JP7768685B2 - Composition containing two types of polyglyceryl fatty acid esters and hyaluronic acid - Google Patents

Description

The present invention relates to a composition, preferably a cosmetic or dermatological composition, comprising at least two different types of polyglyceryl fatty acid esters.

Oil-in-water (O/W) or water-in-oil (W/O) emulsions are well known in the fields of cosmetics and dermatology, in particular for the preparation of cosmetic preparations such as milks, creams, tonics, serums or lotions.

In particular, fine emulsions such as O/W nano- or microemulsions are of particular interest in cosmetics due to their transparent or slightly translucent appearance.

Meanwhile, compositions containing polyglyceryl fatty acid esters are known in the fields of cosmetics and dermatology. Polyglyceryl fatty acid esters can function as surfactants and are therefore typically used to prepare emulsions, such as oil-in-water (O/W) or water-in-oil (W/O) emulsions. Polyglyceryl fatty acid esters are preferred for environmental reasons, such as their low environmental impact, compared to polyoxyethylene surfactants.

WO 2020/110716 discloses a composition in the form of a nano- or micro-emulsion that has a transparent or slightly translucent appearance and contains two types of polyglyceryl fatty acid esters.

On the other hand, hyaluronic acid ingredients such as sodium hyaluronate are known to provide moisturizing effects.

International Publication No. 2020/110716 Brochure

Walter Noll's Chemistry and Technology of Silicones (1968), Academic Press Cosmetics and Toiletries, Vol. 91, January 1976, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics Satoshi Tomomasa et al., Oil Chemistry, Vol. 37, No. 11 (1988), pp. 48-53

However, it has proven difficult to include hyaluronic acid components in compositions containing two classes of polyglyceryl fatty acid esters, such as those disclosed in WO 2020/110716, as they tend not to be transparent or slightly translucent.

The object of the present invention is to provide a composition that is transparent or slightly translucent, even when the composition contains a combination of a hyaluronic acid component and two classes of polyglyceryl fatty acid esters.

The above object of the present invention is to
(a) at least one optional oil;
(b) at least one first polyglyceryl fatty acid ester having an HLB value greater than 11.0, preferably greater than 12.0, and more preferably greater than 13.0;
(c) at least one second polyglyceryl fatty acid ester having an HLB value of less than 11.0, preferably less than 10.0, and more preferably less than 9.0;
(d) at least one hyaluronic acid component selected from the group consisting of hyaluronic acid, hyaluronic acid salts, hyaluronic acid derivatives, hyaluronic acid derivative salts, and mixtures thereof;
(e) at least one polyol having 5 or more carbon atoms, and
(f) a composition comprising water,
the total amount of (b) the first polyglyceryl fatty acid ester and (c) the second polyglyceryl fatty acid ester is 0.01% by mass to 5% by mass, based on the total amount of the composition;
the mass ratio of (a) the amount of oil to (the total amount of (b) the first polyglyceryl fatty acid ester and (c) the second polyglyceryl fatty acid ester) is less than 0.3;
the mass ratio of ((c) the amount of the second polyglyceryl fatty acid ester)/((b) the amount of the first polyglyceryl fatty acid ester) is greater than 0.01 and less than 0.2;
the mass ratio of (e) the amount of polyol having 5 or more carbon atoms to (the total amount of (b) the first polyglyceryl fatty acid ester and (c) the second polyglyceryl fatty acid ester) is greater than 0.1 and less than 5;
The composition comprises a continuous phase and a dispersed phase, the dispersed phase having a size of 300 nm or less, preferably 200 nm or less, more preferably 100 nm or less.
This can be achieved by the composition.

(a) The oil can be selected from polar oils.

The amount of (a) oil in the composition according to the present invention may be less than 0.7% by mass, preferably less than 0.6% by mass, and more preferably less than 0.5% by mass, based on the total mass of the composition.

(b) The first polyglyceryl fatty acid ester may contain 2 to 4 glycerol units, preferably 3 or 4 glycerol units, and more preferably 4 glycerol units.

(b) The fatty acid portion of the first polyglyceryl fatty acid ester may contain 12 or fewer carbon atoms, preferably 11 or fewer carbon atoms, and more preferably 10 or fewer carbon atoms.

The amount of (b) the first polyglyceryl fatty acid ester in the composition according to the present invention may be 0.01% to 5% by weight, preferably 0.1% to 4% by weight, and more preferably 1% to 3% by weight, relative to the total weight of the composition.

(c) The second polyglyceryl fatty acid ester may contain 2 to 4 glycerol units, preferably 2 or 3 glycerol units, and more preferably 2 glycerol units.

(c) The fatty acid portion of the second polyglyceryl fatty acid ester may contain 14 or more carbon atoms, preferably 16 or more carbon atoms, and more preferably 18 or more carbon atoms.

The amount of (c) the second polyglyceryl fatty acid ester in the composition according to the present invention may be 0.001% to 0.5% by weight, preferably 0.01% to 0.4% by weight, and more preferably 0.1% to 0.3% by weight, relative to the total weight of the composition.

(d) The hyaluronic acid component can be selected from hyaluronic acid, hydrolyzed hyaluronic acid, acetylated hyaluronic acid, cationic hyaluronic acid, salts thereof, and mixtures thereof.

The amount of hyaluronic acid component (d) in the composition according to the present invention may be 0.001% to 5% by mass, preferably 0.01% to 4% by mass, and more preferably 0.1% to 3% by mass, relative to the total mass of the composition.

(e) The polyol having 5 or more carbon atoms may be selected from diols having 5 or more carbon atoms, preferably _C5 to _C10 diols, more preferably pentylene glycol, hexylene glycol, and mixtures thereof.

The amount of (e) polyol having 5 or more carbon atoms in the composition according to the present invention may be within the range of 0.01% to 7% by weight, preferably 0.1% to 6% by weight, and more preferably 1% to 5% by weight, based on the total weight of the composition.

The present invention also relates to a cosmetic method for treating keratinous materials, comprising the step of applying a composition according to the present invention to the keratinous materials.

After extensive research, the inventors discovered that it is possible to provide a composition that is transparent or slightly translucent, even when the composition contains a combination of hyaluronic acid or a salt thereof and two classes of polyglyceryl fatty acid esters.

Thus, one aspect of the present invention is
(a) at least one optional oil;
(b) at least one first polyglyceryl fatty acid ester having an HLB value greater than 11.0, preferably greater than 12.0, and more preferably greater than 13.0;
(c) at least one second polyglyceryl fatty acid ester having an HLB value of less than 11.0, preferably less than 10.0, and more preferably less than 9.0;
(d) at least one hyaluronic acid component selected from the group consisting of hyaluronic acid, hyaluronic acid salts, hyaluronic acid derivatives, hyaluronic acid derivative salts, and mixtures thereof;
(e) at least one polyol having 5 or more carbon atoms, and
(f) a composition comprising water,
the total amount of (b) the first polyglyceryl fatty acid ester and (c) the second polyglyceryl fatty acid ester is 0.01% by mass to 5% by mass, based on the total amount of the composition;
the mass ratio of (a) the amount of oil to (the total amount of (b) the first polyglyceryl fatty acid ester and (c) the second polyglyceryl fatty acid ester) is less than 0.3;
the mass ratio of ((c) the amount of the second polyglyceryl fatty acid ester)/((b) the amount of the first polyglyceryl fatty acid ester) is greater than 0.01 and less than 0.2;
the mass ratio of (e) the amount of polyol having 5 or more carbon atoms to (the total amount of (b) the first polyglyceryl fatty acid ester and (c) the second polyglyceryl fatty acid ester) is greater than 0.1 and less than 5;
The composition comprises a continuous phase and a dispersed phase, the dispersed phase having a size of 300 nm or less, preferably 200 nm or less, more preferably 100 nm or less.
It is a composition.

Due to the small size of the dispersed phase, the composition according to the present invention can be transparent or slightly translucent. The composition according to the present invention can have a turbidity of 50 NTU or less, preferably 30 NTU or less, and more preferably 10 NTU or less.

When the composition according to the present invention contains oil, it can be in the form of a nano- or microemulsion, even if it contains hyaluronic acid or a salt thereof.

The surfactant system used in the composition according to the invention comprises:
at least one first polyglyceryl fatty acid ester having a higher HLB value;
It may be characterized by a combination with at least one second polyglyceryl fatty acid ester having a lower HLB value.

The higher HLB value of the first polyglyceryl fatty acid ester can be in a higher HLB value range;
The lower HLB value of the second polyglyceryl fatty acid ester can belong to a lower HLB value range;
and,
The higher HLB value range and the lower HLB value range do not overlap with each other.

The composition according to the present invention can be less sticky, and therefore can reduce the sticky feel. As a result, the composition according to the present invention can provide an excellent feeling when used, and in particular, an excellent feeling on the skin after application of the composition.

The term "sticky" as used herein means the property of producing a sticky feeling on the skin.

The composition according to the present invention can be prepared without using a large amount of energy, such as that required by a homogenizer. Therefore, the composition according to the present invention can be prepared by using a small amount of energy, such as by gently stirring the components of the composition together. Therefore, the composition according to the present invention may be environmentally friendly when considering its preparation method.

The composition according to the present invention is described in more detail below.

[oil]
The composition according to the present invention may comprise (a) at least one oil. If two or more oils are used, they may be the same or different.

As used herein, "oil" refers to a fatty compound or substance that is in the form of a liquid or paste (non-solid) at atmospheric pressure (760 mmHg) and room temperature (25°C). Oils commonly used in cosmetics can be used alone or in combination. These oils may be volatile or non-volatile.

(a) The oil may be a non-polar oil, such as a hydrocarbon oil or a silicone oil, a polar oil, such as a vegetable or animal oil, an ester oil or an ether oil, or a mixture thereof.

(a) The oil may be selected from the group consisting of oils of vegetable or animal origin, synthetic oils, silicone oils, hydrocarbon oils, and fatty alcohols.

Examples of vegetable oils include linseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, camellia oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, sesame oil, soybean oil, peanut oil, and mixtures thereof.

Examples of animal oils include squalene and squalane.

Examples of synthetic oils include alkane oils, such as isododecane and isohexadecane, ester oils, ether oils, and artificial triglycerides.

The ester oil is preferably a liquid ester of a saturated or unsaturated, linear or branched C ₁ -C ₂₆ aliphatic mono- or polyacid with a saturated or unsaturated, linear or branched C ₁ -C ₂₆ aliphatic mono- or polyalcohol, the total number of carbon atoms of which is 10 or more.

Preferably, in the case of esters of monohydric alcohols, at least one of the alcohol and acid from which the esters of the present invention are derived is branched.

Among the monoesters of monoacids and monohydric alcohols, mention may be made of ethyl palmitate, ethylhexyl palmitate, isopropyl palmitate, dicaprylyl carbonate, alkyl myristates such as isopropyl myristate or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isononyl isononanoate, isodecyl neopentanoate, and isostearyl neopentanoate.

Esters of _C4 to _C22 dicarboxylic or tricarboxylic acids with _C1 to _C22 alcohols, as well as esters of monocarboxylic, dicarboxylic, or tricarboxylic acids with non-sugar _C4 to _C26 dihydroxy, trihydroxy, tetrahydroxy, or pentahydroxy alcohols can also be used.

In particular, the following may be mentioned: diethyl sebacate, isopropyl lauroyl sarcosinate, diisopropyl sebacate, bis(2-ethylhexyl) sebacate, diisopropyl adipate, di-n-propyl adipate, dioctyl adipate, bis(2-ethylhexyl) adipate, diisostearyl adipate, bis(2-ethylhexyl) maleate, triisopropyl citrate, triisocetyl citrate, triisostearyl citrate, glyceryl trilactate, glyceryl trioctanoate, trioctyldodecyl citrate, trioleyl citrate, neopentyl glycol diheptanoate, diethylene glycol diisononanoate.

As ester oils, sugar esters and diesters of _C6 to _C30 , preferably _C12 to _C22 fatty acids can be used. It should be remembered that the term "sugar" means an oxygen-bearing hydrocarbon-based compound containing several alcohol functional groups, with or without aldehyde or ketone functional groups, and containing at least four carbon atoms. These sugars may be monosaccharides, oligosaccharides, or polysaccharides.

Examples of suitable sugars that may be mentioned include sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, and lactose, as well as derivatives thereof, particularly alkyl derivatives such as methyl derivatives, for example methylglucose.

Sugar esters of fatty acids may in particular be chosen from the group comprising esters or mixtures of esters of the aforementioned sugars with linear or branched, saturated or unsaturated _C6 to _C30 , preferably _C12 to _C22 fatty acids, which, when unsaturated, may have 1 to 3 conjugated or non-conjugated carbon-carbon double bonds.

The esters in this variant can also be selected from monoesters, diesters, triesters, tetraesters, and polyesters, and mixtures thereof.

These esters may be, for example, oleate, laurate, palmitate, myristate, behenate, coconut fatty acid ester, stearate, linoleate, linolenate, caprate, and arachidonic acid esters, or mixtures thereof, such as, inter alia, mixed esters of oleopalmitate, oleostearate, and palmitostearate, and pentaerythrityl tetraethylhexanoate.

More particularly, monoesters and diesters are used, especially monooleate or dioleate esters, stearates, behenates, oleopalmitates, linoleates, linolenates, and oleostearate esters of sucrose, glucose, or methylglucose.

An example that may be mentioned is the product sold by the company Amerchol under the name Glucate® DO, which is methylglucose dioleate.

Examples of preferred ester oils include diisopropyl adipate, dioctyl adipate, 2-ethylhexyl hexanoate, ethyl laurate, cetyl octanoate, octyldodecyl octanoate, isodecyl neopentanoate, myristyl propionate, 2-ethylhexyl 2-ethylhexanoate, 2-ethylhexyl octanoate, 2-ethylhexyl caprylate/caprate, methyl palmitate, ethyl palmitate, isopropyl palmitate, dicaprylate carbonate, Examples of suitable glyceryl stearate include glyceryl lauroyl sarcosinate, isononyl isononanoate, ethylhexyl palmitate, isohexyl laurate, hexyl laurate, isocetyl stearate, isopropyl isostearate, isopropyl myristate, isodecyl oleate, glyceryl tri(2-ethylhexanoate), pentaerythrityl tetra(2-ethylhexanoate), 2-ethylhexyl succinate, diethyl sebacate, and mixtures thereof.

Examples of artificial triglycerides include caprylic/caprylyl glyceride, glyceryl trimyristate, glyceryl tripalmitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate, capric/caprylic triglyceride, and capric/caprylic/linolenic triglyceride.

Examples of silicone oils include linear organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, cyclic organopolysiloxanes such as cyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane, and mixtures thereof.

Preferably, the silicone oil is selected from liquid polydialkylsiloxanes, in particular liquid polydimethylsiloxanes (PDMS), and liquid polyorganosiloxanes containing at least one aryl group.

These silicone oils may also be organically modified. The organically modified silicones that can be used in accordance with the present invention are silicone oils as defined above, and are silicone oils whose structure contains one or more organic functional groups bonded via hydrocarbon-based groups.

Organopolysiloxanes are further defined in Walter Noll's Chemistry and Technology of Silicones (1968), Academic Press. Organopolysiloxanes may be volatile or nonvolatile.

If volatile, the silicones are more particularly chosen from those having a boiling point between 60° C. and 260° C., and even more particularly chosen from:
(i) Cyclic polydialkylsiloxanes containing 3 to 7, preferably 4 to 5, silicon atoms. These are, for example, octamethylcyclotetrasiloxane, sold in particular under the name Volatile Silicone® 7207 by Union Carbide or under the name Silbione® 70045 V2 by Rhodia, decamethylcyclopentasiloxane, sold in particular under the name Volatile Silicone® 7158 by Union Carbide or under the name Silbione® 70045 V5 by Rhodia, and dodecamethylcyclopentasiloxane, sold under the name Silsoft 1217 by Momentive Performance Materials, as well as mixtures thereof. Mention may also be made of cyclocopolymers of the following type, such as dimethylsiloxane/methylalkylsiloxane, of the following formula, such as Silicone Volatile® FZ 3109 sold by Union Carbide:

Mention may also be made of mixtures of cyclic polydialkylsiloxanes with organosilicon compounds, such as a 50/50 mixture of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol, and a mixture of octamethylcyclotetrasiloxane and oxy-1,1'-bis(2,2,2',2',3,3'-hexatrimethylsilyloxy)neopentane; and
(ii) Linear, volatile polydialkylsiloxanes containing 2 to 9 silicon atoms and having a viscosity of 5 x ^{10-6 m2} /s or less at 25°C. An example is decamethyltetrasiloxane, sold in particular under the name SH 200 by Toray Silicone. Silicones belonging to this category are also described in an article published in Cosmetics and Toiletries, Vol. 91, January 1976, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics. The viscosity of the silicones is measured at 25°C in accordance with ASTM Standard 445, Annex C.

Non-volatile polydialkylsiloxanes may also be used. These non-volatile silicones are more particularly selected from polydialkylsiloxanes, among which polydimethylsiloxanes having primarily trimethylsilyl end groups can be mentioned.

Among these polydialkylsiloxanes, mention may be made, but is not limited to, the following commercially available products:
Silbione® oils of the 47 and 70 047 series or Mirasil® oils sold by the company Rhodia, such as 70 047 V 500 000 oil,
oils of the Mirasil® series sold by the company Rhodia;
Dow Corning 200 series oils, for example DC200, with a viscosity of 60,000 mm ² /s, as well as
Viscasil® oils manufactured by General Electric and certain oils of the SF series manufactured by General Electric (SF 96, SF 18).

Other examples include polydimethylsiloxanes containing dimethylsilanol end groups, known by the name dimethiconol (CTFA), such as the 48 series oils manufactured by Rhodia.

Among the silicones containing aryl groups, mention may be made of polydiarylsiloxanes, especially polydiphenylsiloxanes, and polyalkylarylsiloxanes, such as phenylsilicone oils.

Phenylsilicone oil has the following formula:

[In the formula,
R ₁ to R ₁₀ are, independently of one another, saturated or unsaturated, linear, cyclic or branched C ₁ to C ₃₀ hydrocarbon-based groups, preferably C ₁ to C ₁₂ hydrocarbon-based groups, more preferably C ₁ to C ₆ hydrocarbon-based groups, in particular methyl, ethyl, propyl or butyl groups;
m, n, p, and q are each independently an integer from 0 to 900, inclusive, preferably from 0 to 500, inclusive, and more preferably from 0 to 100, inclusive;
However, the sum of n+m+q is non-zero.
The phenyl silicone may be selected from the following:

Examples that may be mentioned include products sold under the following names:
- Rhodia Silbione® oils, 70 641 series;
oils of the Rhodorsil® 70 633 and 763 series from the company Rhodia;
- Dow Corning 556 Cosmetic Grade Fluid, an oil manufactured by Dow Corning;
- Bayer PK series silicones, e.g. PK20 product,
- Certain oils of the SF series manufactured by General Electric, such as SF 1023, SF 1154, SF 1250 and SF 1265.

As the phenyl silicone oil, phenyl trimethicone (in the above formula, R ₁ to R ₁₀ are methyl, p, q, and n=0, and m=1) is preferred.

Organo-modified liquid silicones may contain, inter alia, polyethyleneoxy and/or polypropyleneoxy groups. Examples include silicone KF-6017 proposed by Shin-Etsu Chemical Co., Ltd., and Silwet® L722 and L77 oils manufactured by Union Carbide.

The hydrocarbon oil can be chosen from:
- linear or branched, optionally cyclic C ₆ -C ₁₆ lower alkanes, examples which may be mentioned include hexane, undecane, dodecane, tridecane, and isoparaffins, such as isohexadecane, isododecane, and isodecane; and
- linear or branched hydrocarbons containing more than 16 carbon atoms, such as liquid paraffin, liquid petroleum jelly, polydecene and hydrogenated polyisobutenes, such as Parleam®, and squalane.

Preferred examples of hydrocarbon oils include linear or branched hydrocarbons such as isohexadecane, isododecane, squalane, mineral oils (e.g., liquid paraffin), paraffin, petrolatum or petrolatum, and naphthalenes, hydrogenated polyisobutene, isoeicosane, and decene/butene copolymers, and mixtures thereof.

The term "aliphatic" in fatty alcohols refers to a relatively large number of carbon atoms. Thus, alcohols having 4 or more, preferably 6 or more, and more preferably 12 or more carbon atoms are included within the scope of fatty alcohols. Fatty alcohols may be saturated or unsaturated. Fatty alcohols may be linear or branched.

The aliphatic alcohol may have the structure R-OH, where R is selected from saturated and unsaturated, straight-chain and branched groups containing from 4 to 40 carbon atoms, preferably from 6 to ₃₀ carbon atoms, and more preferably from 12 to ₂₀ carbon atoms. In at least one embodiment, R may be selected from _C12 to C20 alkyl groups and _C12 to C20 alkenyl groups. R may or may not be substituted with at least one hydroxyl group.

Examples of fatty alcohols include lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, oleyl alcohol, linoleyl alcohol, palmitoleyl alcohol, arachidonyl alcohol, erucyl alcohol, and mixtures thereof.

The fatty alcohol is preferably a saturated fatty alcohol.

Thus, the aliphatic alcohol may be selected from linear or branched, saturated or unsaturated _C6 to _C30 alcohols, preferably linear or branched, saturated _C6 to _C30 alcohols, more preferably linear or branched, saturated _C12 to _C20 alcohols.

The term "saturated fatty alcohol" as used herein means an alcohol having a long, saturated aliphatic carbon chain. The saturated fatty alcohol is preferably selected from any linear or branched, saturated _C6 - _C30 fatty alcohol. Among the linear or branched, saturated _C6 - _C30 fatty alcohols, linear or branched, saturated _C12 - _C20 fatty alcohols can be preferably used. Any linear or branched, saturated _C16 - _C20 fatty alcohols can be more preferably used. Branched _C16 - _C20 fatty alcohols can be even more preferably used.

Examples of saturated fatty alcohols include lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, and mixtures thereof. In one embodiment, cetyl alcohol, stearyl alcohol, octyldodecanol, hexyldecanol, or mixtures thereof (e.g., cetearyl alcohol) and behenyl alcohol can be used as saturated fatty alcohols.

According to at least one embodiment, the fatty alcohol used in the composition according to the invention is preferably selected from cetyl alcohol, octyldodecanol, hexyldecanol, and mixtures thereof.

It is also preferred that the (a) oil is selected from oils having a molecular weight of less than 600 g/mol.

Preferably, the (a) oil has a low molecular weight, such as less than 600 g/mol, and is selected from ester oils having short hydrocarbon chains (C ₁ to C ₁₂ ) (e.g., isopropyl lauroyl sarcosine, isopropyl myristate, isopropyl palmitate, isononyl isononanoate, and ethylhexyl palmitate), silicone oils (e.g., volatile silicones such as cyclohexasiloxane), hydrocarbon oils (e.g., isododecane, isohexadecane, and squalane), branched and/or unsaturated fatty alcohol (C ₁₂ to C ₃₀ ) type oils, such as octyldodecanol and oleyl alcohol, and ether oils such as dicaprylyl ether.

(a) The oil can be selected from polar oils, preferably ester oils, more preferably isopropyl myristate, and non-polar oils, preferably ether oils, more preferably dicaprylyl ether.

The amount of (a) oil in the composition according to the present invention may be 0.001% by mass or more, preferably 0.01% by mass or more, and more preferably 0.1% by mass or more, based on the total mass of the composition.

The amount of (a) oil in the composition according to the present invention may be less than 0.7% by mass, preferably less than 0.6% by mass, and more preferably less than 0.5% by mass, based on the total mass of the composition.

The amount of (a) oil in the composition according to the present invention may be from 0.001% to less than 0.7% by mass, preferably from 0.01% to less than 0.6% by mass, and more preferably from 0.1% to less than 0.5% by mass, relative to the total mass of the composition.

[First polyglyceryl fatty acid ester]
The composition according to the present invention comprises at least one first polyglyceryl fatty acid ester (b) having an HLB value of greater than 11.0, preferably greater than 12.0, and more preferably greater than 13.0. A single type of first polyglyceryl fatty acid ester (b) may be used, or two or more different types of first polyglyceryl fatty acid esters (b) may be used in combination.

(b) The first polyglyceryl fatty acid ester can function as a surfactant, particularly a nonionic surfactant.

(b) The first polyglyceryl fatty acid ester may have an HLB value of greater than 11.0 to 17.0, preferably greater than 12.0 to 16.0, and more preferably greater than 13.0 to 15.0.

The term HLB ("hydrophilic-lipophilic balance") is well known to those skilled in the art and describes the ratio between hydrophilic and lipophilic moieties in a molecule.

When two or more (b) first polyglyceryl fatty acid esters are used, the HLB value is determined by the weighted average of the HLB values of all (b) first polyglyceryl fatty acid esters.

(b) The first polyglyceryl fatty acid ester can be selected from mono-, di-, tri- and higher esters of saturated or unsaturated fatty acids.

(b) The first polyglyceryl fatty acid ester preferably contains 2 to 4 glycerol units, preferably 3 or 4 glycerol units, and more preferably 4 glycerol units.

(b) The fatty acid or fatty acid moiety for the fatty acid portion of the first polyglyceryl fatty acid ester may contain 12 or fewer carbon atoms, preferably 11 or fewer carbon atoms, and more preferably 10 or fewer carbon atoms. (b) The fatty acid or fatty acid moiety for the fatty acid portion of the first polyglyceryl fatty acid ester may contain 4 or more carbon atoms, preferably 6 or more carbon atoms, and more preferably 8 or more carbon atoms. (b) The fatty acid or fatty acid moiety for the fatty acid portion of the first polyglyceryl fatty acid ester may have 4 to 12 carbon atoms, preferably 6 to 11, and more preferably 8 to 10 carbon atoms.

(b) The fatty acid for the fatty acid portion of the first polyglyceryl fatty acid ester may be saturated or unsaturated and may be selected from caprylic acid, capric acid, and lauric acid.

(b) The first polyglyceryl fatty acid ester can be selected from the group consisting of PG3 caprate (HLB: about 14), PG4 caprylate (HLB: 14), PG4 laurate (HLB: about 14), PG4 caprate (HLB: 14), PG5 myristate (HLB: 15.4), PG5 stearate (HLB: 15), PG6 caprylate (HLB: 14.6), PG6 caprate (HLB: 13.1), PG6 laurate (HLB: 14.1), PG10 laurate (HLB: 15.2), PG10 myristate (HLB: 14.9), PG10 stearate (HLB: 14.1), PG10 isostearate (HLB: 13.7), PG10 oleate (HLB: 13.0), PG10 coconut fatty acid (HLB: 16), and mixtures thereof.

(b) It may be preferable that the first polyglyceryl fatty acid ester is selected from the group consisting of PG3 caprate (HLB: approximately 14), PG4 caprylate (HLB: 14), PG4 laurate (HLB: approximately 14), PG4 caprate (HLB: 14), and mixtures thereof.

The amount of (b) the first polyglyceryl fatty acid ester in the composition according to the present invention may be 0.01% by mass or more, preferably 0.1% by mass or more, and more preferably 1% by mass or more, relative to the total mass of the composition.

On the other hand, the amount of (b) first polyglyceryl fatty acid ester in the composition according to the present invention may be 5% by mass or less, preferably 4% by mass or less, and more preferably 3% by mass or less, relative to the total mass of the composition.

The amount of (b) the first polyglyceryl fatty acid ester in the composition according to the present invention may be within the range of 0.01% to 5% by weight, preferably 0.1% to 4% by weight, and more preferably 1% to 3% by weight, relative to the total weight of the composition.

[Second polyglyceryl fatty acid ester]
The composition according to the present invention comprises (c) at least one second polyglyceryl fatty acid ester having an HLB value of less than 11.0, preferably less than 10.0, and more preferably less than 9.0. A single type of (c) second polyglyceryl fatty acid ester may be used, or two or more different types of (c) second polyglyceryl fatty acid esters may be used in combination.

(c) The second polyglyceryl fatty acid ester can function as a surfactant, particularly a nonionic surfactant.

(c) The second polyglyceryl fatty acid ester may have an HLB value of 5.0 to less than 11.0, preferably 6.0 to less than 10.0, and more preferably 7.0 to less than 9.0.

When two or more (c) second polyglyceryl fatty acid esters are used, the HLB value is determined by the weighted average of the HLB values of all (c) second polyglyceryl fatty acid esters.

(c) The second polyglyceryl fatty acid ester can be selected from mono-, di-, tri- and higher esters of saturated or unsaturated fatty acids.

(c) The second polyglyceryl fatty acid ester preferably contains 2 to 4 glycerol units, preferably 2 or 3 glycerol units, and more preferably 2 glycerol units.

(c) The fatty acid or fatty acid moiety for the fatty acid portion of the second polyglyceryl fatty acid ester may contain 14 or more carbon atoms, preferably 16 or more carbon atoms, and more preferably 18 or more carbon atoms. (c) The fatty acid or fatty acid moiety for the fatty acid portion of the second polyglyceryl fatty acid ester may contain 30 or fewer carbon atoms, preferably 24 or fewer carbon atoms, and more preferably 20 or fewer carbon atoms. (c) The fatty acid or fatty acid moiety for the fatty acid portion of the second polyglyceryl fatty acid ester may have 14 to 30, preferably 16 to 24, and more preferably 18 to 20 carbon atoms.

(c) The fatty acid for the fatty acid portion of the second polyglyceryl fatty acid ester may be saturated or unsaturated and may be selected from myristic acid, stearic acid, isostearic acid, and oleic acid.

(c) The second polyglyceryl fatty acid ester is PG2 stearate (HLB: 5.0), PG2 distearate (HLB: 4), PG2 isostearate (HLB: 8), PG2 diisostearate (HLB: 3.2), PG2 triisostearate (HLB: 3), PG2 sesquiisostearate (HLB: approximately 4), PG2 oleate (HLB: 8), PG2 sesquioleate (HLB: 5.3), PG3 distearate (HLB: 5), PG3 diisostearate (HLB: 5), PG3 dicocoate (HLB: 7), PG5 hexastearate (HLB: 4.0), PG5 trioleate (HLB: 7.0), PG10 pentaoleate (HLB: 6.4) ), PG2 sesquicaprylate (HLB: about 8), PG2 caprate (HLB: 9.5), PG2 laurate (HLB: 8.5), PG2 myristate (HLB: 10), PG2 isopalmitate (HLB: 9), PG4 oleate (HLB: 10), PG4 stearate (HLB: 9), PG4 isostearate (HLB: 8.2), PG6 distearate (HLB: 8), PG10 distearate (HLB: about 9), PG10 tristearate (HLB: 8), PG10 diisostearate (HLB: 10), PG10 triisostearate (HLB: 8), PG10 tricoconut fatty acid (HLB: 9), and mixtures thereof.

(c) The second polyglyceryl fatty acid ester is PG2 stearate (HLB: 5.0), PG2 distearate (HLB: 4), PG2 isostearate (HLB: 8), PG2 diisostearate (HLB: 3.2), PG2 triisostearate (HLB: 3), PG2 sesquiisostearate (HLB: approximately 4), PG2 oleate (HLB: 8), PG2 sesquioleate (HLB: 5.3), PG3 distearate (HLB: 5), and diisostearate. In some cases, it may be preferable to select from the group consisting of PG3 (HLB: 5), dicoconut fatty acid PG3 (HLB: 7), sesquicaprylic acid PG2 (HLB: approximately 8), capric acid PG2 (HLB: 9.5), lauric acid PG2 (HLB: 8.5), myristate PG2 (HLB: 10), isopalmitic acid PG2 (HLB: 9), oleic acid PG4 (HLB: 10), stearate PG4 (HLB: 9), isostearic acid PG4 (HLB: 8.2), and mixtures thereof.

The amount of (c) the second polyglyceryl fatty acid ester in the composition according to the present invention may be 0.001% by mass or more, preferably 0.01% by mass or more, and more preferably 0.1% by mass or more, relative to the total mass of the composition.

On the other hand, the amount of (c) the second polyglyceryl fatty acid ester in the composition according to the present invention may be 0.5% by mass or less, preferably 0.4% by mass or less, and more preferably 0.3% by mass or less, relative to the total mass of the composition.

The amount of (c) the second polyglyceryl fatty acid ester in the composition according to the present invention may be within the range of 0.001% to 0.5% by weight, preferably 0.01% to 0.4% by weight, and more preferably 0.1% to 0.3% by weight, relative to the total weight of the composition.

[Hyaluronic acid ingredient]
The composition according to the present invention comprises (d) at least one hyaluronic acid component selected from the group consisting of hyaluronic acid, hyaluronic acid salts, hyaluronic acid derivatives, hyaluronic acid derivative salts, and mixtures thereof. A single type of hyaluronic acid component may be used, or two or more different types of hyaluronic acid components may be used in combination.

Hyaluronic acid is the predominant glycosaminoglycan found in skin. Fibroblasts therefore predominantly synthesize collagen, non-collagenous matrix glycoproteins (fibronectin, laminin), proteoglycans, and elastin. Keratinocytes predominantly synthesize sulfated glycosaminoglycans and hyaluronic acid. Hyaluronic acid is also called hyaluronan.

Hyaluronic acid is present in a free state in the epidermis and dermis and is responsible for skin turgor. This polysaccharide can actually hold large volumes of water, up to 1000 times its own mass. In this sense, hyaluronic acid plays an important role in increasing the amount of water bound in tissues, as well as in the mechanical properties of skin and wrinkle formation.

Hyaluronic acid can be represented by the following chemical formula:

In the context of the present invention, the term "hyaluronic acid" particularly encompasses the basic unit of hyaluronic acid of the formula:

This is the smallest fraction of hyaluronic acid, containing the disaccharide dimer, D-glucuronic acid and N-acetylglucosamine.

The hyaluronic acid derivative may be selected from the group consisting of hydrolyzed hyaluronic acid, acetylated hyaluronic acid, cationic hyaluronic acid, and mixtures thereof.

Cationic hyaluronic acid contains at least one cationic moiety. The cationic moiety may be a trialkylammonium group such as -N ⁺ (CH ₃ ) _3. The cationic moiety may contain at least one hydroxyl group. An example of a cationic group is -CH ₂ -CH(OH)-CH ₂ -N ⁺ (CH ₃ ) ₃ .

An example of cationic hyaluronic acid is hydroxypropyltrimonium hyaluronate.

Examples of hyaluronic acid salts or hyaluronic acid derivative salts include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as magnesium salts, ammonium salts, and mixtures thereof.

The molecular weight of the hyaluronic acid component is not limited. The molecular weight of the hyaluronic acid component may be 5 kDa or more, preferably 20 kDa or more, and more preferably 100 kDa or more. The molecular weight of the hyaluronic acid component may be 20 MDa or less, preferably 10 MDa or less, and more preferably 2,000 kDa or less. Therefore, the molecular weight of the hyaluronic acid component may be 5 kDa to 20 MDa, preferably 20 kDa to 10 MDa, and more preferably 100 kDa to 2,000 kDa.

Unless otherwise defined in the description, "molecular weight" may mean number average molecular weight.

The hyaluronic acid component may in particular be hyaluronic acid supplied by Hyactive under the trade name CPN (MW: 10-150 kDa), by Soliance under the trade name Cristalhyal (MW: 1-1.4 MDa), by Bioland under the name Nutra HA (MW: 820 000 Da), by Bioland under the name Nutra AF (MW: 69 000 Da), or by Bioland under the name Oligo HA (MW: 6100 Da).

A single hyaluronic acid component having a single molecular weight, or a combination of two or more hyaluronic acid components having different molecular weights, can be used.

The amount of the hyaluronic acid component (d) in the composition according to the present invention may be 0.001% by mass or more, preferably 0.01% by mass or more, and more preferably 0.1% by mass or more, relative to the total mass of the composition.

The amount of (d) hyaluronic acid component in the composition according to the present invention may be 5% by mass or less, preferably 4% by mass or less, and more preferably 3% by mass or less, relative to the total mass of the composition.

Accordingly, the amount of hyaluronic acid component (d) in the composition according to the present invention may be within the range of 0.001% to 5% by mass, preferably 0.01% to 4% by mass, and more preferably 0.1% to 3% by mass, relative to the total mass of the composition.

[Polyols with 5 or more carbon atoms]
The composition according to the present invention comprises (e) at least one polyol having 5 or more carbon atoms. A single type of such polyol may be used, or two or more different types of such polyols may be used in combination.

The polyol having 5 or more carbon atoms may be selected from diols having 5 or more carbon atoms, preferably _C5 to _C10 diols, more preferably pentylene glycol, hexylene glycol, and mixtures thereof.

Pentylene glycol includes its isomers. Thus, pentylene glycol can be 1,2-pentylene glycol, 1,3-pentylene glycol, 1,4-pentylene glycol, 1,5-pentylene glycol, 2,3-pentylene glycol, and 2,4-pentylene glycol. 1,2-pentylene glycol may be preferred.

Hexylene glycol includes its isomers. Thus, hexylene glycol can be 1,2-hexylene glycol, 1,3-hexylene glycol, 1,4-hexylene glycol, 1,5-hexylene glycol, 1,6-hexylene glycol, 2,3-hexylene glycol, 2,4-hexylene glycol, 2,5-hexylene glycol, and 2-methyl-2,4-pentanediol. 2-Methyl-2,4-pentanediol may be preferred.

The amount of (e) polyol having 5 or more carbon atoms in the composition according to the present invention may be 0.01% by mass or more, preferably 0.1% by mass or more, and more preferably 1% by mass or more, based on the total mass of the composition.

On the other hand, the amount of (e) polyol having 5 or more carbon atoms in the composition according to the present invention may be 7% by mass or less, preferably 6% by mass or less, and more preferably 5% by mass or less, based on the total mass of the composition.

Therefore, the amount of (e) polyol having 5 or more carbon atoms in the composition according to the present invention may be within the range of 0.01% to 7% by mass, preferably 0.1% to 6% by mass, and more preferably 1% to 5% by mass, based on the total mass of the composition.

[water]
The composition according to the present invention comprises (f) water.

The amount of (f) water in the composition according to the present invention may be 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass or more, based on the total mass of the composition.

On the other hand, the amount of (f) water in the composition according to the present invention may be 95% by mass or less, preferably 90% by mass or less, and more preferably 85% by mass or less, based on the total mass of the composition.

The amount of (f) water in the composition according to the present invention may be within the range of 50% to 95% by weight, preferably 60% to 90% by weight, and more preferably 70% to 85% by weight, based on the total weight of the composition.

[Quantitative requirements]
The total amount of (b) the first polyglyceryl fatty acid ester and (c) the second polyglyceryl fatty acid ester in the composition according to the present invention is from 0.01% to 5% by weight, preferably from 0.02% to 4.5% by weight, more preferably from 1% to 4% by weight, relative to the total weight of the composition.

The mass ratio of (a) the amount of oil to (the total amount of (b) the first polyglyceryl fatty acid ester and (c) the second polyglyceryl fatty acid ester) in the composition according to the present invention is less than 0.3, preferably less than 0.2, and more preferably less than 0.1.

The composition according to the present invention may not contain any (a) oil. In this case, the (b) first polyglyceryl fatty acid ester and the (c) second polyglyceryl fatty acid ester may form micelles, which may form a dispersed phase in the composition according to the present invention and do not contain any (a) oil.

The composition according to the present invention may also contain (a) oil. In this case, (b) the first polyglyceryl fatty acid ester and (c) the second polyglyceryl fatty acid ester may form micelles, which may form a dispersed phase in the composition according to the present invention and contain (a) oil. Micelles containing (a) oil can be thought of as "oil" droplets.

The mass ratio of (amount of (c) second polyglyceryl fatty acid ester)/(amount of (b) first polyglyceryl fatty acid ester) in the composition according to the present invention is greater than 0.01 and less than 0.2, preferably greater than 0.02 and less than 0.19, and more preferably greater than 0.03 and less than 0.18.

The mass ratio of (e) the amount of polyol having 5 or more carbon atoms to (the total amount of (b) the first polyglyceryl fatty acid ester and (c) the second polyglyceryl fatty acid ester) in the composition according to the present invention is greater than 0.1 and less than 5, preferably greater than 0.15 and less than 4.5, and more preferably greater than 0.2 and less than 4.0.

[More polyols]
The composition of the present invention may contain at least one additional polyol other than (e) the polyol having 5 or more carbon atoms. A single type of such additional polyol may be used, or two or more different types of such additional polyols may be used in combination.

The term "polyol" as used herein refers to an alcohol having two or more hydroxy groups and does not include sugars or their derivatives. Sugar derivatives include sugar alcohols obtained by reducing one or more carbonyl groups of a sugar, and sugars or sugar alcohols in which the hydrogen atom in one or more of their hydroxy groups has been replaced with at least one substituent, such as an alkyl group, a hydroxyalkyl group, an alkoxy group, an acyl group, or a carbonyl group.

The polyol may be a _C2 to _C4 polyol, preferably a _C2 to _C4 polyol containing at least two hydroxy groups, preferably from 2 to 5 hydroxy groups.

The polyol may be a natural or synthetic polyol. The polyol may have a linear, branched, or cyclic molecular structure.

The polyol may be selected from glycerin and its derivatives, and glycol and its derivatives. The polyol may be selected from the group consisting of glycerin, ethylene glycol, propylene glycol, and butylene glycol.

The amount of further polyol in the composition according to the present invention may be 20% by weight or less, preferably 15% by weight or less, and more preferably 10% by weight or less, relative to the total weight of the composition.

The amount of further polyol in the composition according to the present invention may be from 1% to 20% by weight, preferably from 3% to 15% by weight, and more preferably from 5% to 10% by weight, relative to the total weight of the composition.

It may be preferable that the composition according to the present invention does not contain butylene glycol.

[Other ingredients]
The composition according to the invention may contain one or more monohydric alcohols that are in liquid form at room temperature (25°C), such as linear or branched monohydric alcohols containing 1 to 6 carbon atoms, such as ethanol, propanol, butanol, isopropanol, isobutanol, pentanol, and hexanol.

The amount of monohydric alcohol in the composition according to the present invention may be 0.01% by mass or more, preferably 0.1% by mass or more, and more preferably 1% by mass or more, based on the total mass of the composition.

On the other hand, the amount of monohydric alcohol in the composition according to the present invention may be 15% by mass or less, preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the composition.

Accordingly, the amount of monohydric alcohol in the composition according to the present invention may be in the range of 0.01% to 15% by weight, preferably 0.1% to 10% by weight, and more preferably 1% to 5% by weight, relative to the total weight of the composition.

The compositions according to the present invention may also contain, in addition to the components described above, various adjuvants conventionally used in cosmetic and dermatological compositions, such as thickeners, anionic, nonionic, cationic, and amphoteric or zwitterionic polymers, anionic, further nonionic, cationic, and amphoteric surfactants, antioxidants, colorants, chelating agents, sequestering agents, fragrances, dispersing agents, conditioning agents, film-forming agents, preservatives, co-preservatives, and mixtures thereof.

In one embodiment, the composition according to the present invention does not contain polyglyceryl fatty acid esters containing 5 or more glycerol units, such as PG5 laurate. The term "free" used here means that the composition according to the present invention may contain limited amounts of polyglyceryl fatty acid esters containing 5 or more glycerol units. However, it is preferred that the amount of polyglyceryl fatty acid esters containing 5 or more glycerol units be limited to less than 1% by weight, more preferably less than 0.1% by weight, and even more preferably less than 0.01% by weight, relative to the total weight of the composition. Most preferably, the composition according to the present invention does not contain polyglyceryl fatty acid esters containing 5 or more glycerol units.

In another embodiment, the composition according to the present invention does not contain a polyoxyethylene-based nonionic surfactant. The term "free" here means that the composition according to the present invention may contain a limited amount of a polyoxyethylene-based nonionic surfactant. However, it is preferred that the amount of polyoxyethylene-based nonionic surfactant is limited to less than 1% by weight, more preferably less than 0.1% by weight, and even more preferably less than 0.01% by weight, relative to the total weight of the composition. Most preferably, the composition according to the present invention does not contain a polyoxyethylene-based nonionic surfactant.

(preparation)
The composition according to the present invention can be prepared by mixing the essential ingredients described above and, if necessary, the optional ingredients described above.

The method and means for mixing the above essential and optional ingredients are not limited. Any conventional method and means can be used to mix the above essential and optional ingredients to prepare a composition according to the present invention.

The composition according to the present invention can be prepared without using a large amount of energy, such as that required by a homogenizer. Therefore, the composition according to the present invention can be prepared by using a small amount of energy, such as by gently stirring the components of the composition together. Therefore, the composition according to the present invention is environmentally friendly when considering its preparation method.

[form]
The composition according to the present invention comprises a continuous phase and a dispersed phase. The dispersed phase is dispersed in the continuous phase. The dispersed phase may therefore be in the form of particles.

The continuous phase can contain (f) water. The dispersed phase can contain at least (b) a first polyglyceryl fatty acid ester and (c) a second polyglyceryl fatty acid ester. When the composition contains (a) oil, the dispersed phase can also contain (a) oil. When the dispersed phase contains (a) oil, the dispersed phase can be recognized as oil droplets. When the dispersed phase does not contain (a) oil, the dispersed phase contains (b) a first polyglyceryl fatty acid ester and (c) a second polyglyceryl fatty acid ester, and the two polyglyceryl fatty acid esters can form micelles.

The size of the dispersed phase is 300 nm or less, preferably 200 nm or less, and more preferably 100 nm or less. The size can be measured as the average size based on volume. The size can be measured by dynamic light scattering, for example, using a dynamic light scattering particle size analyzer ELSZ-2000 (Otsuka Electronics Co., Ltd.). The minimum size of the dispersed phase is not limited, but may be 1 nm or more, 5 nm or more, or 10 nm or more.

The composition according to the present invention may be in the form of a nano- or microemulsion when the composition contains (a).

"Microemulsion" can be defined in two ways: broadly and narrowly. In other words, there is one case in which a microemulsion refers to a thermodynamically stable, isotropic single liquid phase containing a three-component system with an oil component, an aqueous component, and a surfactant ("microemulsion in the narrow sense"). There is also a second case in which a microemulsion includes emulsions that, among typical thermodynamically unstable emulsion systems, have a transparent or slightly translucent appearance due to smaller particle sizes ("microemulsion in the broad sense") (Satoshi Tomomasa et al., Oil Chemistry, Vol. 37, No. 11 (1988), pp. 48-53). As used herein, "microemulsion" refers to a "microemulsion in the narrow sense," i.e., a thermodynamically stable, isotropic single liquid phase.

Microemulsions refer to any one of the following types of microemulsions: O/W (oil-in-water) microemulsions, in which oil is solubilized by micelles; W/O (water-in-oil) microemulsions, in which water is solubilized by reverse micelles; or bicontinuous microemulsions, in which the number of surfactant molecule associations is infinite, resulting in both the aqueous and oily phases having a continuous structure.

Microemulsions may have a dispersed phase with a particle size of 100 nm or less, preferably 80 nm or less, and more preferably 60 nm or less, as measured by laser particle size analysis.

"Nanoemulsion" as used herein refers to an emulsion characterized by a dispersed phase having a size of less than 350 nm, which is stabilized at the dispersed/continuous phase interface by a crown of nonionic surfactants (b) and (c), which can optionally form a lamellar-type liquid crystal phase. In the absence of specific opacifiers, the transparency of nanoemulsions results from the small size of the dispersed phase, which can be achieved through the use of mechanical energy.

Nanoemulsions can be distinguished from microemulsions by their structure. Specifically, microemulsions are thermodynamically stable dispersions formed, for example, from micelles formed by components (b) and (c) and expanded by component (a). Furthermore, microemulsions do not require substantial mechanical energy to prepare.

The nanoemulsion may have a dispersed phase with a particle size of 300 nm or less, preferably 200 nm or less, and more preferably 100 nm or less, as measured by laser particle size analysis.

The composition according to the present invention is preferably in the form of an O/W emulsion, comprising an oil phase dispersed in a continuous aqueous phase. The dispersed oil phase can be oil droplets in the aqueous phase.

An O/W type composition or structure consists of an oil phase dispersed in an aqueous phase, and therefore has an aqueous phase on the outside. Therefore, when the composition according to the present invention has an O/W type composition or structure, it can provide a pleasant sensation when used due to the immediate fresh feeling that the aqueous phase can provide.

(a) The particle size of the oil may be 100 nm or less, preferably 75 nm or less, and more preferably 50 nm or less. The particle size can be measured by dynamic light scattering. The particle size measurement can be performed, for example, using a particle size analyzer, ELSZ-2000 series, commercially available from Otsuka Electronics Co., Ltd.

The particle size may be the volume average particle diameter or the number average particle diameter, preferably the volume average particle diameter.

Compositions according to the present invention may be transparent or slightly translucent.

Clarity can be measured by measuring turbidity (for example, turbidity can be measured using a 2100Q (commercially available from Hach Company) with a round cell (25 mm diameter and 60 mm height) and a tungsten filament bulb capable of emitting visible light (between 400 and 800 nm, preferably 400-500 nm). Measurements can be performed on the undiluted composition. A blank can be determined using distilled water.

The composition according to the present invention may have a turbidity of 50 NTU or less, preferably 30 NTU or less, and more preferably 10 NTU or less.

[Method and Use]
The composition according to the invention is preferably a cosmetic or dermatological composition, preferably a cosmetic composition, more preferably a cosmetic composition for keratinous materials such as the skin.

The compositions according to the present invention can be used in non-therapeutic methods, such as cosmetic methods, for treating keratinous materials such as skin, hair, mucous membranes, nails, eyelashes, eyebrows and/or scalp by applying them to the keratinous material.

The present invention therefore also relates to a cosmetic method for treating keratinous materials, comprising the step of applying a composition according to the present invention to the keratinous materials.

The present invention may also relate to the use of the composition according to the invention as or in cosmetics, such as care products, cleansing products, makeup products, makeup removal products, etc. for the skin of the body and/or face, and/or mucous membranes, and/or scalp, and/or hair, and/or nails, and/or eyelashes, and/or eyebrows.

In other words, the composition according to the present invention can be used as a cosmetic by itself. Alternatively, the composition according to the present invention can be used as one component of a cosmetic. For example, the composition according to the present invention can be used in addition to or in combination with any other components to form a cosmetic.

Care products can be lotions, creams, hair tonics, hair conditioners, sunscreens, etc. Cleansing products can be shampoos, face washes, hand washes, etc. Makeup products can be foundations, mascaras, lipsticks, lip glosses, blushers, eye shadows, nail polishes, etc. Makeup removal products can be makeup cleansers, etc.

Since the composition according to the present invention contains at least one hyaluronic acid or a salt thereof, the composition according to the present invention can preferably be used to moisturize keratinous materials such as skin.

Another aspect of the present invention is a method for producing a semiconductor device comprising:
For the preparation of a composition comprising a continuous phase and a dispersed phase having a size of 300 nm or less, preferably 200 nm or less, more preferably 100 nm or less,
(e) the use of at least one polyol having 5 or more carbon atoms,
the total amount of (b) the first polyglyceryl fatty acid ester and (c) the second polyglyceryl fatty acid ester is 0.01% by mass to 5% by mass, based on the total amount of the composition;
the mass ratio of (a) the amount of oil to (the total amount of (b) the first polyglyceryl fatty acid ester and (c) the second polyglyceryl fatty acid ester) is less than 0.3;
the mass ratio of ((c) the amount of the second polyglyceryl fatty acid ester)/((b) the amount of the first polyglyceryl fatty acid ester) is greater than 0.01 and less than 0.2;
provided that the mass ratio of (e) the amount of polyol)/(the total amount of (b) the first polyglyceryl fatty acid ester and (c) the second polyglyceryl fatty acid ester) is greater than 0.1 and less than 5;
The composition comprises:
(a) at least one optional oil;
(b) at least one first polyglyceryl fatty acid ester having an HLB value greater than 11.0, preferably greater than 12.0, and more preferably greater than 13.0;
(c) at least one second polyglyceryl fatty acid ester having an HLB value of less than 11.0, preferably less than 10.0, and more preferably less than 9.0;
(d) at least one hyaluronic acid component selected from the group consisting of hyaluronic acid, hyaluronic acid salts, hyaluronic acid derivatives, hyaluronic acid derivative salts, and mixtures thereof; and
(f) May be used in conjunction with water.

Another aspect of the present invention also provides a method for preparing a composition comprising a continuous phase and a dispersed phase having a size of 300 nm or less, preferably 200 nm or less, more preferably 100 nm or less, comprising the steps of:
the total amount of (b) the first polyglyceryl fatty acid ester and (c) the second polyglyceryl fatty acid ester is 0.01% by mass to 5% by mass, based on the total amount of the composition;
the mass ratio of (a) the amount of oil to (the total amount of (b) the first polyglyceryl fatty acid ester and (c) the second polyglyceryl fatty acid ester) is less than 0.3;
the mass ratio of ((c) the amount of the second polyglyceryl fatty acid ester)/((b) the amount of the first polyglyceryl fatty acid ester) is greater than 0.01 and less than 0.2;
provided that the mass ratio of (e) the amount of polyol)/(the total amount of (b) the first polyglyceryl fatty acid ester and (c) the second polyglyceryl fatty acid ester) is greater than 0.1 and less than 5;
(a) at least one optional oil;
(b) at least one first polyglyceryl fatty acid ester having an HLB value greater than 11.0, preferably greater than 12.0, and more preferably greater than 13.0;
(c) at least one second polyglyceryl fatty acid ester having an HLB value of less than 11.0, preferably less than 10.0, and more preferably less than 9.0;
(d) at least one hyaluronic acid component selected from the group consisting of hyaluronic acid, hyaluronic acid salts, hyaluronic acid derivatives, hyaluronic acid derivative salts, and mixtures thereof;
(e) at least one polyol having 5 or more carbon atoms, and
(f) mixing with water.

The mixing step is preferably carried out by a so-called low-energy process, which does not use special mechanical agitators such as homogenizers that use a large amount of energy. The low-energy process can be carried out by simply gently stirring components (a) to (f).

When the composition in the use and method according to the present invention contains (a) oil, it is preferably in the form of an O/W nano- or micro-emulsion.

The present invention also provides
(e) the use of at least one polyol having 5 or more carbon atoms,
the total amount of (b) the first polyglyceryl fatty acid ester and (c) the second polyglyceryl fatty acid ester is 0.01% by mass to 5% by mass, based on the total amount of the composition;
the mass ratio of (a) the amount of oil to (the total amount of (b) the first polyglyceryl fatty acid ester and (c) the second polyglyceryl fatty acid ester) is less than 0.3;
the mass ratio of ((c) the amount of the second polyglyceryl fatty acid ester)/((b) the amount of the first polyglyceryl fatty acid ester) is greater than 0.01 and less than 0.2;
provided that the mass ratio of (e) the amount of polyol)/(the total amount of (b) the first polyglyceryl fatty acid ester and (c) the second polyglyceryl fatty acid ester) is greater than 0.1 and less than 5;
(a) at least one oil;
(b) at least one first polyglyceryl fatty acid ester having an HLB value greater than 11.0, preferably greater than 12.0, and more preferably greater than 13.0;
(c) at least one second polyglyceryl fatty acid ester having an HLB value of less than 11.0, preferably less than 10.0, and more preferably less than 9.0;
(d) at least one hyaluronic acid component selected from the group consisting of hyaluronic acid, hyaluronic acid salts, hyaluronic acid derivatives, hyaluronic acid derivative salts, and mixtures thereof; and
(f) In an O/W emulsion containing water,
(a) to make the oil droplets have a particle size of 300 nm or less, preferably 200 nm or less, and more preferably 100 nm or less;
It may also relate to use.

The present invention also provides
(a) at least one oil;
(b) at least one first polyglyceryl fatty acid ester having an HLB value greater than 11.0, preferably greater than 12.0, and more preferably greater than 13.0;
(c) at least one second polyglyceryl fatty acid ester having an HLB value of less than 11.0, preferably less than 10.0, and more preferably less than 9.0;
(d) at least one hyaluronic acid component selected from the group consisting of hyaluronic acid, hyaluronic acid salts, hyaluronic acid derivatives, hyaluronic acid derivative salts, and mixtures thereof; and
(f) A method for making oil droplets in an O/W nano- or micro-emulsion containing water have a particle size of 300 nm or less, preferably 200 nm or less, more preferably 100 nm or less, comprising:
(e) at least one polyol having 5 or more carbon atoms;
The present invention also relates to a method comprising adding the composition to an O/W nano- or micro-emulsion or using the composition in an O/W nano- or micro-emulsion.

The above descriptions of components (a) to (f) and optional components of the compositions according to the present invention are applicable to the components of the uses and methods according to the present invention. The descriptions of the preparation and forms of the compositions according to the present invention are also applicable to the preparation and forms of the compositions described in the uses and methods above.

The present invention will now be described in more detail by way of examples, which should not be construed as limiting the scope of the present invention.

(Example 1 and Comparative Examples 1 to 3)
The following compositions shown in Table 1 according to Example 1 and Comparative Examples 1 to 3 were prepared by mixing the components shown in Table 1. All numerical values for the amounts of components shown in Table 1 are based on "mass %" of the raw materials.

The compositions of Example 1 and Comparative Examples 1 to 3 were in the form of O/W emulsions.

[evaluation]
(Turbidity)
The turbidity of the compositions according to Example 1 and Comparative Example 2 was measured at room temperature by using a turbidity meter (2100Q portable, Hach Company).

The results are shown in Table 1 as "NTU." The lower the NTU value, the more transparent the composition.

The composition of Example 1 was transparent or slightly translucent.

The turbidity of the compositions of Comparative Examples 1 and 3 was not measured because the compositions were clearly opaque (not transparent or slightly translucent).

(Droplet diameter)
The size of the dispersed phase in the compositions of Example 1 and Comparative Example 2 was measured using a dynamic light scattering particle size analyzer ELSZ-2000 (Otsuka Electronics Co., Ltd.).

The size of the dispersed phase in the compositions of Comparative Examples 1 and 3 was not measured because the compositions were clearly opaque.

Example 1 demonstrates that the use of a polyol having 5 or more carbon atoms can provide a clear composition, even when the composition contains hyaluronic acid or a salt thereof.

Comparative Example 1 shows that the use of a polyol having less than 5 carbon atoms does not provide a clear composition when the composition contains hyaluronic acid or a salt thereof.

Comparative Example 2 corresponds to the formulation according to Example 1 disclosed in WO 2020/110716.

Comparative Example 3 shows that adding hyaluronic acid or a salt thereof to the formulation according to Example 1 disclosed in WO 2020/110716 does not provide a transparent composition.

(Examples 2 to 5 and Comparative Example 4)
The following compositions shown in Table 2 according to Examples 2 to 5 and Comparative Example 4 were prepared by mixing the components shown in Table 2. All numerical values for the amounts of components shown in Table 2 are based on "mass %" of the raw materials.

The compositions of Examples 2 to 5 and Comparative Example 4 were in the form of O/W emulsions.

[evaluation]
(Turbidity)
The turbidity of the compositions according to Examples 2 to 5 was measured at room temperature by using a turbidity meter (2100Q portable, Hach Company).

The results are shown in Table 2 as "NTU." The lower the NTU value, the more transparent the composition.

The compositions of Examples 2 to 5 were transparent or slightly translucent.

The NTU value of the composition of Comparative Example 4 was not tested because the composition was opaque.

(Droplet diameter)
The size of the dispersed phase in the compositions of Examples 2 to 5 and Comparative Example 4 was measured using a dynamic light scattering particle size analyzer ELSZ-2000 (Otsuka Electronics Co., Ltd.).

The results are shown in Table 2.

The droplet size of the dispersed phase in the composition of Comparative Example 4 was not tested because the composition was opaque.

Examples 2 to 5 show that the total amount of the first polyglyceryl fatty acid ester having an HLB value greater than 11.0 and the second polyglyceryl fatty acid ester having an HLB value less than 11.0 in the composition should be 0.01% to 5% by weight, based on the total weight of the composition.

Comparative Example 4 shows that when the total amount of the first and second polyglyceryl fatty acid esters in the composition exceeds 5% by mass relative to the total mass of the composition, the composition cannot be made transparent or slightly translucent.

(Examples 6 to 7 and Comparative Example 5)
The following compositions shown in Table 3 according to Examples 6-7 and Comparative Example 5 were prepared by mixing the components shown in Table 3. All numerical values for the amounts of components shown in Table 3 are based on "mass %" of the raw materials.

The composition of Example 6 was a composition containing micelles formed by PG-4 caprate and PG-2 oleate.

The compositions of Example 7 and Comparative Example 5 were in the form of O/W emulsions.

[evaluation]
(Turbidity)
The turbidity of the compositions according to Examples 6-7 was measured at room temperature by using a turbidity meter (2100Q portable, Hach Company).

The results are shown in Table 3 as "NTU." The lower the NTU value, the more transparent the composition.

The compositions of Examples 6 and 7 were transparent or slightly translucent.

The NTU value of the composition of Comparative Example 5 was not tested because the composition was opaque.

(Droplet diameter)
The size of the dispersed phase in the compositions according to Examples 6 and 7 was measured using a dynamic light scattering particle size analyzer ELSZ-2000 (Otsuka Electronics Co., Ltd.).

The results are shown in Table 3.

The droplet size of the composition in Example 6 refers to the average size of the oil-free micelles in the composition.

The droplet size of the composition according to Example 7 refers to the average size of the oil droplets, which can be thought of as micelles containing the oil, in the composition.

The droplet size of the dispersed phase in the composition of Comparative Example 5 was not tested because the composition was opaque.

Examples 6 and 7 show that the mass ratio of (amount of oil) to (total amount of first polyglyceryl fatty acid ester having an HLB value greater than 11.0 and second polyglyceryl fatty acid ester having an HLB value less than 11.0) in the composition should be less than 0.3.

Comparative Example 5 shows that when the mass ratio of (amount of oil)/(total amount of first polyglyceryl fatty acid ester having an HLB value greater than 11.0 and second polyglyceryl fatty acid ester having an HLB value less than 11.0) in the composition is 0.3 or greater, the composition cannot be made transparent or slightly translucent.

(Examples 8 to 9 and Comparative Examples 6 to 7)
The following compositions shown in Table 4 according to Examples 8-9 and Comparative Examples 6-7 were prepared by mixing the components shown in Table 4. All numerical values for the amounts of components shown in Table 4 are based on "mass %" of the raw materials.

The compositions of Examples 8-9 and Comparative Examples 6-7 were in the form of O/W emulsions.

[evaluation]
(Turbidity)
The turbidity of the compositions according to Examples 8-9 was measured at room temperature by using a turbidity meter (2100Q portable, Hach Company).

The results are shown in Table 4 as "NTU." The lower the NTU value, the more transparent the composition.

The compositions of Examples 8 and 9 were transparent or slightly translucent.

The NTU values of the compositions of Comparative Examples 6 and 7 were not tested because the compositions were opaque.

(Droplet diameter)
The size of the dispersed phase in the compositions according to Examples 8 and 9 was measured using a dynamic light scattering particle size analyzer ELSZ-2000 (Otsuka Electronics Co., Ltd.).

The results are shown in Table 4.

The droplet size of the dispersed phase in the compositions of Comparative Examples 6 and 7 was not tested because the compositions were opaque.

Examples 8 and 9 demonstrate that the mass ratio of (amount of second polyglyceryl fatty acid ester having an HLB value less than 11.0) to (amount of first polyglyceryl fatty acid ester having an HLB value greater than 11.0) in the composition should be greater than 0.01 and less than 0.2.

Comparative Examples 6 and 7 show that when the mass ratio of (amount of second polyglyceryl fatty acid ester having an HLB value less than 11.0)/(amount of first polyglyceryl fatty acid ester having an HLB value greater than 11.0) in the composition is 0.01 or less or 0.2 or more, the composition cannot be made transparent or slightly translucent.

(Examples 10-11 and Comparative Examples 8-9)
The following compositions shown in Table 5 according to Examples 10-11 and Comparative Examples 8-9 were prepared by mixing the components shown in Table 5. All numerical values for the amounts of components shown in Table 5 are based on "mass %" of the raw materials.

The compositions of Examples 10-11 and Comparative Examples 8-9 were in the form of O/W emulsions.

[evaluation]
(Turbidity)
The turbidity of the compositions according to Examples 10-11 was measured at room temperature by using a turbidity meter (2100Q portable, Hach Company).

The results are shown in Table 5 as "NTU." The lower the NTU value, the more transparent the composition.

The compositions of Examples 10 and 11 were transparent or slightly translucent.

The NTU values of the compositions of Comparative Examples 8 and 9 were not tested because the compositions were opaque.

(Droplet diameter)
The size of the dispersed phase in the compositions according to Examples 10 and 11 was measured using a dynamic light scattering particle size analyzer ELSZ-2000 (Otsuka Electronics Co., Ltd.).

The results are shown in Table 5.

The droplet size of the dispersed phase in the compositions of Comparative Examples 8 and 9 was not tested because the compositions were opaque.

Examples 10 and 11 show that the mass ratio of (amount of polyol having 5 or more carbon atoms) to (total amount of first polyglyceryl fatty acid ester having an HLB value greater than 11.0 and second polyglyceryl fatty acid ester having an HLB value less than 11.0) in the composition should be greater than 0.1 and less than 5.

Comparative Examples 8 and 9 show that when the mass ratio of (amount of polyol having 5 or more carbon atoms)/(total amount of first polyglyceryl fatty acid ester having an HLB value greater than 11.0 and second polyglyceryl fatty acid ester having an HLB value less than 11.0) in the composition is 0.1 or less or 5 or more, the composition cannot be made transparent or slightly translucent.

Examples 12 to 15
The following compositions shown in Table 6 according to Examples 12-15 were prepared by mixing the ingredients shown in Table 6. All numerical values for the amounts of ingredients shown in Table 6 are based on "% by weight" of the ingredients.

The compositions of Examples 12 to 15 were in the form of O/W emulsions.

[evaluation]
(Turbidity)
The turbidity of the compositions according to Examples 12-15 was measured at room temperature by using a turbidity meter (2100Q portable, Hach Company).

The results are shown in Table 6 as "NTU." The lower the NTU value, the more transparent the composition.

The compositions of Examples 12 to 14 were transparent or slightly translucent.

(Droplet diameter)
The size of the dispersed phase in the compositions according to Examples 12 to 15 was measured using a dynamic light scattering particle size analyzer ELSZ-2000 (Otsuka Electronics Co., Ltd.).

The results are shown in Table 6.

Examples 12 to 15 demonstrate that compositions according to the present invention can be made transparent or slightly translucent even when they contain various amounts of hyaluronic acid or its salts, regardless of the molecular weight of the hyaluronic acid.

(Examples 16 to 18 and Comparative Example 10)
The following compositions shown in Table 7 according to Examples 16-18 and Comparative Example 10 were prepared by mixing the components shown in Table 7. All numerical values for the amounts of components shown in Table 7 are based on "mass %" of the raw materials.

The compositions of Examples 16 to 18 and Comparative Example 10 were in the form of O/W emulsions.

[evaluation]
(Turbidity)
The turbidity of the compositions according to Examples 16-18 was measured at room temperature by using a turbidity meter (2100Q portable, Hach Company).

The results are shown in Table 7 as "NTU." The lower the NTU value, the more transparent the composition.

The compositions of Examples 16 to 18 were transparent or slightly translucent.

The NTU value of the composition of Comparative Example 10 was not tested because the composition was opaque.

(Droplet diameter)
The size of the dispersed phase in the compositions according to Examples 16 to 18 was measured using a dynamic light scattering particle size analyzer ELSZ-2000 (Otsuka Electronics Co., Ltd.).

The results are shown in Table 7.

The droplet size of the dispersed phase in the composition of Comparative Example 10 was not tested because the composition was opaque.

Example 16 shows that the type of polyglyceryl fatty acid ester is not limited.

Example 17 shows that the type of polyol having 5 or more carbon atoms is not limited.

Example 18 shows that the type of oil is not limited.

Comparative Example 10 shows that when a polyol having less than 5 carbon atoms is used in the composition, the composition cannot be made transparent or slightly translucent.

Examples 19 to 25
The following compositions shown in Table 8 according to Examples 19-25 were prepared by mixing the ingredients shown in Table 8. All numerical values for the amounts of ingredients shown in Table 8 are based on "% by weight" of the ingredients.

The compositions of Examples 19 to 25 were in the form of O/W emulsions.

[evaluation]
(Turbidity)
The turbidity of the compositions according to Examples 19-25 was measured at room temperature by using a turbidity meter (2100Q portable, Hach Company).

The results are shown in Table 8 as "NTU." The lower the NTU value, the more transparent the composition.

The compositions of Examples 19 to 25 were transparent or slightly translucent.

(Droplet diameter)
The size of the dispersed phase in the compositions according to Examples 19 to 25 was measured using a dynamic light scattering particle size analyzer ELSZ-2000 (Otsuka Electronics Co., Ltd.).

The results are shown in Table 8.

Examples 19 to 25 demonstrate that the type of hyaluronic acid or its salt is not limited.

Claims (15)

(a) at least one optional oil;
(b) at least one first polyglyceryl fatty acid ester having an HLB value greater than 11.0;
(c) at least one second polyglyceryl fatty acid ester having an HLB value of less than 11.0;
(d) at least one hyaluronic acid component selected from the group consisting of hyaluronic acid, hyaluronic acid salts, hyaluronic acid derivatives, hyaluronic acid derivative salts, and mixtures thereof;
(e) at least one polyol having 5 or more carbon atoms, and
(f) a composition comprising water,
the total amount of (b) the first polyglyceryl fatty acid ester and (c) the second polyglyceryl fatty acid ester is 0.01% by mass to 5% by mass, based on the total amount of the composition;
the mass ratio of (a) the amount of oil to (the total amount of (b) the first polyglyceryl fatty acid ester and (c) the second polyglyceryl fatty acid ester) is less than 0.3;
the mass ratio of ((c) the amount of the second polyglyceryl fatty acid ester)/((b) the amount of the first polyglyceryl fatty acid ester) is greater than 0.01 and less than 0.2;
the mass ratio of (e) the amount of polyol having 5 or more carbon atoms to (the total amount of (b) the first polyglyceryl fatty acid ester and (c) the second polyglyceryl fatty acid ester) is greater than 0.1 and less than 5;
The composition comprises a continuous phase and a dispersed phase, the dispersed phase having a size of 300 nm or less.
composition. The composition of claim 1, wherein (a) the oil is selected from polar oils. 3. The composition according to claim 1, wherein the amount of (a) oil in the composition is less than 0.7% by weight, based on the total weight of the composition. 4. The composition of claim 1, wherein the first polyglyceryl fatty acid ester comprises from 2 to 4 glycerol units. 5. The composition of claim 1, wherein the fatty acid moiety of the first polyglyceryl fatty acid ester comprises 12 or fewer carbon atoms. The composition according to any one of claims 1 to 5, wherein the amount of (b) the first polyglyceryl fatty acid ester in the composition is 0.01% by weight to 5% by weight, relative to the total weight of the composition. 7. The composition of claim 1, wherein (c) the second polyglyceryl fatty acid ester comprises 2 to 4 glycerol units. 8. The composition of claim 1, wherein the fatty acid portion of the second polyglyceryl fatty acid ester comprises 14 or more carbon atoms. The composition according to any one of claims 1 to 8, wherein the amount of (c) the second polyglyceryl fatty acid ester in the composition is 0.001% by weight to 0.5% by weight, relative to the total weight of the composition. (d) The composition according to any one of claims 1 to 9, wherein the hyaluronic acid component is selected from hyaluronic acid, hydrolyzed hyaluronic acid, acetylated hyaluronic acid, cationic hyaluronic acid, salts thereof, and mixtures thereof. The composition according to any one of claims 1 to 10, wherein the amount of the (d) hyaluronic acid component in the composition is 0.001% by weight to 5% by weight, relative to the total weight of the composition. 12. The composition of claim 1, wherein (e) the polyol having 5 or more carbon atoms is selected from a diol having 5 or more carbon atoms. 13. The composition according to any one of claims 1 to 12, wherein the amount of (e) polyol having 5 or more carbon atoms in the composition is in the range of 0.01% by weight to 7% by weight, relative to the total weight of the composition. The composition according to any one of claims 1 to 13, comprising (a) an oil and in the form of an O/W emulsion. A cosmetic method for treating keratinous materials, comprising the step of applying a composition described in any one of claims 1 to 14 to the keratinous materials.