JP2021169433A - Topical skin preparation - Google Patents

Abstract

To provide a topical skin preparation that contains hyaluronic acid or a salt thereof, has high cushioning properties and has reduced stickiness.SOLUTION: A non-emulsifiable, topical skin preparation contains (A) a high-molecular weight hyaluronic acid with a weight average molecular weight of 50,000 or more or a salt thereof, (B) a low-molecular weight hyaluronic acid with a weight average molecular weight of less than 50,000 or a salt thereof, (C) a hyaluronic acid derivative, and (D) water and (E) has an oil content of 0-10 mass% and (F) is substantially free of paraben. The topical skin preparation can further contain a C5-10 alkanediol.SELECTED DRAWING: None

Description

The present invention relates to external skin preparations used as cosmetics, quasi-drugs, or pharmaceuticals.

Hyaluronic acid is a mucopolysaccharide composed of glucuronic acid and N-acetylglucosamine, and is present in a large amount in the dermis as a bonding substance that fills cells and fibers in the living body, and is also present in the epidermis. Hyaluronic acid has high water retention and viscoelasticity, and is therefore widely used as a moisturizer for external use on the skin.

When hyaluronic acid is added to the external skin preparation, a unique feeling of use such as cushioning or thickness can be obtained due to the viscosity and viscoelasticity peculiar to hyaluronic acid. Further, by applying such a preparation to the skin, it is possible to obtain a chewy cushioning feeling or a thick skin feeling that sticks to the hands. This feeling of use is such as cushioning or thickness, and is a unique feeling of use that is preferred by consumers. On the other hand, hyaluronic acid is a component with strong spinnability, so when it is blended, it gives a unique sticky stickiness. In order to improve the cushioning property of the skin at the time of application and after application, it is required to add hyaluronic acid in a high concentration, but as the amount of hyaluronic acid added increases, stickiness occurs. Therefore, it is difficult to achieve both cushioning and a smooth feel.

Patent Document 1 teaches that acetyl hyaluronic acid has an excellent skin softening effect while improving the drawbacks of hyaluronic acid such as high spinnability.

Patent No. 3557044

An object of the present invention is to provide a skin external preparation containing hyaluronic acid or a salt thereof, having high cushioning properties and suppressing stickiness.

The present inventor has conducted repeated studies to solve the above problems, and has added hyaluronic acids to non-emulsifying skin external preparations containing water, having an oil content of 0 to 10% by mass, and substantially containing no parabens. As a result, a high molecular weight hyaluronic acid having a weight average molecular weight of 50,000 or more or a salt thereof and a low molecular weight hyaluronic acid having a weight average molecular weight of less than 50,000 or a salt thereof are blended in combination, and a hyaluronic acid derivative is blended therein. While suppressing the amount of hyaluronic acid that causes stickiness, it is possible to enhance the thickness or cushioning feeling that is felt at the time of application, and the chewy and cushioning skin feel after application, resulting in high cushioning property. We found that both smooth and smooth feeling of use are compatible.
Further, it has been found that by adding an alkanediol having 5 to 10 carbon atoms to this external skin preparation, a decrease in viscosity with time can be suppressed. As a result, the decrease in the cushioning property or the thick feeling of use of the preparation is suppressed, and the decrease in the feeling of thickness of the preparation itself is also suppressed.

The present invention has been completed based on the above findings, and provides the following external skin preparations.
[1] (A) high molecular weight hyaluronic acid having a weight average molecular weight of 50,000 or more or a salt thereof, (B) low molecular weight hyaluronic acid having a weight average molecular weight of less than 50,000 or a salt thereof, (C) a hyaluronic acid derivative, and (D). A non-emulsifying skin external preparation containing water, (E) an oil content of 0 to 10% by mass, and (F) substantially free of parabens.
[2] (A) The content of high molecular weight hyaluronic acid having a weight average molecular weight of 50,000 or more or a salt thereof is 0.001 to 1% by mass with respect to the total amount of the external skin preparation, according to [1]. External skin preparation.
[3] (B) The content of low molecular weight hyaluronic acid having a weight average molecular weight of less than 50,000 or a salt thereof is 0.0001 to 1% by mass with respect to the total amount of the external skin preparation, [1] or [2]. ] The external preparation for skin described in.
[4] The skin external use according to any one of [1] to [3], wherein the content of the (C) hyaluronic acid derivative is 0.00001 to 0.3% by mass with respect to the total amount of the external skin preparation. Agent.
[5] (C) High molecular weight hyaluronic acid having a weight average molecular weight of 50,000 or more or a salt thereof and (B) Low molecular weight hyaluronic acid having a weight average molecular weight of less than 50,000 or The skin external preparation according to any one of [1] to [4], which comprises 0.005 to 200,000 parts by mass of the total amount of the salt.
[6] The external preparation for skin according to any one of [1] to [5], which further contains an alkanediol having 5 to 10 carbon atoms.
[7] The skin external preparation according to [6], wherein the content of the alkanediol having 5 to 10 carbon atoms is 0.0001 to 20% by mass with respect to the total amount of the skin external preparation.
[8] The external skin preparation according to any one of [1] to [7], wherein the L value in the Lab color system is 40 or more.
[9] (A) high molecular weight hyaluronic acid having a weight average molecular weight of 50,000 or more or a salt thereof, (B) low molecular weight hyaluronic acid having a weight average molecular weight of less than 50,000 or a salt thereof, and (D) water are contained, and (E) ) The oil content is 0 to 10% by mass, (F) the non-emulsifying skin external preparation containing substantially no paraben, and (C) the hyaluronic acid derivative is contained, and the stickiness of the non-emulsifying skin external preparation is suppressed. However, a method for improving cushioning or stickiness in the skin feel after application (at the time of application) and / or after application (however, (E) oil content 0 to 10% by mass contains (C) hyaluronic acid derivative. Later content).

The skin external preparation of the present invention is a combination of three specific hyaluronic acids with a non-emulsifying skin external preparation containing water, having an oil content of 0 to 10% by mass and substantially free of parabens. By blending the hyaluronic acid or a salt thereof, the cushioning property or the feeling of thickness is effectively enhanced. Therefore, since the amount of hyaluronic acid that causes stickiness can be suppressed, it has both high cushioning properties and a smooth feel. As described above, the external skin preparation of the present invention has a unique chewy cushioning feeling or thickness that sticks to the hand on the skin after application, in addition to the feeling of use of the preparation such as cushioning property or thickness feeling at the time of application. It has a high commercial value because it gives a feeling of skin and suppresses stickiness.

Hereinafter, the present invention will be described in detail.
The external preparation for skin of the present invention comprises (A) high molecular weight hyaluronic acid having a weight average molecular weight of 50,000 or more or a salt thereof, (B) low molecular weight hyaluronic acid having a weight average molecular weight of less than 50,000 or a salt thereof, and (C) a hyaluronic acid derivative. , And (D) a non-emulsifying skin external preparation containing water, (E) an oil content of 0 to 10% by mass, and (F) substantially free of parabens.
In the present invention, hyaluronic acid having a weight average molecular weight of 50,000 or more or a salt thereof is referred to as "high molecular weight hyaluronic acid or a salt thereof", and hyaluronic acid having a weight average molecular weight of less than 50,000 or a salt thereof is referred to as "low molecular weight hyaluronic acid or a salt thereof". It is called "salt".

(A) High molecular weight hyaluronic acid or a salt thereof Hyaluronic acid is a kind of acidic mucopolysaccharide, and is a polysaccharide containing a disaccharide of glucuronic acid and N-acetylglucosamine as a constituent unit. Hyaluronic acid can be extracted and recovered from animal tissues such as chicken crown, shark skin, umbilical cord, eyeball, skin and cartilage, hyaluronic acid-producing microorganisms such as Streptococcus microorganisms, animal cells, and plant cell cultures. You can also purchase a commercial product.
Such natural hyaluronic acid can be used as the high molecular weight hyaluronic acid having a weight average molecular weight of 50,000 or more. The weight average molecular weight of natural hyaluronic acid is about 500 to 7 million.

Further, the 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. Degraded hyaluronic acid can be prepared, for example, by hydrolysis in the presence of acid or alkali, enzymatic treatment such as hyaluronidase, physical cleavage such as ultrasonic waves or shearing, fermentation by microorganisms, and the like. Moreover, a commercially available product can also be used.

In the present invention, the weight average molecular weight of the high molecular weight hyaluronic acid or a salt thereof is 50,000 or more, preferably 100,000 or more, more preferably 200,000 or more, further preferably 300,000 or more, still more preferably 500,000 or more. .. The weight average molecular weight of the high molecular weight hyaluronic acid or a salt thereof can be, for example, 7 million or less, preferably 6 million or less, more preferably 4 million or less, further preferably 3 million or less, and further 2 million or less. More preferred. Within this range, the effects of the present invention can be achieved by combining with a low molecular weight hyaluronic acid having a weight average molecular weight of less than 50,000 or a salt thereof and a hyaluronic acid derivative.

Commercially available products of high-molecular-weight hyaluronic acid include sodium hyaluronate HA12N (trade name) (Shiseido Co., Ltd .; weight average molecular weight 110 to 1.6 million) and hyaluronic acid FCH-150 (trade name) (Kikkoman Biochemifa Co., Ltd .; weight average). Molecular weight 1.4 to 1.8 million), sodium biohyaluronate SZE (trade name) (Shiseido Co., Ltd .; weight average molecular weight 110 to 1.6 million), hyaluronic acid FCH-120 (trade name) (Kikkoman Biochemifa Co., Ltd .; weight average molecular weight 100) ~ 1.4 million), Hyaluronic Acid HA-LQ (trade name) (KYUP Co., Ltd .; weight average molecular weight 85 to 1.6 million), hyaluronic acid FCH-80 (trade name) (Kikkoman Biochemifa Co., Ltd .; weight average molecular weight 600 to 1 million) ), Hyaluronic acid FCH-60 (trade name) (Kikkoman Biochemifa Co., Ltd .; weight average molecular weight 500,000 to 700,000), hyaluronic acid FCH-SU (trade name) (Kikkoman Biochemifa Co., Ltd .; weight average molecular weight 50,000 to 110,000) ) And so on.

The salt of the high molecular weight hyaluronic acid may be any pharmacologically or physiologically acceptable salt, for example, a salt with an alkali metal such as sodium and potassium; and an alkaline earth metal such as calcium and magnesium. Examples thereof include salts, salts with metals such as zinc and aluminum, ammonium salts, basic amino acid salts, amine salts such as triethanolamine and the like. Of these, alkali metal salts and metal salts are preferable, and sodium salts, potassium salts and zinc salts are particularly preferable. Further, in the high molecular weight hyaluronic acid, it is preferable to use the salted hyaluronic acid because it is more stable than the hyaluronic acid.

As the high molecular weight hyaluronic acid or a salt thereof, one kind or two or more kinds can be used.

The content of the high molecular weight hyaluronic acid or a salt thereof is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, still more preferably 0.01% by mass or more, based on the total amount of the external preparation for skin. 0.02% by mass or more is even more preferable. The content of the high molecular weight hyaluronic acid or a salt thereof is preferably 1% by mass or less, more preferably 0.8% by mass or less, still more preferably 0.6% by mass or less, based on the total amount of the external preparation for skin. Even more preferably 0.3% by mass or less. Within this range, sufficient cushioning or thickness can be obtained in the preparation (at the time of application) and the skin feel after application.
The content of high molecular weight hyaluronic acid or a salt thereof is the total content of a plurality of kinds of high molecular weight hyaluronic acid or salts thereof, if any.

(B) Low molecular weight hyaluronic acid or a salt thereof As the low molecular weight hyaluronic acid having an average molecular weight of less than 50,000, a decomposition product of the high molecular weight hyaluronic acid can be used. Low-molecular-weight hyaluronic acid is a method of hydrolyzing high-molecular-weight hyaluronic acid in the presence of an acid such as hydrochloric acid or an alkali, a method of treating with an enzyme such as hyaluronidase, or a method of physically cutting by ultrasonic waves or shearing. It can be obtained by a method of fermenting with a microorganism.
When a hyaluronic acid oligosaccharide and / or a salt thereof is used as the small molecule hyaluronic acid, about 2 to 16 sugars are preferable, and either a saturated type or an unsaturated type 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 D-glucuronic acid can be mentioned.

In the present invention, the weight average molecular weight of the small molecule hyaluronic acid or a salt thereof is less than 50,000, preferably 40,000 or less, more preferably 30,000 or less, still more preferably 20,000 or less. The weight average molecular weight of the small molecule hyaluronic acid or a salt thereof 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 a high molecular weight hyaluronic acid having a weight average molecular weight of 50,000 or more or a salt thereof and a hyaluronic acid derivative.

In the present invention, the small molecule hyaluronic acid can also be purchased and used as a commercially available product. Commercially available low-molecular-weight hyaluronic acid includes hyalooligo (trade name) (Kupy Co., Ltd .; weight average molecular weight of 10,000 or less) and hyaluronic acid (SL) (trade name) (FAP Japan Co., Ltd .; weight average molecular weight of 10,000 or less). , Microhyaluronic acid FCH (trade name) (Kikkoman Biochemifa Co., Ltd .; weight average molecular weight 5000 or less), HAboxer (trade name) (KYUP Co., Ltd .; weight average molecular weight 2000) and the like.

The salt of the low molecular weight hyaluronic acid may be any pharmacologically or physiologically acceptable salt, for example, a salt with an alkali metal such as sodium and potassium; and an alkaline earth metal such as calcium and magnesium. Examples thereof include salts, salts with metals such as zinc and aluminum, ammonium salts, basic amino acid salts, amine salts such as triethanolamine and the like. Among them, alkali metal salts and metal salts are preferable, sodium salts, potassium salts and zinc salts are more preferable, and sodium salts are even more preferable.

As the small molecule hyaluronic acid or a salt thereof, one kind or two or more kinds can be used.

The content of the small molecule hyaluronic acid or a salt thereof is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, still more preferably 0.001% by mass or more, based on the total amount of the external preparation for skin. Even more preferably 0.005% by mass or more. The content of low molecule hyaluronic acid or a salt thereof is preferably 1% by mass or less, more preferably 0.8% by mass or less, still more preferably 0.5% by mass or less, based on the total amount of the external preparation for skin. Even more preferably 0.2% by mass or less. Within this range, sufficient cushioning or thickness can be obtained in the preparation (at the time of application) and the skin feel after application.
The content of low-molecular-weight hyaluronic acid or a salt thereof is the total content of a plurality of types of low-molecular-weight hyaluronic acid or a salt thereof, if any.

The content of hyaluronic acid or a salt thereof (total content of high molecular weight hyaluronic acid or a salt thereof and low molecular weight hyaluronic acid or a salt thereof) in the external preparation for skin of the present invention is 0. 002% by mass or more is preferable, 0.01% by mass or more is more preferable, 0.05% by mass or more is further preferable, and 0.07% by mass or more is even more preferable. The content of hyaluronic acid or a salt thereof is preferably 2% by mass or less, more preferably 1.5% by mass or less, further preferably 1% by mass or less, and 0.4% by mass, based on the total amount of the external preparation for skin. % Or less is even more preferable. Within this range, sufficient cushioning or thickness can be obtained in the skin feel after the formulation and application.

Hyaluronic acid has spinnability, and generally, when blended in an external preparation at a high concentration, more stickiness occurs, but the external preparation of the present invention contains (A) high molecular weight hyaluronic acid or a salt thereof and (B) low. By combining molecular hyaluronic acid or a salt thereof and further blending (C) a hyaluronic acid derivative, the cushioning property or thickness feeling of hyaluronic acid or a salt thereof can be efficiently enhanced. Thereby, stickiness due to an increase in the amount of (A) high molecular weight hyaluronic acid or a salt thereof and (B) low molecular weight hyaluronic acid or a salt thereof can be suppressed.

The content ratio of the high molecular weight hyaluronic acid or its salt to the low molecular weight hyaluronic acid or its salt in the external preparation for skin of the present invention is low molecular weight hyalurone with respect to 1 part by mass of the content of the high molecular weight hyaluronic acid or its salt. The content of the acid or a salt thereof 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. Further, it may 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, an excellent cushioning property or a feeling of thickness can be given to the external preparation, and stickiness is suppressed even though it contains a high concentration of hyaluronic acid or a salt thereof.

(C) Hyaluronic Acid Derivatives Hyaluronic acid derivatives include acetylated hyaluronic acid, sulfated hyaluronic acid, hydrophobized hydrolyzed hyaluronic acid (alkyl hydrolyzated hyaluronate, glyceryl hydrolyzed hyaluronate, etc.), crosslinked hyaluronic acid, and the like. Examples thereof include carboxymethyl hyaluronic acid, alkylene glycol hyaluronate, silanol hyaluronate, cationized hyaluronic acid, and salts thereof.
Among them, acetylated hyaluronic acid, hydroxypropyltrimonium hyaluronate, hydrolyzed alkyl hyaluronate (alkyl group with 12 to 13 carbon atoms) glyceryl, crosslinked hyaluronic acid, carboxymethyl hyaluronic acid, propylene glycol hyaluronate, dimethylsilanol hyaluronate, And these salts are preferred, among others acetylated hyaluronic acid, hydroxypropyltrimonium hyaluronate, crosslinked hyaluronic acid, propylene glycol hyaluronate, dimethylsilanol hyaluronate, and salts thereof, among others acetylated hyaluronic acid and salts thereof. Is preferable.
The acetylated hyaluronic acid is preferably an acetylated hydroxyl group of the hyaluronic acid. Hyaluronic acid has four hydroxyl groups per constituent unit (disaccharide), and the acetylated hyaluronic acid is preferably one in which 2 to 4 hydroxyl groups are acetylated.

In the present invention, when acetylated hyaluronic acid is blended as the (C) hyaluronic acid derivative, the weight average molecular weight of the acetylated hyaluronic acid is preferably 100 or more, more preferably 1000 or more, still more preferably 10,000 or more. Further, 1 million or less is preferable, 500,000 or less is more preferable, and 300,000 or less is further preferable. Within this range, the cushioning property or the feeling of thickness can be improved by blending acetylated hyaluronic acid.

Commercially available products of hyaluronic acid derivatives include acetylated sodium hyaluronate (trade name) (Shiseido Co., Ltd .; weight average molecular weight 10,000 to 100,000) and hyalover (trade name) (CUP Co., Ltd .; weight average molecular weight 500,000 to 800,000). , Hyaluro Repair (trade name) (Kyupy Co., Ltd .; weight average molecular weight 10,000 or less), Hyalo Catch (trade name) (Kyupy Co., Ltd .; weight average molecular weight 800,000-1.2 million), Hyaluronic (trade name) (Kikkoman Biochemifa stock) Company; propylene glycol hyaluronate), hyalcage system (trade name) (IRAsrl; crosslinked three-dimensional hyaluronic acid; weight average molecular weight 7 million), D.I. S. H. CN6 (trade name) (EXSYSMOL SAM; dimethylsilanol hyaluronate), D.I. S. H. CN (trade name) (EXSYSMOL SAM; dimethylsilanol hyaluronate) and the like can be mentioned.

The salt in the hyaluronic acid derivative may be any pharmacologically or physiologically acceptable salt, for example, a salt with an alkali metal such as sodium, potassium; a salt with an alkaline earth metal such as calcium, magnesium. , Salts with metals such as zinc and aluminum, ammonium salts, basic amino acid salts, amine salts such as triethanolamine and the like. Among them, sodium salt, potassium salt, zinc salt and ammonium salt are preferable, and sodium salt and ammonium salt are more preferable. Specific examples of the salt of the hyaluronic acid derivative include, for example, acetylated sodium hyaluronate, acetylated potassium hyaluronate, acetylated calcium hyaluronate, acetylated magnesium hyaluronate, acetylated zinc hyaluronate, acetylated ammonium hyaluronate, and hyaluronic acid. Examples thereof include cross-polymer acid acid sodium and hydroxypropyltrimonium hyaluronate.

As the hyaluronic acid derivative, one kind or two or more kinds can be used.

The content of the hyaluronic acid derivative is preferably 0.00001% by mass or more, more preferably 0.00004% by mass or more, further preferably 0.00008% by mass or more, and 0.0001% by mass, based on the total amount of the external preparation for skin. % Or more is even more preferable. The content of the hyaluronic acid derivative is preferably 0.3% by mass or less, more preferably 0.2% by mass or less, further preferably 0.1% by mass or less, and 0. 025% by mass or less is even more preferable. Within this range, the cushioning property or the feeling of thickness can be sufficiently improved in the preparation (at the time of application) and the skin feel after application.
The content of the hyaluronic acid derivative is the total content of the plurality of types of hyaluronic acid derivatives when they are contained.

Content of hyaluronic acid or its salt in the external preparation for skin of the present invention ((A) total content of high molecular weight hyaluronic acid or its salt and (B) low molecular weight hyaluronic acid or its salt) and content of hyaluronic acid derivative The content of hyaluronic acid or a salt thereof is preferably 0.005 parts by mass or more, more preferably 0.05 parts by mass or more, and 0.5 parts by mass with respect to 1 part by mass of the content of the hyaluronic acid derivative. More than parts by mass is even more preferable, and more than 2.5 parts by mass is even more preferable. Further, 200,000 parts by mass or less is preferable, 50,000 parts by mass or less is more preferable, 10,000 parts by mass or less is further preferable, and 5,000 parts by mass or less is even more preferable. Further, it may be 1000 parts by mass or less, or 100 parts by mass or less. Within this range, the cushioning property or the feeling of thickness due to the combination of (A) and (B) can be sufficiently enhanced in the skin feel after application (at the time of application) and 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: 0.3 mL / min Injection volume: 100 μL
Standard substance: Pullulan standard product (STANDARD P-82, manufactured by Showa Denko KK)

(D) The content of water and water is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, still more preferably 60% by mass or more, based on the total amount of the external preparation for skin. .. Further, 98% by mass or less is preferable, 95% by mass or less is more preferable, 93% by mass or less is further preferable, and 90% by mass or less is even more preferable. Within this range, the effect of the present invention can be remarkably exhibited.

(E) Oil content The skin external preparation of the present invention does not contain oil, or its content is 10% by mass or less based on the total amount of the external preparation. The oil content is preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, still more preferably 1% by mass or less, based on the total amount of the external preparation. Within this range, it is possible to more effectively obtain a high cushioning property or a feeling of thickness due to hyaluronic acids.

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

Hydrocarbons include liquid paraffin, liquid isoparaffin, squalane, petrolatum, paraffin, microcrystalline wax, polybutene, polyethylene powder, gelled hydrocarbons (plastibase, etc.), ozokelite, α-olefin oligomer, light liquid paraffin, and light isofluid. Paraffin, isododecane, isohexadecan and the like can be mentioned.
Among them, liquid paraffin, liquid isoparaffin, squalane, vaseline, gelled hydrocarbon (plastibase, etc.), α-olefin oligomer, light liquid paraffin, and light iso liquid paraffin are preferable, and liquid paraffin, liquid isoparaffin, squalane, α-olefin oligomer, and light Liquid paraffin and light iso liquid paraffin are more preferable.

Examples of waxes include jojoba oil, beeswax, candelilla wax, rice wax, cotton wax, carnauba wax, lanolin, liquid lanolin, reduced lanolin and the like.
Of these, jojoba oil, beeswax, candelilla wax, and rice bran are preferable, and jojoba oil is particularly preferable.

Examples of silicones include phenyl-modified silicones such as methylpolysiloxane, crosslinked methylpolysiloxane, highly polymerized methylpolysiloxane, and methylphenylpolysiloxane, cyclic silicones such as decamethylcyclopentasiloxane, methylhydrogenpolysiloxane, and methyl. Alkyl-modified silicones such as trimeticon, dimethiconol, dimethiconol crosspolymer, caprylyl methicone, cross-linked alkyl-modified silicone, amino-modified silicone, polyether-modified silicone, polyglycerin-modified silicone, cross-linked polyether-modified silicone, cross-linked alkyl polyether Examples thereof include modified silicone, silicone-alkyl chain co-modified polyether-modified silicone, silicone-alkyl chain co-modified polyglycerin-modified silicone, polyether-modified branched silicone, polyglycerin-modified branched silicone, acrylic silicon, phenyl-modified silicone, and silicone resin. ..
Of these, methylpolysiloxane, crosslinked methylpolysiloxane, highly polymerized methylpolysiloxane, methylphenylpolysiloxane, and decamethylcyclopentasiloxane are preferable.

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

Examples of higher fatty acids include saturated or unsaturated, linear or branched higher alcohols having 8 to 22 carbon atoms. Specific examples thereof 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 preferable, and isostearic acid is more preferable.

As fats and oils, avocado oil, flaxseed oil, camellia oil, macadamia nut oil, kukui nut oil, hazelnut oil, corn oil, olive oil, saflower oil, kyonin oil, cinnamon oil, jojoba oil, grape seed oil, sunflower oil, etc. Almond oil, meadowfoam oil, southern ka oil, rapeseed oil, sesame oil, cacao butter, palm oil, hardened palm oil, palm oil, palm kernel oil, mokuro kernel oil, mokuro, wheat germ oil, rice germ oil, rice bran oil, Examples thereof include cottonseed oil, soybean oil, peanut oil, teaseed oil, evening primrose oil, shea butter, hardened oil, orange raffy oil, and horse oil.
Among them, 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, orange Raffy oil is preferred.

Examples of esters include isopropyl myristate, octyldodecyl myristate, isopropyl palmitate, cetyl palmitate, isononyl isononanoate, diisopropyl adipate, decyl oleate, oleyl oleate, isodecyl oleate, and hexyldecyl dimethyloctanoate. Diisopropyl sebacate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-ethylhexyl palmitate, diisopropyl adipate, isotridecyl isononanoate, cetyl lactate, isostearyl isostearate, cholesteryl 12-hydroxystearate, stearic acid Cholesteryl, cholesteryl oleate, macademia nut fatty acid phytosteryl, phytosteryl oleate, dextrin palmitate, inulin stearate, hydrogenated jojoba oil, di-2-ethylhexylate ethylene glycol, dipentaerythritol fatty acid ester, dicaprate neopentyl glycol, trimeritic acid Tri2-ethylhexyl, tridecyl trimeritoate, trimethylolpropane tri-2-ethylhexylate, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexanoate, glycerin tri-2-ethylhexanoate, triisostearate Methylolpropane, polyglyceryl diisostearate,) polyglyceryl monoisostearate, tri (capric acid / capric acid) glyceryl, tri (capric acid / capric acid / myristic acid / stearic acid) glyceryl, oleyl oleate, di lauroyl glutamate (phytosteryl / octyl) Dodecyl), dilauroyl glutamate (octyldodecyl / phytosteryl / behenyl), triethyl citrate, dimer dilinoleic acid (phytosteryl / isostearyl / cetyl / stearyl / behenyl), dimer dilinoleyl dimer dilinoleate, dipentaerythrityl tripolyhydroxystearate , Tri (bechenic acid / isostearic acid / eicosandioic acid) glyceryl, diisostearyl malate, triethyl citrate and the like.
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, isostear. Isostearyl acid, cholesteryl 12-hydroxystearate, cholesteryl stearate, cholesteryl oleate, macadamia nut fatty acid phytosteryl, phytosteryl oleate, dextrin palmitate, inulin stearate, hydrogenated jojoba oil, di-2-ethylhexylate ethylene glycol, di Pentaerythritol fatty acid ester, neopentyl glycol dicaprate, tri2-ethylhexyl trimeritate, tritridecyl trimeritate, trimethylol propane tri-2-ethylhexylate, trimethylol propane triisostearate, pentaerythritol tetra-2-ethylhexanoate, Glycerin tri-2-ethylhexanoate, trimethylolpropane triisostearate, polyglyceryl diisostearate,) polyglyceryl monoisostearate, tri (capric acid / capric acid) glyceryl, tri (capric acid / capric acid / myristic acid / stearic acid) Glyceryl, oleyl oleate, di lauroyl glutamate (phytosteryl / octyldodecyl), di lauroyl glutamate (octyldodecyl / phytosteryl / behenyl), triethyl citrate, dimer dilinoleic acid (phytosteryl / isostearyl / cetyl / stearyl / behenyl), di. Dimer dilinoleyl merjilinoleic acid, dipentaerythrityl tripolyhydroxystearate, tri (bechenic acid / isostearic acid / eicosandioic acid) glyceryl are preferred.

As the oil content, one type or two or more types can be used.

(F) Paraben The external skin preparation of the present invention is substantially free of parabens. In the present invention, substantially free of parabens means that the paraben content is 0.01% by mass or less based on the total amount of the external 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, it corresponds to not including paraben. For example, when a commercially available ingredient is blended in a skin external preparation and the commercially available product contains paraben and a small amount of paraben is mixed in the skin external preparation, it corresponds to not containing paraben.
Paraben is a paraoxybenzoic acid ester and a salt thereof, and examples thereof include methylparaben, ethylparaben, propylparaben, isopropylparaben, butylparaben, isobutylparaben, benzylparaben and the like, and sodium salt and potassium salt thereof.

Non-emulsifying The external skin preparation of the present invention is a non-emulsifying composition. In the present invention, the fact that the particles are not emulsified means that they do not contain emulsified particles having 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, its average particle size is 0.15 μm or less. The average particle size of the emulsified particles is a value measured by a dynamic light scattering method.

Transparency The skin external preparation of the present invention has a high oil content and is not emulsified, so that it has high transparency, and the appearance is transparent or translucent visually. As an index of transparency, the L value in the Lab color system (Hunter Lab system) can be used. The L value in the Lab color system of cosmetics is a value representing the transparency when the transparency of purified water is 100 and the case where no light is transmitted 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 test solution is placed in a glass cell (CM-A99, thickness 20 mm), and the spectrophotometer CM-5 It is a value measured using (manufactured by Konica Minolta Co., Ltd.) or the like. The L value is a value that hardly changes 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, even more preferably 70 to 100, and particularly preferably 80 to 100.
For example, when the oil is solubilized or contains a microemulsion or nanoemulsion having an average particle size of 0.15 μm or less, which corresponds to the non-emulsification referred to in the present invention, the appearance of the external skin preparation becomes transparent or translucent. ..

Alkanediol The skin external preparation of the present invention preferably contains an alkanediol having 5 to 10 carbon atoms, whereby excellent cushioning properties can be maintained for a long period of time.
The alkanediol preferably has 5 to 10 carbon atoms, more preferably 5 to 8 carbon atoms, and even more preferably 5 to 6 carbon atoms. The alkanediol is preferably 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 can be mentioned. Of these, 1,2-pentanediol, 1,2-hexanediol, and 1,2-octanediol are preferable, 1,2-pentanediol and 1,2-hexanediol are more preferable, and 1,2-pentanediol is even more preferable. ..
Commercially available products of alkanediol having 5 to 10 carbon atoms include HYDROLLITE-5, HYDROLLITE-5 Green (manufactured by Symrise Co., Ltd.), KMO-6 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Microcare Emorient PTGJ, and Microcare Emorient HXD. (Made by THOR) and the like.

As the alkanediol having 5 to 10 carbon atoms, one kind or two or more kinds can be used.

The content of alcandiol having 5 to 10 carbon atoms in the external preparation for skin of the present invention is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, and 0, based on the total amount of the external preparation for skin. 0.01% by mass or more is further preferable, 0.1% by mass or more is even more preferable, and 0.5% by mass or more is particularly preferable. 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, still more preferably 10% by mass or less, and 8% by mass, based on the total amount of the external preparation for skin. The following is even more preferable, and 5% by mass or less is particularly preferable. Within this range, sufficient stability and cushioning properties can be maintained for a long period of time in the preparation (at the time of application) and the skin feel after application.
The content of alkanediol is the total content of a plurality of alkanediols when they are contained.

pH
The pH of the external skin preparation of the present invention may be in the range of 2-9. In order to suppress irritation to the skin and mucous membranes and improve the usability, pH 3 to 8.5 is preferable, pH 4 to 8 is more preferable, pH 4.5 to 7.5 is further preferable, and pH 4.5 to 7 is further preferable. More preferred.

Viscosity The external skin preparation of the present invention preferably has a liquid dosage form having fluidity at 25 ° C., and more preferably a lotion agent. From this point of view, the viscosity (25 ° C.) of the external preparation for skin of the present invention is preferably 10 to 10000 mPa · s, more preferably 10 to 8000 mPa · s, even more preferably 50 to 6000 mPa · s, and 4000 mPa · s. The following are particularly preferred.
Viscosity is an index showing cushioning property. The external skin preparation of the present invention has a high viscosity because it has excellent cushioning properties.
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 measuring method described in the 17th revised Japanese Pharmacopoeia general test method. It is a value measured by the method described in Example.

Formulation form The skin external preparation of the present invention contains the above-described components as a base or carrier usually used for cosmetics, quasi-drugs, or pharmaceuticals, and, if necessary, additives or other physiological or pharmacological activities. By blending with the ingredients, it can be used as a cosmetic, quasi-drug, or pharmaceutical skin external preparation by a conventional method.

The properties of the external composition for skin of the present invention can be liquid, fluid, or the like.
As the formulation form, for example, a liquid agent, a suspension agent, a liniment agent, a lotion agent, an aerosol agent, a pump spray agent, a sheet agent obtained by impregnating a non-woven fabric with a chemical solution, a mist agent, or the like can be used. Among them, liquids, lotions, aerosols, pump sprays, sheet agents (sheet masking agents or sheet pack agents) in which a non-woven fabric is impregnated with a chemical solution, and mist agents are preferable, and liquid agents, lotions, and non-woven fabrics are impregnated with a chemical solution. Sheet agents (sheet masking agents or sheet packing agents) and mist agents are particularly preferable.

Usage When used as a skin lotion for non-pharmaceutical products or cosmetics, for example, basic cosmetics such as lotions, serums, sheet packs, sheet masks, all-in-one gels, and body lotions; hair mist, hair Examples include hair cosmetics such as lotions.

Base or carrier As the base or carrier, those that do not correspond to the above oils may be used. Even when oil is mixed, the content thereof is preferably 50% by mass or less, particularly 40% by mass or less, and particularly preferably 30% by mass or less in the base or carrier.
For example, water; cellulose derivatives such as ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose; vinyl-based polymers such as polyvinylpyrrolidone, carboxyvinyl polymers, alkyl-modified carboxyvinyl polymers, polyvinylbutyrate, alkyl methacrylate copolymers acrylate. Natural polymers such as carrageenan, alginic acid, cellulose, xanthan gum, guar gum, quince seeds, dextran, gellan gum; processed polysaccharides such as dextrin, maltodextrin; lower alcohols such as ethanol, isopropanol; sorbitol, xylitol, erythritol, Sugar alcohols such as mannitol; polyhydric alcohols such as polyethylene glycol, propylene glycol, propanediol, dipropylene glycol, 1,3-butylene glycol, glycerin, diglycerin, isoprene glycol; ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, Examples thereof include glycol ethers such as diethylene glycol monoethyl ether, propylene glycol monoethyl ether and dipropylene glycol monopropyl ether.
As the base or carrier, one kind or two or more kinds can be used.

Additives Additives include surfactants, thickeners, antioxidants, preservatives or preservatives, pH regulators, chelating agents, stabilizers, irritation reducing agents, colorants, dispersants, fragrances, pearl luster. Examples include additives.
As the additive, one kind or two or more kinds can be used. Further, the additive can be used as long as the effect of the present invention is not impaired.

Examples of the surfactant include POE-2-decyltetradecyl alcohol, POE-alkyl ethers such as polyoxyethylene oleyl ether and polyoxyethylene cetyl ether; sorbitan monostearate, sorbitan sesquistearate, sorbitan tristearate, and the like. Solbitan fatty acid esters such as sorbitan monooleate; POE monoisostearate (20) sorbitan, POE monooleate (20) sorbitan, POE monostearate (20) sorbitan, monococonut oil fatty acid POE (20) sorbitan, POE laurate ( 80) POE-sorbitan fatty acid esters such as sorbitan; glycerin fatty acid esters such as glyceryl monostearate and glyceryl oleate; POE-glycerin fatty acid esters such as glyceryl polyoxyethylene stearate and glyceryl polyoxyethylene trioleate; POE -Dihydrocholesterate, POE-hardened castor oil (eg, polyoxyethylene cured castor oil 40 (HCO-40), polyoxyethylene cured castor oil 50 (HCO-50), polyoxyethylene cured castor oil 60 (HCO-60)) ), POE-hardened sardine oil such as polyoxyethylene hardened sardine oil 80; POE-hardened sardine oil (POE (3) sardine oil, POE (20) sardine oil, etc.); POE-hardened sardine oil iso POE-hardened castor oil fatty acid ester such as stearate; POE-alkylaryl ether; glycerin alkyl ether such as cumyl alcohol, bacillus alcohol, ceracyl alcohol; POE-glycerin alkyl ether such as POE-monostearyl glyceryl ether; stearic acid POE fatty acid esters such as polyoxyl; POE stearic acid / hydrogenated stearic acids such as POE (20) phytosterol, POE (30) phytosterol, POE (25) phytostanol, POE (30) chorestanol; sucrose palmitate, sucrose Sucrose fatty acid esters such as stearic acid ester, sucrose oleic acid ester, sucrose isostearic acid ester, sucrose linoleic acid ester, sucrose linolenic acid ester; polyethylene glycol fatty acid ester such as polyethylene glycol dioleate; alkyl polyglycoside, mono Diglyceryl stearate, diglycerate monoisostearate Polyglycerin fatty acid esters such as lyl, decaglyceryl monostearate, decaglyceryl monooleate, decaglyceryl pentaoleate, hexaglyceryl polyricinoleate; nonionic surfactants such as alkyl-modified silicones and emulsified silicone elastomers. Be done.
Also, for example, higher alkyl sulfates (eg, sodium lauryl sulfate, potassium lauryl sulfate, etc.); alkyl ether sulfates (eg, POE-lauryl sulfate triethanolamine, POE-sodium lauryl sulfate, etc.); N-acylsarcosin. Acids (eg sodium lauroyl sarcosin); higher fatty acid amide sulfonates (eg sodium stearoylmethyl taurine, sodium myristylmethyl taurine, sodium cocoyl methyl taurine, sodium cocoyl methyl taurine taurine); phosphate esters and salts thereof (POE) -Sodium oleyl ether phosphate, POE-stearyl ether phosphate, potassium cetyl phosphate, cetyl phosphate, etc.); sulfosuccinate (eg, sodium di-2-ethylhexyl sulfosuccinate); alkylbenzene sulfonate (eg, linearddecyl) Sodium benzenesulfonate, etc.); Higher fatty acid ester sulfate ester salt (eg, hardened coconut oil fatty acid, sodium glycerin sulfate, etc.); N-acylglutamate (eg, monosodium lauroyl glutamate, sodium stearoyl glutamate, sodium myristoyl glutamate, etc.); N -Acylalanine salts (eg, sodium lauroylmethylalanine, cocoylalanine triethanolamine salts, etc.); Sulfated oils (eg, funnel oil, etc.); POE-alkyl ether carboxylic acids; POE-alkylallyl ether carboxylates; α- Olefin sulfonate; higher fatty acid ester sulfonate; secondary alcohol sulfate ester salt; higher fatty acid alkylolamide sulfate ester salt; sodium lauroyl monoethanolamide succinate; N-palmitoyl aspartate ditriethanolamine; anion such as sodium caseinate Sexual surfactants are also included.
Also mentioned are, for example, cationic surfactants such as mono- or di-long chain alkyl tertiary or quaternary ammonium salts having a linear or branched long chain alkyl group to which an alkylene oxide may be added. Be done.
Also included are amphoteric surfactants such as carbobetaine, sulfobetaine, imidazolinium betaine, and amide betaine.
Also included are naturally occurring surfactants such as lecithin, hydrogenated lecithin, saponin, sodium surfactinate, bile acids and the like.

Examples of the thickener include vinyl thickeners such as polyvinyl alcohol, polyvinylpyrrolidone, polyvinylmethyl ether, carboxyvinyl polymer, alkyl methacrylate copolymer, sodium polyacrylate; methyl cellulose, ethyl cellulose, and hydroxyethyl cellulose. , Hydroxymethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose and other cellulose-based thickeners; Polysaccharides such as carrageenan, agar, alginic acid, sodium alginate, fucogel; gelatin, alkyl methacrylate copolymer, sodium polyacrylate, bentonite, dextrin fatty acid ester, dimethyl distearyl ammonium hecterite, propylene glycol alginate, Polyethylene glycol, macrogol, polyacrylamide, (hydroxyethyl acrylate / acryloyldimethyltaurine Na) copolymer, (acryloyldimethyltaurinammonium / vinylpyrrolidone) copolymer, (acryloyldimethyltaurinammonium / behenez methacrylate-25) crosspolymer, (acrylic) Examples thereof include Na acid / acryloyldimethyltaurine Na) copolymer.

Examples of the antioxidant include lignans such as dibutylhydroxytoluene, butylhydroxyanisole, sorbic acid, sodium sulfite, ascorbic acid, erythorbic acid, sodium erythorbate, L-cysteine hydrochloride, and sesamin, curcumin, capsaicin, zincerol, and less. Examples include veratrol, anthocyanin, cyanidin, and bilberry extract.

Examples of the preservative or preservative include benzoic acid, sodium benzoate, dehydroacetic acid, sodium dehydroacetate, isopropylmethylphenol, phenoxyethanol, sodium pyrosulfite and the like.

As pH adjusters, inorganic acids (hydrogen 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.) ), Organic bases (triethanolamine, diisopropanolamine, triisopropanolamine, etc.) and the like.

Examples of the chelating agent include ethylenediaminetetraacetic acid (edetic acid), ethylenediaminetetraacetic acid salt (sodium salt (sodium edetate: Japanese Pharmacy, EDTA-2Na, etc.), potassium salt, etc.), phytic acid, gluconic acid, polyphosphate, etc. , Metaphosphate and the like.

Examples of the stabilizer include sodium polyacrylate, dibutylhydroxytoluene, butylhydroxyanisole and the like.

Examples of the irritation reducing agent include licorice extract, gum arabic, polyvinylpyrrolidone, sodium alginate and the like.

Examples of the colorant include inorganic pigments and natural pigments.

Examples of the pearl gloss imparting agent include ethylene glycol distearate, ethylene glycol monostearate, and triethylene glycol distearate.

Physiologically active or pharmacologically active ingredients Physiologically active or pharmacologically active ingredients include UV scatterers, UV absorbers, ingredients that prevent and / or repair DNA damage, whitening ingredients, anti-inflammatory ingredients, antibacterial ingredients, and refreshing agents. Organic acids, anti-glycation components, cell activation components, astringent components, antioxidant components, anti-aging components, moisturizing components, polyhydric alcohols, keratin softening components, vitamins, blood circulation promoting components, sebum adsorbing components, peptides or derivatives thereof, Examples thereof include amino acids or derivatives thereof.
As the physiologically active or pharmacologically active ingredient, one kind or two or more kinds can be used. Moreover, the physiologically active or pharmacologically active ingredients can be used as long as the effects of the present invention are not impaired.
When a plant component is used in the present invention as a physiologically active or pharmacologically active component, the form of the plant component is not particularly limited, but it can usually be used in the form of a plant extract (plant extract), an essential oil, or the like. The numbers in parentheses in the plant components are the scientific name, alias or crude drug name of the plant.

UV scatterers include, for example, inorganic compounds such as zinc oxide, titanium oxide, iron oxide, cerium oxide, zirconium oxide, titanium silicate, zinc silicate, silicic anhydride, cerium silicate, hydrous silicic acid; Inorganic compounds coated with hydrous silicic acid, aluminum hydroxide, inorganic powders such as mica and talc; composites of these inorganic compounds with resin powders such as polyamide, polyethylene, polyester, polystyrene and nylon. Examples thereof include those obtained by treating these inorganic powders, coatings, or composites with silicone oil, fatty acid aluminum salts, alkyl titanates, or the like.

Examples of the ultraviolet absorber include 2-ethylhexyl paramethoxysilicate, ethylhexyl paramethoxysilicate, 4-tert-butyl-4'-methoxydibenzoylmethane, 2- [4- (diethylamino) -2-hydroxybenzoyl]. Hexyl benzoate, hexyl diethylaminohydroxybenzoyl, hexyl benzoate, 2-ethylhexyl dimethoxybenzylideneoxoimidazolidinepropionate, 2,2'-methylenebis [6- (2H-benzotriazol-2yl) -4- (1,1) , 3,3-Tetramethylbutyl) phenol], 2,4-bis- [{4- (2-ethylhexyloxy) -2-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3 5-triazine, 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine, t-butylmethoxydibenzoylmethane, dibenzylidene dioxoimidazolidine ethylhexyl propylate , Etruhexyltriazoline, paraaminobenzoic acid and its derivatives, octyl paradimethylaminobenzoate, -2-ethylhexyl salicylate, ethylene glycol satylate, dihydroxybenzophenone, dimethicodiethylbenzalmalonate, 2-cyano-3,3- Examples thereof include 2-ethylhexyl ester of diphenylpropa-2-enoic acid and 2-phenylbenzoimidazole-5-sulfonic acid.

Ingredients that have the effect of preventing and / or repairing DNA damage include, for example, components derived from animals (eg, artemia); components derived from plants (eg, cat's claw); DNA, DNA salts, RNA, RNA salts. Nucleic acid components such as.

Examples of whitening ingredients include nicotinic acid amide, placenta, arbutin, kodiic acid, ellagic acid, phytic acid, tranexamic acid, lucinol, chamomile ET, hydroquinone, 4-methoxysalicylic acid potassium salt, linoleic acid and its derivatives, ascorbic acid, and the like. Sodium ascorbic acid, sodium ascorbic acid phosphate, magnesium ascorbic acid phosphate, ascorbic tetra2-hexyldecanoate, 2-O-ethylascorbic acid, 3-O-ethylascorbic acid, ascorbic acid glucoside, isostearyl ascorbic acid 2 sodium, L-ascorbic dipalmitate, trisodium ascorbic acid palmitate, glyceryl ascorbic acid, bisglyceryl ascorbic acid, alkyl glyceryl ascorbic acid, plants (iris, almond, aloe, acerola, ages, augon, auren, otogirisou, Ascorbic acid, seaweed, cucumber, chlorella, rice, rice haiga, oryzanol, rice bran, perilla, ascorbic acid, sohakuhi, soybean, tea, ascorbic acid, hamamelis, buttonpi, yokunin, kiwi, sage, parsley, holly, hop, thyme, chow , Kanzo, chamomile, prunes, shimotsukesou, murasakikibu, sozuku, grab fruit, thorns, lemon, kiwi, pine, neem, artichoke, sugina, obak, mematsuyoigusa, bilberry, himefuuro, akeshisou, seiyoshiroyanagi Ingredients derived from (lavender, ascorbic acid, etc.) can be mentioned.

Examples of the anti-inflammatory component include allantin, caramine, tranexamic acid, glycyrrhizinic acid or a derivative thereof or a salt thereof (for example, dipotassium glycyrrhizinate, monoammonium glycyrrhizinate, etc.), glycyrrhetinic acid or a derivative thereof or a salt thereof (for example, for example. Glycyrrhetinic acid, stearyl glycyrrhetinate, etc.), zinc oxide, aminocaproic acid, azulene and its derivatives (eg, guaiazulene, azulene, etc.), tocopherol acetate, pyridoxin hydrochloride, menthol, camphor, terepine oil, indomethacin, salicylic acid or its derivatives, steroids Alternatively, a derivative thereof or a salt thereof (for example, hydrocortisone, prednisolone), ufenamate, bufexamac, ibuprofenpiconol, glycol salicylate, a component derived from a plant (for example, comfrey, auren, dokudami) and the like can be mentioned.

Examples of the antibacterial component include chlorhexidine, salicylic acid, benzalkonium chloride, acrinol, ethanol, benzethonium chloride, cresol, gluconic acid and its derivatives, popidone iodine, potassium iodide, iodine, isopropylmethylphenol, triclosan, triclosan, and photosensitizer. No. 101, Photosensitizer No. 201, Phenoxyethanol, Alkyldiaminoglycine hydrochloride, Cetylpyridinium chloride, Pyroctolamine, Myconazole or a salt thereof, Chlorhexanol, Ethylhexylglycerin, Propinyl iodide butylcarbamate, Capril hydroxamic acid, Hydroxyacetophenone, Penetyl alcohol, Methyl Examples include isothiazolinone, sorbic acid, β-glycyrrhetinic acid, components derived from plants (eg, clara, rosemary, quail, eucalyptus, etc.).

As the refreshing agent, for example, menthol and its derivatives, camphor, borneol, geraniol, cineole, anethole, limonene, eugenol and other terpenes (these may be d-form, l-form or dl-form); eucalyptus oil. , Bergamot oil, peppermint oil, cool mint oil, spare mint oil, eucalyptol oil, camphor oil, eucalyptol oil, rose oil, terpene oil and other essential oils.

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 and phytin. Examples thereof include acids, 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. Salts include, for example, mineral acid salts such as sulfuric acid, hydrochloric acid or phosphoric acid, organic acid salts such as maleic acid or methanesulfonic acid, alkali metal salts such as sodium or potassium, alkaline earth metal salts, etc. Examples include ammonium salts, basic amino acid salts, amine salts such as triethanolamine and the like.

Examples of anti-glycation components include Budreja axilaris leaf extract, seaweed fruit extract, edelweiss extract, ginkgo extract, cherry leaf extract, pomegranate extract, sardine extract, sardine extract, sardine extract, dokudami extract, bilberry leaf extract, and the like. Green tea extract, tea extract, marronnier extract, roma chamomile extract, yomogi extract and other plant extracts, evening primrose oil, Amler fruit, fruit juice or their extracts, L-arginine, L-lysine, hydrolyzed casein, hydrolyzable tannin , Carnosin and the like.

Examples of cell activating components include amino acids such as γ-aminobutyric acid: vitamins such as retinol, thiamine, riboflavin, pyridoxine hydrochloride, and pyrroloquinolinquinones pantothenate; tannins, flavonoids, saponins, allantin, placenta, proteoglycans, etc. Photosensitizer 301, ingredients derived from plants (eg soybean bilberry, lemongrass, aloe vera, chlorella, corn, yogurt, chamomile, dokudami, hop, carrot, etc.); royal jelly, royal jelly extract; whey, yogurt extract, hydrolyzed milk Examples include whey-derived extracts such as protein and yeast extracts.

Convergent components include, for example, metal salts such as alum, chlorohydroxyaluminum, aluminum chloride, allantoin aluminum salt, zinc paraphenol sulfonate, basic zinc lactate, zinc sulfate, potassium aluminum sulfate; plants (eg seaweed, thyme, thyme, etc. Ingredients derived from tea, oolong tea, green tea, otogirisou, hamamelis, biwa, buttonpi, yukinoshita, luibos, lotus, artichoke, chamomile, eucalyptus, lemon, rosemary, waremokou, etc. can be mentioned.

Antioxidant components include, for example, butylhydroxyanisole, dibutylhydroxytoluene, sodium hydrogen sulfite, sodium pyrosulfite, erythorbic acid and its salt, ascorbic acid and its salt, flavonoids, glutathione, glutathione peroxidase, glutathione-S-transferase, catalase. , Superoxide dismutase, thioredoxin, taurine, thiotaurine, hipotaurin, plants (eg, otogirisou, cucumber, bilberry, ginger, kudamonotokeisou, grapefruit, shakuyaku, shimotsukesou, shiso, watermelon, sage, Ingredients derived from chimpi, Himefuuro, Biwa, Benibana, Buttonpi, Hop, Eucalyptus, Yukinoshita, Louis Boss, Lemongrass, Soybean, Yomogi, Mematsuyoigusa, Rosemary, Lavender, etc. can be mentioned.

Examples of the anti-aging component include hydrolyzed soy protein, pangamic acid, ursoleic acid, turmeric extract, sphingosine derivative, silicon, silicic acid, N-methyl-L-serine, mevalonolactone, and peptides (caprooil tetrapeptide-3). , Oligopeptide-24, etc.) and the like.

Moisturizing ingredients include, for example, amino acids such as alanine, serine, aspartic acid, glycine, proline, hydroxyproline, glucosamine, theanine, arginine and derivatives thereof; glycerin, dipropylene glycol, 1,3-butylene glycol, diglycerin and the like. Polyhydric alcohols; polyoxyalkylene methyl glucoside, polyoxyethylene polyoxypropylene methyl glucoside, PEG / PPG / polybutylene glycol-8 / 5/3 glycerin, polyoxyethylene polyoxypropylene butyl ether, PPG-24 glyceres-24, etc. Polyhydric alcohol derivatives; sugar alcohols such as sorbitol, xylitol, erythritol, maltose-sucrose condensate (glucooligosaccharide), hydrolyzed xylan (xylooligosaccharide); glycosyltrehalose, trehalose; ceramide, glucosylceramide, cholesterol, phytosterol, cholesterol derivatives , Phytosterol derivatives ,; phospholipids such as lecithin, hydrogenated lecithin; NMF-derived components such as urea; collagen, elastin, keratin, chitin, chitosan and their hydrolyzates; hydroxyethylurea; plants (eg, aloe, seaweed) , Cuckon, chlorella, lemongrass, chamomile, hamamelis, cha, perilla, grapefruit, amachaduru, etc.).

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

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

Examples of vitamins include retinol derivatives such as retinol, retinol acetate, retinol palmitate, retinol propionate, and retinol linoleate, retinal, retinoic acid, methyl retinoate, ethyl retinoate, retinol retinoate, and d-δ-toco. Vitamin A such as ferryl retinoate, α-tocopheryl retinoate, β-tocopheryl retinoate; pros such as β-carotene, α-carotene, γ-carotene, δ-carotene, lycopene, zeaxanthin, cryptoxanthin, ekinenone Vitamin A; dl-α-tocopherol, dl-α-tocopherol succinate, dl-α-tocopherol succinate calcium, δ-tocopherol, tocopherol nicotinate, dl-α-tocopherol acetate, tocopherol linoleic acid, (linoleic acid / Vitamin Es such as (oleic acid) tocopherol, (ascorbic / tocopheryl) potassium phosphate; riboflavin, flavin mononucleotide, flavin adenin dinucleotide, riboflavin butyrate, riboflavin tetrabutyric acid ester, riboflavin 5'-sodium phosphate, riboflavin Vitamin B2s such as tetranicotinic acid ester; methyl nicotinate, nicotinic acid, benzyl nicotinate, nicotinic acid amide, dl-α-tocopherol nicotinate, β-butoxyethyl nicotinate, 1- (4-methylphenyl) nicotinate ) Ethyl-like nicotinic acids (vitamins B3); ascorbic stearate, disostearyl ascorbyl phosphate, L-ascorbyl dipalmitate, ascorbyl tetraisopalmitate (ascorbic tetra2-hexyldecanoate), ascorbic acid palmitate Trisodium acid, ascorbic acid, sodium ascorbic acid, dehydroascorbic acid, sodium ascorbic acid phosphate, magnesium ascorbic acid phosphate, ascorbic acid glucoside, 2-O-ethylascorbic acid, 3-O-ethylascorbic acid, glyceryl Vitamin Cs such as ascorbic acid, bisglyceryl ascorbic acid, alkylglyceryl ascorbic acid; vitamin Ds such as methyl hesperidin, ergocalciferol, cholecalciferol; vitamin Ks such as phylloquinone, farnoquinone; thiamine and theirs Salt (eg dibenzoyl Vitamin B1s such as thiamine hydrochloride, thiamine hydrochloride, thiaminniphosphate,); pyridoxine hydrochloride, pyridoxine acetate, pyridoxal hydrochloride, 5'-pyridoxal phosphate, vitamin B6s such as pyridoxamine hydrochloride, cyanocobalamin, hydroxocobalamine , Vitamin B12s such as deoxyadenosylcobalamine; Pyridoxine, Folic acids such as pteroylglutamic acid; Pantothenic acids such as pantothenyl ethyl ether and calcium pantethene sulfonate; vitamins such as biotin and biocithin can be mentioned. Other examples include vitamin-like acting factors such as carnitine, ferulic acid, α-lipoic acid, ollotic acid, γ-oryzanol, pyrroloquinoline quinone, hesperidin and glucosyl herperidin, ubiquinone, and salts thereof.

Examples of blood circulation promoting components include plants (for example, tanen carrot, ash taba, arnica, ginkgo, uikyo, enmeisou, Dutch oak, chamomile, roman chamomile, carrot, gentiana, gobo, rice, sanzashi, shiitake, seiyousanzashi, seiyounezu, senkyu. , Senburi, Thyme, Chouji, Chimpi, Touki, Tounin, Touhi, Carrot, Garlic, Butcher Bloom, Grape, Button, Maronnier, Melissa, Yuzu, Yokuinin, Rosemary, Rosehip, Chimpi, Touki, Touhi, Peach, Anzu, Ingredients derived from walnuts, corn); dl-α-tocopherol acetate, tocopherol nicotinate, glucosyl hesperidin, hesperidin and the like.

Examples of the sebum-adsorbing component include talc, mica, hydroxyapatite, zinc oxide, aluminum silicate and the like.

Examples of the peptide or its derivative include keratin-degrading peptide, hydrolyzed keratin, collagen, fish-derived collagen, atelocollagen, succinylated atelocollagen, gelatin, elastin, elastin-degrading peptide, collagen-degrading peptide, hydrolyzed collagen, hydroxypropylammonium chloride hydrate. Degraded collagen, elastin-degrading peptide, conchiolin-degrading peptide, hydrolyzed conchiolin, silk proteolytic peptide, hydrolyzed silk, lauroyl hydrolyzed silk sodium, soybean proteolytic peptide, hydrolyzed soybean protein, wheat protein, wheat proteolytic peptide, hydrolysis Wheat protein, casein-degrading peptide, acylated peptide (palmitoyl oligopeptide, palmitoyl pentapeptide, palmitoyl tetrapeptide, etc.) and the like can be mentioned.

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, and cystine. , Methionin, leucine, isoleucine, valine, histidine, threonine, tyrosine, taurine, γ-aminobutyric acid, γ-amino-β-hydroxybutyric acid, carnitine, carnosin, creatin, epsilon aminocaproic acid, tryptophan, ornithine, N-stearoyl-L -Sodium glutamate, lysine dilauroyl glutamate and salts thereof, di lauroyl glutamate (phytosteryl / octyldodecyl), di lauroyl glutamate (octyldodecyl / phytosteryl / behenyl) and the like. These amino acids or derivatives thereof may be solvates such as hydrates, and may be d-form, l-form, or dl-form.

The external skin preparation of the present invention can be contained and used in a container of an appropriately selected shape and material according to the purpose of use and use. For example, a spray type, a pump type, a bottle type, a tube type, a dropper type, a dispenser type, a pouch bag, a cheer pack and the like can be exemplified.
Further, as the material of the container, polyethylene terephthalate, polypropylene, polyethylene (HDPE, LDPE, LLDPE, etc.), ABS resin, ethylene vinyl alcohol resin, polystyrene, glass, metal (aluminum, etc.) and the like can be exemplified. In addition, these materials are used as container materials by performing various coating treatments or combining these materials by mixing or laminating in consideration of strength, flexibility, weather resistance, stability of components, and the like. be able to. Examples of the coating material include epoxy resin and polyamide-imide. Among them, polypropylene, polyethylene (HDPE, LDPE, LLDPE, etc.) and ethylene vinyl alcohol resin are preferably used, and polypropylene and polyethylene (HDPE, LDPE, LLDPE, etc.) are more preferable.

The present invention contains (A) high molecular weight hyaluronic acid having a weight average molecular weight of 50,000 or more or a salt thereof, (B) low molecular weight hyaluronic acid having a weight average molecular weight of less than 50,000 or a salt thereof, and (D) water. E) Non-emulsifying skin external preparation containing (C) hyaluronic acid derivative in a non-emulsifying skin external preparation having an oil content of 0 to 10% by mass and substantially free of paraben. Provided is a method for improving cushioning or stickiness in the skin feel after application (during application) and / or after application while suppressing the effect. In this method, the (E) oil content 0 to 10 is the content after the (C) hyaluronic acid derivative is contained in the non-emulsifying skin external preparation.
The type of each component, the blending amount, the properties of the external skin preparation, and the like are as described for the external skin preparation of the present invention.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
(1) Effect of Acetyl Hyaluronic Acid The skin external preparations whose compositions are shown in Tables 1 and 2 were prepared according to a conventional method. These external skin preparations are lotions that do not contain emulsified particles. In addition, the visual appearance of these external skin preparations was transparent.
The viscosity of each external preparation was measured, and the viscosity increase rate was calculated according to the formula (1). In the formula (1), the comparative examples corresponding to Examples 1 to 4 are Comparative Examples 1 to 4, respectively.

Viscosity increase rate = [(viscosity of example) / viscosity of corresponding comparative example] × 100 ... (1)

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

The results are shown in Tables 1 and 2. The unit of the component content in Tables 1 and 2 is mass%.
As shown in Table 1, the viscosity of Standard Examples 1 to 3 containing acetylated hyaluronic acid but not hyaluronic acid or a salt thereof is the same as that of Standard Example 4 containing both acetylated hyaluronic acid and hyaluronic acid or a salt thereof. In addition, it was zero. It can be seen that acetylated hyaluronic acid itself has no viscosity-increasing effect.

Further, as shown in Table 2, high-molecular-weight sodium hyaluronate having a weight average molecular weight of 50,000 or more and low-molecular-weight sodium hyaluronate having a weight average molecular weight of less than 50,000 are used as hyaluronic acid or a salt thereof, and a trace amount of acetyl is used therein. By blending hyaluronic acid, the viscosity was significantly increased. It can be seen that the viscosity was increased by combining high molecular weight sodium hyaluronate having a weight average molecular weight of 50,000 or more, low molecular weight sodium hyaluronate having a weight average molecular weight of less than 50,000, and acetylated hyaluronic acid.
Since the viscosity is one index indicating the cushioning property of the composition, acetylation is performed by including hyaluronic acid or a salt thereof having a weight average molecular weight of 50,000 or more and a weight average molecular weight of less than 50,000. It was shown that the combination of hyaluronic acid greatly improves the cushioning property.

(2) Effect of Alkanediol The external skin preparations shown in Tables 3 to 5 were prepared according to a conventional method, and 50 mL was contained in a glass container having a capacity of 50 mL. These external skin preparations are lotions that do not contain emulsified particles. In addition, the visual appearance of these external skin preparations was transparent. The entire container was stored at 50 ° C. for 1 week, the viscosity was measured before and after storage, and the viscosity reduction rate was calculated according to the formula (2).

Viscosity reduction rate = [(Viscosity after storage-Viscosity before storage) / Viscosity before storage] x 100 ... (2)

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

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 3-5. The unit of the component content in Tables 3 to 5 is mass%.
The rate of decrease in viscosity under harsh conditions at 50 ° C. for 1 week was significantly improved by the addition of alkanediol. On the other hand, even if the same diol compounds dipropylene glycol and polyethylene glycol 400 and the same polyol compound concentrated glycerin were blended, the viscosity reduction rate was not improved at all.

(3) Evaluation of usability The external skin preparations were applied to the arms of five subjects who understood the evaluation criteria, and 1 to 5 points (integer values) were evaluated for the feel of the applied portion. That is, regarding the stickiness at the time of application, 1 point was given for those who strongly felt it, and 5 points were given for those who did not feel it, and the values corresponding to the feeling felt by the subject were shown. Regarding the stickiness of the skin after 1 minute of application, 1 point was given for those who felt strongly, and 5 points were given for those who did not feel it. In addition, 1 point was given for those who did not feel the cushioning property of the skin after 1 minute of application, and 5 points for those who felt strongly. Next, the average value of the scores of each example was calculated and used as the evaluation value of the external skin preparation.

The results are shown in Table 6. From the comparison between Example 1 and Comparative Example 1, the comparison between Example 2 and Comparative Example 2, and the comparison between Example 4 and Comparative Example 4, high molecular weight hyaluronic acid having a weight average molecular weight of 50,000 or more, or a salt and weight thereof. By adding acetylated hyaluronic acid to a skin external preparation containing low-molecular-weight hyaluronic acid having an average molecular weight of less than 50,000 or a salt thereof, the sticky feeling does not change or is rather improved, but the skin after application It can be seen that the cushioning property of is significantly increased.
Further, in Reference Example 2, since hyaluronic acid or a salt thereof was not contained, the cushioning property was very low although the stickiness was small. It was confirmed that acetylated hyaluronic acid itself has no cushioning property.
Further, as shown in Comparative Example 5, when the blending amount of the high molecular weight hyaluronic acid was increased instead of blending the acetylated hyaluronic acid, good cushioning property was obtained, but the stickiness became very strong. It was confirmed that the cushioning property can be enhanced by adding acetylated hyaluronic acid, and the amount of hyaluronic acid or a salt thereof can be reduced accordingly to suppress stickiness.

The weight average molecular weight of the acetylated sodium hyaluronate used in the item of the example is 100,000.

An example of prescribing the external skin preparation of the present invention is shown below. The unit of the component content in Tables 7 and 8 is mass%, and the numerical value in parentheses is the weight average molecular weight.

By containing hyaluronic acids in a specific combination, the external preparation for skin of the present invention has excellent cushioning properties, and despite containing a high concentration of hyaluronic acid, it is less sticky and has a good usability. Therefore, it has a very high commercial value.

Claims (9)

Contains (A) high molecular weight hyaluronic acid having a weight average molecular weight of 50,000 or more or a salt thereof, (B) low molecular weight hyaluronic acid having a weight average molecular weight of less than 50,000 or a salt thereof, (C) a hyaluronic acid derivative, and (D) water. However, (E) a non-emulsifying skin external preparation having an oil content of 0 to 10% by mass and (F) substantially free of parabens. (A) The skin external preparation according to claim 1, wherein the content of the high molecular weight hyaluronic acid having a weight average molecular weight of 50,000 or more or a salt thereof is 0.001 to 1% by mass with respect to the total amount of the skin external preparation. .. (B) The skin according to claim 1 or 2, wherein the content of low molecular weight hyaluronic acid having a weight average molecular weight of less than 50,000 or a salt thereof is 0.0001 to 1% by mass with respect to the total amount of the external skin preparation. External preparation. (C) The skin external preparation according to any one of claims 1 to 3, wherein the content of the hyaluronic acid derivative is 0.00001 to 0.3% by mass with respect to the total amount of the skin external preparation. (C) High molecular weight hyaluronic acid having a weight average molecular weight of 50,000 or more or a salt thereof and (B) Low molecular weight hyaluronic acid having a weight average molecular weight of less than 50,000 or a salt thereof with respect to 1 part by mass of the hyaluronic acid derivative. The external preparation for skin according to any one of claims 1 to 4, which comprises 0.005 to 200,000 parts by mass in total. The external skin preparation according to any one of claims 1 to 5, further comprising an alkanediol having 5 to 10 carbon atoms. The skin external preparation according to claim 6, wherein the content of the alkanediol having 5 to 10 carbon atoms is 0.0001 to 20% by mass with respect to the total amount of the skin external preparation. The external skin preparation according to any one of claims 1 to 7, wherein the L value in the Lab color system is 40 or more. (A) High molecular weight hyaluronic acid having a weight average molecular weight of 50,000 or more or a salt thereof, (B) Low molecular weight hyaluronic acid having a weight average molecular weight of less than 50,000 or a salt thereof, (D) Water, and (E) Oil content The amount is 0 to 10% by mass, and (F) a non-emulsifying skin external preparation containing substantially no paraben, (C) a hyaluronic acid derivative is contained in the preparation and the non-emulsifying skin external preparation while suppressing stickiness. / Or a method for improving the cushioning property or the sticky feeling on the skin after application (however, (E) oil content 0 to 10% by mass is the content after (C) hyaluronic acid derivative is added). ..