Cleansing cosmetics

Abstract

The present invention aims to provide a wipe-off cosmetic that prevents the penetration of basic components into the skin, suppresses skin irritation, exhibits excellent exfoliating effects, and leaves a refreshing feeling with minimal oiliness after use. [Solution] (A) One or more selected from esters of phosphoric acid and aliphatic alcohols and salts thereof having the following characteristics (a-1) Aliphatic alcohols: Aliphatic alcohols obtained by addition polymerization of ethylene oxide (a-2) Esters: Diesters or triesters (B) One or more selected from basic amino acids and organic bases A wipe-off cosmetic composition characterized by containing (A) and having a degree of neutralization of (B) relative to the acid value of (A) of 1.0 or more and 20.0 or less. [Effects] According to the present invention, aging keratin can be removed without putting a burden on the skin. This is expected to restore the skin's natural smoothness and improve dullness.

Description

Technical Field

[0001] The present invention relates to a wiping cosmetic that prevents the infiltration of basic components into the skin, exhibits excellent horny layer removal effect while suppressing skin irritation, and provides a refreshing feeling with less oily feeling after use.

Background Art

[0002] In skin aging, the stratum corneum (hereinafter referred to as aged cutin), which should flake off as dirt in normal metabolism, often does not flake off and remains. This aged cutin is hard and dry, and its moisturizing ability is also significantly reduced. In addition, aged cutin contains melanin pigments that should be excreted. Therefore, when aged cutin does not flake off and remains, the entire stratum corneum also becomes hard and thickened, the skin loses its moisture and smoothness, and further changes to a dull appearance with reduced transparency.

[0003] From the above situation, it is considered that by removing aged cutin, the original moisture and smoothness of the skin can be restored, and dullness can be improved. Cosmetics aimed at this effect are wiping cosmetics. Although the usage method of wiping cosmetics is not limited, generally, it is often used by applying it to a cosmetic tool such as cotton and wiping the skin.

[0004] Washing the face with a general facial cleanser aims to remove various dirt, mainly oil-soluble dirt such as sebum and makeup accumulated on the skin, by the action of the cleaning component. It is known that various skin components such as cholesterol and sebum are removed during face washing with this cleaning component (Non-Patent Document 1). In addition, it is known that cosmetics generally called cleansing and makeup removers are made for the purpose of removing makeup cosmetics, which are oily components, from the skin. On the other hand, unlike general cleaning agents, cleansing, and makeup removers, wiping cosmetics do not aim to remove oily dirt such as cholesterol and sebum, but have the effect of removing water-soluble dirt, particularly aged cutin (Non-Patent Document 2).

[0005] Conventionally, alkaline cosmetics (Patent Document 1) have been known as cosmetics with exfoliating effects. Alkaline cosmetics contain basic substances such as potassium hydroxide and potassium carbonate, which enhance the penetration of water and water-soluble components into aging keratin, making it easier to remove aging keratin. However, alkaline cosmetics can cause skin irritation, raising safety concerns.

[0006] An invention has been reported (Patent Document 2) that prevents the penetration of basic components into the skin and suppresses skin irritation while exhibiting excellent exfoliation effects by forming a surfactant through a neutralization reaction with a basic substance within a specific range of neutralization degrees. However, Patent Document 2 requires the inclusion of a monohydric higher alcohol having a linear structure. Since monohydric higher alcohols having a linear structure are oily components and have high crystallinity, they are prone to quality problems such as separation and precipitation depending on the conditions of other components. Therefore, forming oil-in-water emulsion particles together with oily components such as hydrocarbon oils and ester oils is a suitable way to avoid this problem. However, in this case, there is a problem that the oily feeling remains after use, making it difficult to use for consumers with oily skin that naturally secretes a lot of sebum or combination skin with oily secretion in specific areas. In other words, there has been a need for a technology for wipe-off cosmetics that prevents the penetration of basic components into the skin, suppresses skin irritation while exhibiting excellent exfoliation effects, and provides a refreshing feeling with less oiliness after use. [Prior art documents] [Non-patent literature]

[0007] [Non-Patent Document 1] Fumio Hashimoto, Michiko Haruyama, Tokio Yamashita, Toshiaki Iso, Adsorption of surfactants to the skin and selective cleansing properties of facial cleansers, J.Soc.Cosmet.Chem.Japan.Vol.23,No.2 1989. [Non-Patent Document 2] Mai Horitsuji, Miho Morita, Akinori Inoue, Noritake Kitatani, Evaluation of the usefulness of wipe-off care, J.Soc.Cosmet.Chem.Japan.Vol.53, No.3 2019. [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 11-322570 [Patent Document 2] Japanese Patent Publication No. 2024-044253 [Disclosure of the Invention] [Problems that the invention aims to solve]

[0009] The present invention aims to provide a wipe-off cosmetic that prevents the penetration of basic components into the skin, suppresses skin irritation, exhibits excellent exfoliating effects, and leaves a refreshing feeling with minimal oiliness after use. [Means for solving the problem]

[0010] The inventors of this invention have diligently researched the problem, (A) One or more esters and salts of phosphoric acid and aliphatic alcohol having the following characteristics (a-1) Aliphatic alcohols: Aliphatic alcohols obtained by addition polymerization of ethylene oxide (a-2) Esters: Diesters or triesters (B) One or more selected from basic amino acids and organic bases By incorporating (A) and setting the degree of neutralization of (B) to the acid value of (A) to 1.0 or more and 20.0 or less, we have obtained a wipe-off cosmetic that exhibits excellent exfoliation effects without burdening the skin and provides a refreshing feeling. [Effects of the Invention]

[0011] According to the present invention, aging keratin can be removed without putting a burden on the skin. This is expected to restore the skin's natural smoothness and improve dullness. [Modes for carrying out the invention]

[0012] The present invention is based on the idea that by adopting the above configuration, basic components can be prevented from penetrating the skin, thereby suppressing skin irritation while exhibiting an excellent exfoliating effect. Although the specific mechanism is not clear, (A) esters of phosphoric acid and aliphatic alcohols and their salts contain components in which the phosphate group is in an unneutralized state chemically, and readily react with basic components such as (B) basic amino acids and organic bases to form neutralized products. In the present invention, since this neutralized product is incorporated into the formulation as a surfactant, it is presumed that, compared to the case where basic components are incorporated alone, it prevents penetration into the skin and suppresses skin irritation while exhibiting an excellent exfoliating effect. Furthermore, since the hydrophobic chain of the surfactant is a diester and / or triester, it is presumed that its high emulsifying power emulsifies sebum in the skin during wiping and incorporates it into the formulation. As a result, a less oily feeling after use and a refreshing feeling can be obtained.

[0013] (A) used in the present invention is one or more esters selected from esters of phosphoric acid and aliphatic alcohols and salts thereof having the following characteristics: (a-1) Aliphatic alcohols: Aliphatic alcohols obtained by addition polymerization of ethylene oxide (a-2) Esters: Diesters or triesters (A) is not limited as long as it is used in ordinary cosmetics. The aliphatic alcohol contained in (A) is not particularly limited as long as it is an aliphatic alcohol obtained by addition polymerization of ethylene oxide, but it is preferably an alkyl group having 12 to 18 carbon atoms. (A) may be a diester or a triester, or a mixture thereof. Alternatively, a salt that has been partially neutralized with a basic compound beforehand may be used. The average number of moles of ethylene oxide added to (A) is not particularly limited, but is preferably 2 moles or more, and more preferably 4 moles or more. The HLB of (A) is not particularly limited, but is preferably 6.5 to 17, and more preferably 9 to 15.

[0014] Specific examples of (A) include dipolyoxyethylene lauryl ether sodium phosphate (10 E.O.) (NIKKOL® DLP-10, HLB 17.0, manufactured by Nikko Chemicals Co., Ltd.), dipolyoxyethylene oleyl ether sodium phosphate (8 E.O.) (NIKKOL® DOP-8NV, HLB 12.5, manufactured by Nikko Chemicals Co., Ltd.), dipolyoxyethylene (C12-15) alkyl ether phosphate (2 E.O.) (NIKKOL® DDP-2, HLB 6.5, manufactured by Nikko Chemicals Co., Ltd.), dipolyoxyethylene (C12-15) alkyl ether phosphate (4 E.O.) (NIKKOL® DDP-4, HLB 9.0, manufactured by Nikko Chemicals Co., Ltd.), and dipolyoxyethylene (C12-15) alkyl ether phosphate (6 E.O.) (NIKKOL® DDP-6, HLB 9.0, manufactured by Nikko Chemicals Co., Ltd.), Dipolyoxyethylene (C12-15) alkyl ether phosphate (8 E.O.) (NIKKOL® DDP-8, HLB 11.5, manufactured by Nikko Chemicals Co., Ltd.), Dipolyoxyethylene (C12-15) alkyl ether phosphate (10 E.O.) (NIKKOL® DDP-10, HLB 13.5, manufactured by Nikko Chemicals Co., Ltd.), Tripolyoxyethylene lauryl ether phosphate (4 E.O.) (NIKKOL® TLP-4, HLB 13.0, manufactured by Nikko Chemicals Co., Ltd.), Tripolyoxyethylene cetyl ether phosphate (5 E.O.) (NIKKOL® TCP-5, HLB 10.0, manufactured by Nikko Chemicals Co., Ltd.), Tripolyoxyethylene (C12-15) alkyl ether phosphate (2 E.O.) (NIKKOL® Examples include TDP-2, HLB 7.0 (manufactured by Nikko Chemicals Co., Ltd.), tripolyoxyethylene (C12-15) alkyl ether phosphate (8E.O.) (NIKKOL® registered trademark TDP-8, HLB 11.5, manufactured by Nikko Chemicals Co., Ltd.).

[0015] The (A) used in the present invention can be used after measuring the acid value by an acid value measurement method in advance for the purpose of confirming the degree of neutralization. Alternatively, when using a commercially available product, the acid value indicated in the test report may be used. The acid value measurement method is not particularly limited. For example, a method of measuring the number of milligrams of potassium hydroxide (KOH: 56.11) required to neutralize 1 g of a sample as defined in the Pharmaceutical Excipient Raw Material Standard 2021 issued by the Pharmaceutical and Food Safety Bureau, Ministry of Health, Labour and Welfare can be used and can be calculated from Equation (1). The first method of this operation method is defined as follows. First method Except as otherwise specified, precisely weigh the amount of the sample specified in each article, place it in a 250 mL flask, add 50 mL of ethanol (95) or ethanol (95) / diethyl ether mixture (1:1) or ethanol (95) / diethyl ether mixture (2:1), warm to dissolve, and titrate with 0.1 mol / L potassium hydroxide solution while shaking occasionally. (Indicator: 1 mL of phenolphthalein test solution) However, the end point of the titration is the point where the light red color of the solution persists for 30 seconds. Perform a blank test in the same manner for correction.

[0016]

Equation

[0017] In the present invention, the degree of neutralization calculated using 1 g equivalent of (B) with respect to the acid value of (A) measured in advance by an acid value measurement method is defined by Equation (2). In Equation (2), 1 g equivalent of (B) is the number obtained by dividing the mass per mole of the base by the valence of the base. For example, in the case of sodium hydroxide (NaOH: 40.00), the valence as a base is 1, so 1 g equivalent of sodium hydroxide is 40.00.

[0018]

Equation

[0019] The (A) used in the present invention can be used alone or in combination of two or more types. The amount of (A) used in the present invention is not particularly limited, but from the viewpoint of exfoliating effect, the content is preferably 0.1 to 3% by mass of the total amount of the composition, and more preferably 0.3 to 2% by mass.

[0020] The basic amino acids and organic bases used in the present invention are not particularly limited and can be appropriately selected depending on the purpose. Examples of basic amino acids include lysine and arginine. Examples of organic bases include ammonium monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, and 2-amino-2-hydroxymethyl-1,3-propanediol.

[0021] The amount of (B) used in this invention can be determined in advance using Equation 3, which is a modified version of Equation 2 based on the degree of neutralization. From the viewpoint of preventing the penetration of basic components into the skin and suppressing skin irritation while exhibiting an excellent exfoliating effect, the degree of neutralization is preferably between 1.0 and 20.0, and more preferably between 5.0 and 15.0. The amount of (B) calculated from Equation 3 within this range of the degree of neutralization is desirable.

[0022]

number

[0023] The (B) used in this invention can be used by one type or in combination of two or more types. When two or more types of (A) and (B) are combined, the degree of neutralization can be calculated from the information of multiple (A) and (B) using equation 4, which is an extension of equation 2.

[0024]

number

[0025] Let's look at a specific example using equation 4. If the acid value of (A1) dipolyoxyethylene (C12-15) alkyl ether phosphate (10 E.O.) is 49 and the mass% is 0.8%, the acid value of (A2) tripolyoxyethylene (C12-15) alkyl ether phosphate (8 E.O.) is 28 and the mass% is 0.2%, the 1g equivalent of (B1) 2-amino-2-methyl-1,3-propanediol is 105.16 and the mass% is 0.8%, and the 1g equivalent of (B2) arginine is 174.2 and the mass% is 0.2%, then the degree of neutralization can be calculated from equation 4 as 10.964.

[0026]

number

[0027] In addition to the essential components mentioned above, the cleansing cosmetic composition of the present invention may also contain, as necessary, water, surfactants, polyhydric alcohols, lower alcohols, thickeners, water-soluble polymers, preservatives, chelating agents, medicinal ingredients, oils, silicones, antioxidants, UV absorbers, fragrances, pigments, and other components not commonly used in cosmetics, within qualitative and quantitative limits that do not impair the effects of the present invention.

[0028] The method of using the wipe-off cosmetic composition of the present invention is not particularly limited, but one method of use is to apply it to a cosmetic tool such as a cotton pad and wipe the skin with it. For this reason, it is more preferable that the wipe-off cosmetic composition of the present invention be in liquid form, such as a lotion, emulsion, or serum, which can be applied to a cosmetic tool. [Examples]

[0029] The present invention will be further explained below with reference to examples. These examples do not limit the present invention in any way. The amounts are expressed as mass% relative to the total amount of the composition.

[0030] For the examples and comparative examples, efficacy tests were conducted using the wipe-off cosmetic formulations shown in Table 1 below. [Manufacturing method for wipe-off cosmetics] Samples were prepared by sequentially adding components A, B, and other aqueous components from the table to purified water, stirring and mixing. Components A'1 and B' were added in the same manner as components A and B, respectively. When component A'2 and other oily components were included, purified water and component A'2 were heated and dissolved at 80°C, and other oily components, which had also been heated and dissolved at 80°C, were added. After processing with a homomixer, the mixture was cooled to room temperature to prepare the sample.

[0031] (Exfoliating effect) [Evaluation Method] The amount of aged keratin removed during wiping was confirmed by protein quantification using the cosmetic formulations prepared in the examples and comparative examples. One mL of the cosmetic was applied to a cotton ball, and a 5 cm x 14 cm area was wiped 20 times in a consistent direction on the back of a person who had been washed with warm water. The wiping was performed with consistent pressure. The wiped cotton balls were placed in a tube, 1.5 mL of 8M urea was added, and the tubes were incubated overnight at 37°C to extract the protein. The extract was squeezed out with a syringe, the sample solution was collected, and protein quantification was performed using the BCA method to measure the amount of protein removed. 40 μL of the collected sample solution was added to a 96-cell culture cluster. Reagent A (1% bicinchoninic acid, 2% Na2CO3, 0.16% tartaric acid, 0.4% NaOH, 0.95% NaHCO3 aqueous solution) and Reagent B (4% CuSO4·5H2O aqueous solution) were mixed in a 50:1 ratio and added in 200 μL portions. After incubation at 37°C for 30 minutes, the absorbance at 540 nm was measured. Simultaneously, a calibration curve was created by diluting bovine blood albumin (BSA) three times, starting from a concentration of 0.4 mg / mL and diluting it 2-fold each time. Protein solubility was calculated from this calibration curve. Using this method, a higher value indicates a greater amount of protein removed, and therefore a higher effectiveness in removing aged keratin. [Evaluation Criteria] The protein quantification results were divided into four levels and used as evaluation values. ◎: 0.28mg or more (Particularly effective at removing aging dead skin cells, extremely superior) ○: 0.24mg or more to less than 0.28mg (high effectiveness in removing aging keratin) △: 0.20mg or more but less than 0.24mg (almost no effect on removing aging keratin) ×: Less than 0.20mg (No effect on removing aging dead skin cells)

[0032] (Sebum removal effect) 0.04 g of simulated sebum was applied to the inner side of the forearm and allowed to acclimate for 10 minutes. The amount of oil was then measured using an oil content measuring device (Sebumeter SM815, manufactured by Courage & Khazaka Electronic GmbH) (initial value). 1 mL each of the cosmetic preparations made in the examples and comparative examples was applied to a cotton ball, and the area where the simulated sebum was applied was wiped 20 times in a consistent direction. The amount of oil was measured 10 minutes after wiping, and the percentage decrease from the initial value was calculated as the sebum removal rate using the following formula. The results were then evaluated according to the following criteria. Sebum removal rate (%): {(Initial value - Sebum amount after use) / Initial value} × 100 [Evaluation Criteria] ◎: Sebum removal rate of 30% or more (Sebum removal effect is particularly high and excellent) ○: Sebum removal rate of 20% or more but less than 30% (particularly high sebum removal effect) △: Sebum removal rate is 10% or more but less than 20% (almost no sebum removal effect) ×: Sebum removal rate is less than 10% (no sebum removal effect)

[0033] (skin irritation) [Evaluation Method] Using the lotions prepared according to the example formulation and the comparative example formulation, 10 monitors who had previously experienced skin problems with cleansing cosmetics used the products for one week. A questionnaire was administered regarding the presence or absence of skin problems such as itching and redness, and the safety of the products was evaluated. [Safety Evaluation Criteria] ○: Out of 10 participants, 0 reported experiencing skin problems. △: 1 to 2 out of 10 participants reported experiencing skin problems. ×: More than 3 out of 10 participants reported experiencing skin problems.

[0034] [Table 1]

[0035] According to Table 1, in Examples 1-5, by incorporating a surfactant in which the degree of neutralization of (B) relative to the acid value of (A) was in the range of 1.0 to 20.0, it was confirmed that the basic components could not penetrate the skin, suppress skin irritation, exhibit excellent exfoliation effects, and have excellent sebum removal effects, resulting in less oiliness after use. In Examples 6 and 7, it was confirmed that similar effects could be obtained even when the type of (A) was changed from diester to triester. Furthermore, in Example 8, it was confirmed that similar effects could be obtained even when two types of (B) were used, and in Example 9, when two types of (A) and (B) were used. In Example 10, it was confirmed that similar effects could be obtained even when the aliphatic alcohol of (A) was lauryl alcohol with 12 carbon atoms, and in Example 11, it was confirmed that similar effects could be obtained even when oleyl alcohol with 18 carbon atoms was used. On the other hand, in Comparative Example 1, the degree of neutralization of (B) relative to the acid value of (A) was 1.0 or less, and a sufficient exfoliating effect was not obtained. In Comparative Example 2, the degree of neutralization of (B) relative to the acid value of (A) was 20.0 or more, so it is thought that the basic component penetrated the skin and induced skin irritation. In Comparative Example 3, instead of component (A), a surfactant with an acid value of 1 or less was used, and since there was no functional group to neutralize the basic compound, it is thought that the basic component induced skin irritation. In Comparative Example 4, instead of component (A), potassium cetyl phosphate, which is a monoester salt of phosphoric acid and a higher alcohol with a linear structure, was used. Since potassium cetyl phosphate is a component that has not undergone addition polymerization of ethylene oxide like component (A), it has a small molecular weight, and even if it reacted with the basic component to neutralize it, it is thought to have penetrated the skin and induced irritation. In Comparative Example 5, cetanol was added as another oily component to Comparative Example 4. Cetanol has high crystalline properties, and in Comparative Example 5, which lacked liquid oil, the prepared oil-in-water emulsion particles were unstable, with crystals precipitation after 24 hours, making evaluation impossible. Comparative Example 6 is the result of adding glyceryl tri-2-ethylhexanoate, a liquid oil, to Comparative Example 5. The prepared oil-in-water emulsion particles were stable, but the sebum removal rate was low, and it did not show a sebum removal effect. Furthermore, since the same potassium cetyl phosphate as in Comparative Example 4 was used, it is thought that skin irritation was induced. Comparative Example 7 is the result of using potassium hydroxide, an inorganic salt, as the basic component instead of component (B). When potassium hydroxide reacts with component (A) in a neutralization reaction, the hydrophilic group becomes a potassium salt, but because its molecular weight is extremely small compared to basic amino acids and / or organic bases, it is thought that it penetrated the skin and induced irritation.

[0036] The results in Table 1 show that the wipe-off cosmetic compositions of the examples exhibited excellent exfoliation and sebum removal effects without causing skin irritation, resulting in compositions with less oily feeling after use. By using the present invention, it is possible to provide a wipe-off cosmetic composition that prevents the penetration of basic components into the skin, suppresses skin irritation while exhibiting excellent exfoliation effects, and provides a refreshing feeling with less oiliness after use.

[0037] The compositions for each formulation were prepared using conventional methods. It was confirmed that all formulations exhibited the effects of the present invention.

[0038] (1) Wipe-off gel: Formula example 1 Ingredient name Amount (%) Dipolyoxyethylene (C12-15) alkyl ether phosphate (4E.O.) HLB: 9.0 Acid value: 78.3 1 2-amino-2-hydroxymethyl-1,3-propanediol 1 Hydroxypropyl methylcellulose 0.1 Polyethylene glycol 1 1,3-Butylene glycol 8 Sorbitol solution 3.0 (Acrylates / C10-30 Alkyl Acrylate) Crosspolymer 0.5 Potassium hydroxide 0.2 Disodium edetate (appropriate amount) Preservative (appropriate amount) Purified water residue Total 100 Degree of neutralization: 8.469

[0039] (2) Wipe-off lotion: Formula example 2 Ingredient name Amount (%) Dipolyoxyethylene (C12-15) alkyl ether phosphate (2E.O.) HLB: 6.5 Acid value: 108.3 1 Methylphenylpolysiloxane 3 PCA Dimethicone 1 Dipolyoxyethylene lauryl ether sodium phosphate (10 E.O.) HLB: 17.0 Acid value: 3.0 0.5 2-amino-2-methyl-1,3-propanediol 2 1,3-Butylene glycol 8 Glycerin 4 (Hydroxyethyl Acrylate / Sodium Acryloyldimethyl Taurate) Copolymer 1.2 Disodium edetate (appropriate amount) Preservative (appropriate amount) Purified water residue Total 100 Degree of neutralization: 9.717

[0040] (3) Wipe-off serum: Formula example 3 Ingredient name Amount (%) Tripolyoxyethylene (C12-15) cetyl ether phosphate (5E.O.) HLB: 10.0 Acid value: 5.6 3.0 Arginine 0.2 1,3-Butylene glycol 8 Glycerin 4 Polysorbate 20 0.3 Sodium hyaluronate 0.1 Carboxyvinyl polymer 0.2 Potassium hydroxide 0.1 Ethanol 5 Disodium edetate (appropriate amount) Preservative (appropriate amount) Purified water residue Total 100 Degree of neutralization: 9.786 [Industrial applicability]

[0041] By using the present invention, it is possible to provide a wipe-off cosmetic that prevents the penetration of basic components into the skin, suppresses skin irritation, exhibits excellent exfoliation effects, and provides a refreshing feeling with less oiliness after use.

Claims

1. (A) One or more esters of phosphoric acid and aliphatic alcohols and salts thereof having the following characteristics (a-1) Aliphatic alcohols: Aliphatic alcohols obtained by addition polymerization of ethylene oxide (a-2) Esters: Diesters or triesters (B) One or more selected from basic amino acids and organic bases A wipe-off cosmetic composition characterized by containing (A) and having a degree of neutralization of (B) with respect to the acid value of (A) of 1.0 or more and 20.0 or less.

2. (a-1) The wipe-off cosmetic composition according to claim 1, wherein the aliphatic alcohol is an aliphatic alcohol having an alkyl group with 12 to 18 carbon atoms.

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