JP5813936B2 - Fragrance composition - Google Patents

Description

  The present invention relates to a fragrance composition that dissolves a citrus fragrance or a fruity fragrance in an alcohol and has a viscosity that reduces alcohol odor and has excellent fragrance durability and is easy to apply.

  Conventionally, the most commonly used fragrances in fragrance products are made by dissolving the fragrance in a solvent such as alcohol, and the blending amount of alcohol in the product is extremely high at about 80 to 90%. Immediately after application, there are those that are worried about the smell of alcohol.

  In addition, after applying perfume to the skin, a fragrance product that maintains the strength of the scent immediately after application for a long time and does not change the quality of the scent is desired. In particular, a citrus or fruity fragrance is blended. In some perfumes, a change in scent over time can be remarkably felt.

  In addition, fragrance products are usually applied to the skin by spraying perfume using a dispenser container, or taken from the bottle to the finger and applied to the skin. There were drawbacks such as perfume adhering to the site, and perfume spilled if care was not taken.

JP-A-8-325591

  The present invention provides a fragrance composition having a viscosity that is easy to apply while reducing the odor of alcohol while being a fragrance composition obtained by dissolving a citrus fragrance or a fruity fragrance in alcohol. It is an object of the present invention to provide a fragrance product including an application tool suitable for applying the fragrance composition.

The present inventors have conducted studies, a citrus perfume or fruity-based flavors are dissolved in alcohol in order to solve the above problems, by blending water and two thickening agents, and reducing the alcoholic odor In the fragrance composition having a predetermined viscosity with improved scent persistence, it was found that application using a spatula made of an appropriate material was optimal as a fragrance product , and the present invention was completed.

（式中、Ｒ^１は水素原子またはメチル基、Ｒ^２およびＲ^３はそれぞれ独立して水素原子、メチル基、エチル基またはｔ−ブチル基、Ａは酸素原子または−ＮＨ−基、Ｂは直鎖状または側鎖を有する炭素数１〜４のアルキレン基を示す。）で表されるアミン含有（メタ）アクリル系モノマー １５．０〜８５．０質量％、
(ｂ)一般式（II）：

（式中、Ｒ^１は前記と同じ意味、Ｒ^４は一般式：

（式中、ｐは３または４を示す。）で表される基または式：

で表される基を示す。）で表されるビニルモノマー ０〜８０．０質量％、
(ｃ)一般式（III）：

（式中、Ｒ^１およびＡは前記と同じ意味、Ｒ^５は直鎖状または側鎖を有する炭素数１〜１７のアルキレン基または一般式（IV）：

（式中、ｎは１〜４の整数、ｑは１〜２５の整数を示す。）で表される基、Ｒ^６は水素原子またはメチル基を示す。）で表される（メタ）アクリロイル基含有モノマー １．０〜６０．０質量％、
(ｄ)架橋性ビニルモノマー ０．１〜２０．０質量％
That is, the present invention comprises (A) a citrus fragrance or a fruity fragrance, (B) one or two or more lower alcohols 60-80% by mass selected from ethanol, methanol, ethylene glycol, and isopropyl alcohol , C) 0.05 to 0.2% by mass of a cationic thickener obtained by polymerization reaction of water and (D) a monomer mixture for a thickener containing the following components (a) to (d): (E) A fragrance composition containing 0.2 to 1.0% by mass of a cellulose-based thickener and having a viscosity at 30 ° C. of 200 to 1000 mPa · s is applied using a spatula whose material is polypropylene. A fragrance product characterized by
(a) General formula (I):

(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, an ethyl group or a t-butyl group, A is an oxygen atom or an —NH— group, and B is a direct atom An amine-containing (meth) acrylic monomer represented by 15.0 to 85.0% by mass, represented by a chain or side chain C1-C4 alkylene group.
(b) General 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 formula:

The group represented by these is shown. 0-80.0% by mass of vinyl monomer represented by
(c) General formula (III):

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

(Wherein 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 represented by 1.0 to 60.0% by mass,
(d) Crosslinkable vinyl monomer 0.1 to 20.0% by mass

Furthermore, the present invention is a fragrance product characterized by formulating the fragrance products (E) cellulosic thickener is hydroxypropyl cellulose, hydroxyethyl cellulose, and one or more selected from cellulose.

Furthermore, the present invention is a fragrance product characterized by formulating the fragrance products (B) a lower alcohol is ethanol.

  According to the present invention, in a fragrance composition in which a citrus fragrance or a fruity fragrance is dissolved in alcohol, while reducing the alcohol odor, the fragrance composition has excellent fragrance durability and has a viscosity that is easy to apply. Can do.

  Moreover, the fragrance product provided with the applicator suitable for apply | coating this fragrance | flavor composition can be provided.

The graph which shows the result of having evaluated the alcohol odor immediately after application | coating of the test product 5 and the test product 1 The graph which shows the result of having evaluated the alcohol odor immediately after application | coating of the test product 6 and the test product 2 The graph which shows the result of having evaluated the intensity of the fragrance of the test product 5 and the test product 1 over time The graph which shows the result of having evaluated the intensity of the fragrance of the test product 6 and the test product 2 over time The graph which shows the result of having evaluated the fresh feeling of the fragrance of the test product 5 and the test product 1 over time The graph which shows the result of having evaluated the fresh feeling of the fragrance of the test product 6 and the test product 2 over time Side view of container with spatula (partial cross section)

  The configuration of the present invention will be described below.

(A) Citrus fragrance or fruity fragrance Citrus fragrance contains monoterpene hydrocarbons and other terpene hydrocarbons, etc., which are fragrance components contained in citrus fruits. Orange, Daidai, Sweet Orange, Bitter Orange, Lemon Perfume that emits the scent of citrus fruits (citrus) such as bergamot and grapefruit. Specific components include d-limonene, citral, linalool, linalyl acetate, decanal, octanal, nootkatone and the like.
Fruity flavors include flavors such as alcohol, aldehydes, esters, and lactones, which are flavor components contained in fruits, and give off the scent of fruits such as apples, peaches, and mangoes. Point to. Specific components include amyl acetate, amyl butyrate, ethyl acetate, α-ionone, ethyl butyrate and the like.

  The blending amount of the fragrance is not particularly limited as long as it is a blending amount capable of obtaining a sufficient fragrance as a fragrance product, but is preferably 1.0 to 15.0% by mass.

(B) Lower alcohol The lower alcohol to be blended in the fragrance composition of the present invention includes ethanol, methanol, ethylene glycol, isopropyl alcohol, etc., but it is preferable to use ethanol in terms of safety and practicality. . Commercially available products include general alcohol 95-degree synthesis (Japan Alcohol Sales Co., Ltd.) and the like. The compounding quantity of lower alcohols, such as ethanol, in this composition is 60-80 mass% of the whole composition. If the amount is less than 60% by mass, the fragrance does not completely dissolve, and a part of the fragrance component tends to precipitate and precipitation tends to occur. The reason why the upper limit is 80% by mass is that other components such as a thickener component which is an essential component of the present invention are blended.

(C) Water The water to be blended in the fragrance composition of the present invention is not particularly limited, and specific examples include purified water, ion-exchanged water, and tap water.

  Further, the amount of water is not particularly limited, but the types and amounts of (D) cationic thickener and (E) cellulose-based thickener used in preparing the fragrance composition. Accordingly, the blending amount is appropriately adjusted so that the fragrance composition forms a liquid or gel-like uniform phase having a viscosity of 200 to 1000 mPa · s, and the blending amount in the composition is 10 to 30. Mass% is preferred.

(D) Cationic Thickener The cationic thickener to be blended in the fragrance composition of the present invention is obtained by polymerizing the monomer composition for thickener containing (a) to (d) described above. It is. Hereinafter, each component which comprises this cationic thickener is explained in full detail.

  When the amine-containing (meth) acrylic monomer represented by the general formula (I) is neutralized with a suitable acid, the copolymer obtained by copolymerizing the monomer composition for the thickener, It is a component having a role of imparting cationic ion properties 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, and N, N-dimethylaminopropyl (meth). Although acrylamide etc. are mentioned, this invention is not limited only to this illustration. In the present invention, the amine-containing (meth) acrylic monomers are used alone or in admixture of two or more.

  The ratio of the amine-containing (meth) acrylic monomer in the thickener monomer composition is 15.0 to 85.0% by mass, preferably 25.0 to 75.0% by mass, and more preferably 35.0 to It is prepared so that it may become 65.0 mass%. When the proportion of the amine-containing (meth) acrylic monomer is less than the above range, the amount of the amine-containing (meth) acrylic monomer portion neutralized by the acid in the resulting copolymer becomes too small. Thus, it becomes difficult to obtain a product having a sufficient gel viscosity, and when the above range is exceeded, the flexibility of the film formed after the obtained cationic thickener is dried is lost.

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

  Representative examples of the vinyl monomer include N-vinyl pyrrolidone, N-vinyl piperidone, acrylamide, and methacrylamide, but the present invention is not limited to such examples. In the present invention, the vinyl monomers are used alone or in admixture of two or more.

  The ratio of the vinyl monomer in the monomer composition for the thickener is 80.0% by mass or less, preferably 75.0% by mass or less, and more preferably 60.0% by mass or less. When the proportion of the vinyl monomer exceeds the upper limit, the gel viscosity of the resulting cationic thickener is significantly reduced. In order to sufficiently impart flexibility, gloss, and smoothness to the film formed after the cationic thickener is dried, that is, the effect obtained by blending the vinyl monomer, the thickener is used. The proportion of the vinyl monomer in the monomer composition for use is 3.0% by mass or more, preferably 5.0% by mass or more, and more preferably 20.0% by mass or more.

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

  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, n-butyl (meth) acrylate, and 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) acryl Rate, hydroxybutyl (meth) acrylate, polyoxyethylene (in general formula (IV), n is an integer of 2, and q is an integer of 2 to 9) (meth) acrylate, methoxypolyethylene glycol (in general formula (IV), n is 3, integers in which q is 2 to 23) (meth) acrylates and the like are mentioned, but the present invention is not limited to such examples. In the present invention, the (meth) acryloyl group-containing monomer is used alone or in admixture of two or more.

  The proportion of the (meth) acryloyl group-containing monomer in the thickener monomer composition is 1.0 to 60.0% by mass, preferably 1.0 to 55.0% by mass, and more preferably 2.0 to 30.%. It is prepared to be 0% by mass. When the proportion of the (meth) acryloyl group-containing monomer exceeds the above range, the proportion of the hydrophobic group in the resulting copolymer is increased, and the solubility in water is reduced even after neutralization, It becomes difficult to obtain a smooth gel, and if it is less than the above range, the gel viscosity decreases, so it is necessary to increase the amount of cationic thickener used, and at the same time the amount of various setting resins that can be blended decreases, 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 other monomers.

  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, polypropylene glycol di ( (Meth) acrylic monomers having two or more carbon-carbon unsaturated double bonds in one molecule such as (meth) acrylate; methylene bis (meth) acrylamide, 1,2-bis (meth) acrylamide ethane, 1,5- (Meth) acrylamide monomer having two or more carbon-carbon unsaturated double bonds in one molecule such as bis (meth) acrylamide pentane; Two or more carbon-carbon unsaturated doubles in one molecule such as divinylbenzene And vinyl monomers with bonds That is, the present invention is not limited only to those exemplified. In the present invention, the crosslinkable vinyl monomer is used alone or in combination of two or more.

  The ratio of the crosslinkable vinyl monomer in the thickener monomer composition is 0.1 to 20.0% by mass, preferably 1.0 to 10.0% by mass, and more preferably 2.0 to 8.0% by mass. %. If the ratio of the crosslinkable vinyl monomer is less than the above range, the crosslinking viscosity of the resulting cationic thickener becomes too small, so that the viscosity of the cationic thickener cannot be increased. When the above range is exceeded, the viscosity of the cationic thickener increases, but fine aggregates are formed in the gel, and it becomes difficult to obtain a uniform gel.

  The polymerization reaction of the monomer composition for the thickener containing the amine-containing (meth) acrylic monomer, vinyl monomer, (meth) acryloyl group-containing monomer and crosslinkable vinyl monomer is a general solution polymerization method or bulk polymerization method. For example, it can also be performed by precipitation polymerization, which is a polymerization method for obtaining a powder, and is usually performed while heating in a non-aqueous solvent in an inert gas atmosphere such as nitrogen gas. . As described above, the polymerization reaction is performed in a non-aqueous solvent under an inert gas atmosphere in order to prevent hydrolysis of an ester group present in the monomer or the formed copolymer. .

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

  The good solvent is used in the present invention in order to obtain a uniform copolymer by suppressing the formation of a homopolymer due to the difference in reactivity of each monomer. In the present specification, the good solvent means a solvent in which a copolymer having a molecular weight of 10,000 or more dissolves in a range of 20 g or more with respect to 100 mL of the good solvent at 25 ° C. and no turbidity is observed. . Specific examples of the good solvent include methanol, ethanol, isopropanol, acetone, ethyl acetate, benzene, toluene, xylene and the like. Among these good solvents, ethanol, isopropanol and benzene are particularly preferable because they can obtain a relatively high molecular weight copolymer. Since benzene and the like are harmful, ethanol and isopropanol are most preferable.

  In addition, the poor solvent is used in the present invention in order to easily precipitate the produced copolymer from the polymerization solution. The poor solvent refers to a solvent that dissolves a copolymer having a molecular weight of 10,000 or more in a range of 5 g or less with respect to 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 preferred because of their high boiling points. Moreover, n-hexane, cyclohexane, etc. are preferable from the point that it is cheap and is easy to handle industrially.

  In order to synthesize a cationic thickener without impairing the properties of the resulting cationic thickener, it is preferable to blend the good solvent and the poor solvent in an appropriate ratio. When the proportion of the poor solvent is too large, the polymerization proceeds promptly, and the powder is likely to precipitate within a short time, making it difficult to obtain a cationic thickener having the desired physical properties. The ratio of the poor solvent to the mixed solvent of the good solvent and the poor solvent is 98% by mass or less, preferably 97% by mass or less, and the ratio of the good solvent is 2% by mass or more, preferably 3% by mass or more. It is desirable.

  In order to efficiently obtain the cationic thickener from the reaction solution, it is preferable to use a reaction apparatus for improving the stirring during the polymerization. When using a stirrer for solution polymerization generally used as such a reaction apparatus, it is preferable to dilute with the solvent so that the concentration of the monomer composition for the thickener is 30% by mass or less. In the reaction, it is preferable to sufficiently stir using a stirrer or the like so that the reaction solution does not stagnate. The polymerization reaction is preferably performed at a temperature of 50 to 100 ° C., and is generally performed at the reflux temperature of the solvent used for the reaction. The time required for the polymerization reaction is usually 10 hours or more. The polymerization reaction can be arbitrarily terminated when the amount of the remaining monomer is 10% by mass or less. The amount of the remaining monomer can be determined by adding oxalic acid to a 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 can be obtained. For removal of the mixed solvent, for example, the resulting precipitate of the cationic thickener is collected by filtration and then vacuum-dried or is usually used. By distilling off under reduced pressure or reduced pressure.

  In the polymerization reaction, a polymerization catalyst may be used. Examples of such polymerization catalysts include 2,2'-azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisiso. Azo compounds such as butyrate, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, dialkyl peroxides such as di-t-butyl peroxide, peroxycarbonates such as diisopropylperoxydicarbonate, t-butylperoxide There are peroxides typified by peroxyesters such as oxypivalate, but these catalysts are used alone or in combination. Further, the present invention is not limited to only such examples. In addition, when a large amount of amine monomer is used in the monomer composition for the thickener, undesirable side reactions such as an oxidation reaction may occur together if the peroxide catalyst is used a lot, which may inhibit polymerization. Be careful when using it. In general, it is preferable to mainly use an azo catalyst, but it varies depending on the boiling point of the solvent used. For example, when ethanol or benzene is used, 2,2'-azobisisobutyronitrile is easy to handle. Most preferred. The amount of the polymerization catalyst used is preferably 0.05 to 3.0% by mass, particularly 0.1 to 1.0% by mass, based on the total mass of the monomer of the thickener monomer composition.

  In addition, various aspects are exhibited in the polymerization process of the monomer. For example, when only the above-mentioned good solvent is used, it exhibits the same aspect as in the case of performing general solution polymerization in the initial stage of the polymerization reaction. As the reaction proceeds further, a grease-like product without precipitates is obtained.

  In addition, when a mixed solution of the good solvent and the poor solvent is used, the same aspect as when a general solution polymerization method is adopted is exhibited in the initial stage of polymerization, but as the reaction proceeds The cross-linking reaction proceeds to form a gel, and as the reaction proceeds further, the obtained polymer can no longer be dissolved in the mixed solvent, becomes insoluble and precipitates as a precipitate.

  Thus, a cationic thickener can be obtained. The cationic thickener is described in, for example, Japanese Patent Application Laid-Open No. 5-140531 and Japanese Patent Application No. 5-298659. The cationic thickener itself is non-sticky and has gel-forming ability, and is added to the whole composition in an amount of 0.05 to 0.2% by mass, preferably 0.05 to 0.1% by mass. If it is less than 0.05% by mass, a thickening effect cannot be obtained, and if it exceeds 0.2% by mass, it is difficult to spread when applied to the skin.

(E) Cellulose-based thickener Cellulose-based thickeners to be blended in the fragrance composition of the present invention include, for example, hydroxypropylcellulose, hydroxyethylcellulose, methylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, etc., among which alcohol It has sufficient viscosity even in a high blending area, and (D) since it has a function of reducing viscosity reduction when blended with only a cationic thickener to increase viscosity, hydroxypropylcellulose, hydroxyethylcellulose , And one or more selected from methylcellulose are preferably blended, and hydroxypropylcellulose is particularly preferred.

  The cellulose-based thickener is blended in the total composition in an amount of 0.2 to 1.0% by mass, preferably 0.3 to 0.8% by mass. If it is less than 0.2% by mass, the viscosity may decrease with time. On the other hand, if it exceeds 1.0% by mass, the viscosity becomes too high and the usability is inferior.

  The fragrance composition of the present invention has a viscosity at 30 ° C. of 200 to 1000 mPa · s. By blending the above components (A) to (E) and making the fragrance composition 200 to 1000 mPa · s, reduction of alcohol odor, which is the effect of the present invention, scent sustainability, and good usability It becomes possible to play. The viscosity is measured using a bismetholone viscometer (rotor No. 2, rotation speed 12 rpm) at 30 ° C.

  The perfume composition of the present invention uses a spatula (1) as a tool for application. The fragrance composition has a viscosity (30 ° C.) of 200 to 1000 mPa · s and is higher in viscosity than a normal perfume. (FIG. 7).

  The material of the spatula is preferably polypropylene. As a container equipped with a spatula, a container with an applicator as shown in FIG. 7 is usually employed. In this case, the spatula (1) and the inner cap (3) are integrally formed by injection molding. It becomes the same plastic material. In order to scoop the spatula without leaving the fragrance composition at its tip, dimensional accuracy is required to bring the tip close to the bottom of the container (the distance between the spatula tip and the container bottom is 5 mm). ), It is necessary to select a material with less swelling due to the contents. On the other hand, the inner cap needs to be a relatively soft material that can be deformed to some extent in order to ensure hermeticity when crimped to the container. Therefore, since the material of the spatula (inner cap) of the container with the applicator shown in FIG. 7 needs to select a material that can perform both functions of the spatula and the inner cap, it is relatively soft and swells due to the contents. Polypropylene is preferably used as a plastic material with a small amount.

(Optional component)
In the fragrance composition of the present invention, other optional components can be blended in addition to the essential 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.

  Liquid oils 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, sasanca oil, castor oil, flaxseed Oil, safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagiri oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin, glyceryl trioctanoate, triisopalmitin Acid glycerin etc. are solid fats such as cacao butter, coconut oil, horse fat, hardened coconut oil, palm oil, beef tallow, sheep fat, hardened beef tallow, palm kernel oil, pork tallow, beef bone fat, owl kernel oil, hardened Examples of waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, lobster wax, and sperm , Montan wax, nukarou, lanolin, kapok 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, POE lanolin alcohol acetate, POE cholesterol ether Examples of hydrocarbon oils such as lanolin fatty acid polyethylene glycol and POE hydrogenated lanolin alcohol ether include oils such as liquid paraffin, ozokerite, squalene, pristane, paraffin, ceresin, squalene, petrolatum, and microcrystalline wax.

  Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behen (behenine) acid, oleic acid, 12-hydroxystearic acid, undecylenic acid, tolic acid, isostearic acid, linoleic acid, linolenic acid, ethanol Examples include icosapentaenoic acid (EPA) and docosahexaenoic acid (DHA).

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

  Synthetic ester oils include, for example, isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, Myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearylate, ethylene glycol di-2-ethylhexylate, dipentaerythritol fatty acid ester, N-alkylglycol monoisostearate, neopentyl glycol dicaprate, Diisostearyl malate, glycerin di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexylate, Trimethylolpropane isostearate, pentane erythritol tetra-2-ethylhexylate, glycerol tri-2-ethylhexylate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, tris -2-Heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, oleic oil, cetostearyl alcohol, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester , Di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, palmitic acid 2 Hexyl decyl, 2-hexyldecyl adipate, sebacic acid diisopropyl, 2-ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate, and triethyl citrate.

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

  Vitamins include vitamin A, vitamin A such as retinol and retinol acetate, vitamin B2 such as riboflavin, riboflavin butyrate and flavin adenine nucleotides, vitamin B6 such as pyridoxine hydrochloride and pyridoxine dioctanoate, and L-ascorbine Vitamins such as acid, L-ascorbic acid dipalmitate, L-ascorbic acid-2-sodium sulfate, L-ascorbic acid phosphate, DL-α-tocopherol-L-ascorbic acid diester dipotassium, pantothene Acids, pantothenic acids such as D-pantothenyl alcohol, pantothenyl ethyl ether, acetyl pantothenyl ethyl ether, vitamin Ds such as ergocalciferol, cholecalciferol, nicotinic acid, nicotinic acid And nicotinic acids such as benzyl nicotinate, vitamin E such as α-tocopherol, tocopherol acetate, DL-α-tocopherol nicotinate, DL-α-tocopherol succinate, vitamin P, biotin and the like.

  As the ultraviolet absorber, paraaminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester, N, N-dimethyl PABA ethyl ester, N, Benzoic acid UV absorbers such as N-dimethyl PABA butyl ester, anthranilic acid UV absorbers such as homomenthyl-N-acetylanthranylate, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate , Salicylic acid ultraviolet absorbers such as p-isopropanolphenyl 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-diparamethoxycinnamate, 3-methyl-4- [methylbis (trimethylsiloxy) silyl] butyl 3,4,5-trimethoxycinnamate, etc. Cinnamic acid UV absorber 2,2-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 ultraviolet absorbers such as benzophenone-2-carboxylate, hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone, 3- (4′-methylbenzylidene) -d, l-camphor, 3 -Benzylidene-d, -Camphor, urocanic acid, urocanic acid ethyl ester, 2-phenyl-5-methylbenzoxazole, 2,2'-hydroxy-5-methylphenylbenzotriazole, 2- (2'-hydroxy-5'-t-octyl) Phenyl) 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.

  Examples of humectants 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. Examples include stearate, sodium lactate, bile salt, dl-pyrrolidone carboxylate, short-chain soluble collagen, diglycerin (EO) PO adduct, Izayoi rose extract, yarrow extract, and melloreto extract.

  In addition, plant extracts, drugs, stabilizers, polymer compounds and the like can be mentioned.

  The following examples further illustrate the present invention. In addition, a compounding quantity is the mass%. Prior to the examples, the production method of the cationic thickener used in this example will be described.

"Production method of cationic thickener"
In a three-necked flask equipped with a thermometer, a reflux tube and a nitrogen inlet tube, 50 g of N, N-dimethylaminoethyl methacrylate, 47.5 g of N-vinylpyrrolidone, 2.5 g of stearyl acrylate and tripropylene glycol diacrylate as monomers 1.9 g and a mixed solvent of ethanol (23.1 g) and cyclohexane (554.3 g) (mixing ratio (mass ratio) 4:96) were added, and the mixture was stirred for 2 hours in a nitrogen stream while refluxing at 80 ° C. And deaerated.

  Next, 0.42 g of 2,2′-azobisisobutyronitrile was added to the three-necked flask, and polymerization was started at 80 ° C. After 45 minutes from the start of polymerization, 1.9 g of tripropylene glycol diacrylate was added, and after further 45 minutes, 1.9 g of tripropylene glycol diacrylate was added. After carrying out the polymerization reaction for about 10 hours with 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 dried polymer was pulverized with a pulverizer to obtain a white powdery cationic thickener.

"Manufacture of perfume composition"
According to the prescription described in Table 1, fragrance compositions (test products 1 to 10) were produced. The production was performed by adding other components to ion-exchanged water and ethanol, stirring and dissolving. In addition, the formulation of the citrus fragrance | flavor and the fruity fragrance | flavor mix | blended with the fragrance | flavor composition is shown to Table 2, 3, respectively.

  The viscosity is measured with a bismetholone viscometer at 30 ° C. Specifically, using a digital bismetholone viscometer VDA2 (manufactured by Shibaura System Co., Ltd.), after immersing a test sample in a measurement container in a constant temperature water bath at 30 ° C. for 1 hour, rotor No. 2. It is a value measured under the condition of 12 rpm.

"Sensory evaluation of alcohol odor"
As a result of applying the test products 1 to 10 to the skin and performing sensory evaluation on the alcohol odor immediately after the application, the test products 4 to 9 had a reduced alcohol odor and were able to obtain good results.

  Moreover, since the test products 4-8 had moderate viscosity, they did not sag when applied to the skin, and were excellent in usability when applied. Moreover, the test products 4-8 were reliably applyable to a favorite site | part, without using a spatula (FIG. 7), without soiling a hand.

  In Test 10, since the blending amount of ethanol was small, the fragrance component was not solubilized and a uniform fragrance composition could not be obtained.

"Test of reducing alcohol odor by panelists"
A panel test for confirming the effect of reducing the alcohol odor of the fragrance composition of the present invention was conducted.

<Test conditions>
For test products 5 and 6 (Examples 2 and 3) which are the products of the present invention and test products 1 and 2 (Comparative Examples 1 and 2) which are comparative products, each panel of 8 females in their 10s and 30s A test product was applied to the left and right wrists, and a questionnaire survey was conducted (test products 5 and 6, test products 1 and 2 differ in flavoring by the fragrance). On the first test day, the test product 5 and the test product 1 were applied to the left and right wrists for investigation, and on the second test day, the test product 6 and the test product 2 were investigated.

  Questionnaire survey: 2 points for "I feel very", 1 point for "Somewhat feel", 0 for "None", -1 for "I don't feel much", -2 for "I don't feel at all" The total score by 8 panelists was used as the standard for evaluation of each fragrance.

  The results of evaluating the alcohol odor immediately after application for each test product are shown in FIG. 1 and FIG. FIG. 1 shows the results of test product 5 (Example 2) and test product 1 (Comparative Example 1) that are scented with citrus fragrance, and FIG. 2 is scented with fruity fragrance. The results of the test product 6 (Example 3) and the test product 2 (Comparative Example 2) are shown. The test products 5 and 6 which are the products of the present invention are shown in FIG. It was confirmed that the alcohol odor decreased with respect to 2.

"Panel fragrance sustainability test"
As a test on the persistence of the scent, changes in scent strength and freshness over time were evaluated. The intensity of the scent means the quantitative sensation that the human feels about the scent, and the fresh scent of the scent means that the qualitative sensation (image) that the human feels for the scent immediately after application does not change. To do. In the paneler test, a questionnaire survey was conducted on eight women in the same manner as described above.

  The results of evaluating the strength of the scent for each test product are shown in FIG. 3 and FIG. FIG. 3 shows the results of test product 5 (Example 2) and test product 1 (Comparative Example 1), which are scented with citrus fragrance, and FIG. 4 is scented with fruity fragrance. The results of the test product 6 (Example 3) and the test product 2 (Comparative Example 2) are shown. The test products 5 and 6 which are the products of the present invention are shown in FIG. It was confirmed that a decrease in the strength of the scent over time was suppressed with respect to 2.

  The results of evaluating the fresh scent of each test product are shown in FIG. 5 and FIG. FIG. 5 shows the results of test product 5 (Example 2) and test product 1 (Comparative Example 1), which are scented with citrus fragrance, and FIG. 6 is scented with fruity fragrance. The results of the test product 6 (Example 3) and the test product 2 (Comparative Example 2) are shown. The test products 5 and 6 which are the products of the present invention are shown in FIG. It was confirmed that the decrease in the fragrance freshness over time was suppressed with respect to 2.

"Spatula material selection test"
In the container shown in FIG. 7, since the tip of the spatula is brought close to the bottom of the container, the spatula material is less swelled by the fragrance composition, and the spatula is integrally molded with the inner cap. Therefore, it is necessary to use a relatively soft material that can be deformed to some extent so as to function as an inner cap that maintains airtightness. Therefore, an immersion test was performed on linear low density polyethylene (LLDPE), low density polyethylene (LDPE), and polypropylene (PP).

  In the test, sections of various plastics (length 2 cm × width 2 cm, thickness 2 mm) were immersed in the fragrance composition, and the mass change of the sections under each temperature condition (room temperature, 37 ° C., 50 ° C.) was measured.

  As shown in Table 4, in the mass change of various plastic sections, the estimated increase rate after 3 years at room temperature is 67.49% for linear low density polyethylene (LLDPE) and 52.51 for low density polyethylene (LDPE). %, While polypropylene (PP) was very small at 5.71% and showed good results. From this result, the material of the spatula to which the fragrance composition of the present invention is applied is preferably polypropylene.

1 Spatula 2 Container 3 Inner cap 4 Outer cap

Claims (3)

(A) Citrus flavor or fruity flavor, (B) 60-80% by mass of one or more lower alcohols selected from ethanol, methanol, ethylene glycol, and isopropyl alcohol , (C) water, D) 0.05 to 0.2% by mass of a cationic thickener obtained by polymerizing a monomer mixture for a thickener containing the following components (a) to (d); A fragrance composition containing a thickener 0.2 to 1.0 mass% and having a viscosity at 30 ° C. of 200 to 1000 mPa · s is applied using a spatula whose material is polypropylene. Fragrance product .
(a) General formula (I):

(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, an ethyl group or a t-butyl group, A is an oxygen atom or an —NH— group, and B is a direct atom An amine-containing (meth) acrylic monomer represented by 15.0 to 85.0% by mass, represented by a chain or side chain C1-C4 alkylene group.
(b) General 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 formula:

The group represented by these is shown. 0-80.0% by mass of vinyl monomer represented by
(c) General formula (III):

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

(Wherein 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 represented by 1.0-60.0% by mass,
(d) Crosslinkable vinyl monomer 0.1 to 20.0% by mass The fragrance product according to claim 1, wherein (E) the cellulose-based thickener is one or more selected from hydroxypropylcellulose, hydroxyethylcellulose, and methylcellulose. (B) The fragrance product according to claim 1 or 2, wherein the lower alcohol is ethanol.

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