JP7691175B2 - Clear mascara that prevents curl and sagging - Google Patents

Description

The present invention relates to a transparent cosmetic composition that reduces eyelash drooping.

This application claims priority to Korean Patent Application No. 10-2019-0168740, filed on December 17, 2019, the entire contents of which are incorporated herein by reference in their entirety in the specification and drawings.

Mascara is applied to eyelashes to accentuate the eyeliner and give the eyes a beautiful look. It is important that the cosmetic effects of mascara applied to eyelashes last for a long time. Specific characteristics required for mascara to last include no bleeding or powdering, and no curling or dripping. A typical mascara formulation designed to give such characteristics is a transparent top coat. Top coats are applied over eyelashes already coated with mascara to further improve the durability, or applied over bare eyelashes to achieve a curling effect.

Such transparent topcoats are mainly water-dispersed products that use a water-phase film former. These water-dispersed topcoats form a transparent film after drying, and visually last a long time, but they have the disadvantages of being prone to curling and sagging after application to eyelashes, as well as being easily washed away by tears or sweat.

Another method for improving the durability of eyelash makeup is to use anhydrous or water-in-oil (W/O) mascara. Mascara in this formulation is available as a waterproof mascara, fixer, or top coat. When anhydrous or W/O mascara is applied to eyelashes, moisture does not come into direct contact with the eyelashes, preventing drooping of the curl. However, when the wax and film-forming agent used in the formulation dry, the uneven surface causes diffuse reflection of light, or a solid phase remains, causing a white cast, making it difficult to achieve the desired effect without pigments. To prevent this, pigments must be added to anhydrous or W/O mascara, but this has the disadvantage that the pigments may bleed, making it difficult to achieve a natural makeup effect like that of a bare face, known as ``no-makeup makeup.''

Therefore, there is a need to develop a mascara formulation that overcomes the above shortcomings, maintains transparency even after being applied to the eyelashes and dries, and does not cause the curl to sag.

The problem that the present invention aims to solve is to provide a cosmetic composition that maintains transparency even after being applied to eyelashes and drying, and that reduces drooping of curled eyelashes.

As a result of intensive research and efforts to solve the above-mentioned problems of the prior art, the inventors have discovered the surprising fact that when a styrene-based hydrocarbon main chain polymer thickener, a film-forming agent, and a volatile oil are combined, a cosmetic composition, preferably a mascara composition, is transparent even after drying, and is excellent in preventing eyelash curl and drooping, and in providing a natural cosmetic effect, which has led to the completion of the present invention.

In the present invention, "curl droop" means that after the cosmetic composition of the present invention, preferably the mascara composition, is applied to the eyelashes, the fixed eyelashes gradually droop over time, and the angle of the eyelashes decreases compared to immediately after application of the composition.

The present invention provides a cosmetic composition comprising a styrene-based hydrocarbon main chain polymer thickener, a film-forming agent, and a volatile oil. The film-forming agent forms a film on the eyelashes or skin, and the styrene-based hydrocarbon main chain polymer thickener can prevent the film from being irreversibly formed. In the cosmetic composition of the present invention, the combination of the film-forming agent and the styrene-based hydrocarbon main chain polymer thickener allows for the effective formation of a transparent and uniform cosmetic film.

In one embodiment, the cosmetic composition may be in an oil-dispersed (or anhydrous) formulation based on a volatile oil. The cosmetic composition of the present invention contains a volatile oil, preferably a volatile hydrocarbon oil, so that the styrene-based hydrocarbon main chain polymer thickener and the film-forming agent can be effectively oil-dispersed, and the volatile oil dries quickly during use, so that the cosmetic composition can be effectively used in formulations such as mascara, lip gloss, makeup fixer, or top coat.

In one embodiment, the styrene-based hydrocarbon main chain polymer thickener may be any one or more selected from the group consisting of styrene/isoprene copolymer, styrene/isoprene/styrene copolymer, styrene/butadiene copolymer, styrene/butadiene/styrene copolymer, styrene/ethylene/butylene/styrene copolymer, styrene/ethylene/butylene copolymer, styrene/ethylene/propylene/styrene copolymer, styrene/ethylene/propylene copolymer, styrene/butadiene/butylene/styrene copolymer, and styrene/butadiene/butylene copolymer. Preferably, the styrene-based hydrocarbon main chain polymer thickener may be a hydrogenated styrene/isoprene copolymer.

A thickener has a specific yield value when dissolved or dispersed in a solvent. A thickener with a high yield value makes it difficult to remove fine bubbles that are generated after the dosage form is manufactured. If fine bubbles are present in the dosage form, the surface of the coating formed on the eyelashes is not uniform and does not dry smoothly, which induces diffuse reflection of light and affects the transparency of the dosage form. The styrene-based hydrocarbon main chain polymer thickener has a low yield value, making it easy to remove bubbles and effectively improving the transparency of the dosage form.

前記Ｒは、イソプレンの添加重合で生成され得るすべての構造を含み、望ましくは

であり得る。また、前記水素化スチレン／イソプレン共重合体のうちスチレンブロックの質量比率は０．１～５、望ましくは０．２～４、より望ましくは０．３～４、最も望ましくは０．３５であり得、このような場合、形成された被膜の透明度及び均一性に優れる。例えば、前記水素化スチレン／イソプレン共重合体は、市販中のＫｒａｔｏｎ^ＴＭＧ１７０１ポリマー（製造社：Ｓｈｅｌｌ）を使用できる。 In one embodiment, the hydrogenated styrene/isoprene copolymer used as the styrene-based hydrocarbon main chain polymer thickener may have a chemical structure represented by the following Chemical Formula 1:

The R includes all structures that can be produced by the addition polymerization of isoprene, and preferably

In addition, the mass ratio of the styrene block in the hydrogenated styrene/isoprene copolymer may be 0.1 to 5, preferably 0.2 to 4, more preferably 0.3 to 4, and most preferably 0.35, and in this case, the formed coating has excellent transparency and uniformity. For example, the hydrogenated styrene/isoprene copolymer may be commercially available Kraton ^™ G1701 polymer (manufacturer: Shell).

In one embodiment, the styrene-based hydrocarbon main chain polymer thickener may be 1 to 20% by weight, preferably 3 to 17% by weight, and more preferably 5 to 15% by weight, based on the total weight of the composition. If the styrene-based hydrocarbon main chain polymer thickener is less than 1% by weight, the viscosity is too low and the composition runs off during use, making it unsuitable for use as eyelash makeup (mascara). Also, if the styrene-based hydrocarbon main chain polymer thickener is more than 20% by weight, the viscosity of the formulation may be too high, hindering the feel of use.

In one embodiment, the cosmetic composition may include an additional thickener in addition to the styrene-based hydrocarbon main chain polymer thickener in order to form a uniform cosmetic film and stabilize the phase without forming an irreversible film. When an additional thickener is included, the styrene-based hydrocarbon main chain polymer thickener having a low yield value may be included in an amount of 60% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more, and most preferably 90% by weight or more based on the total weight of the thickener in order to maintain the transparency of the formulation. The additional thickener may include one or more selected from the group consisting of gum arabic, xanthan gum, carrageenan, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose and cellulose derivatives, dextrin palmitate, dextrin palmitate/ethylhexanoate, etc.

In one embodiment, the film-forming agent may be one or more selected from the group consisting of trimethylsiloxysilylcarbamoyl pullulan, acrylate/dimethicone copolymer, polyvinyl alcohol, polyvinyl acetate, polyvinylpyrrolidone, ammonium acrylate copolymer, PVP/eicosine copolymer, acrylic/acrylate copolymer, acrylate copolymer, alkyl acrylate copolymer emulsion, and hydroxyethyl cellulose dimethyl diallyl ammonium chloride copolymer (polyquaternium-4). Preferably, the film-forming agent may be trimethylsiloxysilylcarbamoyl pullulan, acrylate/dimethicone copolymer, or a mixture thereof to form a transparent and uniform film. The film-forming agent may be included in an amount of 1 to 30% by weight, preferably 3 to 25% by weight, based on the total weight of the composition. If the film-forming agent is less than 1% by weight, the film-forming ability of the composition may be insufficient, and if it exceeds 30% by weight, the transparency of the dosage form may be significantly reduced.

In one embodiment, the volatile oil may be any volatile oil used in the industry for the preparation of cosmetic compositions, without limitation, and any liquid, solid, or semi-solid oil, such as silicone oil, hydrocarbon oil, polar oil, or non-polar oil, may be used as the volatile oil of the present invention.

In one embodiment, the volatile oil may be a volatile hydrocarbon oil, which is an oil containing hydrogen and carbon atoms, and may be a volatile oil of a hydrocarbon series such as paraffin or isoparaffin. Specifically, the volatile hydrocarbon oil may be a branched alkane, ester, or a mixture thereof having 8 to 20 carbon atoms, and the alkane may be an isoalkane having 8 to 20 carbon atoms, which may include at least one selected from the group consisting of isodecane, isododecane, and isohexadecane. Preferably, isododecane may be used as the volatile hydrocarbon oil.

The volatile oil may be present in an amount of 50 to 95% by weight, preferably 60 to 90% by weight, based on the total weight of the composition. By including the volatile oil in the above amount, the cosmetic composition of the present invention can effectively disperse the thickener and film-forming agent ingredients in oil, and the volatile oil dries quickly during use, allowing it to be effectively used in the form of mascara, lip gloss, makeup fixer, top coat, etc.

In one embodiment, the cosmetic composition may contain the styrene-based hydrocarbon main chain polymer thickener and the film-forming agent in a weight ratio (styrene-based hydrocarbon main chain polymer thickener: film-forming agent) of 1:0.1-5, preferably 1:0.5-3, and more preferably 1:1-2.5. When the cosmetic composition of the present invention contains the two components in the above specific weight ratio, it is possible to significantly achieve the formation of a transparent and uniform film and the prevention of eyelash curl and drooping.

In one embodiment, the cosmetic composition may be substantially free of any one or more selected from the group consisting of wax, pigment, and mineral thickener, etc., which allows for excellent uniformity and transparency of the formulation and a natural cosmetic effect on the film formed on the eyelashes. The wax, pigment, and mineral thickener (e.g., bentonite) form an uneven surface after application of the composition due to the inherent properties of particles, which may cause a problem of reduced transparency due to diffuse reflection of light. Specifically, the cosmetic composition may contain any one or more selected from the group consisting of wax, pigment, and mineral thickener in an amount of 5% by weight or less, 4% by weight or less, preferably 3% by weight or less, 2% by weight or less, more preferably 1% by weight or less, based on the total weight of the composition, and most preferably may not contain any one or more.

The pigment that is substantially not contained in the cosmetic composition means a pigment-series pigment that induces unevenness in the surface of the film formed on the eyelashes. In the case of dye-based pigments, it is preferable that they are not substantially contained in order to provide a natural cosmetic effect, but they may be contained in an appropriate amount within an acceptable range as long as they do not cause unevenness in the surface of the film formed on the eyelashes. For example, the dye-based pigment is contained in an amount of 5 wt % or less, 4 wt % or less, preferably 3 wt % or less, 2 wt % or less, more preferably 1 wt % or less, based on the total weight of the composition, and most preferably, it may not be contained at all.

In one embodiment, the cosmetic composition can form a transparent film after being applied to eyelashes or skin and dried. In addition, the cosmetic composition is highly effective in preventing eyelash curl and drooping over time due to the formed film.

In one embodiment, after the cosmetic composition is applied and dried, the difference in L value (ΔL) of the formed film measured with a color difference meter may be 2.5 or less, preferably 0.1 to 2.5, and more preferably 0.1 to 2. The ΔL value is the sample measurement value (L) - the black paper measurement value (L0), and can be measured, for example, using a Konica Minolta color difference meter CR-300.

In one embodiment, the cosmetic composition can be used in any one of the forms selected from the group consisting of mascara, lip gloss, makeup fixer, and top coat. The cosmetic composition of the present invention forms a transparent and uniform film, providing excellent makeup fixing power and skin protection, and when used as a mascara or top coat, it is remarkably effective in preventing eyelash curl and drooping.

In one embodiment, the cosmetic composition may further include one or more ingredients selected from the group consisting of emulsifiers, moisturizers, preservatives, pH adjusters, penetration aids, stabilizers, surfactants, conditioning agents, skin softeners, appearance enhancers, fragrances, sequestering agents, etc., to contribute to the production of a cosmetic formulation, within the scope of not interfering with the objectives of the present invention.

The cosmetic composition of the present invention maintains transparency even after it is applied to eyelashes and dries, and is extremely effective in preventing eyelash curl and drooping.

In Experimental Example 1, a film drying experiment was carried out using the compositions of the Examples and Comparative Examples, and the transparency and uniformity of each were observed. In Experimental Example 2, a color difference meter measurement experiment was carried out using the compositions of the examples and comparative examples, and then ΔL was measured three times and the average value was calculated. 1 shows the initial relative angle reduction amounts of Example 1 and Comparative Example 11 measured through an in vitro curl sagging test of Experimental Example 3. 1 shows the angle of eyelashes measured in Example 1 and Comparative Example 11 through the in vivo curl sagging test in Experimental Example 4. 1 shows the amount of decrease in eyelash angle compared to the initial angle measured in Example 1 and Comparative Example 11 through the in vivo curl sagging test in Experimental Example 4.

The present invention will be described in detail below with reference to examples to aid in understanding the present invention. However, the examples according to the present invention can be modified into many other forms, and the scope of the present invention should not be construed as being limited to the following examples. The examples of the present invention are provided to more completely explain the present invention to those with average knowledge in the art.

クレイトン（Ｋｒａｔｏｎ）Ｇ１７０１：（製造社：Ｓｈｅｌｌ、米国）
ベントン（Ｂｅｎｔｏｎｅ）３８ＶＣＧ：ジステアルジモニウムヘクトライト（製造社：Ｅｌｅｍｅｎｔｉｓ Ｓｐｅｃｉａｌｔｉｅｓ、英国）
レオパール（Ｒｈｅｏｐｅａｒｌ）ＴＴ２：デキストリンパルミテート／エチルヘキサノエート（製造社：千葉製粉、日本）
レオパール（Ｒｈｅｏｐｅａｒｌ）ＫＬ２：デキストリンパルミテート（製造社：千葉製粉、日本）
オレオクラフト（Ｏｌｅｏｃｒａｆｔ）ＬＰ－１０：エチレンジアミン／ステアリルダイマージリノレートコポリマー（製造社：Ａｒｉｚｏｎａ Ｃｈｅｍｉｃａｌ、米国）
オレオクラフト（Ｏｌｅｏｃｒａｆｔ）ＬＰ－２０：ポリアミド－８（製造社：Ａｒｉｚｏｎａ Ｃｈｅｍｉｃａｌ、米国）
ＴＳＰＬ－３０－ＩＤ：トリメチルシロキシシリルカルバモイルプルラン（製造社：信越化学、日本）
ＫＰ－５５０：アクリレート／ジメチコンコポリマー（製造社：信越化学、日本）
Mascara compositions of Examples 1 and 2 and Comparative Examples 1 to 11 were prepared according to the compositions shown in Tables 1 and 2 below. Examples 1 and 2 were prepared using a styrene-based hydrocarbon main chain polymer thickener, and Comparative Examples 1 to 10 were prepared using a general thickener used in non-aqueous mascaras. Comparative Example 11 is a general water-dispersed transparent top coat formulation.

Kraton G1701: (Manufacturer: Shell, USA)
Bentone 38 VCG: Disteardimonium hectorite (manufacturer: Elements Specialties, UK)
Rheopearl TT2: Dextrin palmitate/ethylhexanoate (manufacturer: Chiba Flour Mills, Japan)
Rheopearl KL2: dextrin palmitate (manufacturer: Chiba Flour Mills, Japan)
Oleocraft LP-10: Ethylenediamine/Stearyl Dimer Dilinoleate Copolymer (Manufacturer: Arizona Chemical, USA)
Oleocraft LP-20: Polyamide-8 (Manufacturer: Arizona Chemical, USA)
TSPL-30-ID: Trimethylsiloxysilylcarbamoyl pullulan (manufacturer: Shin-Etsu Chemical, Japan)
KP-550: Acrylates/Dimethicone Copolymer (Manufacturer: Shin-Etsu Chemical, Japan)

1. Manufacturing method of Examples 1 and 2 and Comparative Examples 1 to 10 (1) Add a thickener and a film former to isododecane and heat to 80°C (2) When the thickener is completely melted, disperse for 10 minutes with a disper mixer (3) Cool to 28°C and degas 2. Manufacturing method of Comparative Example 11 (1) Add PVA to purified water and heat to 70°C (2) Disperse for 10 minutes with a disper mixer and cool to 50°C (3) Slowly add carbomer and disperse for 10 minutes, then add TEA, ethanol and VP/VA copolymer and disperse for 5 minutes (4) Cool to 28°C and degas

Experimental Example 1: Film Drying Experiment Film drying experiments were carried out using the compositions of the Examples and Comparative Examples according to the following experimental method.
(1) Examples 1 and 2 and Comparative Examples 1 to 10 were each applied to a glass plate in a thickness of 50 μm and dried for 2 hours. (2) Each glass plate was placed on black paper and photographed. (3) The transparency and uniformity of the resulting film was confirmed by visual inspection. The results of the film drying experiment are shown in Figure 1. It was confirmed that Examples 1 and 2 formed transparent and uniform films, whereas Comparative Examples 1 to 10 formed opaque or translucent or non-uniform films.

Experimental Example 2: Colorimeter Measurement Experiment A colorimeter measurement experiment was carried out using the compositions of the examples and comparative examples according to the following experimental method.
(1) Using a color difference meter (Konica Minolta CR-300 color difference meter), measure the L value of black paper as a control group (black paper: LENETA Form 2A opacity chart).
(2) Each of Examples 1 and 2 and Comparative Examples 1 to 10 was applied to a glass plate to a thickness of 50 μm, and the sample was dried for 2 hours. The sample was placed on black paper and the L value was measured with a color difference meter. (3) The L value of the sample was compared with the L value of the black paper (control group) to calculate ΔL. *ΔL=(L- _L0 ) (L=sample measurement value, _L0 =black paper measurement value)
It was confirmed that the smaller the ΔL value, the more transparent the film produced. After measuring ΔL three times using a color difference meter, the average value was calculated and shown in Table 3 and Figure 2 below. The _L0 of the LENETA Form 2A opacity chart used in the experiment was 44.06 (average after three measurements).

The ΔL of a transparent film is 0≦ΔL<2.5, and in the case of a film in this range, it can be judged to be transparent by visual observation. In addition, when 2.5≦ΔL<6.0, it can be judged to be translucent by visual observation. When 6≦ΔL, it can be judged to be opaque by visual observation. In the cases of Examples 1 and 2, it was judged to be transparent by visual observation, and ΔL was measured to be 2.5 or less.

Experimental Example 3: In vitro curl sagging experiment An in vitro curl sagging measurement experiment was carried out using the compositions of the examples and comparative examples according to the following experimental method.
(1) Example 1 and Comparative Example 11 were applied to fixed artificial eyelashes using a brush. (2) Photographs were taken immediately after application, 1 hour, and 4 hours later, and the angle from the root of the curl to the end of the eyelashes was measured and compared (temperature 24°C, humidity 60%).
The measurement angles measured in the experiment are shown in Table 4, and the reduction in the angle from the initial angle is shown in Table 5 and Figure 3. It was confirmed that curl sagging was improved when Example 1 was used compared to Comparative Example 11, which is a general transparent top coat formulation.

Experimental Example 4: In vivo curl drooping experiment (1) After curling the eyelashes of both subjects with a curler, a photograph was taken before application. (2) Example 1 was applied to one eyelash, and Comparative Example 11 was applied to the other eyelash. (3) Photographs were taken immediately after application, 10 minutes later, 1 hour later, and 4 hours later (experimental conditions: temperature 24°C, humidity 60%)
(4) Measure the curl-up angle* using the photograph (Reference: JI Na et al., British Journal of Dermatology, 2006, 155, pp1170-1176)
The measurement angles measured through the experiment are shown in Table 6 and Figure 4, and the reduction in the angle from the initial angle is shown in Table 7 and Figure 5. It was confirmed that curl sagging was improved when Example 1 was used compared to Comparative Example 11, which is a general transparent top coat formulation.

Claims (9)

A mascara cosmetic composition comprising a styrene-based hydrocarbon backbone polymer thickener, a film-forming agent, and a volatile oil ,
The styrene-based hydrocarbon main chain polymer thickener is a hydrogenated styrene/isoprene copolymer;
The cosmetic composition is substantially free of waxes, pigments, and mineral thickeners;
The cosmetic composition is in an oil dispersion form,
The composition forms a transparent film after application and drying.
Mascara cosmetic composition . The mascara cosmetic composition according to claim 1, wherein the styrene-based hydrocarbon main chain polymer thickener is a compound having a chemical structure represented by the following chemical formula 1:
The R is
It is. 2. The mascara cosmetic composition according to claim 1, wherein the mass ratio of the styrene block in the hydrogenated styrene/isoprene copolymer is 0.1 to 5. 2. The mascara cosmetic composition according to claim 1, wherein the styrene-based hydrocarbon main chain polymer thickener is present in an amount of 1 to 20% by weight based on the total weight of the composition. The mascara cosmetic composition according to claim 1 , wherein the styrene-based hydrocarbon main chain polymer thickener accounts for 60% by weight or more of the total weight of the thickener. 2. The mascara cosmetic composition according to claim 1, wherein the film-forming agent is present in an amount of 1 to 30% by weight based on the total weight of the composition. 2. The mascara cosmetic composition according to claim 1, wherein the volatile oil is present in an amount of 50 to 95% by weight based on the total weight of the composition. The mascara cosmetic composition according to claim 1 , wherein the volatile oil is a volatile hydrocarbon oil. 2. The mascara cosmetic composition according to claim 1, wherein after the cosmetic composition is applied and dried, the difference (ΔL) in L value of the formed film measured with a color difference meter is 2.5 or less.