JP7340796B2 - cosmetics - Google Patents

Description

The present invention has a pearlescent appearance, is stable for a long period of time without being affected by temperature changes, maintains its superior appearance, has excellent moisturizing function, and has excellent transdermal absorption of drugs. Regarding excellent cosmetics.

In order to improve the aesthetics of cosmetics, pearl pigments made by coating thin mica particles with titanium dioxide, fish scale powder, and pearlizing agents that utilize the crystallization of glycol distearate are used as techniques to impart pearlescent luster. ing. However, due to the characteristics of the raw materials, the combination of pearl pigments is limited to makeup products, etc., and pearlizing agents are also limited to cleaning products, and it is not possible to impart stable pearl luster to low-viscosity lotions, etc. There wasn't. In addition, formulation technology has been released that gives lotion a pearl-like luster by blending highly crystalline ingredients such as ceramides, but there are problems with stability such as agglomeration and precipitation, and the pearly luster is not sufficient. There wasn't.

Japanese Patent Application Publication No. 2012-167041 Japanese Patent Application Publication No. 2010-241795 JP2006-248925A Japanese Patent Application Publication No. 2002-128639 Japanese Patent Application Publication No. 11-79933 Japanese Patent Application Publication No. 63-287718

The present invention provides cosmetics with pearlescent luster that can maintain stable pearlescent luster over a long period of time, provide excellent moisture retention and barrier properties to the skin, and further promote transdermal absorption of drugs. The purpose is to provide fees.

As a result of extensive studies, the inventors have found that the above problem can be solved by the following method.
(A) A linear POE alkyl ether and/or POE/POP alkyl ether with an HLB value in the range of 10 to 20 and an alkyl chain length in the range of 10 to 24. (B) A linear POE alkyl ether with an alkyl chain length of 14 to 18. A cosmetic comprising a linear higher alcohol (C), a hydrophilic dihydric alcohol (D), and water, and exhibiting pearlescent luster.
This will be explained in detail below.
First, the POE alkyl ether and/or POE/POP alkyl ether (A) is preferably linear, has an HLB value of 10 to 20, and has an alkyl chain length in the range of 10 to 24. Examples include POE decyl ether, POE lauryl ether, POE myristyl ether, POE alkyl (12-14) ether, POE cetyl ether, POE oleyl ether, POE stearyl ether, POE behenyl ether, POE tridecyl ether, POE/POP butyl ether, POE/POP decyl ether, POE/POP lauryl ether, POE/POP myristyl ether, POE/POP alkyl (12-14) ether, POE/POP cetyl ether, POE/POP stearyl ether, POE/POP behenyl ether, POE/POP Decyltetradecyl ether and the like can be used alone or in combination of two or more.

In the present invention, the HLB value is represented by IOB×10 in the organic conceptual diagram. The IOB in the organic conceptual diagram refers to the ratio of the inorganic value (IV) to the organic value (OV) in the organic conceptual diagram, ie, "inorganic value (IV)/organic value (OV)."
The organic conceptual diagram was proposed by Mu Fujita, and its details can be found in "Pharmaceutical Bulletin", 1954, vol. 2, 2, pp. 163-173; “Region of Chemistry”, 1957, vol. 11, 10, pp. 719-725; "Fragrance Journal", 1981, vol. 50, pp. 79-82, etc. In other words, the root of all organic compounds is methane (CH4), and all other compounds are considered to be methane derivatives, and fixed values are set for each of their carbon numbers, substituents, modified parts, rings, etc., and the scores are calculated. Add the organic and inorganic values. These values are plotted on a diagram with organic values on the X axis and inorganic values on the Y axis. This organic concept diagram is also shown in "Organic Concept Diagram - Basics and Applications" (written by Yoshio Koda, Sankyo Publishing, 1984).
Although surfactants other than (A) POE alkyl ether and POE/POP alkyl ether can of course be blended, the blending amount of (A) POE alkyl ether and POE/POP alkyl ether is preferably 30% by weight or less.
The blending amount of the POE alkyl ether or POE/POP alkyl ether (A) is preferably 0.1% to 10% by weight, more preferably 0.3% to 5% by weight.

The higher alcohol (B) is preferably linear and has an alkyl chain length of 14 to 18. For example, myristyl alcohol, cetanol, stearyl alcohol, coconut oil alcohol, etc. can be used alone or in combination of two or more.
The blending amount is preferably 0.1% to 10% by weight, more preferably 0.3% to 3% by weight.
In addition, linear alcohols and branched higher alcohols with alkyl chain lengths exceeding 18 can be blended, but this may vary depending on various conditions, but linear higher alcohols with alkyl chain lengths in the range of 14 to 18 may also be blended. The blending amount is 30% by weight or less, preferably 20% by weight or less.

The pearlescent cosmetic of the present invention can improve pearlescent luster and storage stability by blending (A) and (B) in a specific content ratio. That is, (A):(B) is preferably in the range of 1:0.01 to 1:3, more preferably in the range of 1:0.05 to 2:3. (weight ratio)

The hydrophilic dihydric alcohol (C) is not particularly limited as long as it can be used as a raw material for cosmetics. Examples include ethylene glycol, propylene glycol, 1,3-butylene glycol, dipropylene glycol, tripropylene glycol, isoprene glycol, 1,3-propanediol, 1,2-pentanediol, 1,2-hexanediol, 1, 2-octanediol and the like can be used alone or in combination of two or more. The blending amount thereof is preferably 0.1% to 50% by weight, more preferably 1% to 30% by weight.

The water in (D) may be any water that can be used for cosmetics, and one or more types of water, such as purified water, natural water, and hot spring water, may be used.

Components other than (A) to (D) can also be blended.
One of them is (E) oil. There are no particular restrictions on the oil content as long as it can be used as a cosmetic raw material. Examples include avocado oil, almond oil, olive oil, sesame oil, safflower oil, shea butter, soybean oil, camellia oil, cottonseed oil, palm oil, palm kernel oil, Japanese oak, coconut oil, beef tallow, lard, squalane, beeswax, carnauba wax. , spermaceti, lanolin, liquid lanolin, reduced lanolin, hard lanolin, candelilla wax, montan wax, shellac wax, rice wax, glyceryl tri-2-ethylhexanoate, glyceryl tri(caprylic/capric acid), penta-2-ethylhexanoate Erythritol, various oils and fats such as these hydrogenated products, and waxes.
Cholesterol, cholesteryl lanolin fatty acid, cholesteryl branched fatty acid (C12-31), cholesteryl isostearate, cholesteryl 12-hydroxystearate, cholesteryl ricinoleate, cholesteryl macadamia nut oil fatty acid, dihydrocholester oleate, cholesteryl nonanoate, cholesteryl butyrate, dihydrobutyrate Cholesterol such as cholesteryl or its derivatives, phytosterol, lanolin fatty acid phytosteryl, phytosteryl isostearate, phytosteryl 12-hydroxystearate, phytosteryl ricinoleate, macadamia nut oil fatty acid phytosteryl, phytosteryl oleate, or its derivatives, lanolin, adsorption-purified lanolin, Lanolin or its derivatives such as liquid lanolin, lanolin alcohol, hydrogenated lanolin alcohol, lanolin fatty acid, hexa(hydroxystearic acid/stearic acid/rosin acid) dipentaerythrityl, tetra(hydroxystearic acid/isostearic acid) dipentaerythrityl, dipentaerythrityl hexahydroxystearate , dipentaerythritol derivatives such as dipentaerythrityl tripolyhydroxystearate, dimer dilinoleic acid dimer dilinoleyl bis(behenyl/isostearyl/phytosteryl), dimer dilinoleic acid (phytosteryl/isostearyl/cetyl/stearyl/behenyl), lauroyl Glutamate di(phytosteryl/octyldodecyl), lauroylglutamate di(octyldodecyl/phytosteryl/behenyl), lauroylglutamate di(octyldodecyl/phytosteryl/behenyl), lauroylglutamate di(cholesteryl/behenyl/octyldodecyl), myristoylmethyl-β- Water-retaining oils such as alanine (phytosteryl/decyltetradecyl).
Mineral oils such as paraffin, ceresin, microcrystalline wax, olefin oligomer, liquid paraffin, liquid isoparaffin, pristane, hydrogenated polybutene, hydrogenated polydecene, heavy liquid isoparaffin, etc.
Esters such as isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, oleyl oleate, decyl oleate, octyldodecyl myristate.
Oil-soluble vitamins such as vitamin A oil, vitamin A palmitate, vitamin A acetate, riboflavin, vitamin C dipalmitate, ergocalciferol, vitamin E, vitamin E acetate, vitamin E nicotinate.
Oil-soluble ingredients from plants such as eucalyptus oil, rose oil, chamomile oil, fennel oil, peppermint oil, bergamot oil, peppermint oil, spearmint oil, basil oil, thyme oil, and oil-soluble licorice extract.

Among these, water-retaining oils such as cholesterol or its derivatives, phytosterols or its derivatives, lanolin or its derivatives, and dipentaerythritol derivatives exhibit excellent moisturizing effects and increase the utility value of the cosmetic composition of the present invention. Among the hydrating oils, cholesteryl lanolin fatty acid, cholesteryl branched fatty acid (C12-31), cholesteryl isostearate, cholesteryl 12-hydroxystearate, cholesteryl ricinoleate, cholesteryl macadamia nut oil fatty acid, dihydrocholester oleate, cholesteryl nonanoate, Cholesterol derivatives such as cholesteryl butyrate and dihydrocholesteryl butyrate, phytosterol derivatives such as phytosteryl lanolin fatty acid, phytosteryl isostearate, phytosteryl 12-hydroxystearate, phytosteryl ricinoleate, phytosteryl macadamia nut oil fatty acid, and phytosteryl oleate can further solve the problems of the present invention. I found out that it does.
In addition, when blending cholesterol and phytosterol, it is better to use other oils in combination to increase the utility value of the cosmetic composition of the present invention.
When the oil component of the pearlescent cosmetic of the present invention is blended with a water-retaining oil component, it exhibits a particularly excellent moisturizing effect, which is preferable. The blending amount thereof is preferably 0.01% to 5% by weight, more preferably 0.1% to 1% by weight.

In addition to this, the combination of water-soluble active ingredients (F) is also effective, and it has been found that the present invention enhances transdermal absorption of water-soluble active ingredients.
Examples of water-soluble active ingredients include betaine (trimethylglycine), proline, hydroxyproline, arginine, lysine, serine, glycine, alanine, phenylalanine, tyrosine, β-alanine, threonine, glutamic acid, glutamine, asparagine, aspartic acid, cysteine, Amino acids such as cystine, methionine, leucine, isoleucine, valine, tryptophan, histidine, taurine, γ-aminobutyric acid, γ-amino-β-hydroxybutyric acid, carnitine, carnosine, creatine, and their salts and derivatives; keratin, collagen, elastin , conchiolin, silk, soy protein, wheat protein, hydrolyzed peptides such as casein, or their water-soluble derivatives; vitamin C such as ascorbic acid and its salts such as sodium; ascorbic acid alkyl ethers such as ascorbic acid ethyl ether, ascorbic acid Ascorbic acid glucoside and its fatty acid ester such as -2-glucoside, ascorbic acid phosphate sodium salt and ascorbic acid phosphate magnesium salt, palmitoyl ascorbic acid phosphate sodium salt, tocopheryl ascorbyl phosphate, etc. Ascorbic acid derivatives such as ester salts; thiamine hydrochloride, thiamine sulfate, riboflavin, riboflavin acetate, pyridoxine hydrochloride, flavin adenine dinucleotide, cyanocobalamin, folic acids, nicotinic acids such as nicotinic acid and nicotinamide, and vitamins such as choline. Group B; other vitamins such as pantothenic acid, panthenyl ethyl ether, panthenol, and biotin; water-soluble vitamin E such as tocopherol phosphate; hydroquinone glycosides and their esters such as arbutin and α-arbutin; Kojic acid, ellagate, tranexamate and its derivatives, ferulate and its derivatives, placenta extract, acetylglucosamine, glutathione, glycyrrhizic acid and its derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, guaiazulene, allantoin, indomethacin, Examples include derivatives such as caffeine, α-lipoic acid, rutin and glycosides; derivatives such as hesperidin and glycosides; various plant extracts such as guava and Nishiheliou extract.
One or more of these water-soluble active ingredients are selected depending on the purpose.
There is no problem in adding other water-soluble ingredients.

Components other than the above (A) to (F) may also be blended as necessary. However, it is natural that the ingredients should be blended within a range that maintains the gist of the present invention, such as maintaining pearlescent luster.
For example, below:
Aqueous phase components include polyhydric alcohols such as polyethylene glycol, glycerin, diglycerin, pentaerythritol, xylitol, sorbitol, mannitol, maltitol, and glycerglucoside.
Inorganic salts of sodium chloride, potassium chloride, magnesium chloride, calcium chloride, aluminum chloride, sodium sulfate, potassium sulfate, magnesium sulfate, aluminum sulfate.
Examples include glycolic acid, lactic acid, citric acid, sodium citrate, disodium hydrogen phosphate, sodium dihydrogen phosphate, polysaccharides, chelating agents, preservatives, and pigments, which can be blended as necessary.

The production method of the present invention can be prepared according to a conventional method using an emulsifying machine such as a propeller mixer, paddle mixer, or disper mixer. That is, the oil phase and the aqueous phase are heated as necessary, and the oil phase and the aqueous phase are combined while stirring.

The pearlescent cosmetic of the present invention is translucent to cloudy and exhibits a pearlescent appearance, and is preferably in the form of a liquid to a milky lotion, examples of which include a lotion, a milky lotion, a beauty serum, It can be used as a bath additive, but any formulation can be used as long as it has a pearlescent luster.

Next, the present invention will be specifically explained with reference to Examples, but the technical scope of the present invention is not limited to these examples.

Tables 1 and 2 show the compositions and results of Examples and Comparative Examples. (The amounts are in parts by weight.)
The manufacturing method was to heat the oil phase and the water phase to 80° C., gradually add the oil phase to the water phase while stirring with a disper mixer, and then cool the mixture.
Evaluation was performed using the following items.
(1) Pearl luster immediately after production, (2) Optical anisotropy immediately after production, (3) Pearl luster in 1 month storage stability test products (test temperature: 5°C, 25°C, 40°C). Changes, precipitation, and separation were evaluated by visual observation.
The average score of each temperature was determined based on the following criteria.

(Test 1) Pearl luster (immediately after production)
The sample was filled into a 50 mL transparent glass container, and the pearly luster was visually observed.
(Evaluation criteria)
4: Very strong pearly luster 3: Pearly luster 2: Not much pearlescent luster 1: No pearlescent luster at all (judgment) (average score)
◎: 3.5 points or more ○: 3 points or more and less than 3.5 points △: 2 points or more and less than 3 points ×: Less than 2 points

(Test 2) Optical Anisotropy The presence or absence of optical anisotropy was visually evaluated based on the state in which a sample filled in a 50 mL transparent glass container was placed between orthogonal polarizing plates and observed.

(Test 3) Storage Stability Samples filled in 50 mL transparent glass containers were stored in thermostats at 5°C, 25°C, and 40°C for one month, and then the changes over time of each sample were visually evaluated.
(Evaluation criteria)
3: Almost the same as the pearly luster immediately after, and no precipitation, separation, etc. are observed. 2: Slightly less or slight precipitation, separation, etc. are observed compared to the pearlescent luster immediately after, but the product value 1: Average score at 5°C, 25°C, and 40°C where there is clearly less pearly luster than immediately after, or there is obvious precipitation, separation, etc., which impairs commercial value. It was judged.
(Judgment) (Average score)
◎: 2.5 points or more ○: 2 points or more and less than 2.5 points ×: Less than 2 points

As is clear from the results in Table 1, Examples 1 to 12 had excellent pearly luster immediately after production, and were also excellent in pearlescent luster and stability in the storage stability test. On the other hand, as shown in Table 2, in Comparative Example 1 containing a pearl pigment, the pearl luster was good immediately after production, but the pearl pigment coagulated and precipitated during storage. In addition, in Comparative Examples 2 to 4, which do not contain higher alcohols with alkyl chain lengths of 14 to 18, there is almost no pearl luster, or the pearl luster disappears during storage, and stable pearl luster is easily affected by storage temperature. I couldn't maintain it. In Comparative Examples 5 to 7 using POE alkyl ethers and POE/POP alkyl ethers with HLB values of 10 or less, no pearlescent luster or optical anisotropy was observed.
The HLB value is 10 to 20, but in Comparative Examples 8 to 10 using a surfactant with a structure different from that of a linear POE alkyl ether or a POE/POP alkyl ether with an alkyl chain length in the range of 10 to 24. Some products had a slight pearlescent luster immediately after production, but the pearlescent luster disappeared or separated during storage.
In Comparative Example 11, in which no hydrophilic dihydric alcohol was blended, the pearlescent luster was low immediately after production, and the pearlescent luster disappeared during storage. Comparative Example 12 exhibited optical anisotropy when observed with a polarizing plate and had a lamellar structure, but did not exhibit pearlescent luster.

From these results, linear POE alkyl ether and/or POE/POP alkyl ether with an HLB value in the range of 10 to 20 and an alkyl chain length in the range of 10 to 24, and a linear POE/POP alkyl ether with an alkyl chain length in the range of 14 to 18. It is suggested that the blending of a linear higher alcohol, a hydrophilic dihydric alcohol, and water within a range is an essential component for forming a highly aesthetically pleasing and stable pearlescent luster.

(Test 4) Moisture retention test The skin moisture content when the compositions of Example 1, Comparative Example 1, and Comparative Example 13 were applied to the skin was measured using a skin surface stratum corneum moisture content measuring device. (n=11, 21±2℃, RH45±10%, SKICON-200EX (manufactured by IBS)
The moisture content was expressed as a numerical value with the measured value before application being set as 1. The results are shown in Figure 1.
In Comparative Example 13, a formulation was prepared by replacing the oil content of Example 1 (equal mixture of dihydrocholesteryl oleate and cholesteryl nonanoate with water).Comparative Example 13 did not contain oil content, but α - Forms a gel structure and exhibits pearlescent luster.)

As is clear from FIG. 1, in Example 1, the moisture content of each layer was higher than in Comparative Examples 1 and 13, and there was a tendency for the moisturizing power to last for a long time. In other words, it was shown that the pearlescent cosmetic of the present invention has excellent aesthetics and also has an excellent effect of imparting moisture to the skin, and is highly useful as a cosmetic.

(Test 5) Moisture retention function test The mouth of a container containing water was covered with a membrane filter coated with the compositions of Example 1, Comparative Example 1, and Comparative Example 13, and the weight of water in the container was measured in a low humidity environment. Measurements were taken at the start of the measurement and 48 hours later to observe changes in weight. The moisture evaporation suppression rate was expressed as a percentage obtained by subtracting the amount of water loss in the product coated with the test product from the amount of water loss in the product without composition application, divided by the amount of water loss in the product without coating. The results are shown in Figure 2.

As is clear from FIG. 2, although no moisture evaporation suppression was observed in Comparative Example 1, a remarkable moisture transpiration suppression effect was confirmed in Example 1 even when compared with Comparative Example 13. That is, it was shown that the pearlescent cosmetic of the present invention is not only excellent in aesthetics but also excellent in the effect of imparting moisture to the skin and the function of retaining moisture in the skin, and is highly useful as a cosmetic.

(Test 6) Transdermal absorption 50 mg of the test product was applied to a 2.0 cm square Yucatan micro-pig skin section, stored in a Petri dish lined with filter paper moistened with buffered saline, and placed in an incubator at 32°C. After storage for 4 hours, transdermal absorption was performed. After completion of transdermal absorption, the test product applied to the surface of the skin section was wiped off with a Kimwipe, and the skin surface was peeled off three times using cellophane tape. Thereafter, it was heated at 60° C. for 70 seconds, and the epidermis was collected with tweezers. The collected epidermis was placed in 3 mL of mobile phase, and shaking extraction was performed overnight. Dipotassium glycyrrhizinate in the extract was measured by high performance liquid chromatography. High performance liquid chromatography measurements were performed under the following conditions.
Column: octadecylsilylated silica gel, mobile phase: potassium dihydrogen phosphate/acetonitrile, detection method: ultraviolet absorption, detection wavelength: 254 nm.
The compositions of Example 1 and Comparative Example 1 were used as test articles. The results are shown in Figure 3.

As is clear from FIG. 3, Example 1 exhibited higher transdermal absorbability than Comparative Example 1. That is, it was shown that the pearlescent cosmetic of the present invention has excellent aesthetics, excellent moisturizing function, and excellent percutaneous absorption of active ingredients into the skin, and is highly useful as a cosmetic.

The layered structure (α-gel) can be confirmed by a known method. For example, when X-ray scattering measurements were performed on Example 2, a repetitive scattering pattern originating from the lamellar structure was obtained in the small-angle region, and a sharp single peak scattering image characteristic of the hexagonal crystal system was obtained in the wide-angle region. It was suggested that it had an α-gel structure. In addition, a layered structure was observed by transmission electron microscopy using a freeze-fractured replica (FIG. 4).

(Test 4) In the results of the moisture retention test, the horizontal axis shows the time (minutes) after application, and the vertical axis shows the rate of change, with the skin moisture value before application being 1. (Test 5) These are the results of the moisture retention function test. (Test 6) Results of transdermal absorbability in Example 1 and Comparative Example 1. The vertical axis shows the amount (mg) of GK2 (dipotassium glycyrrhizinate) absorbed per 1 g of epidermis. Transmission electron micrograph using the freeze-fractured replica of Example 2.

Claims (5)

(A) Linear POE alkyl ether and/or POE/POP alkyl ether with an HLB value in the range of 10 to 20 and an alkyl chain length in the range of 10 to 24. (B) A linear POE alkyl ether with an alkyl chain length in the range of 14 to 18. Linear higher alcohols within the range of (C) ethylene glycol, propylene glycol, 1,3-butylene glycol, dipropylene glycol, tripropylene glycol, isoprene glycol, 1,3-propanediol, 1,2-pentanediol , 1,2-hexanediol, and 1,2-octanediol (D) Water (F) Amino acids and their salts and derivatives, hydrolyzed peptides or water-soluble derivatives thereof , ascorbic acid and its salts and derivatives, vitamin B group, pantothenic acid, panthenyl ethyl ether, panthenol, biotin, water-soluble vitamin E, hydroquinone glycosides and their esters, kojic acid, ellagate, tranexam One or more water-soluble active ingredients selected from acid salts and their derivatives, ferulate salts and their derivatives, placenta extract, acetylglucosamine, glutathione, glycyrrhizic acid and its salts and derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, and allantoin. Contains
The blending amount of the higher alcohol in (B) is 0.1% to 3% by weight, and the weight ratio of the POE alkyl ether and/or POE/POP alkyl ether in (A) to the higher alcohol in (B) is ( A liquid or emulsion cosmetic that provides barrier properties to weakly acidic skin , having a ratio of A):(B) of 1:0.05 to 5:4 and exhibiting pearlescent luster. 2. The cosmetic material according to claim 1, further comprising (E) an oil component and exhibiting a pearlescent luster. 3. The cosmetic according to claim 2, wherein the oil component (E) is one or more hydrating oil components selected from cholesterol or its derivatives, phytosterols or its derivatives, lanolin or its derivatives, and dipentaerythritol derivatives. The cosmetic according to any one of claims 1 to 3, which contains dipotassium glycyrrhizinate as the water-soluble active ingredient (F). 5. The cosmetic according to claim 1 , wherein the preparation is a lotion, a liquid beauty serum, or a liquid bath additive.