JP7693283B2 - Skin preparations - Google Patents

Description

The present invention relates to a skin preparation for external use that is used as a cosmetic, quasi-drug, or pharmaceutical.

Hyaluronic acid is a mucopolysaccharide composed of glucuronic acid and N-acetylglucosamine, and exists in large quantities in the dermis as a bonding substance between cells and fibers in the body, and is also present in the epidermis. Hyaluronic acid has high water retention and viscoelasticity, so it is widely used in topical skin preparations as a moisturizer.

When hyaluronic acid is blended into a skin topical preparation, a unique feel in use, such as cushioning or thickness, can be obtained due to the viscosity and viscoelasticity unique to hyaluronic acid. Furthermore, by applying such a preparation to the skin, a bouncy, cushioning or thick feel on the skin can be obtained, as if the skin is sticking to the hand. This feel in use, such as cushioning or thickness, is a unique feel that is popular with consumers. On the other hand, since hyaluronic acid is a component with strong spinnability, blending it gives a unique sticky, tacky feel. In order to improve the cushioning of the skin during and after application, it is necessary to blend hyaluronic acid at a high concentration, but the more hyaluronic acid is blended, the more stickiness occurs. Therefore, it is difficult to achieve both cushioning and a smooth feel in use.

Patent Document 1 teaches that acetylated hyaluronic acid has excellent skin softening properties while improving the shortcomings of hyaluronic acid, such as its high spinnability.

Patent No. 3557044

The present invention aims to provide an external preparation for the skin that contains hyaluronic acid or a salt thereof, has high cushioning properties, and is less sticky.

The present inventors conducted extensive research to solve the above problems, and discovered that by blending a combination of high molecular weight hyaluronic acid or a salt thereof having a weight-average molecular weight of 50,000 or more and low molecular weight hyaluronic acid or a salt thereof having a weight-average molecular weight of less than 50,000 as hyaluronic acids in a non-emulsified topical skin preparation containing water, an oil content of 0 to 10% by mass, and substantially no paraben, and blending a hyaluronic acid derivative therein, it is possible to reduce the amount of hyaluronic acids that cause stickiness, while enhancing the thickness or cushioning feeling felt upon application and the soft, cushioning feel on the skin after application, thereby achieving both high cushioning properties and a smooth feel on use.
It was also found that the decrease in viscosity over time can be suppressed by blending an alkanediol having 5 to 10 carbon atoms in this topical skin preparation, thereby suppressing the decrease in the cushioning properties or thick feel when used of the preparation as well as the decrease in the thickness of the preparation itself.

The present invention has been completed based on the above findings, and provides the following external skin preparation.
[1] A non-emulsified external skin preparation comprising: (A) a polymeric hyaluronic acid or a salt thereof having a weight-average molecular weight of 50,000 or more; (B) a low-molecular-weight hyaluronic acid or a salt thereof having a weight-average molecular weight of less than 50,000; (C) a hyaluronic acid derivative; and (D) water; (E) an oil content of 0 to 10% by mass; and (F) substantially no paraben.
[2] The topical skin preparation according to [1], wherein the content of (A) polymeric hyaluronic acid or a salt thereof having a weight-average molecular weight of 50,000 or more is 0.001 to 1% by mass based on the total amount of the topical skin preparation.
[3] (B) The content of low-molecular-weight hyaluronic acid or a salt thereof having a weight-average molecular weight of less than 50,000 is 0.0001 to 1% by mass based on the total amount of the topical skin preparation according to [1] or [2].
[4] The topical skin preparation according to any one of [1] to [3], wherein the content of the hyaluronic acid derivative (C) is 0.00001 to 0.3 mass% based on the total amount of the topical skin preparation.
[5] The skin external preparation according to any one of [1] to [4], containing 0.005 to 200,000 parts by mass of the total of (A) high molecular weight hyaluronic acid or a salt thereof having a weight-average molecular weight of 50,000 or more and (B) low molecular weight hyaluronic acid or a salt thereof having a weight-average molecular weight of less than 50,000, per part by mass of the hyaluronic acid derivative (C).
[6] The external skin preparation according to any one of [1] to [5], further comprising an alkanediol having 5 to 10 carbon atoms.
[7] The topical skin preparation according to [6], wherein the content of the alkanediol having 5 to 10 carbon atoms is 0.0001 to 20 mass % based on the total amount of the topical skin preparation.
[8] The external skin preparation according to any one of [1] to [7], which has an L value of 40 or more in the Lab color system.
[9] A method for improving the cushioning or bouncy feel of the preparation (at the time of application) and/or the skin feel after application while suppressing stickiness of a non-emulsified topical skin preparation, comprising (A) a high molecular weight hyaluronic acid or a salt thereof having a weight-average molecular weight of 50,000 or more, (B) a low molecular weight hyaluronic acid or a salt thereof having a weight-average molecular weight of less than 50,000, and (D) water, (E) an oil content of 0 to 10% by mass, and (F) substantially no paraben, by incorporating (C) a hyaluronic acid derivative into the non-emulsified topical skin preparation (wherein, however, that (E) oil content of 0 to 10% by mass is the content after incorporating (C) the hyaluronic acid derivative).

The topical skin preparation of the present invention is a non-emulsified topical skin preparation that contains water, has an oil content of 0 to 10% by mass, and is substantially free of parabens, and is formulated with a combination of three specific types of hyaluronic acids, thereby effectively enhancing the cushioning or thickness of hyaluronic acid or its salts. Therefore, the amount of hyaluronic acids that cause stickiness can be reduced, and the topical skin preparation of the present invention combines high cushioning and a smooth feel when used. In this way, the topical skin preparation of the present invention has high commercial value because it not only provides the feel of the preparation when used, such as cushioning or thickness when applied, but also provides a unique, bouncy, cushiony or thick feel to the skin that clings to the hands after application, and is less sticky.

The present invention will be described in detail below.
The topical skin preparation of the present invention is a non-emulsified topical skin preparation that contains (A) high molecular weight hyaluronic acid or a salt thereof having a weight-average molecular weight of 50,000 or more, (B) low molecular weight hyaluronic acid or a salt thereof having a weight-average molecular weight of less than 50,000, (C) a hyaluronic acid derivative, and (D) water, (E) an oil content of 0 to 10 mass%, and (F) substantially no paraben.
In the present invention, hyaluronic acid or its salt having a weight-average molecular weight of 50,000 or more is referred to as "high molecular weight hyaluronic acid or its salt," and hyaluronic acid or its salt having a weight-average molecular weight of less than 50,000 is referred to as "low molecular weight hyaluronic acid or its salt."

(A) High molecular weight hyaluronic acid or its salt Hyaluronic acid is a kind of acidic mucopolysaccharide, and is a polysaccharide that contains disaccharide of glucuronic acid and N-acetylglucosamine as a structural unit. Hyaluronic acid can be extracted and collected from animal tissues such as cockscomb, shark skin, umbilical cord, eyeball, skin, cartilage, etc., and from the culture of hyaluronic acid-producing microorganisms such as Streptococcus genus microorganisms, animal cells, and plant cells. It can also be purchased as a commercial product.
As the polymeric hyaluronic acid having a weight-average molecular weight of 50,000 or more, such natural hyaluronic acid can be used. The weight-average molecular weight of natural hyaluronic acid is about 500,000 to 7,000,000.

Decomposed hyaluronic acid obtained by decomposing natural hyaluronic acid can also be used as long as it has a weight-average molecular weight of 50,000 or more. Decomposed hyaluronic acid can be prepared, for example, by hydrolysis in the presence of acid or alkali, enzyme treatment with hyaluronidase or the like, physical cutting such as ultrasonic waves or shearing, or fermentation by microorganisms. Commercially available products can also be used.

In the present invention, the weight-average molecular weight of the polymeric hyaluronic acid or its salt is 50,000 or more, preferably 100,000 or more, more preferably 200,000 or more, even more preferably 300,000 or more, and even more preferably 500,000 or more. The weight-average molecular weight of the polymeric hyaluronic acid or its salt can be, for example, 7 million or less, preferably 6 million or less, more preferably 4 million or less, even more preferably 3 million or less, and even more preferably 2 million or less. If it is within this range, the effect of the present invention can be achieved by combining it with a low-molecular-weight hyaluronic acid or its salt and a hyaluronic acid derivative having a weight-average molecular weight of less than 50,000.

Commercially available products of high molecular weight hyaluronic acid include sodium hyaluronate HA12N (product name) (Shiseido Co., Ltd.; weight average molecular weight 1.1 to 1.6 million), hyaluronic acid FCH-150 (product name) (Kikkoman Biochemifa Corporation; weight average molecular weight 1.4 to 1.8 million), bio sodium hyaluronate SZE (product name) (Shiseido Co., Ltd.; weight average molecular weight 1.1 to 1.6 million), and hyaluronic acid FCH-120 (product name) (Kikkoman Biochemifa Corporation; weight average molecular weight 100 to 1.4 million), Hyaluronic Acid HA-LQ (trade name) (Kewpie Corporation; weight average molecular weight 850,000 to 1.6 million), Hyaluronic Acid FCH-80 (trade name) (Kikkoman Biochemifa Corporation; weight average molecular weight 600,000 to 1 million), Hyaluronic Acid FCH-60 (trade name) (Kikkoman Biochemifa Corporation; weight average molecular weight 500,000 to 700,000), Hyaluronic Acid FCH-SU (trade name) (Kikkoman Biochemifa Corporation; weight average molecular weight 500,000 to 110,000), etc. can be mentioned.

The salt of polymeric hyaluronic acid may be any salt that is pharmacologically or physiologically acceptable, and examples thereof include salts with alkali metals such as sodium and potassium; salts with alkaline earth metals such as calcium and magnesium; salts with metals such as zinc and aluminum; ammonium salts; basic amino acid salts; and amine salts such as triethanolamine. Among these, alkali metal salts and metal salts are preferred, with sodium salts, potassium salts, and zinc salts being particularly preferred. In addition, when it comes to polymeric hyaluronic acid, it is preferred to use hyaluronic acid in a salt state, as this is more stable than hyaluronic acid.

One or more types of polymeric hyaluronic acid or its salt can be used.

The content of polymeric hyaluronic acid or its salt is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.01% by mass or more, and even more preferably 0.02% by mass or more, based on the total amount of skin external preparation.The content of polymeric hyaluronic acid or its salt is preferably 1% by mass or less, more preferably 0.8% by mass or less, even more preferably 0.6% by mass or less, and even more preferably 0.3% by mass or less, based on the total amount of skin external preparation.Within this range, sufficient cushioning or thickness can be obtained in the preparation (when applied) and in the skin feeling after application.
When multiple types of polymeric hyaluronic acid or salts thereof are contained, the content of polymeric hyaluronic acid or salts thereof refers to the total content thereof.

(B) Low molecular weight hyaluronic acid or its salt As the low molecular weight hyaluronic acid with weight-average molecular weight less than 50,000, the decomposition product of high molecular weight hyaluronic acid can be used.Low molecular weight hyaluronic acid can be obtained by hydrolyzing high molecular weight hyaluronic acid in the presence of acid such as hydrochloric acid or alkali, treating with enzyme such as hyaluronidase, physically cutting by ultrasonic wave or shearing, fermenting by microorganism, etc.
When hyaluronic acid oligosaccharides and/or salts thereof are used as low molecular weight hyaluronic acid, hyaluronic acid oligosaccharides having 2 to 16 sugars are preferable, and either saturated or unsaturated hyaluronic acid may be used. For example, unsaturated hyaluronic acid in which a double bond is formed between the 4-position and the 5-position of some or all of the D-glucuronic acids is included.

In the present invention, the weight-average molecular weight of the low molecular weight hyaluronic acid or its salt is less than 50,000, preferably 40,000 or less, more preferably 30,000 or less, and even more preferably 20,000 or less. The weight-average molecular weight of the low molecular weight hyaluronic acid or its salt is preferably 100 or more, more preferably 200 or more, and even more preferably 500 or more. Within this range, the effects of the present invention can be achieved by combining with high molecular weight hyaluronic acid or its salt and hyaluronic acid derivatives having a weight-average molecular weight of 50,000 or more.

In the present invention, commercially available low molecular weight hyaluronic acid can be purchased and used. Commercially available low molecular weight hyaluronic acid products include Hyalo Oligo (trade name) (Kewpie Corporation; weight average molecular weight 10,000 or less), Hyaluronic Acid (SL) (trade name) (FAP Japan Co., Ltd.; weight average molecular weight 10,000 or less), Micro Hyaluronic Acid FCH (trade name) (Kikkoman Biochemifa Corporation; weight average molecular weight 5,000 or less), and HA Booster (trade name) (Kewpie Corporation; weight average molecular weight 2,000).

The salt of low molecular weight hyaluronic acid may be any salt that is pharmacologically or physiologically acceptable, and examples thereof include salts with alkali metals such as sodium and potassium; salts with alkaline earth metals such as calcium and magnesium; salts with metals such as zinc and aluminum; ammonium salts; basic amino acid salts; and amine salts such as triethanolamine. Among these, alkali metal salts and metal salts are preferred, sodium salts, potassium salts, and zinc salts are more preferred, and sodium salts are even more preferred.

One or more types of low molecular weight hyaluronic acid or its salt can be used.

The content of low molecular weight hyaluronic acid or its salt is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, even more preferably 0.001% by mass or more, and even more preferably 0.005% by mass or more, based on the total amount of skin external preparation.In addition, the content of low molecular weight hyaluronic acid or its salt is preferably 1% by mass or less, more preferably 0.8% by mass or less, even more preferably 0.5% by mass or less, and even more preferably 0.2% by mass or less, based on the total amount of skin external preparation.Within this range, sufficient cushioning or thickness can be obtained in the preparation (when applied) and in the skin touch after application.
When multiple types of low molecular weight hyaluronic acid or salts thereof are contained, the content of low molecular weight hyaluronic acid or salts thereof refers to the total content thereof.

The content of hyaluronic acid or its salt in the topical skin preparation of the present invention (the total content of high molecular weight hyaluronic acid or its salt and low molecular weight hyaluronic acid or its salt) is preferably 0.002% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.05% by mass or more, and even more preferably 0.07% by mass or more, based on the total amount of the topical skin preparation. The content of hyaluronic acid or its salt is preferably 2% by mass or less, more preferably 1.5% by mass or less, even more preferably 1% by mass or less, and even more preferably 0.4% by mass or less, based on the total amount of the topical skin preparation. Within this range, sufficient cushioning or thickness can be obtained in the preparation and in the skin feel after application.

Hyaluronic acid has spinnability, and generally when it is incorporated into a topical preparation at a high concentration, it becomes sticky. However, the topical preparation of the present invention combines (A) high molecular weight hyaluronic acid or its salt with (B) low molecular weight hyaluronic acid or its salt, and further incorporates (C) a hyaluronic acid derivative, thereby efficiently enhancing the cushioning or thickness of hyaluronic acid or its salt. This makes it possible to suppress stickiness caused by increased amounts of (A) high molecular weight hyaluronic acid or its salt and (B) low molecular weight hyaluronic acid or its salt.

The content ratio of high molecular weight hyaluronic acid or its salt to low molecular weight hyaluronic acid or its salt in the skin topical preparation of the present invention can be 0.0001 parts by mass or more, 0.001 parts by mass or more, 0.01 parts by mass or more, 0.1 parts by mass or more, or 0.3 parts by mass or more of low molecular weight hyaluronic acid or its salt per 1 part by mass of high molecular weight hyaluronic acid or its salt. It can also be 1000 parts by mass or less, 50 parts by mass or less, 10 parts by mass or less, or 5 parts by mass or less. Within this range, excellent cushioning or a feeling of thickness can be imparted to the topical preparation, and stickiness can be suppressed despite the inclusion of a high concentration of hyaluronic acid or its salt.

(C) Hyaluronic Acid Derivatives Examples of hyaluronic acid derivatives include acetylated hyaluronic acid, sulfated hyaluronic acid, hydrophobized hydrolyzed hyaluronic acid (hydrolyzed alkyl hyaluronate, hydrolyzed glyceryl hyaluronate, etc.), crosslinked hyaluronic acid, carboxymethyl hyaluronic acid, alkylene glycol hyaluronate, silanol hyaluronate, cationized hyaluronic acid, and salts thereof.
Of these, acetylated hyaluronic acid, hydroxypropyltrimonium hyaluronate, hydrolyzed alkyl hyaluronate (alkyl group having 12 to 13 carbon atoms) glyceryl, crosslinked hyaluronic acid, carboxymethyl hyaluronic acid, propylene glycol hyaluronate, dimethylsilanol hyaluronate, and salts thereof are preferred, and of these, acetylated hyaluronic acid, hydroxypropyltrimonium hyaluronate, crosslinked hyaluronic acid, propylene glycol hyaluronate, dimethylsilanol hyaluronate, and salts thereof are preferred, and of these, acetylated hyaluronic acid and its salts are preferred.
Acetylated hyaluronic acid is preferably hyaluronic acid in which the hydroxyl groups are acetylated. Hyaluronic acid has four hydroxyl groups per structural unit (disaccharide), and the acetylated hyaluronic acid is preferably hyaluronic acid in which two to four hydroxyl groups are acetylated.

In the present invention, when acetylated hyaluronic acid is blended as the hyaluronic acid derivative (C), the weight average molecular weight of the acetylated hyaluronic acid is preferably 100 or more, more preferably 1000 or more, and even more preferably 10,000 or more. Also, it is preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 300,000 or less. If it is within this range, the blending of acetylated hyaluronic acid can improve cushioning or thickness.

Commercially available hyaluronic acid derivatives include acetylated sodium hyaluronate (trade name) (Shiseido Co., Ltd.; weight-average molecular weight 10,000 to 100,000), Hyalobell (trade name) (Kewpie Corporation; weight-average molecular weight 500,000 to 800,000), HyaloRepair (trade name) (Kewpie Corporation; weight-average molecular weight 10,000 or less), Hyalocatch (trade name) (Kewpie Corporation; weight-average molecular weight 800,000 to 1.2 million), Hyalujon (trade name) (Kikkoman Biochemifa Corporation; propylene glycol hyaluronate), Hyalucage System (trade name) (I.R.Asrl; cross-linked three-dimensional hyaluronic acid; weight-average molecular weight 7 million), D.S.H.CN6 (trade name) (EXSYMOL S.A.M; dimethylsilanol hyaluronate), D.S.H. CN (trade name) (EXSYMOL S.A.M; hyaluronic acid dimethylsilanol), etc.

The salt of the hyaluronic acid derivative may be any one that is pharmacologically or physiologically acceptable, and examples thereof include salts with alkali metals such as sodium and potassium; salts with alkaline earth metals such as calcium and magnesium; salts with metals such as zinc and aluminum; ammonium salts; basic amino acid salts; and amine salts such as triethanolamine. Among these, sodium salts, potassium salts, zinc salts, and ammonium salts are preferred, and sodium salts and ammonium salts are more preferred. Specific examples of salts of hyaluronic acid derivatives include, for example, sodium acetylated hyaluronate, potassium acetylated hyaluronate, calcium acetylated hyaluronate, magnesium acetylated hyaluronate, zinc acetylated hyaluronate, ammonium acetylated hyaluronate, sodium hyaluronate crosspolymer, and hydroxypropyltrimonium hyaluronate.

One or more types of hyaluronic acid derivatives can be used.

The content of hyaluronic acid derivative is preferably 0.00001% by mass or more, more preferably 0.00004% by mass or more, more preferably 0.00008% by mass or more, and even more preferably 0.0001% by mass or more, based on the total amount of skin external preparation.The content of hyaluronic acid derivative is preferably 0.3% by mass or less, more preferably 0.2% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.025% by mass or less, based on the total amount of skin external preparation.Within this range, the cushioning or thickness feeling can be sufficiently improved in the preparation (when applied) and the skin feeling after application.
When multiple types of hyaluronic acid derivatives are contained, the content of the hyaluronic acid derivative refers to the total content thereof.

The ratio of the content of hyaluronic acid or its salt in the skin topical preparation of the present invention (the total content of (A) high molecular weight hyaluronic acid or its salt and (B) low molecular weight hyaluronic acid or its salt) to the content of the hyaluronic acid derivative is preferably 0.005 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.5 parts by mass or more, and even more preferably 2.5 parts by mass or more, per part by mass of the content of the hyaluronic acid derivative. Also, it is preferably 200,000 parts by mass or less, more preferably 50,000 parts by mass or less, even more preferably 10,000 parts by mass or less, and even more preferably 5,000 parts by mass or less. It can also be 1,000 parts by mass or less, or 100 parts by mass or less. Within this range, the cushioning or thickness feeling due to the combination of (A) and (B) can be sufficiently enhanced in the preparation (at the time of application) and in the skin feel after application.

In the present invention, the weight average molecular weight is a value measured by size exclusion chromatography.
The conditions are as follows:
Column: TSKgel GMPWXL 7.8 mm x 30 cm (manufactured by Tosoh Corporation)
Column temperature: constant temperature around 40°C Detector: differential refractometer Mobile phase: 0.2 mol/L NaCl
Flow rate: 0.3mL/min Injection volume: 100μL
Standard substance: pullulan standard (STANDARD P-82, Showa Denko K.K.)

(D) Water The content of water is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, and even more preferably 60% by mass or more, based on the total amount of the skin external preparation.Moreover, it is preferably 98% by mass or less, more preferably 95% by mass or less, even more preferably 93% by mass or less, and even more preferably 90% by mass or less.Within this range, the effect of the present invention can be significantly achieved.

(E) oil content The skin external preparation of the present invention does not contain oil content, or its content is 10% by mass or less based on the total amount of external preparation.The oil content is preferably 5% by mass or less based on the total amount of external preparation, more preferably 3% by mass or less, even more preferably 2% by mass or less, and even more preferably 1% by mass or less.Within this range, the high cushioning or thick feeling due to hyaluronic acid can be obtained more effectively.

In the present invention, the oil is an oily substance that is liquid or fluid at 25° C. The oil in the present invention is preferably an oily substance that is liquid, fluid, or semi-solid at 25° C., and more preferably an oily substance that is liquid, fluid, semi-solid, or solid at 25° C. Solid means one that has no fluidity at 25° C., semi-solid means one that has a melting point of 25° C. to 45° C., and liquid means one that has fluidity at 25° C.
Examples of oily substances include hydrocarbons, waxes, silicones, higher alcohols, higher fatty acids, oils and fats, and esters.

Examples of hydrocarbons include liquid paraffin, liquid isoparaffin, squalane, petrolatum, paraffin, microcrystalline wax, polybutene, polyethylene powder, gelled hydrocarbons (such as Plastibase), ozokerite, α-olefin oligomers, light liquid paraffin, light iso liquid paraffin, isododecane, and isohexadecane.
Among these, liquid paraffin, liquid isoparaffin, squalane, Vaseline, gelled hydrocarbons (such as Plastibase), α-olefin oligomers, light liquid paraffin, and light isoliquid paraffin are preferred, and liquid paraffin, liquid isoparaffin, squalane, α-olefin oligomers, light liquid paraffin, and light isoliquid paraffin are more preferred.

Examples of waxes include jojoba oil, beeswax, candelilla wax, rice bran wax, cotton wax, carnauba wax, lanolin, liquid lanolin, and reduced lanolin.
Of these, jojoba oil, beeswax, candelilla wax, and rice bran wax are preferred, with jojoba oil being particularly preferred.

Examples of silicones include phenyl-modified silicones such as methylpolysiloxane, crosslinked methylpolysiloxane, highly polymerized methylpolysiloxane, and methylphenylpolysiloxane, cyclic silicones such as decamethylcyclopentasiloxane, alkyl-modified silicones such as methylhydrogenpolysiloxane, methyltrimethicone, dimethiconol, dimethiconol crosspolymer, and caprylyl methicone, crosslinked alkyl-modified silicones, amino-modified silicones, polyether-modified silicones, polyglycerin-modified silicones, crosslinked polyether-modified silicones, crosslinked alkyl polyether-modified silicones, silicone/alkyl chain co-modified polyether-modified silicones, silicone/alkyl chain co-modified polyglycerin-modified silicones, polyether-modified branched silicones, polyglycerin-modified branched silicones, acrylic silicones, phenyl-modified silicones, and silicone resins.
Of these, methylpolysiloxane, crosslinked methylpolysiloxane, highly polymerized methylpolysiloxane, methylphenylpolysiloxane, and decamethylcyclopentasiloxane are preferred.

Furthermore, examples of higher alcohols include saturated or unsaturated, linear or branched higher alcohols having 8 to 22 carbon atoms. Specific examples include capryl alcohol, lauryl alcohol, myristyl alcohol, cetanol, cetostearyl alcohol, stearyl alcohol, behenyl alcohol, octyldodecanol, isostearyl alcohol, phytosterol, cholesterol, and oleyl alcohol.
Among these, cetanol, cetostearyl alcohol, stearyl alcohol, behenyl alcohol, octyldodecanol, and isostearyl alcohol are preferred, and octyldodecanol and isostearyl alcohol are more preferred.

Furthermore, examples of higher fatty acids include saturated or unsaturated, straight-chain or branched higher alcohols having 8 to 22 carbon atoms. Specific examples include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, and behenic acid.
Of these, isostearic acid, stearic acid and behenic acid are preferred, and isostearic acid is more preferred.

Examples of fats and oils include avocado oil, linseed oil, camellia oil, macadamia nut oil, kukui nut oil, hazelnut oil, corn oil, olive oil, safflower oil, apricot kernel oil, cinnamon oil, jojoba oil, grape seed oil, sunflower oil, almond oil, meadowfoam oil, camellia oil, rapeseed oil, sesame oil, cacao butter, coconut oil, hardened coconut oil, palm oil, palm kernel oil, Japan wax kernel oil, Japan wax, wheat germ oil, rice germ oil, rice bran oil, cottonseed oil, soybean oil, peanut oil, tea seed oil, evening primrose oil, shea butter, hardened oil, orange roughy oil, and horse oil.
Among these, avocado oil, macadamia nut oil, olive oil, grape seed oil, sunflower oil, almond oil, meadowfoam oil, sesame oil, palm oil, palm kernel oil, rice germ oil, rice bran oil, soybean oil, evening primrose oil, shea butter, and orange roughy oil are preferred.

Examples of esters include isopropyl myristate, octyldodecyl myristate, isopropyl palmitate, cetyl palmitate, isononyl isononanoate, diisopropyl adipate, decyl oleate, oleyl oleate, isodecyl oleate, hexyldecyl dimethyloctanoate, diisopropyl sebacate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-ethylhexyl palmitate, diisopropyl adipate, and isotridecyl isononanoate. , cetyl lactate, isostearyl isostearate, cholesteryl 12-hydroxystearate, cholesteryl stearate, cholesteryl oleate, phytosteryl macadamiate, phytosteryl oleate, dextrin palmitate, inulin stearate, hydrogenated jojoba oil, ethylene glycol di-2-ethylhexylate, dipentaerythritol fatty acid ester, neopentyl glycol dicaprate, tri-2-ethylhexyl trimellitate, tridecyl trimellitate Syl, trimethylolpropane tri-2-ethylhexyl acid, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexanoate, glycerin tri-2-ethylhexanoate, trimethylolpropane triisostearate, polyglyceryl diisostearate, polyglyceryl monoisostearate, caprylic/capric triglyceride, caprylic/capric/myristic/stearic triglyceride, oleyl oleate, lauroyl Examples of suitable glyceryl/isostearyl/cetyl/behenyl lauroyl glutamate include phytosteryl/octyldodecyl/phytosteryl/behenyl lauroyl glutamate, triethyl citrate, phytosteryl/isostearyl/cetyl/stearyl/behenyl dimer dilinoleate, dimer dilinoleyl dimer dilinoleate, dipentaerythrityl tri-polyhydroxystearate, glyceryl tri(behenate/isostearate/eicosadioate), diisostearyl malate, and triethyl citrate.
Among them, isopropyl myristate, octyldodecyl myristate, isopropyl palmitate, isononyl isononanoate, oleyl oleate, diisopropyl sebacate, di-2-ethylhexyl sebacate, 2-ethylhexyl palmitate, diisopropyl adipate, isotridecyl isononanoate, isostearyl isostearate, cholesteryl 12-hydroxystearate, cholesteryl stearate, cholesteryl oleate, phytosteryl macadamiate, phytosteryl oleate, dextrin palmitate, inulin stearate, hydrogenated jojoba oil, ethylene glycol di-2-ethylhexylate, dipentaerythritol fatty acid ester, neopentyl glycol dicaprate, tri-2-ethylhexyl trimellitate, tritridecyl trimellitate, trimethylolpropane tri-2-ethylhexylate, triisostearate, Trimethylolpropane tearic acid, pentaerythritol tetra-2-ethylhexanoate, glycerin tri-2-ethylhexanoate, trimethylolpropane triisostearate, polyglyceryl diisostearate, polyglyceryl monoisostearate, tri(caprylic acid / capric acid), tri(caprylic acid / capric acid / myristic acid / stearic acid) glyceryl, oleyl oleate, di(phytosteryl / octyldodecyl) lauroyl glutamate, di(octyldodecyl / phytosteryl / behenyl) lauroyl glutamate, triethyl citrate, dimer dilinoleate (phytosteryl / isostearyl / cetyl / stearyl / behenyl), dimer dilinoleate dimer dilinoleyl, tri-polyhydroxystearate dipentaerythrityl, tri(behenic acid / isostearic acid / eicosandioic acid) glyceryl are preferred.

One or more types of oil can be used.

(F) Paraben The skin topical preparation of the present invention does not substantially contain paraben. In the present invention, substantially not containing paraben means that the paraben content is 0.01% by mass or less based on the total amount of the topical preparation. The paraben content is preferably 0.01% by mass or less, more preferably 0.001% by mass or less, and particularly preferably does not contain paraben. However, if paraben is inevitably mixed in, this corresponds to not containing paraben. For example, if a commercially available ingredient is blended into the skin topical preparation, and the commercially available product contains paraben, and thus a trace amount of paraben is mixed into the skin topical preparation, this corresponds to not containing paraben.
Parabens are paraoxybenzoic acid esters and their salts, such as methylparaben, ethylparaben, propylparaben, isopropylparaben, butylparaben, isobutylparaben, benzylparaben, and the like, as well as their sodium salts and potassium salts.

The skin external preparation of the present invention is a non-emulsified composition.In the present invention, non-emulsified means that it does not contain emulsified particles with an average particle size of more than 0.15 μm.That is, it means that it does not contain emulsified particles, or even if it contains emulsified particles, the average particle size is 0.15 μm or less.The average particle size of emulsified particles is a value measured by dynamic light scattering method.

Transparency: The skin topical preparation of the present invention has a high transparency and a transparent or translucent appearance when viewed visually because the oil content is suppressed and the preparation is not emulsified. The L value in the Lab color system (Hunter Lab system) can be used as an index of transparency. The L value in the Lab color system of a cosmetic is a value that represents the transparency when the transparency of purified water is 100 and the transparency of no light transmission is 0. That is, the closer the L value is to 100, the higher the transparency. In the present invention, the L value is a value measured using a spectrophotometer, specifically, a value measured by putting a test liquid into a glass cell (CM-A99, thickness 20 mm) and using a spectrophotometer CM-5 (manufactured by Konica Minolta, Inc.). The L value is a value that does not change much depending on the type of spectrophotometer or cell.
The external skin preparation of the present invention preferably has an L value of 40 or more. The L value is preferably 40 to 100, more preferably 50 to 100, even more preferably 60 to 100, still more preferably 70 to 100, and particularly preferably 80 to 100.
For example, when the oil is solubilized or a microemulsion or nanoemulsion having an average particle size of 0.15 μm or less is contained, which corresponds to the non-emulsion defined in the present invention, the external preparation for skin will have a transparent or translucent appearance.

Alkanediol The topical skin preparation of the present invention preferably contains an alkanediol having 5 to 10 carbon atoms, which allows excellent cushioning properties to be maintained for a long period of time.
The alkanediol preferably has 5 to 10 carbon atoms, more preferably has 5 to 8 carbon atoms, and even more preferably has 5 to 6 carbon atoms. The alkanediol is preferably a 1,2-alkanediol.
Examples of the alkanediol having 5 to 10 carbon atoms include 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, 1,2-nonanediol, and 1,2-decanediol. Among these, 1,2-pentanediol, 1,2-hexanediol, and 1,2-octanediol are preferred, 1,2-pentanediol and 1,2-hexanediol are more preferred, and 1,2-pentanediol is even more preferred.
Commercially available alkanediols having 5 to 10 carbon atoms include HYDROLITE-5, HYDROLITE-5 Green (manufactured by Symrise Co., Ltd.), KMO-6 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Microcare Emollient PTGJ, and Microcare Emollient HXD (manufactured by THOR Corporation).

One or more types of alkanediols having 5 to 10 carbon atoms can be used.

The content of the alkanediol having 5 to 10 carbon atoms in the skin topical preparation of the present invention is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, even more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, and particularly preferably 0.5% by mass or more, based on the total amount of the skin topical preparation. The content of the alkanediol having 5 to 10 carbon atoms is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 8% by mass or less, and particularly preferably 5% by mass or less, based on the total amount of the skin topical preparation. Within this range, sufficient stability and cushioning properties can be maintained for a long period of time in the preparation (when applied) and in the skin feel after application.
When a plurality of types of alkanediols are contained, the content of alkanediol refers to the total content thereof.

pH
The pH of the external skin preparation of the present invention may be in the range of 2 to 9. In order to suppress irritation to the skin and mucous membranes and to improve the feeling of use, the pH is preferably 3 to 8.5, more preferably 4 to 8, even more preferably 4.5 to 7.5, and even more preferably 4.5 to 7.

The topical skin preparation of the present invention is preferably in the form of a liquid having fluidity at 25° C., and more preferably in the form of a lotion. From this viewpoint, the viscosity (25° C.) of the topical skin preparation of the present invention is preferably 10 to 10,000 mPa·s, more preferably 10 to 8,000 mPa·s, even more preferably 50 to 6,000 mPa·s, and particularly preferably 4,000 mPa·s or less.
Viscosity is an index of cushioning properties. The topical skin preparation of the present invention has excellent cushioning properties and therefore has a high viscosity.
In the present invention, the viscosity is a value measured at a temperature of 25° C. using a B-type viscometer in accordance with the viscosity measurement method described in the General Test Methods of the Japanese Pharmacopoeia, 17th Edition, and specifically, a value measured by the method described in the Examples.

Formulation form The topical skin preparation of the present invention can be prepared in the usual manner as a cosmetic, quasi-drug, or medicinal topical skin preparation by blending the above-described components together with a base or carrier normally used in cosmetics, quasi-drugs, or pharmaceuticals, and, if necessary, additives or other physiologically active or pharmacologically active ingredients.

The external skin composition of the present invention may be in a liquid, flowable or other form.
The formulation may be, for example, a liquid, a suspension, a liniment, a lotion, an aerosol, a pump spray, a sheet in which a nonwoven fabric is impregnated with a drug solution, a mist, etc. Among these, liquids, lotions, aerosols, pump sprays, sheets in which a nonwoven fabric is impregnated with a drug solution (sheet masks or sheet packs), and mist are preferred, and liquids, lotions, sheets in which a nonwoven fabric is impregnated with a drug solution (sheet masks or sheet packs), and mist are particularly preferred.

When used as a quasi-drug or cosmetic for external use on the skin, the applications include, for example, basic cosmetics such as lotion, beauty essence, sheet pack, sheet mask, all-in-one gel, and body lotion; hair cosmetics such as hair mists and hair lotions; and the like.

As the base or carrier , any base or carrier that does not fall under the above-mentioned oil content may be used. Even if oil is mixed, the content of the oil in the base or carrier is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.
Examples of the surfactant include water; cellulose derivatives such as ethyl cellulose, hydroxypropyl cellulose, and hydroxypropyl methyl cellulose; vinyl polymers such as polyvinylpyrrolidone, carboxyvinyl polymer, alkyl-modified carboxyvinyl polymer, polyvinyl butyrate, and alkyl acrylate/methacrylate copolymers; natural polymers such as carrageenan, alginic acid, cellulose, xanthan gum, guar gum, quince seed, dextran, and gellan gum; processed polysaccharides such as dextrin and maltodextrin; lower alcohols such as ethanol and isopropanol; sugar alcohols such as sorbitol, xylitol, erythritol, and mannitol; polyhydric alcohols such as polyethylene glycol, propylene glycol, propanediol, dipropylene glycol, 1,3-butylene glycol, glycerin, diglycerin, and isoprene glycol; and glycol ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monoethyl ether, and dipropylene glycol monopropyl ether.
One or more bases or carriers may be used.

Additives Examples of additives include surfactants, thickeners, antioxidants, preservatives or antiseptics, pH adjusters, chelating agents, stabilizers, irritation reducers, colorants, dispersants, fragrances, and pearlescent agents.
The additives may be used alone or in combination as long as the effects of the present invention are not impaired.

Examples of the surfactant include POE-2-decyltetradecyl alcohol, POE-alkyl ethers such as polyoxyethylene oleyl ether and polyoxyethylene cetyl ether; sorbitan fatty acid esters such as sorbitan monostearate, sorbitan sesquistearate, sorbitan tristearate, and sorbitan monooleate; POE-sorbitan fatty acid esters such as POE(20) sorbitan monoisostearate, POE(20) sorbitan monooleate, POE(20) sorbitan monostearate, POE(20) sorbitan monococonut oil fatty acid, and POE(80) sorbitan laurate; Glycerin fatty acid esters such as glyceryl stearate and glyceryl oleate; POE-glycerin fatty acid esters such as polyoxyethylene glyceryl stearate and polyoxyethylene glyceryl trioleate; POE-dihydrocholesterol ester, POE-hydrogenated castor oil (e.g., polyoxyethylene hydrogenated castor oil 40 (HCO-40), polyoxyethylene hydrogenated castor oil 50 (HCO-50), polyoxyethylene hydrogenated castor oil 60 (HCO-60), polyoxyethylene hydrogenated castor oil 80, etc.); POE-castor oil (POE(3) castor oil, POE(20) castor oil, etc.) OE castor oil; POE-hydrogenated castor oil fatty acid esters such as POE-hydrogenated castor oil isostearate; POE-alkylaryl ethers; glycerin alkyl ethers such as cumyl alcohol, batyl alcohol, and selachyl alcohol; POE-glycerin alkyl ethers such as POE-monostearyl glyceryl ether; POE fatty acid esters such as polyoxyl stearate; POE sterols and hydrogenated sterols such as POE (20) phytosterol, POE (30) phytosterol, POE (25) phytostanol, and POE (30) cholestanol; sucrose palmitate, sucrose stearate sucrose fatty acid esters such as sucrose oleate, sucrose isostearate, sucrose linoleate, and sucrose linolenate; polyethylene glycol fatty acid esters such as polyethylene glycol dioleate; polyglycerin fatty acid esters such as alkyl polyglycosides, diglyceryl monostearate, diglyceryl monoisostearate, decaglyceryl monostearate, decaglyceryl monooleate, decaglyceryl pentaoleate, and hexaglyceryl polyricinoleate; and nonionic surfactants such as alkyl-modified silicones and emulsion-type silicone elastomers.
Further, for example, higher alkyl sulfate salts (e.g., sodium lauryl sulfate, potassium lauryl sulfate, etc.); alkyl ether sulfate salts (e.g., POE-triethanolamine lauryl sulfate, sodium POE-lauryl sulfate, etc.); N-acylsarcosinic acid (e.g., sodium lauroyl sarcosinate, etc.); higher fatty acid amide sulfonates (e.g., sodium stearoyl methyl taurine, sodium myristoyl methyl taurine, sodium cocoyl methyl taurine, sodium cocoyl methyl taurine taurine, etc.); phosphate esters and their salts (sodium POE-oleyl ether phosphate, POE-stearyl ether phosphate, potassium cetyl phosphate, cetyl phosphate, etc.); sulfosuccinates (e.g., sodium di-2-ethylhexyl sulfosuccinate, etc.); alkyl benzene sulfonates (e.g., linear dodecyl benzene sulfone, and the like); higher fatty acid ester sulfate salts (for example, sodium hydrogenated coconut oil fatty acid glycerin sulfate); N-acyl glutamate salts (for example, monosodium lauroyl glutamate, sodium stearoyl glutamate, sodium myristoyl glutamate); N-acylalanine salts (for example, sodium lauroyl methyl alanine, cocoyl alanine triethanolamine salt); sulfated oils (for example, turmeric oil); POE-alkyl ether carboxylic acids; POE-alkyl allyl ether carboxylates; α-olefin sulfonates; higher fatty acid ester sulfonates; secondary alcohol sulfate salts; higher fatty acid alkylol amide sulfate salts; sodium lauroyl monoethanolamide succinate; N-palmitoyl aspartic acid ditriethanolamine; and sodium caseinate.
Further examples include cationic surfactants such as mono- or di-long-chain alkyl tertiary or quaternary ammonium salts having a straight-chain or branched long-chain alkyl group to which an alkylene oxide may be added.
Also included are amphoteric surfactants such as carbobetaines, sulfobetaines, imidazolinium betaines, and amidobetaines.
Other examples include naturally occurring surfactants such as lecithin, hydrogenated lecithin, saponin, sodium surfactin, and bile acid.

Examples of thickeners include vinyl thickeners such as polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl methyl ether, carboxyvinyl polymer, acrylic acid/methacrylic acid alkyl copolymer, and sodium polyacrylate; cellulose thickeners such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, and carboxyethylcellulose; guar gum, sclerotium gum, tamarind gum, xanthan gum, gellan gum, dextran, pectin, pullulan, locust bean gum, carrageenan, agar, alginic acid, and alginic acid. Examples include sodium phosphate, polysaccharides such as fucogel; gelatin, acrylic acid alkyl methacrylate copolymer, sodium polyacrylate, bentonite, dextrin fatty acid ester, dimethyl distearyl ammonium hectorite, propylene glycol alginate ester, polyethylene glycol, macrogol, polyacrylamide, (hydroxyethyl acrylate/sodium acryloyldimethyl taurate) copolymer, (ammonium acryloyldimethyl taurate/vinyl pyrrolidone) copolymer, (ammonium acryloyldimethyl taurate/beheneth-25 methacrylate) crosspolymer, (sodium acrylate/sodium acryloyldimethyl taurate) copolymer, etc.

Examples of antioxidants include dibutylhydroxytoluene, butylhydroxyanisole, sorbic acid, sodium sulfite, ascorbic acid, erythorbic acid, sodium erythorbate, L-cysteine hydrochloride, lignans such as sesamin, curcumin, capsaicin, gingerol, resveratrol, anthocyanin, cyanidin, and bilberry extract.

Preservatives or antiseptics include benzoic acid, sodium benzoate, dehydroacetic acid, sodium dehydroacetate, isopropylmethylphenol, phenoxyethanol, sodium pyrosulfite, etc.

Examples of pH adjusters include inorganic acids (hydrochloric acid, sulfuric acid, etc.), organic acids (lactic acid, sodium lactate, citric acid, sodium citrate, succinic acid, sodium succinate, etc.), inorganic bases (potassium hydroxide, sodium hydroxide, etc.), and organic bases (triethanolamine, diisopropanolamine, triisopropanolamine, etc.).

Examples of chelating agents include ethylenediaminetetraacetic acid (edetic acid), ethylenediaminetetraacetate (sodium salt (sodium edetate: Japanese Pharmacopoeia, EDTA-2Na, etc.), potassium salt, etc.), phytic acid, gluconic acid, polyphosphoric acid, metaphosphoric acid, etc.

Stabilizers include sodium polyacrylate, dibutylhydroxytoluene, and butylhydroxyanisole.

Irritation reducers include licorice extract, gum arabic, polyvinylpyrrolidone, and sodium alginate.

Colorants include inorganic pigments and natural dyes.

Examples of pearlescent luster imparting agents include ethylene glycol distearate, ethylene glycol monostearate, and triethylene glycol distearate.

Physiologically or pharmacologically active ingredients Examples of physiologically or pharmacologically active ingredients include ultraviolet scattering agents, ultraviolet absorbing agents, ingredients that have the effect of preventing and/or repairing DNA damage, whitening ingredients, anti-inflammatory ingredients, antibacterial ingredients, refreshing agents, organic acids, anti-glycation ingredients, cell activating ingredients, astringent ingredients, antioxidant ingredients, anti-aging ingredients, moisturizing ingredients, polyhydric alcohols, keratin softening ingredients, vitamins, blood circulation promoting ingredients, sebum adsorbing ingredients, peptides or derivatives thereof, and amino acids or derivatives thereof.
The physiologically or pharmacologically active ingredient may be used alone or in combination with two or more other ingredients. The physiologically or pharmacologically active ingredient may be used in any amount within a range that does not impair the effects of the present invention.
When a plant component is used as a physiologically or pharmacologically active component in the present invention, the form of the plant component is not particularly limited, but it can usually be used in the form of a plant extract, essential oil, etc. Note that the name in parentheses written in the plant component is the scientific name, alias, or herbal medicine name of the plant.

Examples of UV scattering agents include inorganic compounds such as zinc oxide, titanium oxide, iron oxide, cerium oxide, zirconium oxide, titanium silicate, zinc silicate, anhydrous silicic acid, cerium silicate, and hydrous silicic acid; these inorganic compounds coated with inorganic powders such as hydrous silicic acid, aluminum hydroxide, mica, and talc; these inorganic compounds composited with resin powders such as polyamide, polyethylene, polyester, polystyrene, and nylon; and these inorganic powders, coatings, or composites treated with silicone oil, aluminum salts of fatty acids, alkyl titanates, etc.

Examples of ultraviolet absorbers include 2-ethylhexyl paramethoxycinnamate, ethylhexyl paramethoxycinnamate, 4-tert-butyl-4'-methoxydibenzoylmethane, 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoic acid hexyl ester, diethylamino hydroxybenzoyl benzoic acid hexyl ester, dimethoxybenzylidene oxoimidazolidinepropionate 2-ethylhexyl, 2,2'-methylenebis[6-(2H-benzotriazole-2yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)- nyl)-1,3,5-triazine, 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine, t-butyl methoxydibenzoylmethane, dibenzylidene dioxoimidazolidine ethylhexyl propylonate, etholhexyl triazoline, para-aminobenzoic acid and its derivatives, para-dimethylaminobenzoic acid octyl, 2-ethylhexyl salicylate, ethylene glycol salicylate, dihydroxybenzophenone, dimethicone diethyl benzalmalonate, 2-cyano-3,3-diphenylprop-2-enoic acid 2-ethylhexyl ester, 2-phenylbenzimidazole-5-sulfonic acid, etc.

Examples of components that have the effect of preventing and/or repairing DNA damage include components derived from animals (e.g., Artemia); components derived from plants (e.g., Cat's Claw); and nucleic acid components such as DNA, DNA salts, RNA, and RNA salts.

Examples of whitening ingredients include nicotinamide, placenta, arbutin, kojic acid, ellagic acid, phytic acid, tranexamic acid, rucinol, chamomilla ET, hydroquinone, potassium 4-methoxysalicylic acid, linoleic acid and its derivatives, ascorbic acid, sodium ascorbate, sodium ascorbyl phosphate, magnesium ascorbyl phosphate, ascorbyl tetra-2-hexyldecanoate, 2-O-ethyl ascorbic acid, 3-O-ethyl ascorbic acid, ascorbyl glucoside, disodium isostearyl ascorbyl phosphate, L-ascorbyl dipalmitate, trisodium ascorbyl palmitate phosphate, glyceryl ascorbate, bisglyceryl ascorbate, alkylglyceryl ascorbate, ... Vinyl acid, plants (iris, almond, aloe, acerola, star anise, scutellaria, coptis, hypericum, white lamb, seaweed, pueraria root, chlorella, rice, rice hyacinth, oryzanol, rice bran, perilla, peony, mulberry bark, soybean, tea, calendula, witch hazel, peonies, coix seed, kiwi, sage, parsley, holly, hops, thyme, clove, tangerine) , licorice, chamomile, prune, meadowsweet, purple bark, sorrel, grapefruit, thorn pear, lemon, kiwi, pine, neem, artichoke, horsetail, bark bean, evening primrose, bilberry, geranium gracilis, glasswort, white willow, saxifrage, centella, rosemary, lavender, and Chinese quince).

Examples of anti-inflammatory ingredients include allantoin, calamine, tranexamic acid, glycyrrhizic acid or its derivatives or their salts (e.g., dipotassium glycyrrhizinate, monoammonium glycyrrhizinate, etc.), glycyrrhetinic acid or its derivatives or their salts (e.g., glycyrrhetinic acid, stearyl glycyrrhetinate, etc.), zinc oxide, aminocaproic acid, azulene and its derivatives (e.g., guaiazulene, azulene, etc.), tocopherol acetate, pyridoxine hydrochloride, menthol, camphor, turpentine oil, indomethacin, salicylic acid or its derivatives, steroids or their derivatives or their salts (e.g., hydrocortisone, prednisolone), ufenamate, bufexamac, ibuprofen piconol, glycol salicylate, and ingredients derived from plants (e.g., comfrey, coptis japonica, dokudami).

Examples of antibacterial ingredients include chlorhexidine, salicylic acid, benzalkonium chloride, acrinol, ethanol, benzethonium chloride, cresol, gluconic acid and its derivatives, povidone-iodine, potassium iodide, iodine, isopropylmethylphenol, triclocarban, triclosan, photosensitizer No. 101, photosensitizer No. 201, phenoxyethanol, alkyldiaminoglycine hydrochloride, cetylpyridinium chloride, piroctoolamine, miconazole or its salts, chlorobutanol, ethylhexylglycerin, iodide propynyl butylcarbamate, caprylhydroxamic acid, hydroxyacetophenone, phenethyl alcohol, methylisothiazolinone, sorbic acid, β-glycyrrhetinic acid, and ingredients derived from plants (e.g., sophora flavescens, rosemary, mulberry, eucalyptus, etc.).

Examples of cooling agents include menthol and its derivatives, terpenes such as camphor, borneol, geraniol, cineole, anethole, limonene, and eugenol (which may be in the d-, l-, or dl-form); and essential oils such as eucalyptus oil, bergamot oil, peppermint oil, cool mint oil, spearmint oil, fennel oil, peppermint oil, cinnamon oil, rose oil, and turpentine.

Examples of organic acids include gluconic acid, aspartic acid, aminoethylsulfonic acid, citric acid, glutamic acid, succinic acid, oxalic acid, fumaric acid, malonic acid, maleic acid, propionic acid, malic acid, salicylic acid, glycolic acid, phytic acid, tartaric acid, acetic acid, lactic acid, pantothenic acid, glycyrrhetinic acid, alginic acid, ascorbic acid, benzoic acid, adipic acid, glutamic acid, azelaic acid, and salts thereof. Examples of salts include salts of mineral acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, salts of organic acids such as maleic acid and methanesulfonic acid, alkali metal salts such as sodium and potassium, alkaline earth metal salts, ammonium salts, basic amino acid salts, and amine salts such as triethanolamine.

Examples of anti-glycation ingredients include plant extracts such as Budreja axillaris leaf extract, plum fruit extract, edelweiss extract, ginkgo extract, cherry leaf extract, pomegranate extract, plantain extract, hawthorn extract, peony extract, Houttuynia cordata extract, bilberry leaf extract, green tea extract, black tea extract, horse chestnut extract, Roman chamomile extract, and mugwort extract, evening primrose oil, amla fruit, fruit juice or extracts thereof, L-arginine, L-lysine, hydrolyzed casein, hydrolyzable tannin, and carnosine.

Examples of cell activation ingredients include amino acids such as gamma-aminobutyric acid; vitamins such as retinol, thiamine, riboflavin, pyridoxine hydrochloride, and pantothenic acid pyrroloquinoline quinones; tannins, flavonoids, saponin, allantoin, placenta, proteoglycan, photosensitizer No. 301, ingredients derived from plants (e.g., soybean bilberry, lemongrass, aloe vera, chlorella, bean berry, coix seed, chamomile, dokudami, hops, carrot, etc.); royal jelly, royal jelly extract; whey-derived extracts such as whey, yogurt extract, and hydrolyzed milk protein, and yeast extract.

Examples of astringent ingredients include metal salts such as alum, chlorohydroxyaluminum, aluminum chloride, aluminum allantoin salt, zinc paraphenolsulfonate, basic aluminum zinc lactate, zinc sulfate, and potassium aluminum sulfate; and ingredients derived from plants (such as seaweed, thyme, black tea, oolong tea, green tea, Hypericum perforatum, witch hazel, loquat, peonies, saxifrage, rooibos, astragalus, artichoke, chamomile, eucalyptus, lemon, rosemary, and burnet).

Examples of antioxidant components include butyl hydroxyanisole, dibutyl hydroxytoluene, sodium bisulfite, sodium pyrosulfite, erythorbic acid and its salts, ascorbic acid and its salts, flavonoids, glutathione, glutathione peroxidase, glutathione-S-transferase, catalase, superoxide dismutase, thioredoxin, taurine, thiotaurine, hypotaurine, and plants (e.g., St. John's wort). These include ingredients derived from plants such as lysomnia, pueraria lobata, bilberry, scutellaria, passionflower, grapefruit, peony, meadowsweet, shiso, honeysuckle, sage, yarrow, mallow, meadowsweet, sohakuhi, clove, chinpi, geranium globosum, loquat, safflower, mousseed, hops, eucalyptus, saxifrage, rooibos, lemongrass, soybean, mugwort, evening primrose, rosemary, and lavender.

Examples of anti-aging ingredients include hydrolyzed soy protein, pangamic acid, ursolic acid, turmeric extract, sphingosine derivatives, silicon, silicic acid, N-methyl-L-serine, mevalonolactone, peptides (caproyl tetrapeptide-3, oligopeptide-24, etc.), etc.

Moisturizing ingredients include, for example, amino acids and derivatives thereof such as alanine, serine, aspartic acid, glycine, proline, hydroxyproline, glucosamine, theanine, and arginine; polyhydric alcohols such as glycerin, dipropylene glycol, 1,3-butylene glycol, and diglycerin; polyhydric alcohol derivatives such as polyoxyalkylene methyl glucoside, polyoxyethylene polyoxypropylene methyl glucoside, PEG/PPG/polybutylene glycol-8/5/3 glycerin, polyoxyethylene polyoxypropylene butyl ether, PPG-24, and glycereth-24; sorbitol, xylitol, erythritol, maltitol, and maltitol. These include sugar alcohols such as sucrose-sucrose condensates (glucooligosaccharides) and hydrolyzed xylan (xylooligosaccharides); glycosyltrehalose, trehalose; ceramide, glucosylceramide, cholesterol, phytosterol, cholesterol derivatives, phytosterol derivatives; phospholipids such as lecithin and hydrogenated lecithin; NMF-derived components such as urea; collagen, elastin, keratin, chitin, chitosan, and their hydrolysates; hydroxyethylurea; and components derived from plants (for example, aloe, seaweed, pueraria lobata, chlorella, lemongrass, chamomile, witch hazel, tea, perilla, grapefruit, and gynostemma pentaphyllum).

Examples of polyhydric alcohols include glycerin, diglycerin, triglycerin, propylene glycol, ethylene glycol, diethylene glycol, isoprene glycol, and 1,3-butylene glycol.

Examples of keratin softening ingredients include lanolin, urea, phytic acid, lactic acid, lactate salts, glycolic acid, salicylic acid, malic acid, citric acid, fruit acids, phytic acid, urea, and sulfur.

Examples of vitamins include retinol derivatives such as retinol, retinol acetate, retinol palmitate, retinol propionate, and retinol linoleate; vitamin A such as retinal, retinoic acid, methyl retinoate, ethyl retinoate, retinol retinoic acid, d-δ-tocopheryl retinoate, α-tocopheryl retinoate, and β-tocopheryl retinoate; provitamin A such as β-carotene, α-carotene, γ-carotene, δ-carotene, lycopene, zeaxanthin, cryptoxanthin, and echinenone; dl-α-tocopherol, dl-α-tocopherol succinate, dl-α-tocopherol calcium succinate, δ-tocopherol, tocopherol nicotinate, and dl-α-acetate. Vitamin E such as tocopherol, tocopherol linoleate, tocopherol linoleate/oleate, potassium ascorbyl/tocopheryl phosphate; Vitamin B2 such as riboflavin, flavin mononucleotide, flavin adenine dinucleotide, riboflavin butyrate, riboflavin tetrabutyrate, riboflavin 5'-phosphate sodium, riboflavin tetranicotinate; Nicotinic acids (vitamin B3) such as methyl nicotinate, nicotinic acid, benzyl nicotinate, nicotinamide, dl-α-tocopherol nicotinate, β-butoxyethyl nicotinate, 1-(4-methylphenyl)ethyl nicotinate; Ascorbyl stearate, Isostearyl ascorbyl Vitamin C such as disodium phosphate, L-ascorbyl dipalmitate, ascorbyl tetraisopalmitate (ascorbyl tetra 2-hexyldecanoate), trisodium ascorbyl palmitate phosphate, ascorbic acid, sodium ascorbate, dehydroascorbic acid, sodium ascorbyl phosphate, magnesium ascorbyl phosphate, ascorbic acid glucoside, 2-O-ethyl ascorbic acid, 3-O-ethyl ascorbic acid, glyceryl ascorbic acid, bisglyceryl ascorbic acid, and alkylglyceryl ascorbic acid; Vitamin D such as methylhesperidin, ergocalciferol, and cholecalciferol; Vitamin K such as phylloquinone and farnoquinone Vitamin B1 such as thiamine and salts thereof (e.g., dibenzoylthiamine hydrochloride, thiamine hydrochloride, thiamine diphosphate); vitamin B6 such as pyridoxine hydrochloride, pyridoxine acetate, pyridoxal hydrochloride, 5'-pyridoxal phosphate, and pyridoxamine hydrochloride, vitamin B12 such as cyanocobalamin, hydroxocobalamin, and deoxyadenosylcobalamin; folic acids such as folic acid and pteroylglutamic acid; pantothenic acids such as pantothenic acid, calcium pantothenate, pantothenyl alcohol (panthenol), D-pantetheine, D-pantethine, coenzyme A, pantothenyl ethyl ether, and calcium pantetheine sulfonate; and biotins such as biocytin. Other examples include vitamin-like factors such as carnitine, ferulic acid, α-lipoic acid, orotic acid, γ-oryzanol, pyrroloquinoline quinone, hesperidin and glucosylherperidin, ubiquinone, and salts of these.

Examples of blood circulation-promoting ingredients include ingredients derived from plants (e.g., ginseng, angelica, arnica, ginkgo, fennel, Japanese oak, Dutch oak, chamomile, Roman chamomile, carrot, gentian, burdock, rice, Japanese hawthorn, shiitake mushroom, European hawthorn, European juniper, Cnidium rhizome, Swertia japonica, thyme, clove, tangerine peel, Japanese angelica, Japanese pear, spruce, carrot, garlic, butcher's broom, grape, peony, horse chestnut, melissa, yuzu, coix seed, rosemary, rose hip, tangerine peel, Japanese angelica, spruce, peach, apricot, walnut, corn); dl-α-tocopherol acetate, tocopherol nicotinate, glucosyl hesperidin, hesperidin, etc.

Examples of sebum-absorbing ingredients include talc, mica, hydroxyapatite, zinc oxide, and aluminum silicate.

Examples of peptides or derivatives thereof include keratin hydrolyzed peptides, hydrolyzed keratin, collagen, fish-derived collagen, atelocollagen, succinylated atelocollagen, gelatin, elastin, elastin hydrolyzed peptides, collagen hydrolyzed peptides, hydrolyzed collagen, hydroxypropylammonium chloride hydrolyzed collagen, elastin hydrolyzed peptides, conchiolin hydrolyzed peptides, hydrolyzed conchiolin, silk proteolytic peptides, hydrolyzed silk, sodium lauroyl hydrolyzed silk, soybean proteolytic peptides, hydrolyzed soybean protein, wheat protein, wheat proteolytic peptides, hydrolyzed wheat protein, casein hydrolyzed peptides, and acylated peptides (palmitoyl oligopeptide, palmitoyl pentapeptide, palmitoyl tetrapeptide, etc.).

Examples of amino acids or derivatives thereof include betaine (trimethylglycine), proline, hydroxyproline, arginine, lysine, serine, glycine, alanine, phenylalanine, β-alanine, threonine, glutamic acid, glutamine, asparagine, aspartic acid, cysteine, cystine, methionine, leucine, isoleucine, valine, histidine, threonine, tyrosine, taurine, γ-aminobutyric acid, γ-amino-β-hydroxybutyric acid, carnitine, carnosine, creatine, epsilon aminocaproic acid, tryptophan, ornithine, sodium N-stearoyl-L-glutamate, lysine dilauroyl glutamate and its salts, di(phytosteryl/octyldodecyl) lauroyl glutamate, di(octyldodecyl/phytosteryl/behenyl) lauroyl glutamate, etc. These amino acids or derivatives thereof may be in the form of a solvate such as a hydrate, and may be in the d-, l-, or dl-form.

The skin topical preparation of the present invention can be used by being contained in a container of a shape and material appropriately selected according to the purpose and application of the use. Examples of the container include a spray type, a pump type, a bottle type, a tube type, a dropper type, a dispenser type, a pouch bag, a cheer pack, etc.
Examples of the material of the container include polyethylene terephthalate, polypropylene, polyethylene (HDPE, LDPE, LLDPE, etc.), ABS resin, ethylene vinyl alcohol resin, polystyrene, glass, and metal (aluminum, etc.). These materials can be used as container materials by performing various coating processes or combining these materials by mixing or laminating them, taking into consideration strength, flexibility, weather resistance, stability of components, etc. Examples of the coating material include epoxy resin and polyamideimide. Among them, it is preferable to use polypropylene, polyethylene (HDPE, LDPE, LLDPE, etc.), and ethylene vinyl alcohol resin, and it is more preferable to use polypropylene and polyethylene (HDPE, LDPE, LLDPE, etc.).

The present invention provides a method for improving the cushioning or bouncy feel of the preparation (at the time of application) and/or the skin feel after application while suppressing the stickiness of a non-emulsified topical skin preparation, which comprises (A) a polymeric hyaluronic acid or a salt thereof having a weight-average molecular weight of 50,000 or more, (B) a low-molecular-weight hyaluronic acid or a salt thereof having a weight-average molecular weight of less than 50,000, and (D) water, (E) an oil content of 0-10% by mass, and (F) substantially no paraben, by incorporating (C) a hyaluronic acid derivative into the non-emulsified topical skin preparation. In this method, the (E) oil content of 0-10 is the content after incorporating (C) the hyaluronic acid derivative into the non-emulsified topical skin preparation.
The type and amount of each component, the properties of the topical skin preparation, etc. are as explained for the topical skin preparation of the present invention.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
(1) Effects of acetylated hyaluronic acid
The topical skin preparations shown in Tables 1 and 2 were prepared in a conventional manner. These topical skin preparations were lotions that did not contain emulsified particles. The external appearance of these topical skin preparations was transparent when visually inspected.
The viscosity of each topical preparation was measured, and the viscosity increase rate was calculated according to formula (1). In formula (1), the comparative examples corresponding to Examples 1 to 4 are Comparative Examples 1 to 4, respectively.

Viscosity increase rate=[(viscosity of Example)/corresponding viscosity of Comparative Example]×100 (1)

(Viscosity measurement method)
Measurement was carried out using a VISCOMETER TV-10M (Toyo Sangyo Co., Ltd.) under conditions of a temperature of 25° C., rotor M-2, speed of 60 rpm, and time of 20 seconds.

The results are shown in Tables 1 and 2. The unit of the component contents in Tables 1 and 2 is mass %.
As shown in Table 1, the viscosity of Reference Examples 1 to 3, which contain acetylated hyaluronic acid but do not contain hyaluronic acid or its salt, was zero, as was Reference Example 4, which does not contain either acetylated hyaluronic acid or hyaluronic acid or its salt. It can be seen that acetylated hyaluronic acid itself does not have a viscosity-increasing effect.

In addition, as shown in Table 2, by using high molecular weight sodium hyaluronate with weight-average molecular weight of 50,000 or more and low molecular weight sodium hyaluronate with weight-average molecular weight of less than 50,000 as hyaluronic acid or its salt, and by blending a small amount of acetylated hyaluronic acid therein, viscosity is significantly increased.It can be seen that viscosity is increased by combining high molecular weight sodium hyaluronate with weight-average molecular weight of 50,000 or more and low molecular weight sodium hyaluronate with weight-average molecular weight of less than 50,000 with acetylated hyaluronic acid.
Since viscosity is one index that indicates the cushioning properties of a composition, it has been shown that by including hyaluronic acid or its salts having a weight-average molecular weight of 50,000 or more and hyaluronic acid or its salts having a weight-average molecular weight of less than 50,000, and by incorporating acetylated hyaluronic acid, the cushioning properties are greatly improved.

(2) Effect of Alkanediol The skin preparations shown in Tables 3 to 5 were prepared according to a conventional method, and 50 mL of each was placed in a 50 mL glass container. These skin preparations were lotions that did not contain emulsified particles. The appearance of these skin preparations was transparent when visually inspected. The containers were stored at 50°C for one week, and the viscosity was measured before and after storage, and the viscosity reduction rate was calculated according to formula (2).

Viscosity decrease rate=[(viscosity after storage−viscosity before storage)/viscosity before storage]×100 (2)

Furthermore, the improvement rate of viscosity reduction by blending alkanediol was calculated according to formula (3). In formula (3), the corresponding examples are Example 5 for Example 6, Example 7 for Example 8, Example 9 for Example 10, Example 11 for Example 12, Example 13 for Example 14, Example 15 for Example 16, Example 17 for Example 18, Example 19 for Example 20, Example 21 for Example 22, Example 23 for Example 24, Example 25 for Example 26, and Example 27 for Example 28.

Viscosity reduction improvement rate=[(viscosity reduction rate of example−viscosity reduction rate of corresponding example)/viscosity reduction rate of corresponding example]×100 (3)

The results are shown in Tables 3 to 5. The unit of component contents in Tables 3 to 5 is mass %.
The viscosity reduction rate under harsh conditions at 50°C for one week was significantly improved by adding alkanediol. On the other hand, the viscosity reduction rate was not improved at all when dipropylene glycol, polyethylene glycol 400, which are the same diol compounds, or concentrated glycerin, which is the same polyol compound, were added.

(3) Evaluation of usability Each skin preparation was applied to the arm of five subjects who understood the evaluation criteria, and the feel of the applied area was evaluated on a scale of 1 to 5 (integer value). That is, for stickiness at the time of application, a strong feeling was given a score of 1, and for none was given a score of 5, and the value was shown corresponding to the feel felt by the subject. Similarly, for stickiness on the skin 1 minute after application, a strong feeling was given a score of 1, and for none was given a score of 5. In addition, for cushioning on the skin 1 minute after application, none was given a score of 1, and for none was given a score of 5. Next, the average score of each example was calculated, and this was used as the evaluation value of the skin preparation.

The results are shown in Table 6. Comparison of Example 1 and Comparative Example 1, Comparison of Example 2 and Comparative Example 2, and Comparison of Example 4 and Comparative Example 4 show that, by blending acetylated hyaluronic acid with a skin topical preparation containing high molecular weight hyaluronic acid or its salt having a weight-average molecular weight of 50,000 or more and low molecular weight hyaluronic acid or its salt having a weight-average molecular weight of less than 50,000, the cushioning property of the skin after application is significantly increased, although the sticky feeling remains unchanged or is even improved.
Moreover, since Reference Example 2 did not contain hyaluronic acid or a salt thereof, it was less sticky but had very low cushioning properties. It was confirmed that acetylated hyaluronic acid itself does not have cushioning properties.
In addition, as shown in Comparative Example 5, when the amount of polymeric hyaluronate is increased instead of acetylated hyaluronate, good cushioning property is obtained, but stickiness becomes very strong. It was confirmed that cushioning property can be enhanced by incorporating acetylated hyaluronate, and stickiness can be suppressed by reducing the amount of hyaluronate or its salt.

The weight-average molecular weight of the acetylated sodium hyaluronate used in the Examples section is 100,000.

Formulation examples of the external skin preparation of the present invention are shown below. The unit of the component contents in Tables 7 and 8 is mass %, and the values in parentheses are weight average molecular weights.

The topical skin preparation of the present invention contains a specific combination of hyaluronic acids, which gives it excellent cushioning properties, and even though it contains a high concentration of hyaluronic acid, it is not sticky and feels good when used. Therefore, it is a product of great commercial value.

Claims (8)

(A) a high molecular weight hyaluronic acid or a salt thereof having a weight-average molecular weight of 50,000 or more, (B) a low molecular weight hyaluronic acid or a salt thereof having a weight-average molecular weight of less than 50,000, (C) an acetylated hyaluronic acid or a salt thereof in an amount of 0.00001 to 0.3% by mass based on the total amount of the topical skin preparation, and (D) water in an amount of 40 to 98% by mass based on the total amount of the topical skin preparation, (E) an oil content of 0 to 10% by mass, and (F) substantially free of parabens, and the total content of (A) a high molecular weight hyaluronic acid or a salt thereof having a weight-average molecular weight of 50,000 or more and (B) a low molecular weight hyaluronic acid or a salt thereof having a weight-average molecular weight of less than 50,000 is 0.05 to 10% by mass based on the total amount of the topical skin preparation. 0.4 % by mass , and the ratio of the total content of (A) high molecular weight hyaluronic acid or a salt thereof having a weight-average molecular weight of 50,000 or more and (B) low molecular weight hyaluronic acid or a salt thereof having a weight-average molecular weight of less than 50,000 to 50,000 parts by mass per part by mass of (C) acetylated hyaluronic acid or a salt thereof is 0.5 to 50,000 parts by mass . 2. The non-emulsified topical skin preparation according to claim 1, wherein the content of (A) polymeric hyaluronic acid or its salt having a weight-average molecular weight of 50,000 or more is 0.001 to 1% by mass based on the total amount of the topical skin preparation. 3. The non-emulsified topical skin preparation according to claim 1 or 2, wherein the content of (B) low-molecular-weight hyaluronic acid or its salt having a weight-average molecular weight of less than 50,000 is 0.0001 to 1% by mass based on the total amount of the topical skin preparation. The non-emulsified skin external preparation according to any one of claims 1 to 3, comprising (A) 1 part by mass of high molecular weight hyaluronic acid or its salt having a weight-average molecular weight of 50,000 or more and (B) 0.0001 to 1,000 parts by mass of low molecular weight hyaluronic acid or its salt having a weight-average molecular weight of less than 50,000 . The non-emulsified external skin preparation according to any one of claims 1 to 4 , further comprising an alkanediol having 5 to 10 carbon atoms. 6. The non-emulsified external preparation for skin according to claim 5 , wherein the content of the alkanediol having 5 to 10 carbon atoms is 0.0001 to 20% by mass based on the total amount of the external preparation for skin. 7. The non-emulsified external skin preparation according to claim 1 , which has an L value of 40 or more in the Lab color system. (A) a polymeric hyaluronic acid or a salt thereof having a weight-average molecular weight of 50,000 or more, (B) a low-molecular-weight hyaluronic acid or a salt thereof having a weight-average molecular weight of less than 50,000, and (D) 40 to 98% by mass of water, (E) an oil content of 0 to 10% by mass, and (F) substantially free of parabens, wherein the total content of (A) a polymeric hyaluronic acid or a salt thereof having a weight-average molecular weight of 50,000 or more and (B) a low-molecular-weight hyaluronic acid or a salt thereof having a weight-average molecular weight of less than 50,000 is 0.05 to 1.05% by mass. A method for improving cushioning or bouncy feeling in the preparation and/or skin feel after application while suppressing stickiness of a non-emulsified topical skin preparation, comprising: (C) adding 0.00001 to 0.3% by mass of acetylated hyaluronic acid or a salt thereof such that the ratio of the total content of (A) high molecular weight hyaluronic acid or a salt thereof with a weight average molecular weight of 50,000 or more and (B) low molecular weight hyaluronic acid or a salt thereof with a weight average molecular weight of less than 50,000 is 0.5 to 50,000 parts by mass per part by mass of acetylated hyaluronic acid or a salt thereof (provided that (D) the water content is 40 to 98% by mass, (E) the oil content is 0 to 10% by mass, and the total content of (A) high molecular weight hyaluronic acid or a salt thereof with a weight average molecular weight of 50,000 or more and (B) low molecular weight hyaluronic acid or a salt thereof with a weight average molecular weight of less than 50,000 is 0.05 to 0.4 % by mass). , the content of acetylated hyaluronic acid or a salt thereof is 0.00001-0.3% by mass , and the ratio of the total content of (A) high molecular weight hyaluronic acid or a salt thereof having a weight-average molecular weight of 50,000 or more and (B) low molecular weight hyaluronic acid or a salt thereof having a weight-average molecular weight of less than 50,000 to 1 part by mass of acetylated hyaluronic acid or a salt thereof, 0.5-50,000 parts by mass , is the content relative to the total amount of the non-emulsified external skin preparation after containing (C) acetylated hyaluronic acid or a salt thereof.