JP7301707B2 - Cosmetics for wiping - Google Patents

Description

The present invention relates to a cosmetic composition for wiping. More specifically, it relates to a cosmetic intended to remove keratin without imposing a burden on the skin when wiping off.

In the aging of the skin, a phenomenon is frequently observed in which the stratum corneum (hereinafter referred to as aged keratin), which should be desquamated as dirt in normal metabolism, remains without being desquamated. This aged keratin is in a hard and dry state, and its moisturizing ability is remarkably lowered. In addition, the aged keratin contains melanin pigment to be excreted. Therefore, if the aged keratin remains without desquamation, the stratum corneum as a whole becomes hard and thickened, the skin loses moisture and smoothness, and furthermore, the appearance changes to dullness with decreased transparency.

From the above situation, it is conceivable that the removal of aged keratin can restore the original moisture and smoothness of the skin and improve the dullness. Cosmetics intended for this effect are wiping cosmetics. The method of using the wiping cosmetic is not limited, but in general, it is often used by soaking it in a cosmetic tool such as cotton and wiping off the skin.

The purpose of facial cleansing with general facial cleansers is to remove various stains, mainly oil-soluble stains such as sebum and makeup that have accumulated on the skin, through the action of cleansing ingredients. It is known that various skin components such as cholesterol and sebum are removed when the face is washed with this cleansing component (Non-Patent Document 1). In addition, it is known that cosmetics generally called cleansers and makeup removers are made for the purpose of removing makeup cosmetics, which are oily ingredients, from the skin. On the other hand, unlike general cleansers and cleansers, wiping cosmetics do not have the purpose of removing oily stains such as cholesterol and sebum, but have the effect of removing water-soluble stains, especially aged keratin (non Patent document 2).

Conventionally, alkaline cosmetics (Patent Document 1) are known as cosmetics having a keratin-exfoliating effect. Alkaline cosmetics have the effect of increasing the permeability of water and water-soluble ingredients to aged keratin by blending basic substances such as potassium hydroxide and potassium carbonate, and making the aged keratin easy to remove. However, alkaline cosmetics may cause skin irritation, and there are concerns about safety.

Also, a method of blending a keratin softening component such as α-hydroxy acid used in chemical peeling (Patent Document 2) has been used. However, exfoliation by chemical dissolution has the problem of causing strong skin irritation, itching and redness.

As another method, formulation of a plant extract having a keratin-exfoliating effect (Patent Document 3) and formulation of isodecyl pivalate, an oil agent, have been attempted (Patent Document 4). Although exfoliating with these plant extracts and oils having an exfoliating effect is less irritating to the skin, sufficient exfoliating effect has not yet been obtained.

A water-soluble cellulose derivative is a kind of polymer component. In addition to water-soluble cellulose derivatives, macromolecular components generally used in cosmetics include natural polysaccharides such as xanthan gum, and synthetic anionic compounds such as acrylates/alkyl acrylate (C10-30) crosspolymers. and hydrophobized cellulose derivatives such as hydrophobized hydroxypropylmethyl cellulose. These macromolecular components have been used for the purpose of reducing physical friction during wiping and preventing separation of oily components by imparting viscosity to formulations, but they act on aged keratin and remove aged keratin. No known easing effect.

On the other hand, polyethylene glycol has been used for the purpose of improving the moisturizing power of external preparations for skin (Patent Document 5), improving the foaming properties of cleansing compositions (Patent Document 6), and the like. In addition, mono-2-ethylhexyl glyceryl ether has been used for the purpose of antibacterial action (Patent Document 7) as a substitute for parabens. However, it has not been known or even suggested that these ingredients alone or in combination have the effect of facilitating the removal of aged keratin without imposing a burden on the skin upon wiping.

Fumiaki Hashimoto, Michiko Haruyama, Tokio Yamashita, Toshiaki Iso, Skin Adsorption of Surfactants and Selective Detergency by Face Wash, J. Soc. Cosmet. Chem. Japan. Vol. 23, No. 2 1989 Mai Horitsuji, Miho Morita, Akinori Inoue, Noritake Kitatani, Effectiveness evaluation of wiping care, J. Soc. Cosmet. Chem. Japan. Vol.53, No.3 2019

JP-A-11-322570 JP 2004-123662 A Japanese Patent Application Laid-Open No. 2008-174525 JP 2014-62062 A JP-A-8-20520 JP-A-9-13096 JP 2007-84464 A

An object of the present invention is to provide a wiping cosmetic that can remove aged keratin without imposing a burden on the skin during wiping.

As a result of intensive research on the subject, the present inventors have found that under alkaline conditions, a water-soluble cellulose derivative acts on aged keratin, making it easier to remove. Furthermore, when polyethylene glycol and mono-2-ethylhexyl glyceryl ether are combined, the inventors have found an effect of reducing friction during wiping action and preventing skin irritation, leading to the completion of the present invention.

That is, the present invention is as follows.
(1) As the first invention,
(A) water-soluble cellulose derivative (B) polyethylene glycol (C) basic substance (D) mono-2-ethylhexyl glyceryl ether
and a pH of 8.0 to 11.0.
(2) As the second invention,
The cosmetic composition for wiping according to the first invention, wherein the water-soluble cellulose derivative (A) is methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, or hydroxypropylmethylcellulose.
(3) As the third invention,
The cosmetic composition for wiping according to any one of the first and second inventions, wherein the water-soluble cellulose derivative (A) has a 2% aqueous solution viscosity of 4000 mPa·s or less at 20°C.
(4) As the fourth invention,
The cosmetic composition for wiping according to any one of the first to third inventions, wherein the polyethylene glycol (B) has a mass average molecular weight of 400 to 20,000.

According to the present invention, aged keratin can be removed without imposing a burden on the skin during wiping. This can be expected to restore the original moisture and smoothness of the skin, and improve dullness.

Schematic diagram of artificial skin

The component (A) water-soluble cellulose derivative used in the present invention is derivatized by substituting some of the hydroxyl groups in the cellulose molecule with other groups to make it water-soluble. It is obtained by making cellulose water-soluble by treating it with a derivatizing agent such as an etherification agent to convert it to a crystalline state. Specifically, C1-4 alkyl cellulose such as methyl cellulose and ethyl cellulose; hydroxy C2-4 alkyl cellulose such as hydroxyethyl cellulose and hydroxypropyl cellulose; hydroxy C2-4 alkyl cellulose such as hydroxyethyl methyl cellulose, hydroxyethyl ethyl cellulose and hydroxypropyl methyl cellulose. and C1-4 alkyl cellulose. Most preferred water-soluble cellulose derivatives are methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and hydroxypropylmethylcellulose. Although the viscosity of the water-soluble cellulose derivative is not particularly limited, it is preferably 4000 mPa·s or less for a 2% aqueous solution at 20°C. In the present invention, commercially available products are hydroxypropyl methylcellulose "trade name: METOLOSE 60SH-400 (manufactured by Shin-Etsu Chemical Co., Ltd.)" and methyl cellulose "trade name: METOLOSE SM-400 (manufactured by Shin-Etsu Chemical Co., Ltd.). )”, hydroxyethyl cellulose “trade name: HEC CF-G (manufactured by Sumitomo Seika Co., Ltd.)”, hydroxypropyl cellulose “trade name: NISSO HPC M (manufactured by Nippon Soda Co., Ltd.)”, etc. can be done.

The component (A) water-soluble cellulose derivative used in the present invention includes a hydrophobized cellulose derivative in which part of the hydroxyl group is substituted with a long-chain alkyl group, particularly a hydrophobic group having 12 to 26 carbon atoms, regardless of whether it is branched or not. do not have. When these are included, friction against the skin increases and skin irritation is induced, which is not preferable. Such a component can be produced by the method described in JP-A-3-12401, wherein a water-soluble cellulose derivative is reacted with a glycidyl ether having an alkyl group of 12 to 26 carbon atoms to obtain the water-soluble cellulose derivative. Examples include those that can be prepared by substituting the hydroxyl group within with a hydrophobic group having 12 to 26 carbon atoms. Specific examples thereof include stearoxyhydroxypropyl methylcellulose “trade name: Sangelose 60L (manufactured by Daido Kasei Kogyo Co., Ltd.)”.

Component (B) polyethylene glycol used in the present invention is a polyether obtained by polymerizing ethylene glycol. The average molecular weight of polyethylene glycol is not particularly limited, but a weight average molecular weight of 400 to 20,000 is preferred. In the present invention, two or more kinds having different average molecular weights can be used in combination. The average molecular weight of polyethylene glycol is the mass average molecular weight in terms of polyethylene glycol obtained from a calibration curve prepared using standard polyethylene glycol by gel permeation chromatography (GPC). In the present invention, a polyethylene glycol having a desired average molecular weight may be synthesized and used by a method known per se. (manufactured by NOF Corporation) (mass average molecular weight: 20000).

The basic substance of component (C) used in the present invention is a substance exhibiting weak basicity or strong basicity when dissolved in water. Examples include sodium hydroxide, potassium hydroxide, potassium carbonate, potassium hydrogen carbonate, Examples include sodium carbonate, sodium hydrogencarbonate, guanidine carbonate, arginine, and the like, and one or more of these can be appropriately selected and used. Among these, sodium carbonate is particularly preferred.

In the cosmetic composition for wiping of the present invention, it is more preferable to adjust the pH to 8.0 to 11.0 by blending these basic substances, because the keratin removal effect is good and excessive skin irritation does not occur. become a thing.

Component (D) mono-2-ethylhexyl glyceryl ether used in the present invention is a compound represented by the following structural formula (1).

As a method for producing the compound represented by the general formula (1), any known method may be used. For example, after reacting 2-ethylhexanol with epichlorohydrin, the obtained 2-ethylhexyl glycidyl ether is A method of hydrolysis and the like can be mentioned. Although the amount of 2-ethylhexyl glyceryl ether that can be used in the present invention is not particularly limited, it is preferably 0.01 to 1% by mass. For example, a commercially available product such as "SENSIVA SC-50" (Schalke & Meyer KK) can be used.

In addition to the above-described essential ingredients, the cosmetic composition for wiping of the present invention may optionally contain water, a surfactant, a polyhydric alcohol other than component B, within a qualitative and quantitative range that does not inhibit the effects of the present invention, Lower alcohols, thickeners, water-soluble polymers other than component A, preservatives other than component D, chelating agents, medicinal ingredients, oils, silicones, antioxidants, UV absorbers, fragrances, pigments, etc., which are usually used in cosmetics Ingredients that are described can also be blended.

The method of using the wiping cosmetic composition of the present invention is not particularly limited, but includes, for example, a method of using it in a cosmetic tool such as cosmetic cotton and wiping off the skin. Therefore, the wiping cosmetic composition of the present invention is preferably in a liquid form that can be contained in cosmetic tools.

In the present invention, the viscosity was measured using a Brookfield viscometer: VISCOMETER TVB-10M (manufactured by Tokyo Keiki Co., Ltd., measurement conditions: changing the rotor, number of revolutions, and measurement time according to the viscosity). The measurement was carried out at 20° C., and M1-M4 rotors were used according to the viscosity range of the sample, and the values were measured at a rotation speed of 6-60 rpm for a measurement time of 60 seconds.

The present invention will be further described with reference to the following examples. In addition, these do not limit this invention at all. The blending amount is % by mass with respect to the total amount of the composition.

For Examples and Comparative Examples, effect tests were conducted using cosmetic wipes having formulations shown in Tables 1 to 6 below.
[Manufacturing method of cosmetics for wiping]
After dispersing component A in the table in the purified water of E heated to 80° C. or higher, the mixture was cooled to room temperature. Next, component B, component C, component D, and component E were added in order and dissolved to obtain a wiping cosmetic composition. In addition, component A', component B', component C', and component D' in the table were added according to component A, component B, component C, and component D, respectively. When component A' was difficult to disperse, 1,3-BG and a surfactant were blended as needed.

(frictional force)
[Evaluation method]
Using the cosmetics prepared in Examples and Comparative Examples, static friction coefficients (μS) were measured using a surface property measuring instrument (manufactured by Shinto Kagaku Co., Ltd.: TYPE-14). A cotton pad for wiping (Pure Touch Cotton: manufactured by Naris Cosmetics Co., Ltd.: 310 g/m ² ) cut into a circle with a diameter of 30 mm was sandwiched between an artificial skin holder with an R of 50 mm imitating the curvature of a finger, and 1. 5 ml was added dropwise. This holder was set on the arm of the measuring instrument, and a weight of 50 g weight was placed as a horizontal load. The artificial skin described below was set on the moving table of the measurement device. The static friction coefficient was measured at a moving speed of 3,000 mm/min.
[Evaluation criteria]
The coefficient of static friction was divided into 4 levels and evaluated as an evaluation value. These four grades are evaluation ranges in which a difference can be clearly recognized in a sensory evaluation by an expert panelist.
◎: less than 1.3 (friction on the skin is particularly low, very excellent)
○: 1.3 or more to less than 1.4 (low friction on the skin, excellent)
△: 1.4 or more to less than 1.5 (friction against the skin can be felt)
×: 1.5 or more (high friction against skin)

FIG. 1 is a schematic diagram of the artificial skin used for measurement. An artificial skin having a sulcus cutis pattern was modeled on a flat plate of 50 mm×90 mm×10 mm using a 3D printer. The artificial skin had a pattern as shown in FIG. shape.) and a sulcus depth of 0.025 mm.

(removal of aging keratin)
[Evaluation method]
Using the cosmetics prepared in Examples and Comparative Examples, the amount of aged keratin removed when wiped off was confirmed by protein quantification. A cotton pad was soaked with 1 mL of lotion, and an area of 5 cm x 14 cm was wiped 20 times in one direction on the back washed with warm water. At this time, the film was wiped off with a constant force. The wiped cotton was placed in a tube, 1.5 mL of 8 M urea was added thereto, and the tube was incubated overnight at 37° C. to extract protein. The extract was squeezed out with a syringe, the sample liquid was recovered, protein was quantified by the BCA method, and the wiped protein amount was measured. 40 μL of the collected sample solution was added to the 96 Cell Culture Cluster, and reagent A (1% bicinchoninic acid, 2% Na ₂ CO ₃ , 0.16% tartaric acid, 0.4% NaOH, 0.95% NaHCO ₃ aqueous solution) and reagent B (4% CuSO ₄ .5H ₂ O aqueous solution) were mixed at a ratio of 50:1 and added in 200 μL portions. After 30 minutes incubation at 37° C., absorbance at 540 nm was measured. At the same time, a standard curve was prepared by diluting bovine blood albumin (BSA) from a concentration of 0.4 mg/mL in 3 steps of 2-fold dilutions. The protein dissolution amount was calculated from this calibration curve. Using this method, it can be judged that the higher the numerical value, the greater the amount of protein wiped off, and the higher the effect of removing aged keratin.
[Evaluation criteria]
The results of protein quantification were divided into four grades and used as evaluation values.
◎: 0.28 mg or more (extremely excellent effect of removing aged keratin)
○: 0.24 mg or more to less than 0.28 mg (highly effective in removing aged keratin)
△: 0.20 mg or more to less than 0.24 mg (almost no aging exfoliating effect)
×: less than 0.20 mg (no aging keratin removal effect)

(skin irritation)
[Evaluation method]
Using the lotions prepared with the formulations of Examples and Comparative Examples, 10 monitors who had experienced skin troubles with wiping cosmetics in the past were asked to use them for one week, and whether or not they experienced skin troubles such as itching and redness. We conducted a questionnaire about this and evaluated its safety.
[Safety evaluation criteria]
Good: 0 out of 10 monitors answered that they had skin troubles.
Δ: 1 to 2 out of 10 monitors answered that they had skin troubles.
x: 3 or more out of 10 monitors answered that they had skin troubles.

According to Table 1, in Examples 1-1 to 1-8, by using a water-soluble cellulose derivative, it is possible to obtain a wiping cosmetic that is highly effective in removing aged keratin without causing excessive friction on the skin. was made. On the other hand, in Comparative Examples 1-1 to 1-5, polymer components other than the water-soluble cellulose derivative were used, and although the friction was reduced, the effect of removing aged keratin was not obtained. In Comparative Example 1-6, when hydrophobized hydroxypropylmethylcellulose obtained by introducing a long-chain alkyl group as a hydrophobic group into hydroxypropylmethylcellulose was used, the effect of removing aged keratin was obtained, but the friction on the skin was large, and caused skin irritation. In the case of hydrophobized cellulose derivatives, it was thought that the presence of hydrophobic groups increases affinity with the skin and promotes friction between cotton soaked with cosmetics and the skin.

According to Table 2, in Examples 2-1 to 2-5, by using polyethylene glycol, it was possible to obtain a wiping cosmetic composition highly effective in removing aged keratin without causing excessive friction on the skin. rice field. On the other hand, in Comparative Examples 2-1 to 2-3, a polyalkylene glycol other than polyethylene glycol or a polyalkylene glycol derivative was used, and although the effect of removing aged keratin was exhibited, the friction to the skin was large and the skin was irritated. caused

Table 3 confirms the effect of adjusting the pH using a basic substance. Examples 3-1 and 3-2 showed that it was possible to obtain a wiping cosmetic composition that is highly effective in removing aged keratin without causing skin irritation. On the other hand, in Comparative Example 3-1, when the pH was lower than 8.0, a sufficient effect of removing aged keratin was not obtained, and in Comparative Example 3-2, when the pH was higher than 11.0, skin irritation occurred.

According to Table 4, in Comparative Example 4-1, instead of mono-2-ethylhexyl glyceryl ether, glyceryl caprylate, which is a monoester of straight-chain caprylic acid and glycerin with the same number of carbon atoms as 2-ethylhexyl alcohol, was used in Comparative Example 4-1. In 4-2, isostearylglyceryl, which is a monoether of isostearyl alcohol and glycerin, was used. As a result, although the effect of removing aged keratin was exhibited, the friction against the skin was large and skin irritation occurred.

According to Table 5, in Examples 5-1 to 5-3, wiping cosmetics were prepared by varying the blending amounts of components A, B, and D. A good composition was obtained in each variation range.

According to Table 6, in Comparative Examples 6-1 and 6-3, when a water-soluble cellulose derivative is not used or a basic substance is not used and the pH is 8.0 or less, excessive friction does not occur on the skin. However, sufficient aging exfoliation effect cannot be obtained. On the other hand, in Comparative Examples 6-2 and 6-4, when polyethylene glycol was not used or mono-2-ethylhexyl glyceryl ether was not used, the effect of removing aged keratin was exhibited, but the friction to the skin was large and the skin was irritated. caused

From the results shown in Tables 1 to 6, the wiping cosmetics of Examples were compositions that achieved both reduction of skin friction and effect of removing aged keratin without causing skin irritation. By using the present invention, it is possible to provide a wiping cosmetic that removes aged keratin without imposing a burden on the skin during wiping.

A composition of each formulation was prepared by a conventional method. It was confirmed that the effects of the present invention can be obtained in any formulation.

(1) Wiping cosmetics: Formulation example 1
Ingredient name Amount Hydroxypropyl methylcellulose (viscosity 400 mPa s) 0.05
Methyl cellulose (viscosity 400 mPa s) 0.05
Polyethylene glycol (average molecular weight: 1540) 1
Na bicarbonate 0.05
Na carbonate 0.025
Mono 2-ethylhexyl glyceryl ether 0.2
1,3-BG 2
PPG-6 decyltetradeceth-30 0.1
Preservative Appropriate amount Purified water Total residue 100

(2) Wiping cosmetics: Formulation example 2
Ingredient name Amount Hydroxyethyl cellulose (viscosity 450 mPa s) 0.2
Polyethylene glycol (average molecular weight: 4000) 3
Arginine 0.05
Mono 2-ethylhexyl glyceryl ether 0.4
1,3-BG 8
Glycerin 4
Diphenylsiloxyphenyl trimethicone 0.2
PEG-50 hydrogenated castor oil 0.5
PPG-6 decyltetradeceth-30 0.5
Preservative Appropriate amount Purified water Total residue 100

(3) Wiping cosmetics: Formulation example 3
Ingredient name Amount Hydroxypropyl methylcellulose (viscosity 10000 mPa s) 0.1
Polyethylene glycol (average molecular weight: 20000) 2
K hydroxide 0.05
Mono 2-ethylhexyl glyceryl ether 0.3
1,3-BG 5
Polysorbate 20 1
Hyaluronic acid Na 0.05
Na polyacrylate 0.05
Ethanol 5
EDTA-2Na Appropriate amount of preservative Appropriate amount of purified water Total residue 100

By using the present invention, it is possible to provide a wiping cosmetic that removes aged keratin without imposing a burden on the skin during wiping.

Claims (4)

A cosmetic wipe containing the following components (A) a water-soluble cellulose derivative (B) polyethylene glycol (C) a basic substance (D) mono-2-ethylhexylglyceryl ether and having a pH of 8.0 to 11.0. 2. The wiping cosmetic composition according to claim 1, wherein the water-soluble cellulose derivative (A) is one or more selected from methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose. The cosmetic composition for wiping according to any one of claims 1 and 2, wherein (A) the water-soluble cellulose derivative has a 2% aqueous solution viscosity of 4000 mPa·s or less at 20°C. The cosmetic composition for wiping according to any one of claims 1 to 3, wherein (B) polyethylene glycol has a mass average molecular weight of 400 to 20,000.

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