JP7536490B2 - Skin care composition - Google Patents

Description

The present invention relates to a skin topical composition.

As we age, our skin becomes more wrinkled, which is part of the skin aging process and is influenced by several factors, including changes in skin tissue and the effects of exposure to ultraviolet light.
In the past, skin care products aimed at making wrinkles less noticeable have been studied, but the improvement effect has been extremely low, and women who are troubled by wrinkles have not been satisfied with them.
On the other hand, cosmetics containing a film-forming polymer for the purpose of improving the uniformity of the cosmetic film and the durability of the cosmetic are known. For example, Patent Document 1 describes that a cosmetic containing a film-forming polymer in which a specific functional group is introduced into the backbone of a polycycloolefin polymer has good cosmetic durability and good feel.

JP 2012-17317 A

However, cosmetics containing film-forming polymers have problems such as insufficient wrinkle improvement effects, being heavy to spread when applied, being difficult to apply, and leaving an uncomfortable feeling after application.

The inventors have discovered that by combining a specific film-forming polymer with two specific volatile oils, it is possible to obtain a skin care composition that maintains high shrinkage and improves wrinkles, spreads well when applied, is easy to apply, and does not leave a strange feeling after application, and thus completed the present invention.

The present invention comprises the following components (A) and (B):
(A) 0.1 to 30 mass% of a polymer containing a norbornane structure,
The present invention relates to a skin external preparation composition containing at least (B1) a volatile hydrocarbon oil and (B2) a volatile silicone oil, the volatile oil having a volatilization rate of 14% or more after drying for 30 minutes at 1 atmospheric pressure, 40°C, and 60% R.H.

The skin topical composition of the present invention can improve wrinkles, spreads well when applied, is easy to apply, and does not leave a feeling of discomfort after application.

FIG. 2 is a diagram showing the application form of each topical skin preparation composition when evaluating the wrinkle improvement effect in the examples.

<Component (A)>
The component (A) used in the present invention is a polymer containing a norbornane structure.
When the composition containing component (A) is applied to the skin around wrinkles, such as by coating, and then dried, the film containing component (A) shrinks, and the skin surface that is in contact with the film shrinks.By this action, the skin of the wrinkled part is stretched, so that the wrinkles can be made less noticeable.In addition, since component (A) is also excellent in bending resistance, the film containing component (A) is unlikely to crack, and is easy to shrink while following the shape of the skin.Therefore, even when the film containing component (A) shrinks, it can obtain sufficient adhesion between the film and the skin surface.

In the present invention, the norbornane structure refers to a structure represented by the following formula. Component (A) may have the structure represented by this formula at any site in the polymer.

Component (A) is not particularly limited as long as it is a polymer having the above-mentioned norbornane structure in the molecule, but from the viewpoint of smoothing out wrinkles on the skin and making them less noticeable through the above-mentioned mechanism of action and obtaining a sufficient wrinkle-improving effect (hereinafter also referred to as the "wrinkle-improving effect on the skin"), it is more preferable that component (A) is a silicone-modified polymer containing a norbornane structure.

Examples of norbornane structure-containing silicone modified polymers include polymers having repeating units represented by the following general formula (1) or (2).

In the formula, ^R1 is independently an alkyl group having 1 to 12 carbon atoms, and X is a group represented by the following formula (i): a is an integer of 1 to 3, and b is an integer of 0 to 2.

In the formula, R ² is independently a hydrocarbon group having 1 to 12 carbon atoms, and c is an integer of 1 to 5.

In the formula, R ¹ , R ² and b are the same as defined above, and d is an integer of 2 or more and 5 or less.

In the general formula (1), R ¹ 's each independently represent an alkyl group having 1 to 12 carbon atoms. From the viewpoint of the skin wrinkle improving effect and versatility, a methyl group, an ethyl group, an n-propyl group, a butyl group, or a pentyl group is preferable, and a methyl group is more preferable.
X is a group represented by the formula (i), and in formula (i), ^R2 is each independently a hydrocarbon group having 1 to 12 carbon atoms. From the viewpoint of the skin wrinkle improving effect and versatility, ^R2 is preferably an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms or a phenyl group, even more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group. c is an integer of 1 to 5, and from the viewpoint of versatility, c=1 is preferable. That is, X is preferably a trimethylsiloxy group.
a is an integer of 1 or more and 3 or less, and may be, for example, a polymer in which a repeating unit of a=2 and a repeating unit of a=3 are present in a mixture. From the viewpoint of versatility, a is preferably 3. b is an integer of 0 or more and 2 or less, and from the same viewpoint, is preferably 0, 1 or a combination thereof, and more preferably 0.

In the general formula (2), R ¹ , R ² and b are the same as above. d is an integer of 2 to 5, and from the viewpoint of versatility, d=2 is preferable. From the same viewpoint, it is preferable that R ¹ and R ² are methyl groups and d is 2 or 3 in the cyclic silicone structure in the general formula (2). That is, the cyclic silicone structure in the general formula (2) is preferably a structure represented by the following formula (4) or (5).

From the viewpoint of the effect of improving skin wrinkles, the proportion of the repeating units represented by the general formula (1) or (2) in the norbornane structure-containing silicone modified polymer is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more of the total number of repeating units in the polymer. The upper limit is 100%, and is preferably 95% or less, more preferably 90% or less, and even more preferably 70% or less. The specific range of the number of repeating units represented by the general formula (1) or (2) in the norbornane structure-containing silicone modified polymer is preferably 10 to 100%, more preferably 10 to 95%, even more preferably 30 to 90%, and even more preferably 50 to 70% of the total number of repeating units in the polymer.

The norbornane structure-containing silicone modified polymer may have a repeating unit represented by the following general formula (3) in addition to the repeating unit represented by the general formula (1) or (2).

In the formula, R ³ to R ⁶ are each independently a hydrogen atom, a halogen atom, a substituent selected from an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group and a halogenated hydrocarbon group having 1 to 10 carbon atoms, or an oxetanyl group, an alkoxycarbonyl group, a polyoxyalkylene group, a polyglyceryl group or an alkoxysilyl group. Two groups selected from R ³ to R ⁶ may be bonded to each other to form an alicyclic structure, an aromatic ring structure, a carboimide group or an acid anhydride group. b is the same as above.

The proportion of the repeating unit represented by the above general formula (3) in the norbornane structure-containing silicone modified polymer is preferably 90% or less, more preferably 70% or less, and even more preferably 50% or less of the total number of repeating units in the polymer, from the viewpoint of the effect of improving skin wrinkles. When the repeating unit represented by the above general formula (3) is contained, the proportion is preferably 5% or more, more preferably 10% or more, and even more preferably 30% or more of the total number of repeating units in the polymer. The specific range of the number of repeating units represented by the above general formula (3) in the norbornane structure-containing silicone modified polymer is preferably 5 to 90%, more preferably 10 to 70%, and even more preferably 30 to 50% of the total number of repeating units in the polymer.
The proportion of the repeating units represented by the above general formulas (1) to (3) in the norbornane structure-containing silicone modified polymer can be determined by ¹ H-NMR measurement.

As the norbornane structure-containing silicone-modified polymer, silicone-modified polynorbornene is preferred, and silicone-modified polynorbornene represented by the following formula (6) is more preferred.

In the formula, e and f are the numbers of repeating units and each is independently an integer of 1 or more.
From the viewpoint of the effect of improving skin wrinkles, the ratio of e to f in general formula (6) is preferably e/f=20/80 to 90/10 (mol/mol), more preferably 30/70 to 80/20 (mol/mol), and even more preferably 50/50 to 70/30 (mol/mol).

From the viewpoint of achieving both shrinkage and flex resistance and from the viewpoint of improving skin wrinkles, the number average molecular weight Mn of the norbornane structure-containing silicone modified polymer is preferably at least 50,000, more preferably at least 100,000, even more preferably at least 200,000, and is preferably at most 2,000,000, more preferably at most 1,500,000, even more preferably at most 800,000, and still more preferably at most 600,000. The specific range of the number average molecular weight Mn of the norbornane structure-containing silicone modified polymer is preferably from 50,000 to 2,000,000, more preferably from 100,000 to 1,500,000, even more preferably from 200,000 to 800,000, and still more preferably from 200,000 to 600,000.
The number average molecular weight Mn of the polymer can be measured by gel permeation chromatography (GPC) using polystyrene as a standard substance, specifically, by the method described in the Examples.

Component (A) can be obtained, for example, by addition polymerization of a cyclic olefin monomer that contains a norbornane structure or is capable of forming a norbornane structure, by a known method.
For example, if component (A) is a norbornane structure-containing silicone modified polymer having a repeating unit represented by the above general formula (1) or (2), it can be obtained by addition polymerization of a cyclic olefin monomer represented by the following general formula (1a) or (2a). Furthermore, a cyclic olefin monomer represented by the following general formula (3a) may be copolymerized.

In the formula, ^R1 is independently an alkyl group having 1 to 12 carbon atoms, and X is a group represented by the following formula (i): a is an integer of 1 to 3, and b is an integer of 0 to 2.

In the formula, R ² is independently a hydrocarbon group having 1 to 12 carbon atoms, and c is an integer of 1 to 5.

In the formula, R ¹ , R ² and b are the same as defined above, and d is an integer of 2 or more and 5 or less.

In the formula, R ³ to R ⁶ are each independently a hydrogen atom, a halogen atom, a substituent selected from an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group and a halogenated hydrocarbon group having 1 to 10 carbon atoms, or an oxetanyl group, an alkoxycarbonyl group, a polyoxyalkylene group, a polyglyceryl group or an alkoxysilyl group. Two groups selected from R ³ to R ⁶ may be bonded to each other to form an alicyclic structure, an aromatic ring structure, a carboimide group or an acid anhydride group. b is the same as above.

When the cyclic olefin monomer represented by the above general formula (3a) is copolymerized, the amount used is preferably 90 mol% or less, more preferably 70 mol% or less, and even more preferably 50 mol% or less, based on 100 mol% of the total monomers used in the polymerization, and is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 30 mol% or more, from the viewpoint of the skin wrinkle improving effect.

The silicone-modified polynorbornene represented by the formula (6) can be obtained by addition polymerization of tris(trimethylsiloxy)silylnorbornene represented by the following formula (6a) with norbornene.

From the viewpoint of improving skin wrinkles, the copolymerization ratio of tris(trimethylsiloxy)silylnorbornene to norbornene is preferably 20/80 to 90/10 (mol/mol), more preferably 30/70 to 80/20 (mol/mol), and even more preferably 50/50 to 70/30 (mol/mol).

The repeating units shown in the general formulas (1) to (3) and the formula (6) all represent 2,3-addition structural units of the cyclic olefin monomers that are raw material monomers, but may also include 2,7-addition structural units formed by addition polymerization of the cyclic olefin monomers.

As the norbornane structure-containing silicone modified polymer, norbornene/tris(trimethylsiloxy)silylnorbornene copolymer is preferred, which is a compound represented by the INCI name (International Cosmetic Ingredient Dictionary and Handbook, 16th Edition, Vol. 2, 2016, p. 2274): NORBORNENE/TRIS(TRIMETHYLSILOXY)SILYLNORBORNENE COPOLYMER.
An example of a commercially available silicone modified polymer containing a norbornane structure is "NBN-30-ID" (a solution of norbornene/tris(trimethylsiloxy)silylnorbornene) copolymer in isododecane, manufactured by Shin-Etsu Chemical Co., Ltd.

Component (A) may be used alone or in combination of two or more types, and the solid content is, from the viewpoint of the skin wrinkle improving effect, 0.1 mass% or more in the total composition, preferably 1 mass% or more, more preferably 3 mass% or more, even more preferably 4 mass% or more, 30 mass% or less, preferably 25 mass% or less, more preferably 20 mass% or less, and even more preferably 18 mass% or less. The solid content of component (A) is 0.1 to 30 mass% in the total composition, preferably 1 to 25 mass%, more preferably 3 to 20 mass%, and even more preferably 4 to 18 mass%.

<Component (B)>
Component (B) used in the present invention is a volatile oil having a volatilization rate of 14% or more after drying for 30 minutes at 1 atmospheric pressure, 40°C, and 60% R.H. When component (B) is contained, the drying speed of a composition containing component (A) is improved, accelerating the contraction of component (A) during the drying process, and the effect of smoothing out wrinkles on the skin to make them less noticeable is further improved.
From the viewpoint of obtaining the above-mentioned effect, the volatilization rate of component (B) after drying for 30 minutes at 1 atmospheric pressure, 40° C., and 60% R.H. is preferably 18% or more, more preferably 25% or more, even more preferably 30% or more, still more preferably 45% or more, still more preferably 65% or more, still more preferably 80% or more, and still more preferably 95% or more. The upper limit is 100%.
The volatilization rate of component (B) is calculated by placing 0.5 g of a sample in a glass petri dish having a diameter of 40 mm, leaving it to dry at 40° C. for 30 minutes under an atmosphere of 1 atmosphere and 60% RH, and calculating the value of {(W ₀ -W ₁ )/W ₀ } x 100, where W ₀ (g) is the mass of the sample before drying and W ₁ (g) is the mass of the sample after drying. The larger this value, the faster the volatilization rate and the easier it is to dry.
Two or more types of volatile oils may be used as component (B).
The volatility rate can be specifically measured by the method described in the Examples.

From the viewpoint of enhancing the effect of improving skin wrinkles, component (B) is a volatile oil having a volatility rate in the above range and contains at least (B1) a volatile hydrocarbon oil and (B2) a volatile silicone oil.
(B1) Examples of the volatile hydrocarbon oil include isododecane (volatility: 33%).
The volatile hydrocarbon oil of component (B1) can be used alone or in combination of two or more, and the content is preferably 0.1% by mass or more in the total composition from the viewpoint of improving skin wrinkles, more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 3% by mass or more, even more preferably 6% by mass or more, preferably 98% by mass or less, more preferably 70% by mass or less, even more preferably 50% by mass or less, even more preferably 40% by mass or less, and even more preferably 35% by mass or less. The content of component (B1) is preferably 0.1 to 98% by mass in the total composition, more preferably 1 to 70% by mass, even more preferably 2 to 50% by mass, even more preferably 3 to 40% by mass, and even more preferably 6 to 35% by mass.
In the present invention, it is preferable to use a volatile hydrocarbon oil as component (B1) as a solvent for the polymer as component (A).

Examples of the volatile silicone oil (B2) include hexamethyldisiloxane (volatility 100%), methyltrimethicone, and dimethylpolysiloxane having a kinetic viscosity of 2 cSt or less at 25° C., and one or more selected from hexamethyldisiloxane, methyltrimethicone, and octamethyldimethylpolysiloxane are preferred. The kinetic viscosity can be measured, for example, using an Ubbelohde viscometer.
From the viewpoint of enhancing the effect of improving skin wrinkles, component (B2) is more preferably one or more selected from the group consisting of hexamethyldisiloxane and dimethylpolysiloxanes having a kinetic viscosity of 1.5 cSt or less at 25°C, even more preferably one or more selected from the group consisting of hexamethyldisiloxane and dimethylpolysiloxanes having a kinetic viscosity of 1 cSt or less at 25°C, and even more preferably hexamethyldisiloxane.

Commercially available products of hexamethyldisiloxane and dimethylpolysiloxane with a kinetic viscosity of 2 cSt or less at 25°C include "KF-96L-0.65cs" (hexamethyldisiloxane), "TMF-1.5", "KF-96L-1cs" (octamethyltrisiloxane), "KF-96L-1.5cs", and "KF-96L-2cs" manufactured by Shin-Etsu Chemical Co., Ltd., "SH200C Fluid 1cs" and "SH200C Fluid 1.5cs" manufactured by Dow Corning Toray Co., Ltd., "TSF451-0.65" manufactured by Momentive Performance Materials Japan LLC, and "BELSIL DM0.65" manufactured by Wacker Asahi Kasei Silicones Co., Ltd.

The volatile silicone oil of component (B2) can be used alone or in combination of two or more kinds. The content is preferably 0.5% by mass or more in the total composition, more preferably 5% by mass or more, even more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 50% by mass or more, preferably 98% by mass or less, more preferably 97% by mass or less, even more preferably 96% by mass or less, even more preferably 95% by mass or less, and even more preferably 90% by mass or less, from the viewpoints of improving wrinkles, spreading well when applied, being easy to apply, and suppressing the feeling of discomfort during drying after application. The content of component (B2) is preferably 0.5 to 98% by mass in the total composition, more preferably 5 to 97% by mass, even more preferably 10 to 96% by mass, even more preferably 15 to 95% by mass, and even more preferably 50 to 90% by mass.

In the present invention, the mass ratio (B2)/((B1)+(B2)) of component (B2) to the total amount of components (B1) and (B2) is preferably 0.3 or more, more preferably 0.5 or more, even more preferably 0.6 or more, preferably 0.98 or less, more preferably 0.95 or less, and even more preferably 0.9 or less, from the viewpoints of improving wrinkles, spreading well when applied, being easy to apply, and suppressing an uncomfortable feeling during drying after application. In addition, the mass ratio (B2)/((B1)+(B2)) of component (B2) to the total amount of components (B1) and (B2) is preferably 0.3 to 0.98, more preferably 0.5 to 0.95, and even more preferably 0.6 to 0.9.

Component (B) includes components (B1) and (B2), and may be used alone or in combination of two or more. From the viewpoint of enhancing the effect of improving skin wrinkles, the content is preferably 1% by mass or more in the total composition, more preferably 15% by mass or more, even more preferably 30% by mass or more, even more preferably 50% by mass or more, even more preferably 70% by mass or more, preferably 99% by mass or less, more preferably 98% by mass or less, even more preferably 97% by mass or less, even more preferably 96% by mass or less, and even more preferably 95% by mass or less. The content of component (B) in the total composition is preferably 1 to 99% by mass, more preferably 15 to 98% by mass, even more preferably 30 to 97% by mass, even more preferably 50 to 96% by mass, and even more preferably 70 to 95% by mass.

In the present invention, the mass ratio (A)/(B) of component (A) to component (B) is preferably 0.002 or more, more preferably 0.02 or more, even more preferably 0.04 or more, even more preferably 0.05 or more, preferably 1 or less, more preferably 0.7 or less, even more preferably 0.4 or less, and even more preferably 0.2 or less, from the viewpoint of the effect of improving skin wrinkles. In addition, the mass ratio (A)/(B) of component (A) to component (B) is preferably 0.002 to 1, more preferably 0.02 to 0.7, even more preferably 0.04 to 0.4, and even more preferably 0.05 to 0.2.

<Component (C)>
The skin external preparation composition of the present invention may further contain (C) a surfactant, and an anionic surfactant, a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant is preferred.
There are no limitations on the surfactant of component (C) so long as it is one that is commonly used in topical skin preparations. However, from the viewpoints of dissolving in volatile oils, suppressing stickiness, and inhibiting peeling or whitening of the coating film over time, nonionic surfactants are preferred.
Examples of nonionic surfactants include sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, polyethylene glycol fatty acid esters, sucrose fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid esters, polyoxyethylene phytostanol ethers, polyoxyethylene phytosterol ethers, polyoxyethylene cholestanol ethers, polyoxyethylene cholesteryl ethers, alkyl glyceryl ether-modified silicones, polyoxyalkylene-modified silicones, polyoxyalkylene-alkyl co-modified silicones, and polyoxyalkylene-fluoroalkyl co-modified silicones.

Of these, from the viewpoint of enhancing the dispersibility and solubility of water and water-soluble components in oil, silicone surfactants are preferred, and those containing one or more of alkyl glyceryl ether-modified silicones and polyoxyalkylene-modified silicones are more preferred, with those containing polyoxyalkylene-modified silicones being even more preferred.
Examples of polyoxyalkylene-modified silicones that can be used include commercially available products such as SH3771M, SH3772M, SH3773M, SH3775M, SH3749, and DC5200 manufactured by Dow Corning Toray Co., Ltd., and KF-6011, KF-6012, KF-6013, KF-6015, KF-6016, KF6017, and KF-6004 manufactured by Shin-Etsu Chemical Co., Ltd.

From the viewpoint of improving the dispersibility and solubility of water and water-soluble components in oil, the nonionic surfactant preferably has an HLB value of 1 or more and 7 or less, and more preferably an HLB value of 2 or more and 6 or less.

Here, HLB (Hydrophilic-Lipophilic Balance) indicates the molecular weight of the hydrophilic group portion in the total molecular weight of a surfactant, and for nonionic surfactants, it can be calculated by Griffin's formula.
The HLB of a mixed surfactant consisting of two or more nonionic surfactants can be calculated as follows: The HLB of the mixed surfactant is the arithmetic average of the HLB values of each nonionic surfactant based on the blending ratio.

Mixed HLB=Σ(HLBx×Wx)/ΣWx
HLBx indicates the HLB value of nonionic surfactant X.
Wx is the weight (g) of nonionic surfactant X having a value of HLBx

Nonionic surfactants can be used alone or in combination of two or more. From the viewpoint of dissolving in volatile oils and suppressing stickiness, the content is preferably 30% by mass or less in the total composition, more preferably 10% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, and even more preferably 1% by mass or less.

<Component (D)>
The skin external preparation composition of the present invention may further contain (D) a non-volatile oil. The term "non-volatile" refers to an oil whose mass loss rate after 1 g of the oil is spread on a glass petri dish having a diameter of 48 mm and left at 25° C. and normal pressure for 24 hours is 1% or less.
The non-volatile oil of component (D) may be any oil commonly used in cosmetics, and may be in any form, such as liquid, paste, or solid, including, for example, ester oil, hydrocarbon oil, ether oil, higher alcohol, silicone oil, and solid wax.

Examples of ester oils include isononyl isononanoate, isodecyl isononanoate, isotridecyl isononanoate, tricyclodecane methyl isononanoate, hexyl laurate, octyldodecyl malate, cetyl 2-ethylhexanoate, 2-hexyldecyl 2-ethylhexanoate, isopropyl myristate, 2-hexyldecyl myristate, octyldodecyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, ethyl isostearate, isopropyl isostearate, isostearic acid Monoester oils such as isobutyl, 2-hexyldecyl isostearate, 2-ethylhexyl hydroxystearate, octyldodecyl oleate, oleyl oleate, octyldodecyl ricinoleate, octyl paramethoxycinnamate, and propylene carbonate; di-2-hexylhexyl succinate, bis-ethoxydiglycol succinate, di(caprylic/capric)propanediol, neopentyl glycol diisononanoate, neopentyl glycol dicaprate, glyceryl diisostearate, and poly(diisostearate). Diester oils such as glyceryl, propanediol diisostearate, diisostearyl malate, di(phytosteryl/octyldodecyl) lauroyl glutamate, di(cholesteryl/behenyl/octyldodecyl) lauroyl glutamate, di(octyldodecyl/phytosteryl/behenyl) lauroyl glutamate, neopentyl glycol di-2-ethylhexanoate, and neopentyl glycol dioctanoate; trimethylolpropane triisostearate, glyceryl triisostearate, and triisostearin. Triester oils such as diglyceryl acid, jojoba oil, trimethylolpropane tri-2-hexylhexanoate, glyceryl tri-2-ethylhexanoate, tri(caprylic/capric acid)glyceryl, trioctanoate, tritridecyl trimellitate, macadamia nut oil, olive oil, castor oil, jojoba oil, avocado oil, and sunflower oil; pentaerythrityl tetraoctanoate, diglyceryl tetraisostearate, dipentaerythrityl tetraisostearate, and pentaerythritol tetraisostearate.

Examples of the hydrocarbon oil include squalane, liquid paraffin, liquid isoparaffin, polybutene, hydrogenated polyisobutene, hydrogenated polydecene, and petrolatum.
Examples of ether oils include cetyl dimethyl butyl ether and dicaprylyl ether.

Examples of higher alcohols include those having a straight or branched alkyl or alkenyl group having 10 to 24 carbon atoms, such as lauryl alcohol, myristyl alcohol, isocetyl alcohol, isostearyl alcohol, 2-octyldodecanol, and oleyl alcohol.
Examples of silicone oils include dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, acryl-modified silicone, and fluorine-modified silicone.

The solid wax is an oily component that is solid at 25°C, and examples of such wax include vegetable waxes such as candelilla wax, rice wax, sunflower wax, carnauba wax, and wood wax; animal waxes such as beeswax and whale wax; mineral waxes such as montan wax and ozokerite; petroleum waxes such as microcrystalline wax, paraffin, and ceresin; synthetic waxes such as hydrogenated castor oil, hydrogenated jojoba oil, 12-hydroxystearic acid, stearic acid amide, phthalic anhydride, silicone wax, fluorine-based wax, polyethylene wax, and synthetic beeswax; fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and lanolin fatty acid; and higher alcohols such as cetyl alcohol, stearyl alcohol, behenyl alcohol, and hydrogenated dilinoleyl alcohol.

From the viewpoint of spreading easily when applied and not feeling unnatural after application, component (D) preferably contains ester oil, hydrocarbon oil, or silicone oil, and among these, non-volatile oils that are liquid at 25°C are preferred.

From the viewpoints of good spreadability during application and no discomfort after application, component (D) preferably contains at least one or more types of ester oil (D1), more preferably a monoester oil, a diester oil, or a triester oil, even more preferably contains at least a diester oil, and even more preferably a diester oil that is liquid at 25°C.

Component (D) can be used alone or in combination of two or more types. From the viewpoint of good spreadability during application and no discomfort after application, the content is preferably 0.001% by mass or more in the total composition, more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 2% by mass or less. The content of component (D) is preferably 0.001 to 20% by mass in the total composition, more preferably 0.01 to 10% by mass, and even more preferably 0.1 to 2% by mass.

<Other ingredients>
In the present invention, from the viewpoint of obtaining a non-sticky feel while maintaining the wrinkle improving effect on the skin, the water content is preferably 50% by mass or less of the total composition, more preferably 30% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less.

In addition to the above-mentioned components, the skin topical composition of the present invention can contain any of a variety of commonly used components within the scope of the invention, so long as the effects of the present invention are not impaired. Examples of these components include oily components other than those mentioned above, powders, water-soluble polymers, antioxidants, UV absorbers, vitamins, preservatives, pH adjusters, fragrances, plant extracts, moisturizers, colorants, cooling agents, antiperspirants, disinfectants, skin activators, etc.

The skin external preparation composition of the present invention can be applied in any form such as an oily composition, an emulsion composition, etc., which can be produced by a conventional method. The preparation can be applied in the form of a liquid, emulsion, paste, cream, gel, solid, sheet, etc.
The skin topical preparation composition of the present invention can be used for cosmetics, quasi-drugs, and pharmaceutical purposes, and can be applied as skin care cosmetics such as lotions, milky lotions, creams, beauty essences, dispersions, gels, ointments, packs, mousses, aerosols, poultices, and cleansers; UV protection cosmetics such as sunscreen milky lotions and sunscreen creams; and makeup cosmetics such as makeup bases, foundations, concealers, blushers, eye shadows, mascaras, eyeliners, eyebrows, overcoats, and lipsticks.
Examples of containers for housing the skin topical composition include bottles, jars, tubes, pumps, syringe containers, mist containers, pillow containers, and the like.

With respect to the above-mentioned embodiment, the present invention further discloses the following composition.

<1> The following components (A) and (B):
(A) 0.1 to 30 mass% of a polymer containing a norbornane structure,
(B) A skin external preparation composition containing a volatile oil having a volatilization rate of 14% or more after drying for 30 minutes at 1 atmospheric pressure, 40°C, and 60% R.H., the volatile oil including at least (B1) a volatile hydrocarbon oil and (B2) a volatile silicone oil.

<2> The skin topical preparation composition described in <1> above, in which component (A) is preferably a norbornane structure-containing silicone modified polymer, more preferably a polymer having a repeating unit represented by the following general formula (1) or (2).

In the formula, ^R1 is independently an alkyl group having 1 to 12 carbon atoms, and X is a group represented by the following formula (i): a is an integer of 1 to 3, and b is an integer of 0 to 2.

In the formula, R ² is independently a hydrocarbon group having 1 to 12 carbon atoms, and c is an integer of 1 to 5.

In the formula, R ¹ , R ² and b are the same as defined above, and d is an integer of 2 or more and 5 or less.

<3> The skin topical preparation composition according to <1> or <2> above, wherein component (A) is preferably a silicone-modified polynorbornene represented by the following formula (6), and more preferably a norbornene/tris(trimethylsiloxy)silylnorbornene) copolymer.

In the formula, e and f are the number of repeating units and are each independently an integer of 1 or more.

<4> The skin topical preparation composition according to <3> above, wherein in the component (A), the ratio of e to f in formula (6) is preferably e/f=20/80 to 90/10 (mol/mol), more preferably 30/70 to 80/20 (mol/mol), and even more preferably 50/50 to 70/30 (mol/mol).
<5> The content of component (A) in the total composition is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 4% by mass or more, and is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 18% by mass or less. The skin topical composition according to any one of <1> to <4> above.

<6> The skin external preparation composition according to any one of <1> to <5> above, wherein the volatilization rate of component (B) after drying for 30 minutes at 1 atmospheric pressure, 40°C, and 60% R.H. is preferably 18% or more, more preferably 25% or more, even more preferably 30% or more, even more preferably 45% or more, even more preferably 65% or more, even more preferably 80% or more, and even more preferably 95% or more.
<7> The skin external preparation composition according to any one of the above <1> to <6>, wherein the component (B1) is preferably isododecane.
<8> The content of component (B1) is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 3% by mass or more, even more preferably 6% by mass or more, preferably 98% by mass or less, more preferably 70% by mass or less, even more preferably 50% by mass or less, even more preferably 40% by mass or less, and even more preferably 35% by mass or less, based on the total composition.
<9> The skin external preparation composition according to any one of the above <1> to <8>, wherein the volatile hydrocarbon oil of component (B1) is preferably used as a solvent for the polymer of component (A).

<10> The topical skin preparation composition according to any one of the above <1> to <9>, wherein the component (B1) is preferably one or more selected from the group consisting of hexamethyldisiloxane, methyltrimethicone, and dimethylpolysiloxanes having a kinetic viscosity at 25°C of 2 cSt or less, more preferably one or more selected from the group consisting of hexamethyldisiloxane and dimethylpolysiloxanes having a kinetic viscosity at 25°C of 1.5 cSt or less, even more preferably one or more selected from the group consisting of hexamethyldisiloxane and dimethylpolysiloxanes having a kinetic viscosity at 25°C of 1 cSt or less, and even more preferably hexamethyldisiloxane.
<11> The content of component (B2) in the entire composition is preferably 0.5% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 50% by mass or more, and is preferably 98% by mass or less, more preferably 97% by mass or less, even more preferably 96% by mass or less, even more preferably 95% by mass or less, and even more preferably 90% by mass or less.

<12> The external skin preparation composition according to any one of the above <1> to <11>, wherein the mass ratio of the component (B2) to the total amount of the components (B1) and (B2), (B2)/((B1)+(B2)), is preferably 0.3 or more, more preferably 0.5 or more, even more preferably 0.6 or more, and is preferably 0.98 or less, more preferably 0.95 or less, and even more preferably 0.9 or less.
<13> The content of component (B) in the entire composition is preferably 1% by mass or more, more preferably 15% by mass or more, even more preferably 30% by mass or more, even more preferably 50% by mass or more, even more preferably 70% by mass or more, and is preferably 99% by mass or less, more preferably 98% by mass or less, even more preferably 97% by mass or less, even more preferably 96% by mass or less, and even more preferably 95% by mass or less.
<14> The composition for external use on the skin according to any one of the above <1> to <13>, wherein the mass ratio (A)/(B) of the component (A) to the component (B) is preferably 0.002 or more, more preferably 0.02 or more, even more preferably 0.04 or more, even more preferably 0.05 or more, and is preferably 1 or less, more preferably 0.7 or less, even more preferably 0.4 or less, and even more preferably 0.2 or less.

<15> The following components (A) and (B):
(A) 0.1 to 30 mass% of a silicone-modified polymer containing a norbornane structure,
(B) 0.1 to 99% by mass of a volatile oil having a volatilization rate of 14% or more after drying for 30 minutes at 1 atmospheric pressure, 40°C, and 60% R.H., the volatile oil including at least (B1) a volatile hydrocarbon oil and (B2) a volatile silicone oil.
A skin topical composition comprising:
<16> The following components (A) and (B):
(A) 0.1 to 30 mass% of a silicone-modified polymer containing a norbornane structure,
(B) A volatile oil having a volatility of 14% or more after drying for 30 minutes at 1 atmospheric pressure, 40°C, and 60% R.H., the volatile oil containing at least (B1) a volatile hydrocarbon oil and (B2) a volatile silicone oil, the mass ratio of component (B2) to the total amount of components (B1) and (B2) being (B2)/((B1)+(B2)), being 0.3 to 0.98: 0.1 to 99 mass%
A skin topical composition comprising:

<17> The following components (A) and (B):
(A) 0.1 to 30 mass% of a silicone-modified polymer containing a norbornane structure,
(B) 0.1 to 99% by mass of a volatile oil having a volatilization rate of 14% or more after drying for 30 minutes at 1 atmospheric pressure, 40°C, and 60% R.H., the volatile oil containing at least (B1) isododecane, and (B2) one or more selected from hexamethyldisiloxane, methyltrimethicone, and octamethyldimethylpolysiloxane.
A skin topical composition comprising:

<18> The composition for external use on the skin according to any one of the above <1> to <17>, further comprising preferably a surfactant, more preferably a nonionic surfactant, and even more preferably a nonionic surfactant having an HLB of 1 to 7.
<19> The skin topical preparation composition according to <18>, wherein the content of the nonionic surfactant is preferably 30% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, still more preferably 3% by mass or less, and even more preferably 1% by mass or less, of the total composition.

<20> The skin external preparation composition according to any one of <1> to <19>, further comprising preferably a non-volatile oil, more preferably one or more selected from ester oil, hydrocarbon oil, and silicone, even more preferably at least an ester oil, and even more preferably at least a diester oil.
<21> The skin topical preparation composition according to <20>, wherein the content of the non-volatile oil is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.1% by mass or more, of the total composition, and is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 2% by mass or less.
<22> The composition for external use on the skin according to any one of the above <1> to <21>, wherein the water content is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 10% by mass or less, still more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total composition.

The present invention will be described below with reference to examples, but the present invention is not limited to the scope of the examples. In the examples, various measurements and evaluations were carried out by the following methods.
Moreover, Examples 4 and 5 are reference examples.

(Volatilization rate)
0.5 g of the sample was placed in a glass petri dish with a diameter of 40 mm, and dried by leaving it to stand on a hot plate set at 40° C. for 30 minutes under an environment of 1 atmosphere and 60% RH. The mass of the sample before drying was W ₀ (g), the mass of the sample after drying was W ₁ (g), and the value of {(W ₀ -W ₁ )/W ₀ } x 100 was taken as the volatilization rate (%). The larger this value, the faster the volatilization rate and the easier it was to dry.

(Wrinkle improvement effect)
Five expert panelists applied 0.2 g of each composition with their fingers to one side of the face, pinching the nasolabial folds around the mouth, in the manner shown in Figure 1. After drying for 10 minutes at room temperature (25°C), the anti-wrinkle effect was sensorily evaluated according to the following criteria. The results were shown as the total score of the five panelists.
5: Wrinkles have become significantly lighter.
4: Wrinkles have become less noticeable.
3: Wrinkles have become slightly lighter.
2: Wrinkles remain and there is not much change.
1: No change.

(Spread when applied)
Each composition was applied to the skin and evaluated by five expert panelists for spreadability upon application according to the following criteria. The results were expressed as the total score given by the five panelists.
5: Very good stretch.
4: Good stretch.
3: Stretches somewhat well.
2: Stretches somewhat heavily.
1: It stretches heavily.

(handling)
Five expert panelists evaluated each composition for ease of application to the skin according to the following criteria, and the results were expressed as the total score given by the five panelists.
5: Very easy to handle.
4: Easy to handle.
3: Somewhat easy to handle.
2: Difficult to handle.
1: Very difficult to handle.

(No discomfort after application)
Each composition was applied to the skin by five expert panelists, and after drying, the absence of discomfort was evaluated according to the following criteria. The results were expressed as the total score given by the five panelists.
5: No discomfort at all.
4: There is almost no discomfort.
3: There is a slight feeling of discomfort.
2: It feels strange.
1: There is a strong sense of discomfort.

Examples 1 to 6, Comparative Examples 1 to 2
Skin topical compositions having the compositions shown in Table 1 were prepared and evaluated for wrinkle improving effect, spreadability upon application, handling, and lack of discomfort after application. The results are also shown in Table 1.

(Production method)
The oil phase component, which was a mixture of components (A), (B) and other components, was dispersed using a disper and then stirred using a homomixer to obtain a skin external preparation composition.

In Table 1, *1 to *8 are as follows.
*1: Shin-Etsu Chemical Co., Ltd. "NBN-30-ID" (in the following formula (6), e / f = 60 / 40 (mol / mol), Mn = 360,000, norbornene / tris (trimethylsiloxy) silylnorbornene) copolymer is an isododecane solution, effective component concentration: 30% by mass)

*2: The "NBN-30-ID" manufactured by Shin-Etsu Chemical Co., Ltd. in *1 was dried under reduced pressure at 50°C for 24 hours to obtain a solid content. The obtained solid content and decamethylcyclopentasiloxane (D5) ("KF-995" manufactured by Shin-Etsu Chemical Co., Ltd.) were stirred at room temperature to obtain a homogeneous solution. The solid content was 30%.
*3: "NBN-30-ID" manufactured by Shin-Etsu Chemical Co., Ltd. in *1 was dried under reduced pressure at 50°C for 24 hours, and the obtained solid was used.
*4: Maruzen Petrochemical Co., Ltd. "Marukasol R"
*5: "KF-96L-0.65cs" manufactured by Shin-Etsu Chemical Co., Ltd.
*6: "KF-96L-1cs" manufactured by Shin-Etsu Chemical Co., Ltd.
*7: "TMF-1.5" manufactured by Shin-Etsu Chemical Co., Ltd.
*8: "KF-995" manufactured by Shin-Etsu Chemical Co., Ltd.

Examples 7 and 8
In the same manner as in Examples 1 to 6, skin external preparation compositions having the compositions shown in Table 2 were produced.
All of the obtained skin topical compositions have an excellent wrinkle improving effect, spread well when applied, are easy to apply, and do not leave a feeling of discomfort after application.

Example 9
A skin topical composition (liquid) having the composition of Example 1 shown in Table 1 was produced and filled into a mist container. The skin topical composition was sprayed from this mist container onto the nasolabial folds and surrounding areas of the face. As a result, the composition had an excellent wrinkle improving effect, spread well when applied, was easy to apply, and did not feel strange after application.

Claims (5)

The following components (A) and (B):
(A) 0.1 to 30% by mass of a silicone-modified polynorbornene represented by the following formula (6) ,

In the formula, e and f are the numbers of repeating units and each is independently an integer of 1 or more.
(B) A skin external preparation composition containing a volatile oil having a volatilization rate of 65 % or more after drying for 30 minutes at 1 atmospheric pressure, 40°C, and 60% R.H., the volatile oil containing at least (B1) 3 to 50% by mass of isododecane and (B2) 15 to 95% by mass of hexamethyldisiloxane . 2. The skin external preparation composition according to claim 1 , wherein in formula (6), the ratio of e to f is e/f=20/80 to 90/10 (mol/mol). The composition for external skin preparation according to claim 1 or 2 , wherein the content of component (B) is 30 to 99 mass %. The skin external preparation composition according to any one of claims 1 to 3 , wherein the mass ratio of component (B2) to the total amount of components (B1) and (B2), (B2)/((B1)+(B2)), is 0.3 to 0.98. 5. The skin external preparation composition according to claim 1 , wherein the solvent for the polymer of component (A) is (B1) isododecane .