JP2017178892A - Oil-in-water type emulsified composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oil-in-water type emulsified composition comprising glycosaminoglycan and proteoglycan, which has good penetrating feeling during application, can impart moist feeling and an excellent tensed feeling to the skin after applied and further is excellent in storage stability.SOLUTION: There is provided an oil-in-water type emulsified composition which comprises the following components (A) to (D): (A) 0.005 to 0.1 mass% of glycosaminoglycan, (B) 0.005 to 0.1 mass% of proteoglycan, (C) phospholipid and (D) an oil agent which is pasty at 25°C.SELECTED DRAWING: None

Description

  The present invention relates to an oil-in-water emulsion composition. More specifically, the penetrating sensation at the time of application is good, the moist feeling of the back skin and the excellent firmness can be imparted, and the storage stability is also excellent. Is.

  Conventionally, an oil-in-water emulsion composition can have an effect derived from both an aqueous component and an oily component, and it has been preferred to have a good feeling such as freshness and penetration when applied. It has been widely used as cosmetics such as liquids and skin external preparations. In recent years, in cosmetics, high moisturizing effect, moist feeling and firmness are required from the anti-aging trend. For example, techniques for blending specific oils (for example, see Patent Documents 1 and 2), Techniques for blending active ingredients (for example, see Patent Documents 3 and 4) are known. However, although these techniques are excellent in terms of the moisturizing effect, because they contain a high amount of oily components, their stickiness is worrisome, and the good feel inherent in the oil-in-water emulsion composition cannot be obtained. There was also a concern in terms of storage stability.

  On the other hand, among the polysaccharides called glycosaminoglycans, there is a report (Non-patent Document 1) on the interaction between hyaluronic acid and chondroitin sulfate, and even in a skin external preparation, a high water retention function and stability of an emulsified composition It was expected to contribute to

JP 2009-040705 A JP 2006-29883 A JP 2001-072570 A JP 2009-256268 A

Masahiro Nishimura: Study on the interaction between hyaluronic acid and chondroitin sulfate. University of Dentistry, 29, 32-39.1997.

  Therefore, the present invention has an object to provide an oil-in-water emulsion composition that has a high moisturizing effect, has no stickiness, has a good feel such as a penetrating feeling during coating, and is excellent in storage stability. And

  As a result of intensive studies in view of the above circumstances, the present inventors have found an interaction between glycosaminoglycan and proteoglycan that is a complex thereof, and phospholipid and a paste-like oil agent at 25 ° C. By making it an oil-in-water emulsion composition to be contained, the composition has good penetration feeling at the time of application, excellent storage stability, and also has a moist and firm feeling on the back skin. It was.

That is, the present invention provides an oil-in-water emulsion composition (A) glycosaminoglycan containing 0.005 to 0.1% by mass of the following components (A) to (D):
(B) Proteoglycan 0.005-0.1% by mass
(C) Phospholipid (D) relates to a paste-like oil agent at 25 ° C.
The present invention also relates to an oil-in-water emulsion composition in which the component (D) is a diester of dimer acid, and further to the component (E) the oil-in-water emulsion composition containing an ester oil that is liquid at 25 ° C. It is.

  The oil-in-water emulsified composition of the present invention has a good penetration into the skin, a high effect of improving the firmness of the back skin, and a quality excellent in storage stability. Therefore, it is possible to provide a cosmetic or a skin external preparation having an excellent moisturizing function.

Hereinafter, the configuration of the present invention will be described in detail.
The component (A) glycosaminoglycan used in the present invention is also called mucopolysaccharide, and is based on a disaccharide repeating unit of amino sugar (galactosamine, glucosamine) and uronic acid (glucuronic acid, iduronic acid) or galactose. Configured as a skeleton. Specific examples include hyaluronic acid, chondroitin, chondroitin sulfate (chondroitin sulfate A, chondroitin sulfate C, chondroitin sulfate E, chondroitin sulfate K, etc.), chondroitin polysulfate, dermatan sulfate, heparin, keratan sulfate, keratan polysulfate and the like. However, it is not limited to these. In the present invention, any of those extracted from natural products such as animals, those obtained by culturing microorganisms, and those synthesized chemically or enzymatically can be used. These glycosaminoglycans may be pharmacologically acceptable salts that are usually used, and one or more of them may be used as necessary.

  Content of the component (A) in this invention is 0.005-0.1 mass% in conversion of solid content with respect to the whole quantity of a composition, and when it exceeds 0.1 mass%, when apply | coating to skin It is not preferable because the feeling of use deteriorates, for example, the feel is sticky. On the other hand, 0. If it is less than 005% by mass, the effect of interaction with the component (B) tends not to be obtained, which is not preferable.

  The component (B) proteoglycan used in the present invention is a complex polysaccharide in which glycosaminoglycan is covalently bound with a protein as a core, and is present in a large amount in animal tissues, particularly cartilage tissues. Proteoglycans are also known to exist in vivo with a structure in which a core protein is further bound to hyaluronic acid, and its molecular weight is as high as tens of thousands to tens of millions. Among them, in the present invention, those having an average molecular weight of 200,000 to 20 million are preferable, and those having an average molecular weight of 5 million to 20 million are more preferable. Proteoglycans are not only separated and purified, but also crude products can be used. Proteoglycan can be quantified by performing molecular weight fractionation using gel chromatography and measuring the dried product of fractions having a molecular weight of 10,000 or more and the presence of acidic sugars and proteins. The presence of acidic sugar can be confirmed by the carbazole sulfate method, and the presence of protein can be confirmed by absorbance measurement at around 280 nm. These proteoglycans can be used alone or in combination of two or more as required.

  The content of the component (B) in the present invention is 0.005 to 0.1% by mass with respect to the total amount of the composition, and when it exceeds 0.1% by mass, the touch when applied to the skin is sticky. This is not preferable because the feeling of use deteriorates. On the other hand, 0. If it is less than 005% by mass, the effect of interaction with the component (A) tends not to be obtained, which is not preferable.

  The component (C) phospholipid used in the present invention has a structure in which two long-chain fatty acids and a phosphate group are bonded to glycerin as a basic skeleton, and a structure in which an alcohol is bonded to a phosphate group. Examples of fatty acids constituting phospholipids include saturated and unsaturated carboxylic acids having 7 to 22 carbon atoms, and alcohols constituting phospholipids often contain nitrogen, and include choline, ethanolamine, inositol, and serine. Etc. In the present invention, lysophospholipid from which one of the fatty acids of the phospholipid is removed may be included.

  The component (C) may be any component as long as it is used in ordinary cosmetics and skin external preparations. For example, soybean-derived phospholipid, soybean-derived hydrogenated phospholipid, egg yolk-derived phospholipid, egg yolk-derived hydrogenated phospholipid , Hydrogenated lysophospholipids, and the like. These phospholipids may be used alone or in combination of two or more as required. Specifically, NIKKOL Resinol S-10 provided by Nikko Chemicals Co., Ltd., Basis LS-60HR provided by Nisshin Oilio Group Co., Ltd., egg yolk lecithin PL-100P provided by Kewpie Co., Ltd., Nippon Seika Commercial products such as LP70H provided by a corporation can be used.

  Although content in particular of the component (C) in this invention is not restrict | limited, 0.01-5.0 mass% is preferable with respect to the whole quantity of a composition, Furthermore, 0.05-3.0 mass% is more preferable. If it is this range, since emulsification stability is good and it becomes a smoother usability | use_condition, it is preferable.

  Component (D) used in the present invention is a paste-form oil agent at 25 ° C. The oil agent is distinguished from liquid oil or solid oil in that it has a melting point at a temperature exceeding 25 ° C. and does not completely solidify at 25 ° C. or less. It is. For example, lanolin, trilanoline fatty acid glyceryl, soft lanolin fatty acid, dimer acid diester, petrolatum, shea fat, branched fatty acid (C12-31) cholesteryl, dipentaerythritol fatty acid ester (hexaoxystearate dipentaerythritol, etc.), isostearin Examples include acid-hardened castor oil, monohydroxystearic acid-hardened castor oil, macadamia nut oil fatty acid phytosteryl, tri (capryl / caprin / myristine / stearic acid) glyceride, and myristyl lactate. These can be used alone or in combination of two or more.

  Among the pasty oil agents, dimer acid diesters are particularly preferable, and as alcohols constituting the esters, saturated and unsaturated alcohols having 7 to 22 carbon atoms, sterols, and the like are preferable. For example, dimer linoleic acid (phytosteryl / isostearyl / cetyl / stearyl / behenyl) and dimer linoleic acid di (isostearyl phytosteryl) are preferable in terms of giving a moist and firm feeling when applied to the skin.

  Although content of the component (D) in this invention is not specifically limited, 0.01 to 3% with respect to the whole quantity of a composition is preferable, and. 1 to 2% is more preferable. If it is this range, since the osmosis | permeation feeling to skin improves more and it is excellent in the effect which improves a firm feeling, it is preferable.

  In the present invention, in addition to the above components, component (E) contains an ester oil that is liquid at 25 ° C., so that the skin familiarity (adhesion feeling) at the time of application is improved, and the penetration feeling and moisture feeling are further improved. preferable. The component (E) is not particularly limited, and any component oil can be used as long as it is a liquid ester oil at 25 ° C. that can be used in cosmetics and external preparations for skin. For example, regardless of the origin of animal oil, vegetable oil, synthetic oil, etc., jojoba oil, cetyl 2-ethylhexanoate, isononyl isononanoate, isotridecyl isononanoate, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, isotridecyl isononanoate, Ethyl oleate, glyceryl tri-2-ethylhexanoate, propylene glycol dicaprate, neopentyl glycol dicaprate, polyglyceryl-2 triisostearate, glyceryl tribehenate, diisostearyl malate, ethylhexyldimethyl p-aminobenzoate, ethylhexyl salicylate , Ethyl hexyl methoxycinnamate, tocopherol acetate, olive oil, castor oil, mink oil, macadamian nut oil, meadow foam oil, rosehip It can be exemplified rice bran oil, avocado oil and the like.

  The component (E) is particularly preferably an ester oil having a molecular weight of 200 to 1,000, and a composition having a better feel on the back skin such as a moist feeling after application and no stickiness can be obtained. Examples of those having a molecular weight of 200 to 1000 include propylene glycol dicaprate, propylene glycol dicaprylate, neopentyl glycol dicaprate, isononyl isononanoate, isotridecyl isononanoate, cetyl 2-ethylhexanoate, glyceryl tri-2-ethylhexanoate, Examples include polyglyceryl-2 triisostearate, ethylhexyl methoxycinnamate, and the like. These can use 1 type, or 2 or more types as needed.

  In the oil-in-water emulsion composition of the present invention, in addition to the above-described components, components used for normal skin external preparations can be blended within the range that does not interfere with the effects of the present invention. Specifically, aqueous components, surfactants, oily components, humectants, polymers, powders, dyes, UV absorbers, film forming agents, pH adjusters, antifading agents, antioxidants, antifoaming agents Beauty ingredients, preservatives, fragrances and the like.

  Aqueous components include water such as distilled water, purified water, hot spring water, deep water, plant-derived steam distilled water such as lavender water, rose water, orange flower water, and alcohols such as ethyl alcohol and isopropyl alcohol. , Glycols such as propylene glycol, polypropylene glycol, 1,3-butylene glycol, dipropylene glycol, and polyethylene glycol; glycerols such as glycerin, diglycerin, and polyglycerin; sugar alcohols such as sorbitol, maltitol, and glucose 1 type, or 2 or more types can be used. In this invention, as a compounding quantity of an aqueous component, it is 10-80 mass% with respect to the whole quantity of a composition from a viewpoint of ensuring the solubility of a component (A) and a component (B), and making it easy to exhibit an effect. It is preferable that

  As the surfactant, any surfactant can be used as long as it is used in ordinary cosmetics and the like, other than the component (C), nonionic surfactant, anionic surfactant, cation Ionic surfactants, amphoteric surfactants and the like. Specifically, glycerin fatty acid ester and its alkylene glycol adduct, polyglycerin fatty acid ester and its alkylene glycol adduct, sorbitan fatty acid ester and its alkylene glycol adduct, sucrose fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyalkylene Examples thereof include alkyl co-modified organopolysiloxane and polyether-modified organopolysiloxane. These surfactants can be used alone or in combination of two or more as required. In this invention, when using a nonionic surfactant, it is preferable to mix | blend nonionic surfactant more than HLB7 from a stability viewpoint as an emulsion composition.

  The oily component is not particularly limited as long as it is used for ordinary cosmetics, etc. In addition to the components (D) and (E), solid oil, liquid oil of origin such as animal oil, vegetable oil, synthetic oil, Regardless of the nature of the volatile oil, hydrocarbons, fats and oils, waxes, hardened oils, ester oils, fatty acids, higher alcohols, silicone oils, fluorinated oils, lanolin derivatives, oily gelling agents And oil-soluble resins. In the present invention, it is preferable to contain an oily component that is compatible with the component (D) from the standpoint of stability as an emulsified composition and the effect of the present application being easily exhibited.

The method for producing an oil-in-water emulsion composition of the present invention is usually a method for producing an oil-in-water emulsion composition such as cosmetics, and is not particularly limited, and is prepared by a conventional method.
In addition, the composition of the present invention includes cosmetics such as lotions, milky lotions, creams, eye creams, beauty essences, massages, packs, hand creams, body creams, cleansings, scalp cares, and external preparations, It can be implemented as a skin external preparation such as an external gel, cream, ointment, liniment, lotion, haptic, and plaster.

  The method for applying the oil-in-water emulsified composition of the present invention to the skin is not limited, but the method of directly applying the cosmetic or the like to the skin by hand or finger, the method of applying it by impregnating a nonwoven fabric or the like, the pressure resistance together with the propellant Examples of the method include a method of storing in a container and discharging and applying on the skin in the form of a spray or foam, and a method of storing in a non-gas type pump spray container and spraying on the skin.

  The oil-in-water emulsion composition of the present invention can be filled into a pump-type dispenser container. The container is preferred by consumers because it is easy to handle and easy to adjust the discharge rate, but in order to make the discharge from the pump outlet smooth, the viscosity (25 ° C.) of the composition of the present invention is reduced. It is preferable to have a relatively low viscosity not exceeding 20,000 m · Pa / s. The viscosity here is measured using a single-cylinder rotary viscometer (manufactured by Shibaura System Co., Ltd.) after filling a standard bottle with an oil-in-water emulsion composition and leaving it in a constant temperature bath at 25 ° C. for 24 hours. It can be calculated from the obtained value.

  EXAMPLES Next, although an Example is given and this invention is demonstrated still in detail, this invention is not limited by these.

Examples 1 to 10 and Comparative Examples 1 to 8: Cosmetic liquids Cosmetic liquids of oil-in-water emulsification were prepared by the compositions shown in Table 1 and the following production methods, and each sample was evaluated and determined by the following evaluation methods. The results are also shown in Table 1.

(Production method)
A: Components 1 to 7, 13, and 14 are heated to 70 ° C. and mixed uniformly.
B: Components 10 to 12 and 16 are uniformly dissolved and heated to 70 ° C.
C: A is added to B and emulsified.
D: C was cooled to 35 ° C. and ingredients 8, 9, and 15 were added to obtain a cosmetic liquid.

(Evaluation method)
Each sample was used by 10 specialist panels, and the following (i) 5-step evaluation was made for each of the evaluation items of "penetration feeling during application", "moisture feeling of the back skin", and "feel of elasticity of the back skin". I was given a score according to the standard. And the average value of the score of all the panels was determined in accordance with the following (b) 4-step criteria. In addition, regarding “time stability”, each sample was allowed to stand in a high temperature environment of 40 ° C. for one month, and then visually checked for the presence or absence of changes. did.

(B) Five-level evaluation criteria (score): (Evaluation)
5 points: 4 points felt strongly: 3 points felt: 2 points felt a little: 1 point not felt so much: Not felt at all

(B) Four-step criteria (average score): (Judgment)
4.5 or more: ◎
3.5 or more and less than 4.5: ○
1.5 or more and less than 3.5: △
Less than 1.5: ×

(C) 4-step criteria (evaluation): (judgment)
No change: ◎
There is very little creaming: ○
Clearly there is creaming: △
Separated: ×

  As is clear from the results in Table 1, the cosmetic liquids of Examples 1 to 10 have good results in all the items of penetrating feeling at the time of application, moist feeling of the back skin, firmness of the back skin, and stability over time. It has been shown that both have excellent quality. On the other hand, Comparative Examples 1 and 2 in which the components (A) and (B) are outside the range of the content of the present invention were inferior in all evaluation items, and particularly poor in terms of elasticity and stability over time. . Similarly, in Comparative Example 3 in which other water-soluble polymers were used, all the evaluation items were inferior. Comparative Examples 5 and 6 emulsified using a nonionic surfactant or an anionic surfactant instead of the component (C) were inferior in touch. In Comparative Examples 7 and 8 using other oil agents in place of the component (D), the penetration feeling at the time of application was not obtained, and good results were not obtained even in the moist feeling and firmness of the back skin. .

Example 11: Emulsion An emulsion of oil-in-water emulsification was prepared by the following composition and production method.
(Ingredient) (mass%)
1. Hydrogenated soybean phospholipid (Note 1) 2
2. Tocopherol acetate 0.1
3. Ethyl oleate 2
4). Jojoba alcohol 0.5
5). Hexa (hydroxystearic acid / stearic acid / rosinic acid)
Dipentaerythrityl 1
6). Dimer linoleic acid (phytosteryl / isostearyl / cetyl /
Stearyl / behenyl) 1
7). PEG-400 2
8). Cetanol 1
9. Propylene glycol dicaprate 1
10. Propylene glycol 10
11. Glycerin 10
12 Sodium chondroitin sulfate (Note 4) 0.1
13. Proteoglycan extract (Note 5) 0.1
14 Tranexamic acid 2
15. Sodium pyrosulfite 0.01
16. Sodium monohydrogen phosphate 0.1
17. Sodium dihydrogen phosphate 0.1
18. Phenoxyethanol 0.3
19. Cyclic lysophosphatidic acid sodium 0.01
20. Suizenjinori polysaccharide 0.01
21. Carrageenan 0.1
22. Fragrance 0.1
23. Purified water remaining amount Note 4: Sodium chondroitin sulfate (manufactured by Maruha)
Note 5: Natural proteoglycan (manufactured by Biomatech Japan)

(Production method)
A: Components 1 to 11 are dissolved by heating at 70 ° C.
B: Component 23 is heated to 70 ° C., added to A and emulsified.
C: B was cooled, and components 12 to 22 were added to obtain an emulsion.

  The emulsion of Example 11 had good permeation to suitable skin, little stickiness, high effect of improving the firmness of the back skin, and excellent storage stability without separation or creaming.

Example 12: Cream A cream was prepared by the following composition and production method.
(Ingredient) (mass%)
1. Hydrogenated soybean lysophospholipid (Note 6) 1
2. Squalane 5
3. Heavy liquid isoparaffin 2
4). Neopentyl glycol dicaprate 5
5). Glyceryl tri-2-ethylhexanoate 5
6). Phytosteryl oleate 1
7). Dimer linoleic acid (phytosteryl / isostearyl / cetyl /
Stearyl / behenyl) 1
8). Cetostearyl alcohol 3
9. Behenyl alcohol 2
10. Dipropylene glycol 20
11. Polyoxyethylene sorbitan monooleate 0.5
12 Suizenjinori polysaccharide 0.01
13. Sodium chondroitin sulfate (Note 4) 0.5
14 Proteoglycan extract (Note 5) 0.5
15. Methyl paraoxybenzoate 0.2
16. Acrylic acid / Acroyldimethyltaurine sodium copolymer 1
17. Hydroxypropyl methylcellulose 0.1
18. Cholesterol 0.1
19. Ceramide 2 0.1
20. Ascorbic acid 2-glucoside 0.1
21. Purified water remaining amount Note 6: LP70H (Nippon Seika Co., Ltd.)

(Production method)
A: Components 1 to 11 are dissolved by heating at 70 ° C.
B: Component 21 is heated to 70 ° C., added to A and emulsified.
C: B was cooled and ingredients 12 to 20 were added and mixed to obtain a cream.

  The cream of Example 12 had good penetration into the skin, little stickiness, a high effect of improving the firmness of the back skin, and excellent storage stability without separation or creaming.

Example 13: Sunscreen A sunscreen was prepared by the following composition and production method.
(Ingredient) (mass%)
1. Hydrogenated soybean lysophospholipid (Note 6) 1.2
2. Stearic acid 0.5
3. Light liquid isoparaffin 5
4). Isohexadecane 5
5). Propylene glycol dicaprate 5
6). Ethyl hexyl methoxycinnamate 5
7). Diethylaminohydroxybenzoyl hexyl benzoate 5
8). Dimer linoleic acid (phytosteryl / isostearyl / cetyl /
Stearyl / behenyl) 1
9. Stearyl alcohol 2
10.1,3-butylene glycol 2
11. Dipropylene glycol 20
12 Proteoglycan extract (Note 5) 0.1
13. Acetylated sodium hyaluronate 0.1
14 Sodium hydroxide 0.1
15. Ascorbic acid 2-glucoside 2
16. Sodium monohydrogen phosphate 0.1
17. Sodium dihydrogen phosphate 0.1
18. Phenoxyethanol 0.2
19. Alkyl-modified carboxyvinyl polymer 0.2
20. Xanthan gum 0.1
21. Dimethicone-treated fine particle titanium oxide 5
22. Fragrance 0.1
23. Purified water remaining

(Production method)
A: Components 1 to 11 are dissolved by heating at 70 ° C.
B: Component 23 is heated to 70 ° C., added to A and emulsified.
C: B was cooled, and components 12 to 22 were added and mixed to obtain a sunscreen.

  The sunscreen of Example 13 has good penetration into the skin, less stickiness, has a high effect of improving the firmness of the back skin, and has excellent storage stability without separation or creaming. It was.

Claims (4)

An oil-in-water emulsion composition containing the following components (A) to (D).
(A) Glycosaminoglycan 0.005 to 0.1% by mass
(B) Proteoglycan 0.005-0.1% by mass
(C) Phospholipid (D) oil agent in paste form at 25 ° C   The oil-in-water emulsion composition according to claim 1, wherein the component (D) is a dimer acid diester.   The oil-in-water emulsion composition according to claim 1 or 2, further comprising an ester oil that is liquid at 25 ° C as component (E).   The oil-in-water emulsion composition according to any one of claims 1 to 3, wherein the oil-in-water emulsion composition is a cosmetic or a skin external preparation.