined by adding bromine 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 performed by vacuum drying or by distilling off under normal pressure or reduced pressure.

In the polymerization reaction, a polymerization catalyst may be used. Examples of such a polymerization catalyst include 2,2'-
Azobisisobutyronitrile, 2,2'-azobis (4
-Methoxy-2,4-dimethylvaleronitrile), dimethyl 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, but these catalysts are one or two kinds. The above is mixed and used. Further, the present invention is not limited to such an example. When a large amount of an amine-based monomer is used in the thickener monomer composition, undesired side reactions such as an oxidation reaction may occur when a peroxide catalyst is used in a large amount, and thus polymerization may be hindered. Be careful when using.
Generally, 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 easy to handle. Most preferable 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 thickener monomer composition.

In the course of the polymerization of the monomers,
There are various aspects. For example, when only the good solvent is used, it has the same appearance as in the case of performing general solution polymerization in the initial stage of the polymerization reaction, but as the reaction progresses, the crosslinking reaction progresses and a gel state is formed. And a grease-like product free of precipitates is obtained as the reaction proceeds.

When a mixed solution of the above-mentioned good solvent and poor solvent is used, at the initial stage of the 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 in, for example, JP-A-5-140531.
Japanese Patent Application No. 5-298659.
The cationic thickening agent itself is not sticky and has a gel forming ability, and is added in an amount of 0.05 to 10.0% by weight, preferably 0.1 to 5.0% by weight in the total composition. 0.
If it is less than 05% by weight, the thickening effect cannot be obtained, and if it exceeds 10.0% by weight, it is not preferable because it feels sticky when applied to the skin.

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

Specific examples of powders include talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, phlogopite, biotite, lithia mica, vermiculite, magnesium carbonate, calcium carbonate, and silica. Aluminum oxide, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (calculated 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, polymethylmethacrylate powder, polystyrene powder, Copolymer resin powder styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder, organic powders such as cellulose powder, titanium dioxide, inorganic white pigments such as zinc oxide, iron oxide (red iron oxide),
Inorganic red pigments such as iron titanate, inorganic brown pigments such as γ-iron oxide, yellow iron oxide, inorganic yellow pigments such as ocher black iron oxide, carbon black, inorganic black pigments such as low order titanium oxide, Inorganic purple pigments such as mango violet and cobalt violet, inorganic green pigments such as chromium oxide, chromium hydroxide and cobalt titanate, inorganic blue pigments such as ultramarine blue 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 No. 201, Red No. 202, Red No. 204, Red No. 205, Red 220
No. Red 226, Red 228, Red 405, Orange 203, Orange 204, Yellow 205, Yellow 401
And organic pigments such as Blue No. 404, Red No. 3, Red No. 1
04, red 106, red 227, red 230,
Red 401, Red 505, Orange 205, Yellow 4
No. 5, Yellow No. 5, Yellow No. 202, Yellow No. 203, Green No. 3, Blue No. 1, etc., organic pigments such as zirconium, barium or aluminum lake, and natural pigments such as chlorophyll and β-caroline. Of these powders, polyamide resin powder, silica and polyethylene powder are particularly preferable.

In the present invention, the addition of powder further gives a fragrance composition having a smooth feel and a better feeling in use. When blending powders,
The blending amount is 0.01 to 20.0% by weight, preferably 0.1 to 10.0% by weight.

In the present invention, the blending amount of water is 20.0 to.
It is 99.0% by weight. If it is less than 20.0% by weight, the amount of ethanol will be increased as a result, and the skin treatment effect and the fragrance persistence will be insufficient. The blending amount of ethanol is 0.1 to 79.0% by weight, preferably 10.
It is 0 to 60.0% by weight. The smaller the amount of ethanol is, the less the skin irritation is, and the fragrance composition having the excellent skin treatment effect is obtained.

In addition to the above-mentioned essential components, the fragrance composition of the present invention may contain other optional components as long as the quality is not impaired. Examples of such optional components include the following.

Acids such as lactic acid, phosphoric acid, citric acid, maleic acid and succinic acid for adjusting viscosity and gel strength can be mentioned.

The 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 tung oil, jojoba oil, germ oil, triglycerin, glyceryl trioctanoate, glyceryl triisopalmitate, etc., are solid cacao. Fat, coconut oil, horse fat, hydrogenated coconut oil, palm oil, beef tallow, sheep fat, hydrogenated beef tallow, palm kernel oil, pork fat, beef bone fat, mokuro kernel oil, hydrogenated oil, beef tallow, mokurou, hydrogenated castor oil Examples of waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ivota wax, whale wax, montan wax, nukarou, lanolin, capock wax, lanolin acetate, liquid lanolin, sugarcane wax, lanolin fatty acid isopropyl, hexyl laurate, reduced lanolin. , Jojoba wax, hard lanolin, shellac wax, POE lanolin alcohol ether Hydrocarbon oils such as POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, and POE hydrogenated lanolin alcohol ether include liquid paraffin, ozokerite, squalene, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax, etc. Oil is included.

Examples of the higher fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid (beheninic acid), oleic acid, 12-hydroxystearic acid, undecylenic acid, tall acid, isostearic acid, linoleic acid, and linolein. Acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), and the like.

Examples of higher alcohols include linear alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol and cetostearyl alcohol, monostearyl glycerin ether (batyl alcohol), 2-decyltetradecyl alcohol. Examples thereof include branched chain alcohols such as knoll, lanolin alcohol, cholesterol, phytosterol, hexyldecanol, isostearyl alcohol, and octyldodecanol.

Examples of synthetic ester oils include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl dimethyloctanoate, Cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearyl acid, ethylene glycol di-2-ethylhexylate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, neocaproic acid Pentyl glycol, diisostearyl malate, glycerin di-2-heptylundecanoate, trimethylol tri-2-ethylhexylate Bread, trimethylol propane triisostearate, tetra-2-ethylhexanyl pentane erythritol, glycerin tri-2-ethylhexyl acid, trimethylol propane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, trimyristic acid 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 chain polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane and methylhydrogenpolysiloxane, and cyclic polysiloxanes such as decamethylpolysiloxane, dodecamethylpolysiloxane and tetramethyltetrahydrogenpolysiloxane. Examples thereof include polysiloxane, silicone resin having a three-dimensional network structure, and silicone rubber.

As vitamins, vitamin A such as vitamin oil, retinol, retinol acetate, etc., vitamin B ₂ such as riboflavin, riboflavin butyrate, flavin adenine nucleotide, etc., vitamin B ₆ such as pyridoxine hydrochloride, pyridoxine dioctanoate, etc. , L-ascorbic acid, L-ascorbic acid dipalmitate,
L-ascorbic acid-2-sulfate sodium, L-ascorbic acid phosphate, DL-α-tocopherol-L
-Vitamin Cs such as ascorbic acid diester dipotassium phosphate, calcium pantothenate, pantothenic acids such as D-pantothenyl alcohol, pantothenyl ethyl ether, acetylpantothenyl ethyl ether, vitamin Ds such as ergocalciferol, cholecalciferol , Nicotinic acid, nicotinic acid amide, nicotinic acid benzyl and other nicotinic acids, α-tocopherol, tocopherol acetate, DL-α-tocopherol nicotinate, vitamin Es such as DL-α-tocopherol succinate, vitamin P, biotin, etc. Can be mentioned.

As the ultraviolet absorber, para-aminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester, N,
Benzoic acid type UV absorbers such as N-dimethyl PABA ethyl ester, N, N-dimethyl PABA butyl ester, anthranilic acid type UV absorbers such as homomenthyl-N-acetylanthranilate, amyl salicylate,
Salicylic acid type UV absorbers such as menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, octylcinnamate, ethyl-4-isopropylcinnamate, methyl-2,5-diisopropylcinnamate , 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-
Methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl-diparamethoxy Cinnamate, 3,4,5-trimethoxycinnamic acid 3-methyl-4- [methylbis (trimethylsiloxy) silyl] butyl and other cinnamic acid type UV absorbers, 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, 2
-Ethylhexyl-4'-phenyl-benzophenone-
Benzophenone-based UV absorbers such as 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, dibenzalazine, dianisoylmethane, 4-methoxy-4'-t-butyldibenzoylmethane, 5- (3,3-dimethyl-2-norbornylidene)
-3-Pentan-2-one and the like can be mentioned.

Examples of moisturizers 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-hydroxy stearate, sodium lactate, bile salt, dl-pyrrolidone carboxylate, short-chain soluble collagen, diglycerin (EO) PO adduct, Issai rose extract, Astragalus membranaceus extract, melilot extract, etc. Can be mentioned.

Other examples include plant extracts, drugs, stabilizers, polymer compounds and the like.

[0059]

EXAMPLES The present invention will be further described with reference to examples.
In addition, the compounding amount is weight%.

Example 1, Comparative Examples 1 to 4 Perfume compositions having the compositions shown in Table 1 were produced and evaluated for stickiness. Table 1 shows the results.

[Production Method] (1) Production Method of Cationic Thickener In a three-necked flask equipped with a thermometer, a reflux tube and a nitrogen introduction tube, 50 g of N, N-dimethylaminoethyl methacrylate as a monomer and N- Vinylpyrrolidone 47.5
g, stearyl acrylate 2.5 g and tripropylene glycol diacrylate 1.9 g, and a mixed solvent of 23.1 g of ethanol and 554.3 g of cyclohexane (mixing ratio (weight ratio) 4:96) was added, and the mixture was heated at 80 ° C. While refluxing, the mixture was degassed by stirring under a nitrogen stream for 2 hours.

Next, 0.41 g of 2,2'-azobisisobutyronitrile was added to the three-necked flask, and polymerization was started at 80 ° C. After 45 minutes from the initiation of the polymerization, 1.9 g of tripropylene glycol diacrylate was added, and after 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 content was dried under reduced pressure. The obtained dry polymer was pulverized with a pulverizer to obtain a white powdery cationic thickener.

(2) Method for producing perfume composition After dissolving (1) to (9) described in Table 1, (10) is added.

[Evaluation Method] (1) Evaluation of Stickiness Feeling Ten usability evaluation monitors applied the appropriate amount of the fragrance compositions of Examples and Comparative Examples to the skin and evaluated the stickiness feeling. The evaluation results are represented by the following display. ⊚: 8 out of 10 people answered that there was no sticky feeling. ○: 6 out of 10 people answered that there was no sticky feeling. Δ: Out of 10 people, 4 or more people answered that there was no sticky feeling. ×: Less than 4 out of 10 responded that there was no sticky feeling.

[0065]

[Table 1] ─────────────────────────────────── Examples Comparative examples ───── ── ─────────── 1 1 2 3 4 ────────────────────────────────── ─ (1) Ion-exchanged water 40.0 40.0 40.0 40.0 40.0 (2) Ethanol 50.0 50.0 50.0 50.0 50.0 (3) Perfume 2.0 2.0 2.0 2.0 2.0 (4) Cationic thickener 1.0 − − − − (5) Carboxymethyl cellulose − 1.0 − − − (6) Hydroxypropyl cellulose − − 1.0 − − (7) Hydroxyethyl cellulose − − − 1.0 − (8) Carboxyvinyl polymer − − − − 1.0 (9) Lactic acid 0.3 − − − − (10) Potassium hydroxide − − − − 0.3 ─────────────────────────────────── Evaluation A. Stickiness ○ × △ △ × ────────── ────────────────────────

From the results shown in Table 1, the fragrance composition of the present invention is
It was clarified that it was not sticky as compared with the one containing a conventional polymer thickener.

Examples 2 to 7 Fragrance compositions having the compositions shown in Table 2 were produced and evaluated for their silky feel. The results are shown in Table 2.

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

(2) Production of perfume composition (5) was added to a solution of (1) to (4) described in Table 2,
Then add (6).

[Evaluation Method] (1) Evaluation of Sticky Feeling Evaluation was made by the same evaluation method as in Example 1.

(2) Evaluation of dryness The usability evaluation monitors applied the appropriate amounts of the fragrance compositions of Examples and Comparative Examples to the skin by 10 monitors, and evaluated the dryness after drying. The evaluation results will be expressed as follows. ⊚: 8 out of 10 respondents answered that they felt dry. ○: 6 or more out of 10 respondents answered that they felt dry. △: Of 10 people, 4 or more people answered that they felt dry. ×: Less than 4 out of 10 respondents answered that they felt dry.

[0072]

[Table 2] ───────────────────────────────── Example No. 2 3 4 5 6 7 7 ──── ───────────────────────────── (1) Ion-exchanged water 30.0 30.0 30.0 30.0 30.0 30.0 (2) Ethanol 40.0 40.0 40.0 40.0 40.0 40.0 (3) Perfume 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) Polyamide resin powder 1.0 3.0 5.0 7.0 10.0 − (6) Phosphoric acid 0.3 0.3 0.3 0.3 0.3 0.3 ── ─────────────────────────────── Evaluation A. Stickiness ◎ ◎ ◎ ◎ ◎ ◎ ◎ B. Smoothness △ △ ○ ◎ ○ × ─────────────────────────────────

As is clear from the results in Table 2, by adding the powder, not only a sticky feeling but also a smooth feeling was obtained.

Example 8 (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 Thickener 0.3 (5) Lactic acid 0.1 (6) Ethanol 60.0 (7) Citric acid 0.1 (8) Sodium citrate 0.05 (9) Hydroxymethoxybenzophenone Sodium sulfonate Suitable amount (10) Perfume 1.0 (11) Methylparaben Appropriate amount (12) Trisodium edetate Appropriate amount (13) Ion-exchanged water Residual

[Production Method] Citric acid, sodium citrate, trisodium edetate, sodium hydroxymethoxybenzophenone sulfonate, dipropylene glycol, 1,3-butylene glycol, cationic thickener and lactic acid are dissolved in ion-exchanged water. (Aqueous phase). Separately, polyoxyethylene (20) oleyl alcohol ether in ethanol,
The fragrance and methyl paraben were dissolved, and this was added to the above-mentioned aqueous phase to solubilize it to obtain a liquid cologne.

Example 9 (1) Squalane 3.0% by weight (2) Polyoxyethylene (60) Glyceryl monoisostearate 3.0 (3) Ethylparaben Appropriate amount (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) Lactic acid 0. 3 (11) Ion-exchanged water Residual

[Production Method] (1) to (5) were dissolved by heating and added to (6) to (11) heated to 70 ° C with stirring. The mixture was treated with a homomixer to make the emulsified particles fine, and then rapidly cooled with stirring to obtain a colon.

Example 10 (1) Liquid paraffin 3.0% by weight (2) Polyoxyethylene (40) Hydrogenated castor oil 4.0 (3) Ethylparaben Appropriate amount (4) Perfume 4.0 (5) Silica 2. 0 (6) Ethanol 30.0 (7) 1,3-butylene glycol 5.0 (8) Trisodium edetate 0.05 (9) Cationic thickener 3.0 (10) Phosphoric acid 0.3 ( 11) Deionized water residual

[Production Method] (1) to (4) were dissolved by heating and added to (5) to (11) heated to 70 ° C. with stirring. The mixture was treated with a homomixer to make the emulsified particles fine, and then rapidly cooled with stirring to obtain a colon.

Example 11 (1) Glycerin 20.0% by weight (2) Ethanol 25.0 (3) Cationic thickener 3.0 (4) Citric acid 1.0 (5) Polyethylene powder 3.0 ( 6) Polyoxyethylene (10) methyl polysiloxane copolymer 2.0 (7) Isopropyl myristate 2.0 (8) Squalane 1.0 (9) Perfume 8.0 (10) Ion exchange water Residual

[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 cologne.

Comparative Examples 5 to 8 Perfume compositions were prepared in the same manner as in Examples 8 to 11 except that ethanol was used in place of the ion-exchanged water in Examples 8 to 11, and Comparative Examples 5 to 8 respectively. Got

[Effect Test] Examples 8 to 11 and Comparative Example 5
8 to 8 were used to compare and evaluate the persistence of the scent 3 hours after application, and the skin treatment effect represented by the moistness and smoothness of the skin, by 10 specialist panels.
The results are shown in Tables 3 and 4. The evaluation criteria for the odor persistence and skin treatment effect are as follows.

[0084]

[0085]

[0086]

[Table 3] (1) Persistence of fragrance ─────────────────────────── Score 4 3 2 1 1 ──────── ──────────────────── Example 8 0 4 4 2 Example 9 6 3 1 0 Example 10 8 2 0 0 Example 11 11 10 0 0 0 ─ ────────────────────────── Comparative Example 5 0 0 1 9 Comparative Example 6 0 0 2 8 Comparative Example 7 0 1 3 6 Comparative Example 8 0 2 4 4 ────────────────────────────

[0087]

[Table 4] (2) Skin treatment effect ─────────────────────────── Score 4 3 2 1 1 ─────── ───────────────────── Example 8 0 4 5 1 Example 9 10 0 0 0 Example 10 9 1 0 0 Example 11 10 0 0 0 ─────────────────────────── Comparative Example 5 0 0 1 9 Comparative Example 6 0 0 2 8 Comparative Example 7 0 0 2 8 Comparative Example 8 0 1 1 8 ───────────────────────────

[0088]

Industrial Applicability As described above, the fragrance composition of the present invention has a high scent persistence, is not sticky to the skin even when dried after being applied to the skin, and has an excellent treatment effect. Further, by blending the powder, a fragrance composition for skin having a dry feel can be obtained.

Claims (4)

[Claims] 1. The following component (A) is added in an amount of 0.05 to 10.0% by weight, a fragrance component in an amount of 0.5 to 30.0% by weight, and water in an amount of 20.
A liquid or gel skin fragrance composition comprising 0 to 99.0% by weight and 0.1 to 79.0% by weight of ethanol. (A) A cationic thickener obtained by polymerizing a monomer composition for a thickener containing the following items. General formula (I): (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² and R ³
Each independently represent 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 side chain 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 general formula (II): (In the formula, R ¹ has the same meaning as described above, and R ⁴ has the general formula: (In the formula, p represents 3 or 4.) or a group represented by the formula: Represents a group represented by. ) Vinyl monomer represented by 0
~ 80.0% by weight, general formula (III): (In the formula, R ¹ and A have the same meanings as described above, R ⁵ is a linear or side-chain alkylene group having 1 to 17 carbon atoms or the general formula (IV): (In the formula, n represents an integer of 1 to 4 and q represents an integer of 1 to 25.), R ⁶ represents a hydrogen atom or a methyl group. ) (Meth) acryloyl group-containing monomer 1.0 to 60.0% by weight, crosslinkable vinyl monomer 0.1 to 20.0% by weight 2. The fragrance composition according to claim 1, which is of a coating type. 3. The fragrance composition according to claim 1, further comprising a powder. 4. The fragrance composition according to claim 3, wherein the powder is one or more selected from polyamide resin powder, silica and polyethylene powder.