External preparation for skin

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

Technical Field

[0001] The present invention relates to an external preparation for skin used as a cosmetic, quasi-drug, or pharmaceutical product.

Background Art

[0002] Hyaluronic acid is a mucopolysaccharide composed of glucuronic acid and N-acetylglucosamine, and is present in large amounts in the dermis as a conjugate substance filling between cells and fibers in vivo, and is also present in the epidermis. Since hyaluronic acid has high water retention and viscoelasticity, it is widely used in external skin preparations as a moisturizing agent and the like.

[0003] When hyaluronic acid is blended in an external skin preparation, a unique feeling of use such as cushioning or a feeling of thickness can be obtained due to the viscosity and viscoelasticity peculiar to hyaluronic acid. Furthermore, by applying such a preparation to the skin, a moist and cushioned or thick feeling of the skin texture that adheres to the hand can be obtained. This feeling of use is a cushioning or thick feeling, and is a unique feeling of use preferred by consumers. On the other hand, since hyaluronic acid is a component with strong drawability, blending it gives a sticky feeling. In order to improve the cushioning of the skin during and after application, it is required to blend hyaluronic acid at a high concentration, but the stickier it becomes as the blending amount of hyaluronic acid increases. Therefore, it is difficult to achieve both cushioning and a smooth feeling of use.

[0004] Patent Document 1 teaches that acetyl hyaluronic acid has an excellent skin softening effect while improving the drawbacks of hyaluronic acid such as high drawability.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] An object of the present invention is to provide a topical skin preparation containing hyaluronic acid or a salt thereof, having high cushioning properties, and suppressing stickiness.

Means for Solving the Problems

[0007] In order to solve the above problems, the present inventors have conducted repeated studies and added, as hyaluronic acids, 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 to a non-emulsified topical skin preparation containing water, having an oil content of 0 to 10% by mass, and substantially free of parabens. By further adding a hyaluronic acid derivative thereto, while suppressing the blending amount of hyaluronic acids that causes stickiness, it is possible to enhance the thickness or cushioning feeling felt during application and the cushioned texture of the skin after application. As a result, it has been found that high cushioning properties and a smooth feeling in use can be achieved simultaneously. In addition, it has been found that by adding an alkanediol having 5 to 10 carbon atoms to this topical skin preparation, a decrease in viscosity over time can be suppressed. As a result, a decrease in the cushioning properties or the thick feeling in use of the preparation is suppressed, and a decrease in the thickness feeling of the preparation itself is also suppressed.

[0008] The present invention has been completed based on the above findings, and provides the following topical skin preparation. 〔1〕 A non-emulsified topical skin preparation containing (A) a high-molecular-weight hyaluronic acid having a weight-average molecular weight of 50,000 or more or a salt thereof, (B) a 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, (E) having an oil content of 0 to 10% by mass, and (F) being substantially free of parabens. 〔2〕 The topical skin preparation according to 〔1〕, wherein the content of (A) a 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 based on the total amount of the topical skin preparation. 〔3〕(B) The content of low-molecular-weight hyaluronic acid with a weight-average molecular weight of less than 50,000 or its salt is 0.0001 to 1% by mass based on the total amount of the external preparation for skin, the external preparation for skin according to 〔1〕or 〔2〕. 〔4〕(C) The content of the hyaluronic acid derivative is 0.00001 to 0.3% by mass based on the total amount of the external preparation for skin, the external preparation for skin according to any one of 〔1〕to 〔3〕. 〔5〕(C) Based on 1 part by mass of the hyaluronic acid derivative, the total of (A) high-molecular-weight hyaluronic acid with a weight-average molecular weight of 50,000 or more or its salt and (B) low-molecular-weight hyaluronic acid with a weight-average molecular weight of less than 50,000 or its salt is 0.005 to 200,000 parts by mass, the external preparation for skin according to any one of 〔1〕to 〔4〕. 〔6〕Furthermore, the external preparation for skin according to any one of 〔1〕to 〔5〕, which contains an alkanediol having 5 to 10 carbon atoms. 〔7〕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, the external preparation for skin according to 〔6〕. 〔8〕The external preparation for skin according to any one of 〔1〕to 〔7〕, wherein the L value in the Lab color system is 40 or more. 〔9〕A method for improving the cushioning property or the mochi-mochi feeling in the texture of the preparation (during application) and / or after application while suppressing the stickiness of a non-emulsified external preparation for skin, which contains (A) high-molecular-weight hyaluronic acid with a weight-average molecular weight of 50,000 or more or its salt, (B) low-molecular-weight hyaluronic acid with a weight-average molecular weight of less than 50,000 or its salt, and (D) water, has an oil content of 0 to 10% by mass, and is substantially free of parabens, and includes (C) a hyaluronic acid derivative (however, the oil content of 0 to 10% by mass in (E) is the content after including (C) the hyaluronic acid derivative).

Advantages of the Invention

[0009] The external preparation for skin of the present invention contains water, has an oil content of 0 to 10% by mass, is a non-emulsified external preparation for skin that is substantially free of parabens, and is formulated by combining three specific types of hyaluronic acids. As a result, the cushioning property or thickness feeling of hyaluronic acid or its salt is effectively enhanced. Therefore, since the blending amount of hyaluronic acids that causes stickiness can be suppressed, it has both a high cushioning property and a smooth feeling of use. Thus, the external preparation for skin of the present invention, in addition to the feeling of use of the preparation such as the cushioning property or thickness feeling during application, gives a unique firm and cushioned or thick feeling to the skin after application, like sticking to the hand, and since stickiness is suppressed, it has a high commercial value.

Embodiments for Carrying Out the Invention

[0010] Hereinafter, the present invention will be described in detail. The external preparation for skin of the present invention contains (A) a high-molecular-weight hyaluronic acid having a weight-average molecular weight of 50,000 or more or a salt thereof, (B) a 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, (E) has an oil content of 0 to 10% by mass, and (F) is a non-emulsified external preparation for skin that is substantially free of parabens. In the present invention, a 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 a 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".

[0011] (A) High molecular weight hyaluronic acid or its salt Hyaluronic acid is a type of acidic mucopolysaccharide and is a polysaccharide containing a disaccharide of glucuronic acid and N-acetylglucosamine as a structural unit. Hyaluronic acid can be extracted and recovered from animal tissues such as chicken combs, shark skins, umbilical cords, eyeballs, skin, and cartilage, hyaluronic acid-producing microorganisms such as Streptococcus microorganisms, animal cells, and plant cell cultures. Also, commercial products can be purchased. As the high-molecular-weight hyaluronic acid with 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.

[0012] Also, the degraded hyaluronic acid obtained by degrading natural hyaluronic acid can be used as long as its weight-average molecular weight is 50,000 or more. The degraded hyaluronic acid can be prepared, for example, by hydrolysis in the presence of an acid or an alkali, enzymatic treatment such as hyaluronidase, physical cleavage such as ultrasonic waves or shearing, fermentation by microorganisms, etc. Also, commercially available products can be used.

[0013] In the present invention, the weight-average molecular weight of the high-molecular-weight hyaluronic acid or its salt is 50,000 or more, preferably 100,000 or more, more preferably 200,000 or more, still more preferably 300,000 or more, and even more preferably 500,000 or more. Also, the weight-average molecular weight of the high-molecular-weight hyaluronic acid or its salt can be, for example, 7,000,000 or less, preferably 6,000,000 or less, more preferably 4,000,000 or less, still more preferably 3,000,000 or less, and even more preferably 2,000,000 or less. Within this range, by combining with the low-molecular-weight hyaluronic acid or its salt and hyaluronic acid derivatives with a weight-average molecular weight of less than 50,000, the effects of the present invention can be achieved.

[0014] Examples of commercially available high molecular weight hyaluronic acids include sodium hyaluronate HA12N (trade name) (Shiseido Company, Limited; weight average molecular weight 1.1 - 1.6 million), hyaluronic acid FCH-150 (trade name) (Kikkoman Biochemifa Co., Ltd.; weight average molecular weight 1.4 - 1.8 million), sodium biohyaluronate SZE (trade name) (Shiseido Company, Limited; weight average molecular weight 1.1 - 1.6 million), hyaluronic acid FCH-120 (trade name) (Kikkoman Biochemifa Co., Ltd.; weight average molecular weight 1.0 - 1.4 million), Hyaluron San HA-LQ (trade name) (Kewpie Corporation; weight average molecular weight 0.85 - 1.6 million), hyaluronic acid FCH-80 (trade name) (Kikkoman Biochemifa Co., Ltd.; weight average molecular weight 0.6 - 1.0 million), hyaluronic acid FCH-60 (trade name) (Kikkoman Biochemifa Co., Ltd.; weight average molecular weight 0.5 - 0.7 million), hyaluronic acid FCH-SU (trade name) (Kikkoman Biochemifa Co., Ltd.; weight average molecular weight 0.05 - 0.11 million), and the like.

[0015] The salts of high molecular weight hyaluronic acid may be any pharmacologically or physiologically acceptable salts, and examples 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, amine salts such as triethanolamine, and the like. Among them, alkali metal salts and metal salts are preferred, and sodium salts, potassium salts, and zinc salts are particularly preferred. Also, in high molecular weight hyaluronic acid, it is preferred to use hyaluronic acid in a salt state because it is more stable compared to hyaluronic acid.

[0016] One or more kinds of high molecular weight hyaluronic acid or its salts can be used.

[0017] The content of high-molecular-weight hyaluronic acid or its salt 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, and even more preferably 0.02% by mass or more, based on the total amount of the external preparation for skin. Also, the content of high-molecular-weight hyaluronic acid or its salt is preferably 1% by mass or less, more preferably 0.8% by mass or less, still more preferably 0.6% by mass or less, and even more preferably 0.3% by mass or less, based on the total amount of the external preparation for skin. Within this range, sufficient cushioning or thickness feeling can be obtained in the texture of the preparation (during application) and the skin after application. When the content of high-molecular-weight hyaluronic acid or its salt includes a plurality of types of high-molecular-weight hyaluronic acid or its salts, it is the total content thereof.

[0018] (B) Low molecular weight hyaluronic acid or its salt As the low-molecular-weight hyaluronic acid having a weight-average molecular weight of less than 50,000, the degradation product of high-molecular-weight hyaluronic acid can be used. The low-molecular-weight hyaluronic acid can be obtained by 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, a method of physically cleaving by ultrasonic waves or shear, a method of fermenting with microorganisms, or the like. When using hyaluronic acid oligosaccharide and / or its salt as the low-molecular-weight hyaluronic acid, about 2 to 16 sugars are preferable, and either a saturated type or an unsaturated type can be used. For example, an unsaturated type hyaluronic acid in which a double bond is formed between the 4th and 5th positions of some or all of D-glucuronic acid can be mentioned.

[0019] 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 still more preferably 20,000 or less. Also, 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 still more preferably 500 or more. Within this range, by combining with high-molecular-weight hyaluronic acid or its salt having a weight-average molecular weight of 50,000 or more and hyaluronic acid derivatives, the effects of the present invention can be achieved.

[0020] In the present invention, low-molecular-weight hyaluronic acid can also be purchased and used as a commercially available product. Examples of commercially available products of low-molecular-weight hyaluronic acid include Hyalo-oligo (trade name) (Kewpie Corporation; weight-average molecular weight of 10,000 or less), Hyaluronic acid (SL) (trade name) (FAP Japan Co., Ltd.; weight-average molecular weight of 10,000 or less), Micro-Hyaluronic acid FCH (trade name) (Kikkoman Biochemifa Co., Ltd.; weight-average molecular weight of 5,000 or less), HAbooster (trade name) (Kewpie Corporation; weight-average molecular weight of 2,000), and the like.

[0021] The salt of low-molecular-weight hyaluronic acid may be any pharmacologically or physiologically acceptable one. For example, 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, amine salts such as triethanolamine, and the like can be mentioned. Among them, 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.

[0022] One or more kinds of low-molecular-weight hyaluronic acid or its salts can be used.

[0023] 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 with respect to the total amount of the external preparation for skin. Also, 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 with respect to the total amount of the external preparation for skin. Within this range, sufficient cushioning properties or a feeling of thickness can be obtained in the formulation (during application) and the skin feel after application. When the content of low-molecular-weight hyaluronic acid or its salt contains a plurality of kinds of low-molecular-weight hyaluronic acid or its salts, it is the total content thereof.

[0024] The content of hyaluronic acid or its salt (total content of high-molecular-weight hyaluronic acid or its salt and low-molecular-weight hyaluronic acid or its salt) in the external preparation for skin of the present invention is preferably 0.002% by mass or more, more preferably 0.01% by mass or more, still 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 external preparation for skin. Further, the content of hyaluronic acid or its salt is preferably 2% by mass or less, more preferably 1.5% by mass or less, still more preferably 1% by mass or less, and even more preferably 0.4% by mass or less, based on the total amount of the external preparation for skin. Within this range, sufficient cushioning property or thickness feeling can be obtained in terms of the formulation and the skin feel after application.

[0025] Hyaluronic acid has drawability, and generally, when formulated in an external preparation at a high concentration, stickiness is more likely to occur. However, the external preparation of the present invention combines (A) high-molecular-weight hyaluronic acid or its salt and (B) low-molecular-weight hyaluronic acid or its salt, and further incorporates (C) a hyaluronic acid derivative, thereby efficiently enhancing the cushioning property or thickness feeling of hyaluronic acid or its salt. Thereby, the stickiness due to the increase in the amount of (A) high-molecular-weight hyaluronic acid or its salt and (B) low-molecular-weight hyaluronic acid or its salt can be suppressed.

[0026] The content ratio of the high-molecular-weight hyaluronic acid or its salt and the low-molecular-weight hyaluronic acid or its salt in the external preparation for skin of the present invention can be such that the content of the low-molecular-weight hyaluronic acid or its salt is 0.0001 part by mass or more, 0.001 part by mass or more, 0.01 part by mass or more, 0.1 part by mass or more, or 0.3 part by mass or more, with respect to 1 part by mass of the content of the high-molecular-weight hyaluronic acid or its salt. Further, it can 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 property or thickness feeling can be imparted to the external preparation, and stickiness can be suppressed despite the inclusion of a high concentration of hyaluronic acid or its salt.

[0027] (C) Hyaluronic acid derivative Examples of hyaluronic acid derivatives include acetylated hyaluronic acid, sulfated hyaluronic acid, hydrophobized hydrolyzed hyaluronic acid (such as alkyl hydrolyzed hyaluronic acid and glyceryl hydrolyzed hyaluronic acid), crosslinked hyaluronic acid, carboxymethyl hyaluronic acid, alkylene glycol hyaluronic acid, silanol hyaluronic acid, cationized hyaluronic acid, and salts thereof. Among them, acetylated hyaluronic acid, hydroxypropyltrimonium hyaluronic acid, glyceryl alkyl hydrolyzed hyaluronic acid (alkyl group having 12 to 13 carbon atoms), crosslinked hyaluronic acid, carboxymethyl hyaluronic acid, propylene glycol hyaluronic acid, dimethylsilanol hyaluronic acid, and salts thereof are preferable. Among them, acetylated hyaluronic acid, hydroxypropyltrimonium hyaluronic acid, crosslinked hyaluronic acid, propylene glycol hyaluronic acid, dimethylsilanol hyaluronic acid, and salts thereof are more preferable. Among them, acetylated hyaluronic acid and salts thereof are particularly preferable. Acetylated hyaluronic acid is preferably one in which the hydroxyl groups of hyaluronic acid are acetylated. Hyaluronic acid has four hydroxyl groups per structural unit (disaccharide). As acetylated hyaluronic acid, those in which 2 to 4 of the hydroxyl groups are acetylated are preferable.

[0028] In the present invention, when acetylated hyaluronic acid is blended as the (C) hyaluronic acid derivative, the weight average molecular weight of 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. Within this range, the cushioning property or thickness feeling can be improved by blending acetylated hyaluronic acid.

[0029] Examples of commercially available hyaluronic acid derivatives include sodium acetylated hyaluronate (trade name) (Shiseido Company, Limited; weight average molecular weight 10,000 - 100,000), Hyalovair (trade name) (Kewpie Corporation; weight average molecular weight 500,000 - 800,000), Hyalrepair (trade name) (Kewpie Corporation; weight average molecular weight 10,000 or less), Hyalocatch (trade name) (Kewpie Corporation; weight average molecular weight 800,000 - 1,200,000), Hyaluderm (trade name) (Kikkoman Biochemifa Co., Ltd.; hyaluronic acid propylene glycol), Hyal Cage System (trade name) (I.R.Asrl; crosslinked three-dimensional hyaluronic acid; weight average molecular weight 7,000,000), D.S.H.CN6 (trade name) (EXSYMOL S.A.M; hyaluronic acid dimethylsilanol), D.S.H.CN (trade name) (EXSYMOL S.A.M; hyaluronic acid dimethylsilanol), and the like.

[0030] The salt in the hyaluronic acid derivative may be any pharmacologically or physiologically acceptable salt, and examples 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, amine salts such as triethanolamine, and the like. Among them, sodium salts, potassium salts, zinc salts, and ammonium salts are preferred, and sodium salts and ammonium salts are more preferred. Specific examples of the salt of the hyaluronic acid derivative include, for example, sodium acetylated hyaluronate, potassium acetylated hyaluronate, calcium acetylated hyaluronate, magnesium acetylated hyaluronate, zinc acetylated hyaluronate, ammonium acetylated hyaluronate, sodium hyaluronate crosspolymer, hydroxypropyltrimonium hyaluronate, and the like.

[0031] One or more hyaluronic acid derivatives can be used.

[0032] The content of the hyaluronic acid derivative is preferably 0.00001% by mass or more, more preferably 0.00004% by mass or more, still more preferably 0.00008% by mass or more, and even more preferably 0.0001% by mass or more, based on the total amount of the external preparation for skin. Also, the content of the hyaluronic acid derivative is preferably 0.3% by mass or less, more preferably 0.2% by mass or less, still more preferably 0.1% by mass or less, and even more preferably 0.025% by mass or less, based on the total amount of the external preparation for skin. Within this range, the cushioning property or the sense of thickness can be sufficiently improved in the formulation (during application) and the feel of the skin after application. When the content of the hyaluronic acid derivative includes a plurality of types of hyaluronic acid derivatives, it is the total content thereof.

[0033] The ratio of the content of hyaluronic acid or its salt ((A) the total content of 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 in the external preparation for skin of the present invention is preferably 0.005 part by mass or more, more preferably 0.05 part by mass or more, still more preferably 0.5 part by mass or more, and even more preferably 2.5 part by mass or more, with respect to 1 part by mass of the content of the hyaluronic acid derivative. Also, it is preferably 200000 parts by mass or less, more preferably 50000 parts by mass or less, still more preferably 10000 parts by mass or less, and even more preferably 5000 parts by mass or less. Also, it can be 1000 parts by mass or less, or 100 parts by mass or less. Within this range, the cushioning property or the sense of thickness due to the combination of (A) and (B) can be sufficiently enhanced in the formulation (during application) and the feel of the skin after application.

[0034] 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 × 30 cm (manufactured by Tosoh Corporation) Column temperature: A constant temperature near 40°C Detector: Differential refractive index meter 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.)

[0035] (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. Also, 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.

[0036] (E) Oil component 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 based on the total amount of the 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.

[0037] 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. The term "solid" refers to one that has no fluidity at 25° C., the term "semi-solid" refers to one that has a melting point of 25° C. to 45° C., and the term "liquid" refers to 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.

[0038] Examples of hydrocarbons include liquid paraffin, liquid isoparaffin, squalane, petrolatum, paraffin, microcrystalline wax, polybutene, polyethylene powder, gelled hydrocarbon (such as plastic base), ozokerite, α-olefin oligomer, light liquid paraffin, light isoliquid paraffin, isododecane, isohexadecane, etc. Among them, liquid paraffin, liquid isoparaffin, squalane, petrolatum, gelled hydrocarbon (such as plastic base), α-olefin oligomer, light liquid paraffin, light isoliquid paraffin are preferred, and liquid paraffin, liquid isoparaffin, squalane, α-olefin oligomer, light liquid paraffin, light isoliquid paraffin are more preferred.

[0039] Examples of waxes include jojoba oil, beeswax, candelilla wax, rice bran wax, cotton wax, carnauba wax, lanolin, liquid lanolin, reduced lanolin, etc. Among them, jojoba oil, beeswax, candelilla wax, rice bran wax are preferred, and jojoba oil is particularly preferred.

[0040] Examples of silicones include phenyl-modified silicones such as methylpolysiloxane, cross-linked methylpolysiloxane, highly polymerized methylpolysiloxane, methylphenylpolysiloxane, cyclic silicones such as decamethylcyclopentasiloxane, methylhydrogenpolysiloxane, methyltrimethicone, dimethiconol, dimethiconol crosspolymer, alkyl-modified silicones such as caprylyl methicone, cross-linked alkyl-modified silicones, amino-modified silicones, polyether-modified silicones, polyglycerin-modified silicones, cross-linked polyether-modified silicones, cross-linked 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 silicone, phenyl-modified silicones, silicone resin, etc. Among them, methylpolysiloxane, crosslinked methylpolysiloxane, highly polymerized methylpolysiloxane, methylphenylpolysiloxane, and decamethylcyclopentasiloxane are preferable.

[0041] In addition, examples of the higher alcohols include saturated or unsaturated, linear or branched higher alcohols having 8 to 22 carbon atoms. Specifically, capryl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, cetostearyl alcohol, stearyl alcohol, behenyl alcohol, octyldodecanol, isostearyl alcohol, phytosterol, cholesterol, oleyl alcohol, and the like can be mentioned. Among them, cetyl alcohol, cetostearyl alcohol, stearyl alcohol, behenyl alcohol, octyldodecanol, and isostearyl alcohol are preferable, and octyldodecanol and isostearyl alcohol are more preferable.

[0042] In addition, examples of the higher fatty acids include saturated or unsaturated, linear or branched higher fatty acids having 8 to 22 carbon atoms. Specifically, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, and behenic acid can be mentioned. Among them, isostearic acid, stearic acid, and behenic acid are preferable, and isostearic acid is more preferable.

[0043] In addition, examples of the fats and oils include avocado oil, linseed oil, camellia oil, macadamia nut oil, kukui nut oil, hazelnut oil, corn oil, olive oil, safflower oil, ginger oil, cinnamon oil, jojoba oil, grape seed oil, sunflower oil, almond oil, meadowfoam oil, southernwood oil, rapeseed oil, sesame oil, cocoa butter, coconut oil, hydrogenated coconut oil, palm oil, palm kernel oil, candlenut kernel oil, candlenut, wheat germ oil, rice germ oil, rice bran oil, cottonseed oil, soybean oil, peanut oil, tea seed oil, evening primrose oil, shea butter, hydrogenated oil, orange raffia oil, horse oil, and the like. 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 bran oil, rice bran oil, soybean oil, evening primrose oil, shea butter, and orange raffia oil are preferred.

[0044] 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, isotridecyl isononanoate, cetyl lactate, isostearyl isostearate, cholesteryl 12-hydroxystearate, cholesteryl stearate, cholesteryl oleate, phytosteryl macadamia nut fatty acid, phytosteryl oleate, dextrin palmitate, inulin stearate, hydrogenated jojoba oil, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, neopentyl glycol dicaprate, tri-2-ethylhexyl trimellitate, tritridecyl trimellitate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexanoate, glycerin tri-2-ethylhexanoate, trimethylolpropane triisostearate, polyglyceryl diisostearate, polyglyceryl monoisostearate, glyceryl tri(caprylic / capric acid), glyceryl tri(caprylic / capric / myristic / stearic acid), oleyl oleate, di(phytosteryl / octyldodecyl) lauroyl glutamate, di(octyldodecyl / phytosteryl / behenyl) lauroyl glutamate, triethyl citrate, (phytosteryl / isostearyl / cetyl / stearyl / behenyl) dimer dilinoleate, dimer dilinoleyl dimer dilinoleate, dipentaerythrityl tripolyhydroxystearate, glyceryl tri(behenic acid / isostearic acid / eicosanedioic acid), diisostearyl malate, triethyl citrate, etc. 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 macadamia nut fatty acid, phytosteryl oleate, dextrin palmitate, inulin stearate, hydrogenated jojoba oil, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, neopentyl glycol dicaprate, tri-2-ethylhexyl trimellitate, tritridecyl trimellitate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexanoate, glycerin tri-2-ethylhexanoate, trimethylolpropane triisostearate, polyglyceryl diisostearate, polyglyceryl monoisostearate, glyceryl tri(caprylic acid / capric acid), glyceryl tri(caprylic acid / capric acid / myristic acid / stearic acid), oleyl oleate, di(phytosteryl / octyldodecyl) lauroyl glutamate, di(octyldodecyl / phytosteryl / behenyl) lauroyl glutamate, triethyl citrate, (phytosteryl / isostearyl / cetyl / stearyl / behenyl) dimer dilinoleate, dimer dilinoleyl dimer dilinoleate, dipentaerythrityl tripolyhydroxystearate, glyceryl tri(behenic acid / isostearic acid / eicosanedioic acid) are preferred.

[0045] One or more kinds of oil components can be used.

[0046] (F) Paraben The external preparation for skin of the present invention substantially does not contain parabens. In the present invention, substantially not containing 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 parabens. However, when parabens are unavoidably mixed in, it corresponds to not containing parabens. For example, when a commercially available component is blended in the external preparation for skin and trace amounts of parabens are mixed in the external preparation for skin because the commercially available product contains parabens, it corresponds to not containing parabens. Parabens are paraoxybenzoic acid esters and their salts, and examples include methylparaben, ethylparaben, propylparaben, isopropylparaben, butylparaben, isobutylparaben, benzylparaben, etc., and their sodium salts, potassium salts, etc.

[0047] Non-emulsified The external preparation for skin of the present invention is a non-emulsified composition. In the present invention, not being emulsified means not containing emulsified particles having an average particle diameter exceeding 0.15 μm. That is, it means not containing emulsified particles or, even if containing emulsified particles, the average particle diameter thereof is 0.15 μm or less. The average particle diameter of the emulsified particles is a value measured by the dynamic light scattering method.

[0048] Transparency The external preparation for skin of the present invention has a suppressed oil content and, since it is not emulsified, has high transparency and a transparent or translucent appearance to the naked eye. 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 represents the transparency value when the transparency of purified water is set to 100 and the case where there is no light transmission at all is set to 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, it is a value measured by putting a test solution in a glass cell (CM-A99, thickness 20 mm) and using a spectrophotometer CM-5 (manufactured by Konica Minolta, Inc.). The L value hardly changes depending on the type of spectrophotometer or cell. The external preparation for skin of the present invention preferably has an L value of 40 or more. The L value is preferably from 40 to 100, more preferably from 50 to 100, still more preferably from 60 to 100, even more preferably from 70 to 100, and particularly preferably from 80 to 100. For example, when the oil is solubilized or when it falls under the non-emulsified state referred to in the present invention by containing a microemulsion or nanoemulsion having an average particle diameter of 0.15 μm or less, the appearance of the external preparation for skin becomes transparent or translucent.

[0049] Alkane diol The external preparation for skin of the present invention preferably contains an alkanediol having 5 to 10 carbon atoms, whereby excellent cushioning properties can be maintained over a long period of time. The alkanediol preferably has 5 to 10 carbon atoms, more preferably 5 to 8 carbon atoms, and still more preferably 5 to 6 carbon atoms. Also, 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. Among them, 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. Examples of commercially available products of the alkanediol having 5 to 10 carbon atoms include HYDROLITE - 5, HYDROLITE - 5 Green (manufactured by Simrise Co., Ltd.), KMO - 6 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Microcare Emollient PTGJ, Microcare Emollient HXD (manufactured by THOR), and the like.

[0050] One kind or two or more kinds of the alkanediol having 5 to 10 carbon atoms can be used.

[0051] The content of the alkanediol 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, 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 external preparation for skin. Also, 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 external preparation for skin. Within this range, sufficient stability and cushioning properties can be maintained for a long time in the formulation (during application) and the skin feel after application. When the alkanediol content contains a plurality of kinds of alkanediols, it is the total content thereof.

[0052] pH The pH of the topical 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 improve the usability, a pH of 3 to 8.5 is preferred, a pH of 4 to 8 is more preferred, a pH of 4.5 to 7.5 is even more preferred, and a pH of 4.5 to 7 is even more preferably.

[0053] Viscosity The topical skin preparation of the present invention preferably has a liquid dosage form having fluidity at 25°C, and more preferably is a lotion. From such a viewpoint, the viscosity (25°C) of the topical skin preparation 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 particularly preferably 4000 mPa·s or less. Viscosity is one of the indicators showing cushioning properties. Since the topical skin preparation of the present invention is excellent in cushioning properties, it 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 method of the 17th revised Japanese Pharmacopoeia, and specifically, it is a value measured by the method described in the examples.

[0054] Form of preparation The topical skin preparation of the present invention can be prepared by mixing the above-described components with a base or carrier commonly used in cosmetics, quasi-drugs, or pharmaceuticals, and additives and other physiologically active or pharmacologically active components as necessary, and making it into a topical skin preparation of cosmetics, quasi-drugs, or pharmaceuticals by a conventional method.

[0055] The properties of the topical skin composition of the present invention can be liquid, fluid, etc. As the dosage form, for example, it can be preparations such as solutions, suspensions, liniments, lotions, aerosols, pump sprays, sheet preparations impregnated with a chemical solution on non-woven fabrics, mists, etc. Among them, solutions, lotions, aerosols, pump sprays, sheet preparations impregnated with a chemical solution on non-woven fabrics (sheet mask preparations or sheet pack preparations), mists are preferred, and solutions, lotions, sheet preparations impregnated with a chemical solution on non-woven fabrics (sheet mask preparations or sheet pack preparations), mists are particularly preferred.

[0056] Use and application As the uses in the case of being a topical skin preparation for quasi-drugs or cosmetics, for example, there can be mentioned basic cosmetics such as lotions, essences, sheet packs, sheet masks, all-in-one gels, body lotions; hair cosmetics such as hair mists, hair lotions, etc.

[0057] Base or carrier As the base or carrier, those not corresponding to the above oil components can be used. Even when the oil component is mixed, its content is preferably 50% by mass or less, particularly 40% by mass or less, and particularly 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 polymers such as polyvinyl pyrrolidone, carboxyvinyl polymer, alkyl-modified carboxyvinyl polymer, polyvinyl butyrate, alkyl acrylate-methacrylate copolymer; natural polymers such as carrageenan, alginic acid, cellulose, xanthan gum, guar gum, quince seed, dextran, gellan gum; processed polysaccharides such as dextrin, maltodextrin; lower alcohols such as ethanol, isopropanol; sugar alcohols such as sorbitol, xylitol, erythritol, mannitol; polyhydric alcohols such as polyethylene glycol, propylene glycol, propanediol, dipropylene glycol, 1,3-butylene glycol, glycerin, diglycerin, isoprene glycol; glycol ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monoethyl ether, dipropylene glycol monopropyl ether, etc. can be mentioned. As the base or carrier, one or more than two kinds can be used.

[0058] Additive Examples of the additive include a surfactant, a thickener, an antioxidant, a preservative or antiseptic, a pH adjuster, a chelating agent, a stabilizer, an irritation reducer, a coloring agent, a dispersant, a fragrance, a pearlescent agent, etc. As the additive, one or more than two kinds can be used. Also, the additive can be used within a range that does not impair the effects of the present invention.

[0059] As surfactants, for example, POE-alkyl ethers such as POE-2-decyltetradecyl alcohol, 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 mono coconut oil fatty acid, POE(80)sorbitan laurate, etc.; 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-dihydrocholesterol ester, POE-hydrogenated castor oil (for example, 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.) of POE-hydrogenated castor oil; POE-castor oil (POE(3)castor oil, POE(20)castor oil, etc.) of POE-castor oil; POE-hydrogenated castor oil fatty acid esters such as POE-hydrogenated castor oil isostearate; POE-alkylaryl ether; glycerin alkyl ethers such as cumyl alcohol, batyl alcohol, and ceralkyl alcohol; POE-glycerin alkyl ethers such as POE-monostearyl glyceryl ether; POE-fatty acid esters such as polyoxyl stearate; POE-sterol·hydrogenated sterols such as POE(20)phytosterol, POE(30)phytosterol, POE(25)phytostanol, POE(30)cholestanol, etc.; sucrose fatty acid esters such as sucrose palmitate, sucrose stearate, sucrose oleate, sucrose isostearate, sucrose linoleate, sucrose linolenate, etc.; polyethylene glycol fatty acid esters such as polyethylene glycol dioleate;Polymeric glycerol fatty acid esters such as alkyl polyglycoside, diglyceryl monostearate, diglyceryl monoisostearate, decaglyceryl monostearate, decaglyceryl monooleate, decaglyceryl pentaoleate, hexaglyceryl polyricinoleate, etc.; nonionic surfactants such as alkyl-modified silicone, emulsified silicone elastomer, etc. Also, for example, higher alkyl sulfate salts (e.g., sodium lauryl sulfate, potassium lauryl sulfate, etc.); alkyl ether sulfate salts (e.g., triethanolamine POE-lauryl sulfate, sodium POE-lauryl sulfate, etc.); N-acyl sarcosinic acid (e.g., sodium lauroyl sarcosinate, etc.); higher fatty acid amide sulfonate salts (e.g., sodium stearoyl methyl taurate, sodium myristoyl methyl taurate, sodium cocoyl methyl taurate, sodium cocoyl methyl taurate taurate, etc.); phosphate esters and their salts (sodium POE-oleyl ether phosphate, POE-stearyl ether phosphate, potassium cetyl phosphate, cetyl phosphate, etc.); sulfosuccinate salts (e.g., sodium di-2-ethylhexyl sulfosuccinate, etc.); alkylbenzene sulfonate salts (e.g., sodium linear dodecylbenzene sulfonate, etc.); higher fatty acid ester sulfate salts (e.g., sodium hardened coconut oil fatty acid glycerol sulfate, etc.); N-acyl glutamate salts (e.g., monosodium lauroyl glutamate, sodium stearoyl glutamate, sodium myristoyl glutamate, etc.); N-acyl alanine salts (e.g., sodium lauroyl methyl alanine, triethanolamine salt of cocoyl alanine, etc.); sulfated oils (e.g., castor oil, etc.); POE-alkyl ether carboxylic acid; POE-alkyl allyl ether carboxylate; α-olefin sulfonate salts; higher fatty acid ester sulfonate salts; secondary alcohol sulfate salts; higher fatty acid alkylol amide sulfate salts; sodium lauroyl monoethanolamide succinate; ditriethanolamine N-palmitoyl aspartate; anionic surfactants such as sodium caseinate are also included. Examples of cationic surfactants include mono- or di-long-chain alkyl tertiary or quaternary ammonium salts having a linear or branched long-chain alkyl group which may have an alkylene oxide added thereto, and the like. Examples of amphoteric surfactants include carbobetaines, sulfobetaines, imidazolinium betaines, and amide betaines. Examples of surfactants derived from natural sources include lecithin, hydrogenated lecithin, saponin, sodium surfactin, and bile acids.

[0060] Examples of thickeners include vinyl thickeners such as polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, carboxyvinyl polymer, alkyl methacrylate copolymer, and sodium polyacrylate; cellulose thickeners such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, and carboxyethyl cellulose; polysaccharides such as guar gum, sclerotium gum, tamarind gum, xanthan gum, gellan gum, dextran, pectin, pullulan, locust bean gum, carrageenan, agar, alginic acid, sodium alginate, and fucogel; gelatin, alkyl methacrylate copolymer, sodium polyacrylate, bentonite, dextrin fatty acid ester, dimethyldistearylammonium hectorite, propylene glycol alginate, polyethylene glycol, macrogol, polyacrylamide, (hydroxyethyl acrylate / acryloyl dimethyl taurine Na) copolymer, (acryloyl dimethyl taurine ammonium / vinyl pyrrolidone) copolymer, (acryloyl dimethyl taurine ammonium / beheneth-25 methacrylate) cross-polymer, (sodium acrylate / acryloyl dimethyl taurine Na) copolymer, and the like.

[0061] Examples of antioxidants include, for example, dibutylhydroxytoluene, butylhydroxyanisole, sorbic acid, sodium sulfite, ascorbic acid, erythorbic acid, sodium erythorbate, L-cysteine hydrochloride, lignans such as sesamin, curcumin, capsaicin, gingerol, resveratrol, anthocyanins, cyanidin, bilberry extract, and the like.

[0062] Examples of preservatives or antiseptics include benzoic acid, sodium benzoate, dehydroacetic acid, sodium dehydroacetate, isopropylmethylphenol, phenoxyethanol, sodium pyrosulfite, and the like.

[0063] Examples of pH adjusters include inorganic acids (such as hydrochloric acid, sulfuric acid), organic acids (such as lactic acid, sodium lactate, citric acid, sodium citrate, succinic acid, sodium succinate), inorganic bases (such as potassium hydroxide, sodium hydroxide), organic bases (such as triethanolamine, diisopropanolamine, triisopropanolamine), and the like.

[0064] Examples of chelating agents include, for example, ethylenediaminetetraacetic acid (EDTA), ethylenediaminetetraacetate (sodium salt (sodium edetate: Japanese Pharmacopoeia, EDTA-2Na, etc.), potassium salt, etc.), phytic acid, gluconic acid, polyphosphoric acid, metaphosphoric acid, and the like.

[0065] Examples of stabilizers include sodium polyacrylate, dibutylhydroxytoluene, butylhydroxyanisole, and the like.

[0066] Examples of irritation reducers include licorice extract, gum arabic, polyvinylpyrrolidone, sodium alginate, and the like.

[0067] Examples of colorants include inorganic pigments, natural pigments, and the like.

[0068] Examples of the pearl luster imparting agent include ethylene glycol distearate, ethylene glycol monostearate, and triethylene glycol distearate.

[0069] Bioactive or pharmacologically active ingredient Examples of the physiologically active or pharmacologically active ingredient include an ultraviolet ray scattering agent, an ultraviolet ray absorber, a component having a preventive and / or repair effect on DNA damage, a whitening component, an anti-inflammatory component, an antibacterial component, a cooling agent, an organic acid, an anti-glycation component, a cell activating component, an astringent component, an antioxidant component, an anti-aging component, a moisturizing component, a polyhydric alcohol, a cutin softening component, vitamins, a blood circulation promoting component, a sebum adsorbing component, a peptide or its derivative, an amino acid or its derivative, and the like. One or more kinds of the physiologically active or pharmacologically active ingredients can be used. Further, the physiologically active or pharmacologically active ingredient can be used within a range that does not impair the effects of the present invention. When a plant component is used in the present invention as the physiologically active or pharmacologically active ingredient, 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), essential oil, or the like. The content in parentheses in the plant component is the scientific name, alias, or crude drug name of the plant.

[0070] Examples of the ultraviolet ray scattering agent include inorganic compounds such as zinc oxide, titanium oxide, iron oxide, cerium oxide, zirconium oxide, titanium silicate, zinc silicate, silicic anhydride, cerium silicate, and hydrous silicic acid; those obtained by coating these inorganic compounds with inorganic powders such as hydrous silicic acid, aluminum hydroxide, mica, and talc; those obtained by compounding these inorganic compounds with resin powders such as polyamide, polyethylene, polyester, polystyrene, and nylon; and those obtained by treating these inorganic powders, coatings, or composites with silicone oil, aluminum fatty acid salt, alkyl titanate, or the like.

[0071] Examples of the ultraviolet absorber include 2-ethylhexyl paramethoxycinnamate, ethylhexyl paramethoxycinnamate, 4-tert-butyl-4'-methoxydibenzoylmethane, hexyl 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoate, hexyl diethylaminohydroxybenzoylbenzoate, 2-ethylhexyl dimethoxybenzylideneoxoimidazolidinepropionate, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-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, ethylhexyl dibenzylidenedioxoimidazolidinepropionate, etylhexyl triazoline, para-aminobenzoic acid and its derivatives, octyl para-dimethylaminobenzoate, 2-ethylhexyl salicylate, ethylene glycol salicylate, dihydroxybenzophenone, dimethyldiethylbenzalmalonate, 2-ethylhexyl 2-cyano-3,3-diphenylprop-2-enoate, 2-phenylbenzimidazole-5-sulfonic acid, and the like.

[0072] Examples of the component having a DNA damage-preventing and / or DNA damage-repairing effect 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.

[0073] Examples of whitening ingredients include, for example, niacinamide, placenta, arbutin, kojic acid, ellagic acid, phytic acid, tranexamic acid, lucinol, Chamomilla ET, hydroquinone, potassium 4-methoxysalicylate, linoleic acid and its derivatives, ascorbic acid, sodium ascorbate, sodium ascorbyl phosphate, magnesium ascorbyl phosphate, tetrahexyldecyl ascorbate, 2-O-ethyl ascorbic acid, 3-O-ethyl ascorbic acid, ascorbic acid glucoside, disodium isostearyl ascorbyl phosphate, L-ascorbyl dipalmitate, trisodium ascorbyl palmitate phosphate, glyceryl ascorbic acid, bisglyceryl ascorbic acid, alkyl glyceryl ascorbic acid, ingredients derived from plants (iris, almond, aloe, acerola, asparagus, saffron, ginseng, viola, anemone, seaweed, burdock, chlorella, rice, rice bran, oryzanol, rice bran, perilla, peony, sophora flavescens, soybean, tea, honeysuckle, witch hazel, button mushroom, yokuinin, kiwi, sage, parsley, holly, hops, thyme, clove, chimpi, licorice, chamomile, prune, purple gromwell, bupleurum, grapefruit, thistle, lemon, kiwi, pine, neem, artichoke, field horsetail, great plantain, blueberry, dwarf buttercup, akebia, silver birch, snowdrop, pennywort, rosemary, lavender, evodia rutaecarpa, etc.).

[0074] Examples of anti-inflammatory ingredients include allantoin, calamine, tranexamic acid, glycyrrhizic acid or its derivatives or salts thereof (e.g., dipotassium glycyrrhizinate, monoammonium glycyrrhizinate, etc.), glycyrrhetinic acid or its derivatives or salts thereof (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, terebene oil, indomethacin, salicylic acid or its derivatives, steroids or their derivatives or salts thereof (e.g., hydrocortisone, prednisolone), ufenamate, bufexamac, ibuprofen piconol, glycol salicylate, ingredients derived from plants (e.g., comfrey, aloe, houttuynia cordata), etc.

[0075] 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, alkyl diamino glycine hydrochloride, cetylpyridinium chloride, piroctolamine, miconazole or its salt, chlorobutanol, ethylhexylglycerin, propiolyl iodide butylcarbamate, caprylic hydroxamic acid, hydroxyacetophenone, phenethyl alcohol, methylisothiazolinone, sorbic acid, β-glycyrrhetinic acid, ingredients derived from plants (e.g., clary, rosemary, mulberry, eucalyptus, etc.), etc.

[0076] Examples of cooling agents include terpenes such as menthol and its derivatives, camphor, borneol, geraniol, cineole, anethole, limonene, eugenol (these may be in the form of the d-form, l-form or dl-form); essential oils such as eucalyptus oil, bergamot oil, peppermint oil, cool mint oil, spearmint oil, perilla oil, peppermint oil, cinnamon oil, rose oil, terebene oil, etc.

[0077] 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, or phosphoric acid, salts of organic acids such as maleic acid or methanesulfonic acid, alkali metal salts such as sodium or potassium, alkaline earth metal salts, ammonium salts, basic amino acid salts, amine salts such as triethanolamine, and the like.

[0078] Examples of anti-glycation components include plant extracts such as Buddleja axillaris leaf extract, Japanese apricot fruit extract, edelweiss extract, ginkgo extract, cherry leaf extract, pomegranate extract, common tobacco leaf extract, blackthorn extract, peony extract, Houttuynia cordata extract, bilberry leaf extract, green tea extract, black tea extract, mulberry extract, Roman chamomile extract, mugwort extract, evening primrose oil, amla fruit, fruit juice or their extracts, L-arginine, L-lysine, hydrolyzed casein, hydrolyzable tannin, carnosine, and the like.

[0079] Examples of cell-activating components include amino acids such as γ-aminobutyric acid; vitamins such as retinol, thiamine, riboflavin, pyridoxine hydrochloride, pantothenic acid, pyrroloquinoline quinones; tannins, flavonoids, saponins, allantoin, placenta, proteoglycan, photosensitizer No. 301, components derived from plants (such as soybean, bilberry, lemongrass, aloe vera, chlorella, magnolia officinalis, bupleurum falcatum, chamomile, Houttuynia cordata, hops, carrot, etc.); royal jelly, royal jelly extract; whey-derived extracts such as whey, yogurt extract, hydrolyzed milk protein, yeast extract, and the like.

[0080] Examples of the convergent components include metal salts such as alum, chloro-hydroxy aluminum, aluminum chloride, aluminum allantoin salt, zinc para-phenolsulfonate, zinc basic aluminum lactate, zinc sulfate, and potassium aluminum sulfate; components derived from plants (such as seaweed, thyme, black tea, oolong tea, green tea, chickweed, witch hazel, loquat, buttonweed, saxifrage, rooibos, Chinese buttercup, artichoke, chamomile, eucalyptus, lemon, rosemary, and valerian).

[0081] Examples of the 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 components derived from plants (such as chickweed, turmeric, bilberry, saffron, kudzu, grapefruit, peony, Japanese knotweed, perilla, honeysuckle, sage, English plantain, Japanese knotweed, sorrel, star anise, cinnamon, Chinese cinnamon, Japanese spikenard, loquat, safflower, buttonweed, hops, eucalyptus, saxifrage, rooibos, lemongrass, soybean, mugwort, Japanese buttercup, rosemary, and lavender).

[0082] Examples of the anti - aging components include hydrolyzed soy protein, pangamic acid, ursolic acid, turmeric extract, sphingosine derivatives, silicon, silicic acid, N - methyl - L - serine, mevalonolactone, and peptides (such as caprooyl tetrapeptide - 3, oligopeptide - 24, etc.).

[0083] Examples of moisturizing ingredients include amino acids and their derivatives such as alanine, serine, aspartic acid, glycine, proline, hydroxyproline, glucosamine, theanine, arginine, etc.; polyhydric alcohols such as glycerin, dipropylene glycol, 1,3-butylene glycol, diglycerin, etc.; 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 glyceryl ether-24, etc.; sugar alcohols such as sorbitol, xylitol, erythritol, maltose / sucrose condensate (glucooligosaccharide), hydrolyzed xylan (xylooligosaccharide), etc.; glycosyl trehalose, trehalose; ceramides, glucosylceramides, cholesterol, phytosterols, cholesterol derivatives, phytosterol derivatives, etc.; phospholipids such as lecithin, hydrogenated lecithin, etc.; NMF-derived components such as urea; collagen, elastin, keratin, chitin, chitosan, etc. and their hydrolyzates; hydroxyethyl urea; components derived from plants (such as aloe, seaweed, cockscomb, chlorella, lemongrass, chamomile, witch hazel, tea, perilla, grapefruit, amacha tsuru, etc.).

[0084] Examples of polyhydric alcohols include glycerin, diglycerin, triglycerin, propylene glycol, ethylene glycol, diethylene glycol, isoprene glycol, 1,3-butylene glycol, etc.

[0085] Examples of horny layer softening ingredients include lanolin, urea, phytic acid, lactic acid, lactate, glycolic acid, salicylic acid, malic acid, citric acid, fruit acid, phytic acid, urea, sulfur, etc.

[0086] Examples of vitamins include retinol derivatives such as retinol, retinol acetate, retinol palmitate, retinol propionate, retinol linoleate, etc., retinal, retinoic acid, methyl retinoate, ethyl retinoate, retinol retinoate, d-δ-tocopheryl retinoate, α-tocopheryl retinoate, β-tocopheryl retinoate, etc. (vitamins A); provitamins A such as β-carotene, α-carotene, γ-carotene, δ-carotene, lycopene, zeaxanthin, cryptoxanthin, echinenone, etc.; vitamin E such as dl-α-tocopherol, dl-α-tocopherol succinate, calcium dl-α-tocopherol succinate, δ-tocopherol, tocopherol nicotinate, dl-α-tocopherol acetate, tocopherol linoleate, (linoleic acid / oleic acid) tocopherol, potassium (ascorbyl / tocopheryl) phosphate; vitamin B2 such as riboflavin, flavin mononucleotide, flavin adenine dinucleotide, riboflavin butyrate, riboflavin tetrabutyrate, sodium riboflavin 5'-phosphate, riboflavin tetranicotinate; nicotinic acids (vitamins B3) such as methyl nicotinate, nicotinic acid, benzyl nicotinate, nicotinamide, nicotinic acid dl-α-tocopherol, β-butoxyethyl nicotinate, 1-(4-methylphenyl)ethyl nicotinate; vitamin C such as ascorbyl stearate, disodium isostearyl ascorbyl phosphate, L-ascorbyl dipalmitate, ascorbyl tetraisopalmitate (tetra-2-hexyldecanoic acid ascorbyl), trisodium ascorbyl palmitate phosphate, ascorbic acid, sodium ascorbate, dehydroascorbic acid, sodium ascorbyl phosphate, magnesium ascorbyl phosphate, ascorbyl glucoside, 2-O-ethyl ascorbic acid, 3-O-ethyl ascorbic acid, glyceryl ascorbic acid, bisglyceryl ascorbic acid, alkyl glyceryl ascorbic acid; vitamins D such as methyl hesperidin, ergocalciferol, cholecalciferol; vitamins K such as phylloquinone, pharnoquinone;Vitamin B1s such as thiamine and their salts (e.g., dibenzoyl thiamine hydrochloride, thiamine hydrochloride, thiamine nirinate); vitamin B6s such as pyridoxine hydrochloride, pyridoxine acetate, pyridoxal hydrochloride, pyridoxal 5'-phosphate, pyridoxamine hydrochloride; vitamin B12s such as cyanocobalamin, hydroxocobalamin, deoxyadenosylcobalamin; folic acids such as folic acid, pteroylglutamic acid; pantothenic acids such as pantothenic acid, calcium pantothenate, pantothenyl alcohol (panthenol), D-pantetheine, D-pantethine, coenzyme A, pantothenyl ethyl ether, calcium pantetheine sulfonate; biotins such as biotin, biocytin, etc. Other vitamin-like active factors such as carnitine, ferulic acid, α-lipoic acid, orotic acid, γ-oryzanol, pyrroloquinoline quinone, hesperidin and glucosyl hesperidin, ubiquinone, and their salts, etc. are also included.

[0087] Examples of blood circulation promoting components include components derived from plants (e.g., parsley, ashitaba, arnica, ginkgo, wikstroemia, polygonatum, dutch cassia, chamomile, roman chamomile, carrot, gentiana, burdock, rice, Japanese quince, shiitake mushroom, European quince, European spindle tree, senkyu, senburi, thyme, clove, chinpi, toki, tonin, tohii, carrot, garlic, butcher's broom, grape, button, plane tree, lemon balm, yuzu, yokukinin, rosemary, rose hip, chinpi, toki, tohii, peach, apricot, walnut, corn). Examples also include dl-α-tocopherol acetate, tocopherol nicotinate, glucosyl hesperidin, hesperidin, etc.

[0088] Examples of sebum adsorbing components include talc, mica, hydroxyapatite, zinc oxide, aluminum silicate, etc.

[0089] Examples of the peptide or its derivative include keratinolytic peptide, hydrolyzed keratin, collagen, fish-derived collagen, atelocollagen, succinylated atelocollagen, gelatin, elastin, elastinolytic peptide, collagenolytic peptide, hydrolyzed collagen, hydroxypropylammonium chloride hydrolyzed collagen, elastinolytic peptide, conchiolinolytic peptide, hydrolyzed conchiolin, silk proteolytic peptide, hydrolyzed silk, lauroyl hydrolyzed silk sodium, soy protein hydrolytic peptide, hydrolyzed soy protein, wheat protein, wheat protein hydrolytic peptide, hydrolyzed wheat protein, caseinolytic peptide, acylated peptide (such as palmitoyl oligopeptide, palmitoyl pentapeptide, palmitoyl tetrapeptide), and the like.

[0090] Examples of the amino acid or its derivative 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, dilauroyl glutamate lysine and its salts, lauroyl glutamate di(phytosteryl / octyldodecyl), lauroyl glutamate di(octyldodecyl / phytosteryl / behenyl), and the like. These amino acids or their derivatives may be solvates such as hydrates, and may be in any of the d-form, l-form, and dl-form.

[0091] The external preparation for skin of the present invention can be contained in a container of appropriately selected shape and material according to the purpose of use and application, and can be used. For example, a spray type, a pump type, a bottle type, a tube type, a spatula type, a dispenser type, a pouch bag, a tea pack, etc. can be exemplified. Examples of the material of the container include polyethylene terephthalate, polypropylene, polyethylene (such as HDPE, LDPE, LLDPE), ABS resin, ethylene vinyl alcohol resin, polystyrene, glass, and metal (such as aluminum). Further, these materials can be used as container materials by performing various coating treatments, combining these materials by mixing or laminating, etc., in consideration of strength, flexibility, weather resistance, or stability of components. Examples of the coating material include epoxy resin, polyamideimide, etc. Among them, it is preferable to use polypropylene, polyethylene (such as HDPE, LDPE, LLDPE), ethylene vinyl alcohol resin, and more preferably to use polypropylene, polyethylene (such as HDPE, LDPE, LLDPE).

[0092] The present invention provides a method for improving the cushioning property or the mochi-mochi feeling in the skin feel during and / or after application of a non-emulsified external preparation for skin, while suppressing stickiness of the non-emulsified external preparation for skin, which contains (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, and (E) has an oil content of 0 to 10% by mass and (F) substantially does not contain parabens, by including (C) a hyaluronic acid derivative. In this method, the oil content of (E) 0 to 10% is the content after including (C) a hyaluronic acid derivative in the non-emulsified external preparation for skin. The type and blending amount of each component, the properties of the external preparation for skin, etc. are as described for the external preparation for skin of the present invention.

Examples

[0093] 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 External preparations for skin having the compositions shown in Tables 1 and 2 were prepared according to a conventional method. These external preparations for skin are lotion agents that do not contain emulsified particles. Also, the visual appearance of these external preparations for skin was transparent. The viscosities of the external preparations were 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 the example) / (viscosity of the corresponding comparative example)] × 100 ····· (1)

[0094] (Viscosity measurement method) Measurement was carried out using VISCOMETER TV-10M (manufactured by Toyo Sangyo Co., Ltd.) under the conditions of a temperature of 25 °C, rotor M-2, a speed of 60 rpm, and for 20 seconds.

[0095] 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 viscosities of Reference Examples 1 to 3, which contain acetylated hyaluronic acid but do not contain hyaluronic acid or its salt, were zero, similar to Reference Example 4, which contains neither acetylated hyaluronic acid nor hyaluronic acid or its salt. It can be seen that acetylated hyaluronic acid itself has no viscosity increasing effect.

[0096] Also, as shown in Table 2, as the hyaluronic acid or its salt, high molecular weight sodium hyaluronate with a weight average molecular weight of 50,000 or more and low molecular weight sodium hyaluronate with a weight average molecular weight of less than 50,000 were used, and by blending a trace amount of acetylated hyaluronic acid therein, the viscosity increased significantly. It can be seen that the viscosity increased by combining high molecular weight sodium hyaluronate with a weight average molecular weight of 50,000 or more, low molecular weight sodium hyaluronate with a weight average molecular weight of less than 50,000, and acetylated hyaluronic acid. Since viscosity is one of the indicators showing the cushioning property of the composition, it was shown that by including hyaluronic acid or its salt with a weight average molecular weight of 50,000 or more and hyaluronic acid or its salt with a weight average molecular weight of less than 50,000, the cushioning property becomes very good by blending acetylated hyaluronic acid.

[0097]

Table 1

[0098]

Table 2

[0099] (2) Effect of alkane diol External skin preparations having the compositions shown in Tables 3 to 5 were prepared according to a conventional method and contained in a 50 mL glass container. These external skin preparations were lotion agents that did not contain emulsified particles. Further, the visual appearance of these external skin preparations was transparent. Each container was stored at 50°C for one week, the viscosity was measured before and after storage, and the viscosity reduction rate was calculated according to formula (2). Viscosity reduction 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: for Example 6, it is Example 5; for Example 8, it is Example 7; for Example 10, it is Example 9; for Example 12, it is Example 11; for Example 14, it is Example 13; for Example 16, it is Example 15; for Example 18, it is Example 17; for Example 20, it is Example 19; for Example 22, it is Example 21; for Example 24, it is Example 23; for Example 26, it is Example 25; for Example 28, it is Example 27. Viscosity reduction improvement rate = [(viscosity reduction rate of the example - viscosity reduction rate of the corresponding example) / viscosity reduction rate of the corresponding example] × 100 ····· (3)

[0100]

Table 3

[0101]

Table 4

[0102]

Table 5

[0103] The results are shown in Tables 3 to 5. The unit of the component content in Tables 3 to 5 is mass%. The rate of viscosity decrease under severe conditions at 50°C for one week was significantly improved by the addition of alkanediol. On the other hand, even when dipropylene glycol, polyethylene glycol 400, which are the same diol compounds, or concentrated glycerin, which is the same polyol compound, were added, the rate of viscosity decrease was not improved at all.

[0104] (3) Evaluation of the feeling of use Five subjects who understood the evaluation criteria had each topical skin preparation applied to their arms, and an evaluation of 1 to 5 points (integer values) was made regarding the feel of the applied area. That is, regarding the stickiness during application, those who felt it strongly were given 1 point, and those who did not feel it were given 5 points, and the value corresponding to the feel felt by the subject was shown. Similarly, regarding the stickiness of the back of the skin one minute after application, those who felt it strongly were given 1 point, and those who did not feel it were given 5 points. Also, regarding the cushioning property of the back of the skin one minute after application, those who did not feel it were given 1 point, and those who felt it strongly were given 5 points. Next, the average value of the scores for each example was calculated and used as the evaluation value of the topical skin preparation.

[0105]

Table 6

[0106] The results are shown in Table 6. From the comparison between Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, and Example 4 and Comparative Example 4, it can be seen that in a topical skin preparation containing high molecular weight hyaluronic acid or its salt with a weight average molecular weight of 50,000 or more and low molecular weight hyaluronic acid or its salt with a weight average molecular weight of less than 50,000, by blending acetylated hyaluronic acid, the stickiness does not change or rather improves, yet the cushioning property of the skin after application increases significantly. In addition, since Reference Example 2 does not contain hyaluronic acid or its salt, the stickiness was low but the cushioning property was very low. It was confirmed that acetylated hyaluronic acid itself has no cushioning property. Also, as shown in Comparative Example 5, when the blending amount of the high molecular weight hyaluronate was increased instead of blending acetylated hyaluronic acid, good cushioning properties were obtained, but stickiness became extremely strong. It was confirmed that cushioning properties can be enhanced by blending acetylated hyaluronic acid, and accordingly, the blending amount of hyaluronic acid or its salt can be reduced to suppress stickiness.

[0107] The weight average molecular weight of the sodium acetylated hyaluronate used in the examples is 100,000.

[0108] Formulation examples of the external preparation for skin of the present invention are 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.

Table 7

Table 8

Industrial Applicability

[0109] The external preparation for skin of the present invention contains hyaluronic acids in a specific combination, and thus has excellent cushioning properties. Moreover, despite containing a high concentration of hyaluronic acid, it has little stickiness and a good feeling in use. Therefore, it has very high commercial value.

Claims

1. (A) a high molecular weight hyaluronic acid having a weight average molecular weight of 50,000 or more or a salt thereof; (B) a low molecular weight hyaluronic acid having a weight average molecular weight of less than 50,000 or a salt thereof; (C) 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 external preparation for skin; and (D) water in an amount of 40 to 98% by mass based on the total amount of the external preparation for skin, (E) the oil content is 0 to 10% by weight, (F) substantially free of parabens, the total content of (A) a high molecular weight hyaluronic acid having a weight average molecular weight of 50,000 or more or a salt thereof and (B) a low molecular weight hyaluronic acid having a weight average molecular weight of less than 50,000 or a salt thereof is 0.05 to 0.4% by mass based on the total amount of the external preparation for skin, and the ratio of the total content of (A) a high molecular weight hyaluronic acid having a weight average molecular weight of 50,000 or more or a salt thereof and (B) a low molecular weight hyaluronic acid having a weight average molecular weight of less than 50,000 or a salt thereof to 1 part by mass of (C) acetylated hyaluronic acid or a salt thereof is 0.5 to 50,000 parts by mass, a non-emulsified external preparation for skin.

2. The non-emulsified external preparation for skin according to claim 1, wherein the content of (A) a 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 based on the total amount of the external preparation for skin.

3. The non-emulsified external preparation for skin according to claim 1 or 2, wherein the content of (B) a 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 based on the total amount of the external preparation for skin.

4. The non-emulsified external preparation for skin according to any one of claims 1 to 3, which contains 0.0001 to 1000 parts by mass of (B) a 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 (A) a high molecular weight hyaluronic acid having a weight average molecular weight of 50,000 or more or a salt thereof.

5. The non-emulsified external preparation for skin according to any one of claims 1 to 4, further containing 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 topical skin preparation according to any one of claims 1 to 6, wherein the L value in the Lab color system is 40 or more. **Claim 8** A non-emulsified topical skin preparation containing (A) a high molecular weight hyaluronic acid having a weight average molecular weight of 50,000 or more or a salt thereof, (B) a low molecular weight hyaluronic acid having a weight average molecular weight of less than 50,000 or a salt thereof, and (D) 40 to 98% by mass of water, (E) having an oil content of 0 to 10% by mass, (F) substantially free of parabens, and the total content of (A) a high molecular weight hyaluronic acid having a weight average molecular weight of 50,000 or more or a salt thereof and (B) a low molecular weight hyaluronic acid having a weight average molecular weight of less than 50,000 or a salt thereof being 0.05 to 0.4% by mass, wherein (C) 0.00001 to 0.3% by mass of acetylated hyaluronic acid or a salt thereof is included such that the ratio of the total content of (A) a high molecular weight hyaluronic acid having a weight average molecular weight of 50,000 or more or a salt thereof and (B) a low molecular weight hyaluronic acid having a weight average molecular weight of less than 50,000 or a salt thereof to 1 part by mass of acetylated hyaluronic acid or a salt thereof is 0.5 to 50,000 parts by mass, to improve the cushioning property or the mochi-mochi feeling in the texture of the preparation and / or after application while suppressing the stickiness of the non-emulsified topical skin preparation (however, (D) the water content is 40 to 98% by mass, (E) the oil content is 0 to 10% by mass, the total content of (A) a high molecular weight hyaluronic acid having a weight average molecular weight of 50,000 or more or a salt thereof and (B) a low molecular weight hyaluronic acid having a weight average molecular weight of less than 50,000 or a salt thereof is 0.05 to 0.4% by mass, the content of acetylated hyaluronic acid or a salt thereof is 0.00001 to 0.3% by mass, and the ratio of the total content of (A) a high molecular weight hyaluronic acid having a weight average molecular weight of 50,000 or more or a salt thereof and (B) a low molecular weight hyaluronic acid having a weight average molecular weight of less than 50,000 or a salt thereof to 1 part by mass of acetylated hyaluronic acid or a salt thereof is 0.5 to 50,000 parts by mass are the contents with respect to the total amount of the non-emulsified topical skin preparation after including (C) acetylated hyaluronic acid or a salt thereof).

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