KR102760871B1 - Gel sheet for skin adhesion - Google Patents

Abstract

The present invention provides a skin-attachable gel sheet having excellent moisturizing effect and usability (film strength, absence of film burden, solubility in water), and sheet formability. A skin-attachable gel sheet containing the following components (a) to (f); (a) polyvinyl alcohol, (b) an acrylic acid polymer, (c) 40 to 93 wt% of a polyhydric alcohol, (d) 0.1 to 16 wt% of an emulsion which is solid and/or semi-solid at 25°C, (e) 1.0 to 30 wt% of an emulsion which is liquid at 25°C, and (f) 10 wt% or less of water.

Description

Gel sheet for skin adhesion

The present invention relates to a gel sheet for skin attachment.

Conventionally, for the purpose of use in cosmetics, medicines, etc., sheets or patches for skin attachment have been developed in which water-based ingredients, moisturizing ingredients, active ingredients, etc. are solidified with water-soluble film-forming agents or gelling agents. Such sheets or patches for skin attachment have the advantage of excellent moisturizing effects and drug penetration promotion effects because they can maintain various ingredients at high concentrations without flowing off on the skin for a long time. Various studies have been conducted to improve these functions or usability.

Based on a pack that aims to peel off aged keratinocytes, and as an approach to improve the moisturizing effect by suppressing adhesion, a low-peeling pack containing polyacrylic acid, polyhydric alcohol, and water as main components and having excellent water retention properties (see, for example, Patent Document 1) or a pack containing sodium polyacrylate gel, aluminum hydroxide gel, and silica as excipients to solidify the aqueous component has been proposed (see, for example, Patent Document 2). In addition, as an approach for improving the moisturizing effect by retaining moisturizing ingredients with water-soluble polysaccharides or thickeners, a sheet-like pack that solidifies polyhydric alcohols, water, etc. with gelatin and polyacrylate (see, for example, Patent Document 3), or a gel patch that combines gellan gum and a cellulose derivative or other water-soluble polysaccharides (see, for example, Patent Document 4) have been proposed. In addition, as a technology that utilizes a gel with an excellent moisturizing effect by blending alcohol as the main ingredient rather than a hydrogel containing a large amount of water, a cosmetic gel sheet has been disclosed that gels polyhydric alcohols by causing an acid to act on a water-soluble polymer containing a carboxyl group (see, for example, Patent Document 5).

In addition, as an approach for imparting an emollient effect by an oil agent by maintaining an emulsifying composition on a support, a pack cosmetic in which a sheet-like base material is impregnated with an emulsion containing a nonionic surfactant, a moisturizer, and an oil agent (see, for example, Patent Document 6), a cosmetic gel sheet in which a gel composition produced by solidifying a polyhydric alcohol, water, and an oil component using a polyacrylic acid-based polymer and an epoxy-based crosslinking agent is maintained on a support and/or within a support (see, for example, Patent Document 7), a sheet-like pack cosmetic in which an emulsifying composition containing a polyhydric alcohol, a higher alcohol, an oily component other than a higher alcohol, an emulsifier, and water is maintained on a support and/or within a support (see, for example, Patent Document 8), a composition in which a large amount of a polyhydric alcohol, water, and silicone oil are emulsified by an anionic activator and a higher alcohol is maintained on a support. And/or a sheet-like pack cosmetic maintained within a support (see, for example, Patent Document 9) is disclosed.

Meanwhile, as approaches for improving the penetration of effective ingredients, a skin-attachable patch that maintains effective ingredients for transdermal administration in polyvinyl alcohol (see, for example, Patent Document 10), or a bioadhesive gel sheet that contains a hydrogel combining gelatin or a derivative thereof, a water-soluble polysaccharide, and an O/W type emulsion containing carotenoids and that improves the skin penetration of carotenoids (see, for example, Patent Document 11) have been proposed.

Patent Document 1: Japanese Patent Publication No. 54-49334 Patent Document 2: Japanese Patent Publication No. 63-15243 Patent Document 3: Japanese Patent Publication No. 8-188527 Patent Document 4: Japanese Patent Publication No. 2000-86496 Patent Document 5: Japanese Patent Publication No. 2017-200899 Patent Document 6: Japanese Patent Publication No. 2003-342125 Patent Document 7: Japanese Patent Publication No. 11-228340 Patent Document 8: Japanese Patent Publication No. 2004-35459 Patent Document 9: Japanese Patent Publication No. 2009-84240 Patent Document 10: Japanese Patent Publication No. 64-16718 Patent Document 11: Japanese Patent Publication No. 2009-73764

However, the technologies of Patent Documents 1 and 2, which are based on peel-off packs and seek to improve moisturizing functions, were not satisfactory in terms of a feeling of burden due to a pulling or straining sensation during use because the film was hard. In addition, the technologies of Patent Documents 3 and 4, which use water-soluble polysaccharides or gelatin as a gelling agent, have excellent film flexibility and reduce the feeling of burden, but are formed as hydrogels in which highly volatile water is the main liquid component, and since the amount of moisturizing ingredients remaining after the water evaporates over time is small, they are inferior in terms of moisturizing properties. Similarly, the technology of Patent Document 10 is a hydrogel sheet in which water is impregnated in polyvinyl alcohol, so it is suitable for promoting penetration of water-soluble active ingredients, but it still has issues with moisturizing properties.

To solve this, the technology of Patent Document 5, which uses polyhydric alcohol as the main moisturizer, has excellent moisturizing properties, but requires the use of a water-soluble nonwoven fabric or a water-soluble film as a gel support, which has led to an increase in the number of manufacturing processes. In addition, as a method of use, a method has been proposed in which a sheet is attached to the skin, an appropriate amount of water is added, and the sheet is massaged to dissolve in water and adapt to the skin. However, in reality, since the gel constituting the sheet is hard and also includes a support, it is inferior in terms of solubility in water.

On the other hand, the technologies of Patent Documents 6 to 9, which blend an emulsion having an emollient effect in addition to a moisturizing component of an aqueous system, require the concomitant use of a support because the film strength decreases due to emulsification, and furthermore, since it cannot be removed as a single film, it is necessary to wipe off the emulsion remaining on the skin after use, and thus it is not satisfactory in terms of usability. In addition, in the technology of Patent Document 11, by adding an O/W emulsion to a hydrogel using gelatin or a derivative thereof as the main gelling agent, sheetification is achieved with the gel composition alone without the concomitant use of a support, while blending an emulsion. However, as with the technologies of Patent Documents 3 and 4, since it is a hydrogel, it is not sufficient in terms of moisturizing properties.

In this way, it was not easy to realize a gel sheet that had excellent moisturizing effect and excellent usability due to high film strength. If the film strength is too high, it is easy to feel burdened because it cannot flexibly follow the movement of the skin, etc.; the solubility in water is also easy to be low; and adaptation to the skin is not good; etc. On the other hand, if the film strength is low, it is difficult to peel the gel sheet from the peeling substrate when attaching; it is difficult to attach the peeled gel sheet to the skin; and also, a supporter is required for the gel sheet to stabilize or maintain the shape after attachment to the skin, so it is difficult to perform massage, etc. because of the supporter; etc.

Thus, a gel sheet for skin attachment with excellent moisturizing effect and usability (film strength, no burden on the film, solubility in water) was required.

In addition, it was not easy to prepare a gel sheet composition for skin attachment by mixing a high proportion of an emulsion with a gel as a base, and to obtain a gel sheet with excellent usability without using a support after attachment. At this time, by mixing an emulsion with the gel sheet for skin attachment, the emollient effect of the gel sheet can be exhibited more favorably. In addition, when assuming a usage method in which an appropriate amount of water is added after attaching the sheet to the skin to allow the ingredients to adapt to the skin, it is not easy to have a technique that also has high solubility in water.

In this way, a gel sheet for skin attachment that has excellent sheet formability and is easy for users to apply to the skin has been in demand.

However, since the direction or technology for obtaining a skin-attachable gel sheet having excellent moisturizing effect and usability (film strength, absence of film burden, solubility in water) and also excellent sheet formability has not yet been established, obtaining such a skin-attachable gel sheet entails technical difficulties. For this reason, it is a reality that a skin-attachable gel sheet having excellent moisturizing effect, usability (film strength, absence of film burden, solubility in water) and sheet formability has not yet been achieved.

Therefore, the main purpose of the present invention is to provide a gel sheet for skin attachment that has excellent moisturizing effect, usability (film strength, absence of film burden, solubility in water), and sheet formability.

Under these circumstances, the inventors of the present invention have conducted preliminary studies in consideration of the above-mentioned problems, and as a result, (a) polyvinyl alcohol and (b) acrylic acid-based polymer having film-forming ability, and (c) polyhydric alcohol and (f) water as aqueous agents, and (d) a specific amount of solid and/or semi-solid emulsion and (e) a specific amount of liquid emulsion are mixed and dispersed to obtain an O/W emulsion composition, and a gel sheet having a specific amount of water or less is obtained from the O/W emulsion composition.

The skin-attachment gel sheet of the present invention has excellent moisturizing properties and also has a film strength that can be used without a support, while having flexible followability to the skin. In this way, the gel sheet of the present invention has excellent moisturizing properties, flexibility, and strength, so that it does not require a support during use, and also has excellent usability. In addition, the gel sheet of the present invention has the unique property of having both flexibility and strength, but is unlikely to deform during manufacture, and has excellent sheet moldability. In addition, the gel sheet of the present invention has high solubility in water and does not require a support during use, so that it can easily dissolve or swell in water and adapt to the skin without causing discomfort to the skin, and also allows the ingredients contained in the gel sheet to adapt to the skin and easily penetrate therein. In addition, the gel sheet of the present invention has the advantage of excellent moisturizing effect and usability as described above even without a support after attachment, so it can be used without a support, and there is also the advantage of being able to use the gel sheet of the present invention together with an aqueous composition containing various components.

That is, the inventors of the present invention have found that a gel sheet for skin attachment having excellent moisturizing effect, usability (film strength, absence of film burden, solubility in water) and formability can be obtained by containing (a) polyvinyl alcohol, (b) an acrylic acid polymer, (c) a specific amount of polyhydric alcohol, (d) a specific amount of solid and/or semi-solid emulsion, (e) a specific amount of liquid emulsion and (f) a specific amount or less of water, thereby completing the present invention.

That is, the present invention,

The following components (a) to (f);

(a) polyvinyl alcohol

(b) Acrylic acid polymer

(c) Polyhydric alcohol 40 to 93 mass%

(d) 0.1 to 16 mass% of solid or semi-solid emulsion at 25°C

(e) 1.0 to 30 mass% of liquid emulsion at 25°C

(f) Water 10 mass% or less

The present invention provides a gel sheet for skin attachment containing a pharmaceutical composition.

Additionally, the thickness of the gel sheet may be 50 to 2000 μm.

In addition, the mass ratio (a)/(b) of the components (a) and (b) may be 3 to 160.

In addition, the mass ratio (a)/(c) of the components (a) and (c) may be 0.02 to 0.5.

Additionally, the mass ratio (d)/(e) of the components (d) and (e) may be 0.001 to 3.5.

Additionally, the above component (c) may be glycerin and/or 1,3-butylene glycol.

In addition, the above component (b) may be a polymer obtained by polymerizing or copolymerizing one or more raw material monomers selected from acrylic acid, methacrylic acid, acrylic acid alkyl ester, methacrylic acid alkyl ester, and acryloyldimethyl taurine.

In addition, the above component (b) may be one or a combination of two or more selected from a carboxyvinyl polymer, an alkyl-modified carboxyvinyl polymer, a crosslinked copolymer of acrylamide and 2-acrylamide-2-methylpropane sulfonic acid, and a sodium acrylate-acryloyldimethyl taurine copolymer.

Additionally, the saponification degree of the above component (a) may be 70 to 90 mol%.

The content of the above component (a) may be 1.5 to 29 mass%.

The content of the above component (b) may be 0.03 to 4.5 mass%.

Another aspect of the present invention provides a method of using a gel sheet for skin attachment, comprising attaching the gel sheet for skin attachment to the skin, or adding water or a composition containing water to the attached gel sheet after attachment to the skin, to adapt the gel sheet to the skin.

The above skin-attaching gel sheet may be used without requiring a support.

According to the present invention, it is possible to provide a gel sheet for skin attachment which has excellent moisturizing effect, usability (film strength, no burden on the film, solubility in water), and sheet formability. In addition, the effect described herein is not necessarily limited, and may be any one of the effects described in the present technology.

The details of the present invention are described below. In addition, the embodiments described below are representative examples of embodiments of the present technology, and the scope of the present invention is not construed narrowly because of this. In addition, percentages in this specification are expressed by mass unless specifically stated. In addition, mass % is sometimes simply expressed as "%." In this specification, "~" means a range including the numerical values before and after it.

＜1. Gel sheet for skin attachment of the present invention＞

The skin-attaching gel sheet of the present invention comprises the following components (a) to (f);

(a) polyvinyl alcohol,

(b) Acrylic acid polymer

(c) Polyhydric alcohol 40 to 93 mass%

(d) 0.1 to 16 mass% of solid and/or semi-solid emulsion at 25°C

(e) 1.0 to 30 mass% of liquid emulsion at 25°C

(f) Contains water 10 mass% or less.

The present invention is a gel sheet for skin attachment, which has excellent moisturizing effect, usability (film strength, absence of film burden, solubility in water), and sheet formability.

The present invention comprises mixing and dispersing a film-forming component (a) polyvinyl alcohol and a component (b) acrylic acid-based polymer, a water-based component (c) a specific amount of a polyhydric alcohol, an emulsifier component (d) a specific amount of a solid and/or semi-solid emulsion and a component (e) a specific amount of a liquid emulsion, and a component (f) water to obtain an O/W emulsion composition, and from the O/W emulsion composition, a gel sheet having a water content of a specific amount or less can be formed.

The skin-attachment gel sheet of the present invention contains components (a) polyvinyl alcohol, (b) an acrylic acid polymer, (c) a specific amount of a polyhydric alcohol, (d) a specific amount of a solid and/or semi-solid emulsion, (e) a specific amount of a liquid emulsion, and (f) water of not more than a specific amount. The skin-attachment gel sheet of the present invention has both flexibility and strength, and is therefore easy to use even without a support, and further, since it contains a large amount of an aqueous component containing a polyhydric alcohol in the gel sheet, it has excellent moisturizing properties. Furthermore, the skin-attachment gel sheet of the present invention also has high solubility in water, and thus, when adding water or a composition containing water or when further applying the gel sheet after adding it, the shape of the sheet can be collapsed, allowing the components to penetrate into the skin. In this way, the skin-attachment gel sheet of the present invention has excellent usability such as film strength, absence of film burden, and solubility in water, and also has a moisturizing effect.

＜1 (1) Component (a) Polyvinyl alcohol＞

Component (a) polyvinyl alcohol used in the present invention is known as a raw material for cosmetics, pharmaceuticals, etc., and is generally used as an aqueous film-forming agent. Polyvinyl alcohol is manufactured by saponifying the acetyl group of vinyl acetate, and is broadly divided into a complete saponification type in which almost complete saponification is performed, and a partial saponification type in which the acetyl group remains to some extent. In general, it is classified into a complete saponification type (more than 98 mol%), an intermediate saponification type (more than 90 mol% and 98 mol% or less), and a partial saponification type (70 mol% or more and 90 mol% or less). In addition, in the present invention, polyvinyl alcohols having different degrees of saponification can be appropriately combined and used.

In addition, the polyvinyl alcohol used in the present invention is suitably a water-soluble polyvinyl alcohol that can be dissolved in water at about 10 to 30°C.

In the present invention, any saponification type can be used, but the lower limit of the saponification degree is suitably 70 mol% or more, more suitably 75 mol% or more, more suitably 80 mol% or more, and even more suitably 85 mol% or more, and the upper limit of the saponification degree is suitably 98 mol% or less, more suitably 97 mol% or less, more suitably 95 mol% or less, and even more suitably 90 mol% or less, and the numerical range is more suitably 70 to 90 mol%, more suitably 80 to 90 mol%, and even more suitably 85 to 90 mol%. By setting it within the above range, a gel sheet having good flexibility and membrane strength can be obtained. In addition, by setting it within the above range, a gel sheet in which solubility in water, disintegration property due to swelling in water, formability, or a combination thereof is well-adjusted can be obtained.

In the skin-attachable gel sheet of the present invention, suitably using a partially saponified polyvinyl alcohol having a degree of saponification of 80 to 90 mol% is preferable because it has high solubility in the component (c) polyhydric alcohol, thus enabling high blending, and furthermore, because the skin-attachable gel sheet of the present invention has excellent solubility in water. Meanwhile, although the molecular weight and the degree of polymerization are effective indicators for controlling the film strength, they are not particularly limited and can be appropriately selected because the combination with the component (b) acrylic acid polymer or the respective contents of the components (a) and (b) can be adjusted.

＜Method for measuring the degree of saponification＞

The degree of saponification is the ratio (in mole %) of the acetic acid group (acetoxy group: -OCOCH ₃ ) contained in the polyvinyl acetate resin, which is the raw material for the polyvinyl alcohol resin, to a hydroxyl group through the saponification process, and is defined by the following formula: degree of saponification (mol %) = 100 × (number of hydroxyl groups) ÷ (number of hydroxyl groups + number of acetic acid groups).

The degree of saponification can be obtained according to JIS K 6726-1994.

The degree of polymerization of component (a) polyvinyl alcohol used in the present invention is not particularly limited, and a product within the range of commercially available products can be used, and the degree of polymerization is suitably 100 to 4000, more suitably 100 to 2000, even more suitably 100 to 1000, and even more suitably 200 to 700.

In addition, the component (a) polyvinyl alcohol used in the present invention may have both the degree of saponification and the degree of polymerization adjusted, and is suitably a partially saponified type and a degree of polymerization of 100 to 4000, more suitably a degree of saponification of 80 to 90 mol% and a degree of polymerization of 100 to 1000, and still more suitably a degree of saponification of 80 to 90 mol% and a degree of polymerization of 200 to 700.

＜Method for measuring the degree of polymerization of polyvinyl alcohol＞

The degree of polymerization of polyvinyl alcohol can be measured by the solution viscosity measurement method in accordance with JIS K6726-1994 (polyvinyl alcohol test method).

The weight average molecular weight of component (a) polyvinyl alcohol used in the present invention is not particularly limited, and a product within the range of commercially available products can be used, and is suitably 200 to 3000.

The weight average molecular weight of the above component (a) polyvinyl alcohol can be measured by the <Method for Measuring Weight Average Molecular Weight of Water-soluble Polymer> described below.

As commercial products of the polyvinyl alcohol of component (a) used in the present invention, examples thereof include KURARAY POVAL 204C, KURARAY POVAL 205C, KURARAY POVAL 217C, KURARAY POVAL 220C, KURARAY POVAL 224C (all having a degree of saponification of 88 mol%, manufactured by Kuraray Co. Ltd.) and GOHSENOL EG-05, GOHSENOL EG-40 (all having a degree of saponification of 88 mol%, manufactured by Nippon Synthetic Chem Industry Co., Ltd.), but the present technology is not limited to these. In the present invention, one or two or more types can be selected from these various polyvinyl alcohols and used.

Component (a) polyvinyl alcohol used in the present invention is a film-forming polymer that serves as the main skeleton in the skin-attachment gel sheet of the present invention, and can form a flexible film by solidifying component (c) polyhydric alcohol.

The content of component (a) polyvinyl alcohol used in the present invention is not particularly limited, but in the gel sheet for skin attachment, the lower limit thereof is suitably 1.5 mass% or more, more suitably 2 mass% or more, more suitably 3 mass% or more, and even more suitably 5 mass% or more, and the upper limit thereof is suitably 29 mass% or less, more suitably 26 mass% or less, more suitably 25 mass% or less, even more suitably 20 mass% or less, and even more suitably 15 mass% or less. A more preferable numerical range of the component (a) is suitably 1.5 to 29 mass%, more suitably 2 to 26 mass%, more suitably 3 to 20 mass%, and even more suitably 5 to 20 mass%. By falling within the above range, a gel sheet having good flexibility and film strength can be obtained. In addition, a gel sheet can be obtained that is well-controlled in terms of solubility in water, disintegration by swelling in water, formability, or a combination thereof.

In addition, the content of component (a) polyvinyl alcohol in the gel sheet for skin attachment is preferably 3.0 to 25 mass%, so that the sheet strength is appropriate and better, and 5.0 to 20 mass% is more preferable.

＜1 (2) Component (b) Acrylic acid polymer＞

The component (b) acrylic acid polymer used in the present invention is not particularly limited, and it is preferable to form a gel by using an alkaline agent in combination (suitably neutralizing it), and it may be in the form of a salt when blended as a raw material. It is preferable to use what is generally called a water-soluble alkaline thickening polymer as the acrylic acid polymer.

The component (b) acrylic acid polymer used in the present invention is preferably a polymer obtained by polymerizing or copolymerizing a raw material monomer containing a C=C-COOH skeleton as a monomer component.

The raw material monomers for obtaining the above acrylic acid-based polymer are not particularly limited, and examples thereof include carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, vinyl acetate, tiglic acid, 2-trifluoromethyl acrylic acid, itaconic acid, fumaric acid, maleic acid, citraconic acid, mesaconic acid, and gluconic acid; sulfonic acids such as 2-acrylamide-2-methylpropane sulfonic acid and acryloyldimethyl taurine; esters such as methyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, and 2-hydroxyethyl acrylate (the alkyl or hydroxyalkyl of the ester portion is suitably one having 1 to 4 carbon atoms), and salts thereof such as ammonium salts, alkali metal salts, and alkyl amine salts.

Among the above raw material monomers, one or a combination of two or more selected from acrylic acid, methacrylic acid, acrylic acid alkyl ester, methacrylic acid alkyl ester, and acryloyldimethyl taurine is suitable.

The acrylic acid polymer of the present invention can use one or more types selected from the above raw material monomers.

It is preferable to use at least an acrylic acid monomer as a raw material monomer of the above acrylic acid-based polymer, and it is more preferable to use it as a main component, and specifically, the amount of a structural unit derived from acrylic acid in the polymer is preferably 40 mol% or more, more preferably 50 mol% or more.

When the above methacrylic acid-based polymer is a copolymer of methacrylic acid and a monomer capable of copolymerizing with the methacrylic acid, the ratio of methacrylic acid to the total amount of monomers is preferably 40 mol% or more and less than 100 mol%, more preferably 70 mol% or more and less than 100 mol%.

These acrylic acid polymers include carboxyvinyl polymers, alkyl-modified carboxyvinyl polymers, cross-linked copolymers of acrylamide and 2-acrylamide-2-methylpropane sulfonic acid, cross-linked copolymers of acrylic acid and 2-acrylamide-2-methylpropane sulfonic acid, copolymers of acrylic acid and alkyl acrylic acid esters, copolymers of acrylic acid, alkyl acrylic acid esters and alkyl methacrylic acid esters, copolymers of acrylic acid, alkyl acrylic acid esters and alkyl methacrylic acid esters, copolymers of acrylic acid, alkyl acrylic acid esters and polyethylene glycol esters, copolymers of alkyl acrylic acid esters and alkyl acrylic acid esters, copolymers of alkyl acrylic acid esters and alkyl acrylic acid esters and alkyl acrylic acid esters, copolymers of alkyl acrylic acid esters and alkyl acrylic acid esters and alkyl methacrylic acid esters, copolymers of alkyl acrylic acid esters and alkyl methacrylic acid esters and alkyl methacrylic acid esters, copolymers of itaconic acid, alkyl acrylic acid esters and alkyl methacrylic acid esters. Examples thereof include, but are not limited to, copolymers of acrylic acid·acrylic acid alkyl ester and itaconic acid (polyoxyethylene monoalkyl ether) ester, hydroxyethyl acrylic acid·sodium acryloyldimethyl taurine copolymer, sodium acryloyldimethyl taurine copolymer, and acrylamide·sodium acryloyldimethyl taurine copolymer. In addition, one or more types can be selected and used from these acrylic acid-based polymers.

As commercial products of the above component (b) acrylic acid polymer, the following may be mentioned, but are not limited thereto, and one or more types may be selected and used from the commercial products.

Examples of commercially available products of carboxyvinyl polymers, which are examples of the above component (b), include Carbopol 940, Carbopol 941, Carbopol 980, Carbopol 981 (all manufactured by LUBRIZOL ADVANCED MATERIALS), AQUPEC HV-501, AQUPEC HV-504 (all manufactured by SUMITOMO SEIKA CHEMICALS CO.,LTD.).

Examples of commercially available products of alkyl-modified carboxyvinyl polymers, which are examples of the above component (b), include Carbopol 1342, Carbopol 1382 (all manufactured by LUBRIZOL ADVANCED MATERIALS), PEMULEN TR-1, PEMULEN TR-2 (all manufactured by LUBRIZOL ADVANCED MATERIALS), etc. In addition, the alkyl-modified carboxyvinyl polymer is a copolymer of acrylic acid and alkyl methacrylate (preferably the alkyl group has 8 to 30 carbon atoms (more preferably 10 to 30 carbon atoms)).

Examples of commercially available dispersions of crosslinked copolymers of acrylamide and 2-acrylamide-2-methylpropane sulfonic acid, which are examples of the above component (b), include SEPIGEL 305 and SEPIGEL 501 (both manufactured by SEPPIC).

Examples of commercially available products of dispersions of sodium acrylate and acryloyldimethyl taurine copolymer, which are examples of the above component (b), include SIMULGEL EG (manufactured by SEPPIC).

Examples of commercially available products of dispersions of hydroxyethyl acrylate/sodium acryloyldimethyl taurate copolymer, which are examples of the above component (b), include SIMULGEL NS and SIMULGEL FL (both manufactured by SEPPIC).

Among the above component (b) acrylic acid polymers, one or more selected from a carboxyvinyl polymer (also called a carbomer), an alkyl-modified carboxyvinyl polymer, a crosslinked copolymer of acrylamide and 2-acrylamide-2-methylpropane sulfonic acid, and a sodium acrylate-acryloyldimethyl taurine copolymer is more preferable because it forms a film with appropriate hardness. By containing such an acrylic acid polymer, a gel sheet having good flexibility and film strength can be obtained, and furthermore, a gel sheet in which solubility in water, disintegration due to swelling in water, formability, or a combination thereof is well-adjusted can be obtained.

In addition, the acrylic acid polymer of component (b) used in the present invention may be used by reacting or neutralizing and thickening it with a neutralizing agent such as an alkali metal salt such as potassium hydroxide, sodium hydroxide, sodium carbonate, or sodium bicarbonate; an amine salt such as ammonia or triethanolamine; or an amino acid salt such as L-arginine or L-lysine when obtaining an O/W emulsion composition, and it is suitable to use it as a raw material after reacting or neutralizing it with a neutralizing agent.

The weight average molecular weight of the acrylic acid polymer of component (b) is preferably 500 or more, more preferably 1500 or more, and even more preferably 5000 or more. In addition, there is no particular limitation on the upper limit, but it is preferably 5 million or less, and more preferably 500 or more and 5 million or less.

The weight average molecular weight of the acrylic acid polymer of the above component (b) can be measured by <Method for measuring the weight average molecular weight of a water-soluble polymer>.

＜Method for measuring the weight average molecular weight of water-soluble polymers＞

The weight average molecular weight of the water-soluble polymer used in the present invention can be measured by GPC (gel permeation chromatography) analysis using standard polystyrene as a standard material (see, for example, Reference Document 1: Japanese Patent Application Laid-Open No. 2014-140056, etc.).

The content of the component (b) acrylic acid-based polymer used in the present invention is not particularly limited, but the lower limit thereof is suitably 0.03 mass% or more, more suitably 0.05 mass% or more, more suitably 0.1 mass% or more, and even more suitably 0.2 mass% or more, in the gel sheet for skin attachment, and the upper limit thereof is suitably 4.5 mass% or less, more suitably 4 mass% or less, more suitably 3 mass% or less, even more suitably 2 mass% or less, more suitably 1.5 mass% or less, and even more suitably 1 mass% or less. A more preferable numerical range of the above component (b) is suitably 0.03 to 4.5 mass%, more suitably 0.05 to 3 mass%, more suitably 0.1 to 2 mass%, more suitably 0.1 to 1.5 mass%, and more suitably 0.1 to 1.0 mass%. By making it within the above range, a gel sheet having good flexibility and membrane strength can be obtained, and furthermore, a gel sheet whose solubility in water, disintegration property due to swelling in water, formability, or a combination thereof is well-adjusted can be obtained.

In addition, the content of the component (b) acrylic acid polymer in the skin-attaching gel sheet is preferably 0.1 to 2.0 mass%, more preferably 0.1 to 1.0 mass%. By setting it within this range, the viscosity of the O/W emulsion before sheeting can be appropriately made, making it easy to spread, and also, when combined with (a) polyvinyl alcohol, a gel sheet having appropriate flexibility and strength can be obtained.

The component (b) acrylic acid polymer used in the present invention forms a soft film with excellent strength by combining with the component (a) polyvinyl alcohol which forms a film with high flexibility to form a film with excellent uniformity and continuity and high hardness, and contributes to the film strength and lack of burden in the skin-attaching gel sheet of the present invention. In addition, by adjusting the components (a) and (b), it is possible to obtain a gel sheet in which the solubility in water, the disintegration property due to swelling in water, the formability, or a combination thereof are well-adjusted.

In the present invention, the mass ratio (a)/(b) of component (a) polyvinyl alcohol and component (b) acrylic acid-based polymer in the skin-attachable gel sheet is suitably 2 or more as the lower limit, more suitably 3.5 or more, more suitably 4 or more, more suitably 5 or more, more suitably 6 or more, and even more suitably 9 or more as the upper limit, and is suitably 160 or less, more suitably 150 or less, more suitably 100 or less, and even more suitably 70 or less as the upper limit. A more preferable numerical range of the mass ratio (a)/(b) of the component is suitably 3 to 160, more suitably 4 to 150, more suitably 5 to 100, and even more suitably 6 to 70. By making it within the above range, a gel sheet having good flexibility and membrane strength can be obtained, and also a gel sheet having good solubility in water, disintegration due to water swelling, formability, or a combination thereof can be obtained.

In addition, in order to adjust the flexibility and hardness of the gel sheet by combining component (a) polyvinyl alcohol and component (b) acrylic acid-based polymer among the above-mentioned skin-attachable gel sheets, the mass ratio (a)/(b) of the components (a) and (b) is preferably 4.0 to 150, more preferably 5.0 to 100. Within this range, a skin-attachable gel sheet having excellent film strength and freedom from burden is obtained because it has appropriate flexibility. It is also possible to obtain a gel sheet having well-adjusted solubility in water, disintegration property due to swelling in water, formability, or a combination thereof.

＜1 (3) Component (c) Polyhydric alcohol＞

The component (c) polyhydric alcohol used in the present invention is an alcohol having a structure having two or more hydroxyl groups in the skeleton, and is not particularly limited to those commonly used in cosmetics, etc. The component (c) polyhydric alcohol is suitably one having 3 to 9 carbon atoms in the skeleton. The component (c) polyhydric alcohol is suitably one having a structure having 1 to 3 alkyl groups or alkylene glycol moieties in the skeleton, and furthermore, the alkyl group or alkylene moiety is suitably one having 3 to 6 carbon atoms. Furthermore, the component (c) polyhydric alcohol is suitably one having 2 or 3 or more hydroxyl groups in the skeleton.

Examples of these polyhydric alcohols include, but are not limited to, 1,3-butylene glycol, dipropylene glycol, tripropylene glycol, glycerin, diglycerin, propylene glycol, and 1,2-pentane diol. One or more of these can be appropriately selected and used.

Among these, dihydric alcohols and/or trihydric alcohols are suitable, and among these, glycerin and/or 1,3-butylene glycol are preferable because they have excellent solubility of component (a) polyvinyl alcohol and component (b) acrylic acid-based polymer, and a moisturizing effect, and are also inexpensive. By containing a polyhydric alcohol in this way, a moisturizing effect can be imparted. Furthermore, by such a polyhydric alcohol, a gel sheet having better flexibility and film strength can be obtained in the relationship between the components (a) and (b), and furthermore, a gel sheet in which the disintegration property and the moldability due to the dispersibility or the swelling property are better adjusted can be obtained.

The content of the component (c) polyhydric alcohol in the present invention is not particularly limited, but in the gel sheet for skin attachment, the lower limit thereof is suitably 30 mass% or more, more suitably 35 mass% or more, more suitably 40 mass% or more, more suitably 45 mass% or more, and more suitably 50 mass% or more, and the upper limit thereof is suitably 95 mass% or less, more suitably 94 mass% or less, more suitably 93 mass% or less, more suitably 90 mass% or less, more suitably 85 mass% or less, and more suitably 80 mass% or less. A more preferable numerical range of the component (c) is suitably 35 to 95 mass%, more suitably 40 to 93 mass%, and more suitably 50 to 80 mass%. By falling within the above range, a gel sheet having good flexibility and film strength can be obtained. In addition, a gel sheet with better control over disintegration and formability due to dispersibility and swelling can be obtained.

The content of component (c) polyhydric alcohol in the present invention is preferably 50 to 95 mass% of the gel sheet for skin attachment, more preferably 50 to 80 mass%. Within this range, the gel sheet has excellent film strength and also obtains high moisturizing properties after use.

The content of trihydric alcohol in the above skin-attaching gel sheet is not particularly limited, but is suitably 25 to 85 mass%, more suitably 40 to 80 mass%, and even more suitably 50 to 70 mass%.

The content of dihydric alcohol in the above-mentioned skin-attaching gel sheet is not particularly limited, but is suitably 1 to 30 mass%, more suitably 1 to 20 mass%, and even more suitably 5 to 15 mass%.

The mass ratio (trihydric alcohol/dihydric alcohol) of the above-mentioned skin-attaching gel sheet is suitably 3 to 9, more suitably 4 to 8, and even more suitably 4 to 7.

The polyhydric alcohol of component (c) used in the present invention is a main solvent forming the skin-attaching gel sheet of the present invention and can provide a high moisturizing effect to the skin.

In the present invention, since component (a) polyvinyl alcohol has the main film-forming ability to form a gel by maintaining (c) polyhydric alcohol, there is a suitable mixing ratio between components (a) and (c), and therefore it is preferable to use the suitable mixing ratio. By setting the components (a) and (c) in the skin-attachable gel sheet within a suitable range, a gel sheet having good flexibility and film strength can be obtained, and furthermore, a gel sheet in which the disintegration property and the formability due to the dispersibility or the swelling property are more preferably adjusted can be obtained.

In the present invention, the mass ratio (a)/(c) of component (a) polyvinyl alcohol and component (c) polyhydric alcohol in the skin-attaching gel sheet is suitably 0.01 or more as the lower limit, more suitably 0.02 or more, more suitably 0.03 or more, still more suitably 0.04 or more, and still more suitably 0.05 or more as the upper limit, and is suitably 0.5 or less, more suitably 0.4 or less, still more suitably 0.3 or less, and still more suitably 0.25 or less as the upper limit. A more preferable numerical range of the mass ratio (a)/(c) of the component is suitably 0.02 to 0.5, more suitably 0.03 to 0.4, and still more suitably 0.04 to 0.3.

In the present invention, the mass ratio (a)/(c) of component (a) polyvinyl alcohol and component (c) polyhydric alcohol in the gel sheet for skin attachment is preferably 0.03 to 0.4, more preferably 0.05 to 0.3. Within this range, a gel sheet for skin attachment is obtained which has better film strength and less burdensomeness and also better solubility in water.

＜1 (4) Component (d) Solid and/or semi-solid emulsion at 25℃＞

The component (d) used in the present invention is an emulsion that is solid or semi-solid at 25°C, and the component (d) solid and/or semi-solid emulsion at 25°C (hereinafter also referred to as “solid and/or semi-solid emulsion”) is not particularly limited as long as it is contained in ordinary cosmetics, etc. As the component (d) solid and/or semi-solid emulsion, examples thereof include hydrocarbon oils, ester oils, higher alcohol oils, ether oils, and silicone oils derived from animal oils, vegetable oils, and synthetic oils, and one or more of these can be used.

In addition, the semi-solid or solid state as referred to in the present invention means a gel hardness (maximum load applied to the decompressor shaft when the decompressor shaft is pushed in to a depth of 5 mm in a penetration test at a specimen storage temperature of 25°C, a needle diameter of 10 mmφ of the decompressor shaft (adapter), and a needle penetration speed of 60 mm/min) measured by a rheometer (manufactured by FUDO kougyou, Inc.) of 15 gf or more, preferably 50 gf or more, and does not exhibit fluidity at room temperature (approximately 20 to 30°C).

As the solid emulsion of the above component (d), for example, one or more kinds selected from hydrocarbon-based solid oil, ester-based solid oil, higher alcohol-based solid oil, silicone-based solid oil, etc. can be used, but is not limited to these.

Examples thereof include hydrocarbon solid oils such as paraffin wax, ceresin wax, microcrystalline wax, polyethylene wax, ethylene-propylene copolymer, montan wax, and Fischer-Tropsch waxes; ester solid oils such as hydrogenated jojoba oil, beeswax, carnauba wax, candelilla wax, rice wax, eicosene/vinyl pyrrolidone) copolymer, α-olefin/vinyl pyrrolidone copolymer, and glyceryl tribehenate; higher alcohol solid oils such as stearyl alcohol, cetyl alcohol, lauryl alcohol, and behenyl alcohol; and silicone solid oils such as (acrylates/behenyl acrylate/dimethicone methacrylate) copolymer, and (acrylates/stearyl acrylate/dimethicone methacrylate). From these, one or more types can be appropriately selected and used.

In addition, as the semi-solid emulsion of the above component (d), one or more kinds selected from, for example, hydrocarbon-based semi-solid oil, ester-based semi-solid oil, ether-based semi-solid oil, silicone-based semi-solid oil, etc. can be used, but is not limited to these.

For example, hydrocarbon semi-solid oils such as petrolatum, hexa(hydroxystearic acid/stearic acid/rosinic acid) dipentaerythrityl, (hydroxystearic acid/stearic acid/rosinic acid) dipentaerythrityl, hexahydroxystearic acid dipentaerythrityl, tetra(hydroxystearic acid/isostearic acid) dipentaerythrityl, (hydroxystearic acid/isostearic acid) dipentaerythrityl, etc., hydrogenated castor oil fatty acid esters such as stearic acid hydrogenated castor oil, isostearic acid hydrogenated castor oil, hydroxystearic acid hydrogenated castor oil, cholesterol fatty acid esters such as hydroxystearic acid cholesteryl, phytosterol fatty acid esters such as oleic acid phytosteryl, macademia nut oil fatty acid phytosteryl, hydrogenated Examples thereof include hydrogenated vegetable oils such as coconut oil and hydrogenated palm oil; ester semi-solid oils such as dimer dilinoleic acid (phytosteryl/isosteryl/cetyl/stearyl/behenyl), sucrose pentahydroxystearate, and di(octyldodecyl/phytosteryl/behenyl) glutamate; ether semi-solid oils such as hydroxyalkyl dimer silinoleyl ether; triglyceride semi-solid oils such as tribehenin; and silicone semi-solid oils such as dimethicone crosspolymer and (dimethicone/vinyl dimethicone) crosspolymer. From these, one or more types can be appropriately selected and used.

The component (d) used in the present invention, which is solid and/or semi-solid at 25°C, plays a role in increasing the film strength of the gel sheet and also imparting viscosity to the O/W emulsion before sheet formation, and therefore also contributes to improving the formability. From this point of view, solid oils such as hydrocarbon-based, ester-based, higher alcohol-based, and silicone-based oils having a melting point of 50°C or higher are preferable in terms of film strength and formability. It is preferable that the solid and/or semi-solid emulsion contains one or more kinds selected from these, and it is preferable that it is 30 to 100 mass% with respect to the total amount of component (d).

By containing a solid and/or semi-solid emulsion in the present invention, a moisturizing effect can be imparted, and also, in terms of the relationship between the components (a) and (b), a gel sheet having good flexibility and film strength can be obtained. In addition, a gel sheet having good solubility in water, disintegration property due to swelling in water, formability, or a combination thereof can be obtained.

The content of the solid and/or semi-solid emulsion at 25°C of component (d) in the present invention is not particularly limited, but in the gel sheet for skin attachment, the lower limit thereof is suitably 0.05 mass% or more, more suitably 0.08 mass% or more, more suitably 0.1 mass% or more, more suitably 0.5 mass% or more, more suitably 1 mass% or more, more suitably 3 mass% or more, and the upper limit thereof is suitably 20 mass% or less, more suitably 19 mass% or less, more suitably 16 mass% or less, more suitably 15 mass% or less, more suitably 13 mass% or less. A more preferable numerical range of the above component (d) is suitably 0.08 to 19 mass%, more suitably 0.1 to 16 mass%, more suitably 0.5 to 15 mass%, and even more suitably 1 to 15 mass%. By making it within the above range, a gel sheet having good flexibility and membrane strength can be obtained. In addition, a gel sheet having good solubility in water, disintegration property due to swelling in water, formability, or a combination thereof can be obtained.

The content of the component (d) of the present invention in a solid and/or semi-solid state at 25°C is preferably 0.1 to 16 mass%, more preferably 1.0 to 15 mass%, of the gel sheet for skin attachment. Within this range, the gel sheet has excellent film strength and solubility in water and good formability.

＜1 (5) Component (e) Liquid emulsion at 25℃＞

The component (e) used in the present invention, an emulsion that is liquid at 25°C (hereinafter also referred to as “liquid emulsion”), means an emulsion that has fluidity at 25°C, and is not particularly limited as long as it is used in cosmetics, etc. As the component (e) liquid emulsion at 25°C, examples thereof include, but are not limited to, hydrocarbons, fats and oils, ester oils including ultraviolet absorbers, fatty acids, higher alcohols, silicone oils, fluorinated oils, lanolin derivatives, etc., regardless of whether they are volatile or nonvolatile, or of animal oil, vegetable oil, or synthetic oil, but are not limited to these. One or two or more of these can be appropriately selected and used.

The above component (e) is a liquid emulsion (e.g., polar oil) at 25°C, specifically, oils such as olive oil, castor oil, mink oil, macadamia nut oil, avocado oil, and meadowfoam oil; Jojoba oil, diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptyl undecyl adipate, alkyl glycol monoisostearate, isocetyl isostearate, trimethylolpropane triisostearate, ethylene glycol di-2-ethylhexanoate, neopentyl glycol di-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, cetyl 2-ethyl hexanoate, oleyl oleate, octyl dodecyl oleate, decyl oleate, neopentyl glycol dicapric acid, triethyl citrate, 2-ethylhexyl succinate, isocetyl stearate, butyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, lactic acid Myristyl, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptyl undecyl palmitate, dipentaerythritol fatty acid ester, isononyl isononanoate, isotridecyl isononanoate, isopropyl myristate, isopropyl palmitate, 2-octyl dodecyl myristate, 2-hexyldecyl myristate, myristyl myristate, hexyldecyl dimethyloctanoate, ethyl laurate, hexyl laurate, 2-ethylhexyl methoxycinnamic acid, diisostearyl malate, tri 2-ethylhexanoate glyceryl, tri(capryl·caprin) acid glyceryl, tricapric acid glyceryl, triisostearate glyceryl, diglyceryl diisostearate, diglyceryl triisostearate, Esters such as tetraisostearate diglyceryl, decaisostearate decaglyceryl, triisopalmitate glyceryl, trimyristate glyceryl, myristate isostearate diglyceryl, trimellitate tritridecyl, N-lauroyl-L-glutamic acid-2-octyl dodecyl ester, N-lauroyl-L-glutamic acid di(phytostearyl·2-octyl dodecyl); fatty acids such as isostearic acid and oleic acid; higher alcohols such as oleyl alcohol, isostearyl alcohol, octyldodecanol, and decyltetradecanol; lanolin derivatives such as lanolin acetate, lanolin fatty acid isopropyl, and lanolin alcohol; and polar oils such as these can be appropriately selected and used.

In addition, as the component (e) at 25°C, a liquid emulsion (for example, a nonpolar oil) specifically, silicone oils such as low-polymerization dimethyl polysiloxane, high-polymerization dimethyl polysiloxane, methyl phenyl polysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, and fluorine-modified organopolysiloxane; fluorine-containing emulsions such as perfluorodecane, perfluorooctane, and perfluoropolyether; hydrocarbons such as isododecane, isohexadecane, light liquid isoparaffin, liquid paraffin, heavy liquid isoparaffin, α-olefin oligomers, squalene, polyisobutylene, and polybutene, and the like, nonpolar oils can be exemplified. From these, one or two or more can be appropriately selected and used.

The above component (e) is suitable as a liquid emulsion at 25°C, and liquid oils such as ester-based, higher alcohol-based, silicone oil-based, and hydrocarbon-based are suitable. The above liquid emulsion preferably contains one or more of these, and it is preferable that it is 30 to 100% of the total amount of the component (e).

The component (e) used in the present invention, which is a liquid emulsion at 25°C, can be appropriately selected from one or more polar oils and nonpolar oils.

The component (e) liquid emulsion at 25°C used in the present invention can provide an emollient effect, and thus, not only contributes to improving the moisturizing effect of the skin-attaching gel sheet of the present invention, but also improves the feeling of burden by providing plasticity to the film. In addition, the component (e) liquid emulsion at 25°C can play a role of promoting penetration into the skin when a skin-soluble effective ingredient is blended. From this viewpoint, it is more preferable to include a low-viscosity liquid oil having a viscosity of 500 mPa·s or less at 20°C, and is particularly preferable if it is 200 mPa·s or less. It is preferable that such a low-viscosity liquid oil is 30 to 100% of the total amount of the component (e).

Such low viscosity oils include liquid paraffin, tri 2-ethylhexanoate glyceryl, tetra 2-ethylhexanoate pentaerythrityl, dimethylpolysiloxane, cetyl 2-ethylhexanoate, isotridecyl isononanoate, isopropyl myristate, octyldodecanol, decyltetradecanol, isononyl isononanoate, ethyl linoleate, and cetyl lactate. One or more of these may be appropriately selected and used.

In addition, in the present invention, the viscosity of the liquid emulsion of component (e) is obtained by the following method. It is measured using a single-cylinder rotational viscometer Vismetron (registered trademark) (manufactured by S HIBAURA SYSTEM), which is a Brookfield type viscometer. The measurement method is to fill a glass bottle with a measurement sample having an outer diameter of 45 mm, an inner diameter of 38 mm, and a height of 82 mm so as not to create an air space, close the lid, and leave it in a constant temperature bath at 20°C for one day and one night. The next day, in a room adjusted to 20°C, the single-cylinder rotational viscometer Vismetron (registered trademark) is used to rotate the attached No. 1 to 4 rotor for 6 to 30 rotations, and the viscosity value is obtained by multiplying each multiplier.

The content of the liquid emulsion of component (e) in the present invention is not particularly limited, but in the gel sheet for skin attachment, the lower limit thereof is suitably 0.5 mass% or more, more suitably 1 mass% or more, and even more suitably 3 mass% or more, and the upper limit thereof is suitably 32 mass% or less, more suitably 30 mass% or less, even more suitably 25 mass% or less, and even more suitably 20 mass% or less. A more preferable numerical range of the component (e) is suitably 0.5 to 32 mass%, more suitably 1 to 30 mass%, and even more suitably 1 to 20 mass%. By making it within the above range, a gel sheet having good flexibility and film strength can be obtained, and furthermore, a gel sheet in which solubility in water, disintegration property due to swelling in water, formability, or a combination thereof is well-adjusted can be obtained.

In addition, the content of the liquid emulsion of component (e) in the skin-attaching gel sheet is preferably 1.0 to 30%, more preferably 1.0 to 20%. Within this range, a skin-attaching gel sheet having an excellent moisturizing effect can be obtained.

In the present invention, the component (d) emulsion that is solid and/or semi-solid at 25°C contributes to improving the membrane strength of the gel sheet, and the component (e) emulsion that is liquid at 25°C contributes to improving the plasticity of the membrane.

In the present invention, in order to adjust the film strength of the skin-attaching gel sheet to an appropriate film strength, the mass ratio (d)/(e) of the solid and/or semi-solid emulsion of component (d) and the liquid emulsion of component (e) is suitably 0.001 or more as the lower limit, more suitably 0.005 or more, more suitably 0.01 or more, more suitably 0.05 or more, more suitably 0.1 or more, more suitably 0.5 or more, and its upper limit is suitably 4 or less, more suitably 3.5 or less, more suitably 3.1 or less, more suitably 3 or less, more suitably 2.5 or less, more suitably 2 or less. A more preferable numerical range of the mass ratio (d)/(e) of the above-mentioned component content is suitably 0.001 to 3.5, more suitably 0.003 to 3.1, more suitably 0.1 to 2.5, and even more suitably 0.5 to 2. By making it within the above range, a gel sheet having good flexibility and membrane strength can be obtained, and furthermore, a gel sheet having well-controlled solubility in water, disintegration property due to swelling in water, formability, or a combination thereof can be obtained.

In the present invention, in order to adjust the film strength of the skin-attaching gel sheet to an appropriate level, the mass ratio (d)/(e) of the solid and/or semi-solid emulsion of component (d) and the liquid emulsion of component (e) is preferably 0.003 to 3.1, more preferably 0.003 to 3.0, and even more preferably 0.01 to 3.0. Within this range, a skin-attaching gel sheet having excellent film strength and freedom from burden is obtained.

＜1 (6) Component (f) Water＞

The gel sheet for skin attachment of the present invention may contain component (f) water. The water is not particularly limited as long as it is commonly used in compositions such as cosmetics, and for example, purified water, steam distilled water from plants, etc., etc. may be arbitrarily selected and used.

The content of the component (f) water is not particularly limited, but is more preferably 10 mass% or less in the skin-attaching gel sheet, because the moisturizing effect, film strength, and sheet formability are excellent. The content of the component (f) water in the skin-attaching gel sheet is suitably 8 mass% or less, more suitably 5 mass% or less, and even more suitably 3 mass% or less.

The water content of the above component (f) can be adjusted to 10 to 0 mass% by drying or the like when forming a gel sheet from the O/W emulsion composition of the present technology.

The amount of the above component (f) water can be adjusted by forming the prepared O/W emulsion composition into a sheet of a desired thickness and shape, and then drying and removing moisture using a known drying method such as hot air drying, infrared drying, vacuum drying, suction drying, steam drying, hot plate drying, or freeze drying.

＜Method for measuring water content: Karl-Fischer method＞

The water content in the skin-attaching gel sheet of the present invention can be measured using the Karl Fischer method described in JIS K 0068. In the present invention, as a moisture meter using the Karl Fischer method, a Karl Fischer volumetric moisture meter (such as a trace moisture measuring device (AQV-7) manufactured by HIRANUMA SANGYO Co., Ltd.) can be used, and methanol is used as a solvent.

＜1 (7) Optional ingredients＞

The gel sheet for skin attachment of the present invention may contain, as necessary, any optional components contained in conventional external skin preparations, within a range that does not interfere with the effects of the present invention, for example, powder components, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, water-soluble polymers or film-forming agents other than the above components (a) and (b), thickeners, ultraviolet absorbers, metal ion sequestering agents, lower alcohols, sugars, amino acids, organic amines, pH adjusters, skin nutrients, vitamins, antioxidants, antioxidant aids, fragrances, etc.

In the present invention, from the viewpoint of easily producing a good emulsion composition, it is suitable to further use a surfactant as a component (g) in the skin-attachment gel sheet of the present invention.

The above-mentioned surfactant component is not particularly limited, but may include anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants (lipophilic and hydrophilic), and one or more types may be appropriately selected and used. In addition, one or more types may be used from the examples below.

Among these, higher fatty acid amide sulfonates (suitably, sodium stearoylmethyl taurine, etc.) and/or phospholipids (suitably, lecithin, hydrogenated lecithin, etc.) are preferable.

In addition, the content of the surfactant in the present invention is not particularly limited, but in the gel sheet for skin attachment, the lower limit is suitably 0.05 mass% or more, more suitably 0.1 mass% or more, and more suitably 0.5 mass% or more, and the upper limit is suitably 3 mass% or less, more suitably 2.5 mass% or less, and more suitably 2 mass% or less. A more preferable numerical range is suitably 0.1 to 3 mass%, and more suitably 0.5 to 2 mass%. By using the surfactant, a good O/W emulsion composition for obtaining the gel sheet for skin attachment of the present invention can be obtained. By the above-mentioned component surfactant, a gel sheet having good flexibility and film strength can be obtained. In addition, a gel sheet whose solubility in water, disintegration property due to water swelling, formability, or a combination thereof is well-adjusted can be obtained.

Examples of the anionic surfactants include fatty acid soaps (e.g., sodium laurate, sodium palmitate, etc.); higher alkyl sulfate ester salts (e.g., sodium lauryl sulfate, potassium lauryl sulfate, etc.); alkyl ether sulfate ester salts (e.g., POE-lauryl triethanolamine sulfate, POE-sodium lauryl sulfate, etc.); N-acyl sarcosinic acid (e.g., sodium lauroyl sarcosine, etc.); higher fatty acid amide sulfonates (e.g., sodium N-myristoyl-N-methyl taurine, sodium palm oil fatty acid methyl tauride, sodium stearoylmethyl tauride, sodium laurylmethyl tauride, etc.); sulfosuccinates (e.g., sodium di-2-ethylhexyl sulfosuccinate, monolauroylmonoethanolamide polyoxyethylene sodium sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc.); Alkyl benzene sulfonates (e.g., sodium linear dodecyl benzene sulfonate, linear dodecyl benzene sulfonate triethanolamine, linear dodecyl benzene sulfonic acid, etc.); Higher fatty acid ester sulfuric acid ester salts (e.g., hydrogenated palm oil fatty acid glycerin sodium sulfate, etc.); N-acyl glutamate salts (e.g., N-lauroyl monosodium glutamate, N-stearoyl disodium glutamate, N-myristoyl-L-glutamic acid monosodium, etc.); Sulfated oils (e.g., lot oil, etc.); POE-alkyl ether carboxylic acids; POE-alkyl allyl ether carboxylates; α-olefin sulfonates; Higher fatty acid ester sulfonates; Secondary alcohol sulfuric acid ester salts; Higher fatty acid alkylolamide sulfuric acid ester salts; Sodium lauroyl monoethanolamide succinate; N-palmitoyl aspartic acid ditriethanolamine; Examples include sodium caseinate.

Examples of the cationic surfactants include alkyl trimethyl ammonium salts (e.g., stearyl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride, etc.); alkyl pyridinium salts (e.g., cetyl pyridinium chloride, etc.); dialkyl dimethyl ammonium chloride salts (e.g., distearyl dimethyl ammonium chloride salt, etc.); poly(N,N'-dimethyl-3,5-methylenepiperidinium chloride); alkyl quaternary ammonium salts; alkyl dimethyl benzyl ammonium salts; alkyl isoquinolinium salts; dialkyl morphonium salts; POE-alkyl amines; alkyl amine salts; polyamine fatty acid derivatives; amyl alcohol fatty acid derivatives; benzalkonium chloride; benzethonium chloride, etc.

Examples of the above-mentioned amphoteric surfactants include imidazoline amphoteric surfactants (e.g., 2-undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, etc.); betaine surfactants (e.g., 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryl dimethyl aminoacetic acid betaine, alkyl betaines, amidobetaines, sulfobetaines, etc.); phospholipids (e.g., lecithin, hydrogenated lecithin, etc.). In addition, soybeans, eggs, etc. can be mentioned as sources of lecithin.

Examples of the lipophilic nonionic surfactants include sorbitan fatty acid esters (e.g., sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, penta-2-ethylhexylate diglycerol sorbitan, tetra-2-ethylhexylate diglycerol sorbitan, etc.); glycerin polyglycerin fatty acids (e.g., monocotton seed fatty acid glycerin, monoercaic acid glycerin, sesquioleic acid glycerin, monostearic acid glycerin, α,α'-oleic acid pyroglutamic acid glycerin, monostearic acid glycerin malic acid, etc.); Examples thereof include propylene glycol fatty acid esters (e.g., propylene glycol monostearate, etc.); hydrogenated castor oil derivatives; and glycerin alkyl ethers.

Examples of the hydrophilic nonionic surfactants include POE-sorbitan fatty acid esters (e.g., POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan tetraoleate, etc.); POE sorbitan fatty acid esters (e.g., POE-sorbitan monolaurate, POE-sorbitan monooleate, POE-sorbitan pentaoleate, POE-sorbitan monostearate, etc.); POE-glycerin fatty acid esters (e.g., POE-monooleates such as POE-glycerin monostearate, POE-glycerin monoisostearate, POE-glycerin triisostearate, etc.); POE-fatty acid esters (e.g., POE-distearate, POE-monodioleate, ethylene glycol distearate, etc.); POE alkyl ethers (e.g., POE lauryl ether, POE oleyl ether, POE stearyl ether, POE behenyl ether, POE-2-octyl dodecyl ether, POE-cholestanol ether, etc.); Pluronic type (e.g., Pluronic, etc.); POE·POP-alkyl ethers (e.g., POE·POP-cetyl ether, POE·POP-2-decyl tetradecyl ether, POE·POP-monobutyl ether, POE·POP-hydrogenated lanolin, POE·POP-glycerin ether, etc.); Tetra POE·tetra POP-ethylene diamine condensates (e.g., Tetronic, etc.); Examples thereof include POE-castor oil hydrogenated castor oil derivatives (e.g., POE-castor oil, POE-hydrogenated castor oil, POE-hydrogenated castor oil monoisostearate, POE-hydrogenated castor oil triisostearate, POE-hydrogenated castor oil monopyroglutamic acid monoisostearic acid diester, POE-hydrogenated castor oil maleic acid, etc.); POE-beeswax/lanolin derivatives (e.g., POE-sorbitol beeswax, etc.); alkanol amides (e.g., palm oil fatty acid diethanol amide, lauric acid monoethanol amide, fatty acid isopropanol amide, etc.); POE-propylene glycol fatty acid esters; POE-alkyl amines; POE-fatty acid amides; sucrose fatty acid esters; alkyl ethoxy dimethyl amine oxide; trioleyl phosphoric acid, etc.

Powder components include, for example, inorganic powders (for example, talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, lepidolite, biotite, permiculite, magnesium carbonate, calcium carbonate, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (gypsum), calcium phosphate, fluoroapatite, hydroxyapatite, ceramic powder, metal soaps (for example, zinc myristate, calcium palmitate, aluminum stearate), boron nitride, etc.); Organic powder (e.g., polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, polystyrene powder, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, etc.); Inorganic white pigment (e.g., titanium dioxide, zinc oxide, etc.); Inorganic red pigment (e.g., iron oxide (Bengala), iron titanate, etc.); Inorganic brown pigment (e.g., γ-iron oxide, etc.); Inorganic yellow pigment (e.g., iron sulfur oxide, yellow earth, etc.); Inorganic black pigment (e.g., black iron oxide, low-order titanium oxide, etc.); Inorganic purple pigment (e.g., mango violet, cobalt violet, etc.); Inorganic green pigment (e.g., chromium oxide, chromium hydroxide, cobalt titanate, etc.); Inorganic blue pigment (e.g., ultramarine, prussian blue, etc.); Pearl pigments (e.g., titanium oxide-coated mica, titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, colored titanium oxide-coated mica, bismuth oxychloride, fish scale foil, etc.); Metallic powder pigments (e.g., aluminum powder, copper powder, etc.); Organic pigments such as zirconium, barium or aluminum lakes (e.g., Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 228, Red No. 405, Orange No. 203, Orange No. 204, Yellow No. 205, Yellow No. 401, Blue No. 404, Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Green No. 3 and Blue No. 1, etc.); natural pigments (e.g., chlorophyll, β-carotene, etc.).

Examples of natural water-soluble polymers include plant-based polymers (e.g., gum arabic, gum tragacanth, galactan, guar gum, CAROB gum, karaya gum, carrageenan, pectin, agar, quince seed (quince), algae colloid (brown algae extract), starch (rice, corn, potato, wheat), glycyrrhizic acid); microbial polymers (e.g., xanthan gum, dextran, succinoglucan, pullulan, etc.); and animal-based polymers (e.g., collagen, casein, albumin, gelatin, etc.).

Examples of semi-synthetic water-soluble polymers include starch polymers (e.g., carboxymethyl starch, methyl hydroxypropyl starch, etc.); cellulose polymers (methyl cellulose, ethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, hydroxypropyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, crystalline cellulose, cellulose powder, etc.); and alginic acid polymers (e.g., sodium alginate, alginic acid propylene glycol ester, etc.).

Examples of synthetic water-soluble polymers include vinyl polymers (e.g., polyvinyl methyl ether, polyvinyl pyrrolidone, etc.); polyoxyethylene polymers (e.g., polyoxyethylene polyoxy propylene copolymers of polyethylene glycol 20,000, 40,000, 60,000); polyethyleneimine; and cationic polymers.

Thickeners include, for example, gum arabic, carrageenan, gum karaya, gum tragacanth, gum carob, quince seed (quince), casein, dextrin, gelatin, sodium pectinate, sodium araginate, methyl cellulose, ethyl cellulose, CMC, hydroxyethyl cellulose, hydroxypropyl cellulose, PVM, PVP, locust bean gum, guar gum, tamarind gum, dialkyldimethylammonium cellulose sulfate, xanthan gum, magnesium aluminum silicate, bentonite, hectorite, AlMg silicate (VEEGUM), laponite, and anhydrous silicic acid.

Examples of the ultraviolet absorbent include benzoic acid ultraviolet absorbents (e.g., para-aminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N,N-dipropoxy PABA ethyl ester, N,N-diethoxy PABA ethyl ester, N,N-dimethyl PABA ethyl ester, N,N-dimethyl PABA butyl ester, N,N-dimethyl PABA ethyl ester, etc.); anthranilic acid ultraviolet absorbents (e.g., homomenthyl-N-acetyl anthranilate, etc.); salicylic acid ultraviolet absorbents (e.g., amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanolphenyl salicylate, etc.); Cinnamic acid type UV absorbers (e.g., octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl-2,5-diisopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4-diisopropyl cinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, octyl-p-methoxycinnamate (2-ethylhexyl-p-methoxycinnamate), 2-ethoxy ethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate, etc.); Benzophenone UV absorbers (e.g., 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-Hydroxy-3-carboxybenzophenone, etc.); 3-(4'-methylbenzylidene)-d,l-camphor-, 3-benzylidene-d,l-camphor-; 2-phenyl-5-methylbenzoxazole; 2,2'-hydroxy-5-methylphenylbenzotriazole; 2-(2'-hydroxy-5'-t-octylphenyl) benzotriazole; 2-(2'-hydroxy-5'-methylphenylbenzotriazole; dibenzarazine; dianisoyl methane; 4-methoxy-4'-t-butyldibenzoylmethane; 5-(3,3-dimethyl-2-norbornylidene)-3-pentan-2-one, etc.

Examples of metal ion sequestering agents include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, tetrasodium edetate, sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, ethylenediamine hydroxyethyl triacetate trisodium, and the like.

Lower alcohols (preferably having 1 to 4 carbon atoms) include, for example, ethanol, propanol, isopropanol, isobutyl alcohol, and t-butyl alcohol.

Monosaccharides include, for example, tricarbon sugars (for example, D-glycerylaldehyde, dihydroxyacetone, etc.); tetracarbon sugars (for example, D-erythrose, D-erythrulose, D-threose, erythritol, etc.); pentacarbon sugars (for example, L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose, etc.); hexcarbon sugars (for example, D-glucose, D-talose, D-psicose, D-galactose, D-fructose, L-galactose, L-mannose, D-tagatose, etc.); heptacarbon sugars (for example, aldheptose, heptose, etc.); octcarbon sugars (for example, octulose, etc.); Examples thereof include deoxysugars (e.g., 2-deoxy-D-ribose, 6-deoxy-L-galactose, 6-deoxy-L-mannose, etc.); aminosugars (e.g., D-glucosamine, D-galactosamine, sialic acid, aminouronic acid, muramic acid, etc.); uronic acids (e.g., D-glucuronic acid, D-mannuronic acid, L-guluronic acid, D-galacturonic acid, L-iduronic acid, etc.).

Examples of oligosaccharides include sucrose, gunthianose, unbelliferose, lactose, prantheose, isolychnose, α,α-trehalose, raffinose, lychnose, umbilicin, and stachyose verbascose.

Examples of polysaccharides include cellulose, quince seed, chondroitin sulfate, starch, galactan, dermatan sulfate, glycogen, gum arabic, heparan sulfate, hyaluronic acid, gum tragacanth, keratan sulfate, chondroitin, xanthan gum, mucoitin sulfate, guar gum, dextran, kerato sulfate, locust bean gum, succinoglucan, and carotenoic acid.

As amino acids, examples thereof include acidic amino acids (e.g., glutamic acid, aspartic acid, etc.), neutral amino acids (e.g., threonine, cysteine, etc.), and basic amino acids (e.g., hydroxylysine, etc.). In addition, as amino acid derivatives, examples thereof include sodium acyl sarcosine (sodium lauroyl sarcosine), acyl glutamate, sodium acyl β-alanine, glutathione, pyrrolidone carboxylic acid, etc.

Examples of organic amines include monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, and 2-amino-2-methyl-1-propanol.

Examples of pH adjusters include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.

Vitamins include, for example, vitamins A, B1, B2, B6, C, E and their derivatives, pantothenic acid and its derivatives, biotin, etc.

Examples of antioxidants include tocopherols, dibutyl hydroxy toluene, butyl hydroxy anisole, and gallic acid esters.

Examples of antioxidants include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, cephalin, hexametaphosphate, phytic acid, and ethylenediaminetetraacetic acid.

Other possible ingredients include, for example, preservatives (ethylparaben, butylparaben, etc.); anti-inflammatory agents (for example, glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, etc.); whitening agents (for example, placenta extract, rock azalea extract, arbutin, etc.); various extracts (for example, phellodendron amurense, coptis chinensis, lily, iris, grape, yiris, sedum, lily, saffron, cnidium officinalis, ginger, pepper plant, ononis, garlic, red pepper, tangerine peel, angelica, seaweed, etc.), revitalizers (for example, royal jelly, photosensitizer, cholesterol derivatives, etc.); Examples thereof include blood circulation promoters (e.g., nonylic acid vanillyl amide, nicotinic acid benzyl ester, nicotinic acid β-butoxyethyl ester, capsaicin, zingeron, cantharides tincture, ichthammol, tannic acid, α-borneol, nicotinate tocopherol, inositol hexanicotinate, cyclandelate, cinnarizine, trazoline, acetylcholine, verapamil, cepharanthine, γ-oryzanol, etc.); antiseborrheic agents (e.g., sulfur, thianthol, etc.); and anti-inflammatory agents (e.g., tranexamic acid, thiotaurine, hypotaurine, etc.).

The gel sheet for skin attachment of the present invention may contain an effective ingredient that can be contained in cosmetics or quasi-drugs, for example, an effective ingredient that exhibits a whitening effect or an anti-aging effect, within a range that does not impair the effects of the present invention. More specifically, examples thereof include, but are not limited to, antibacterial agents, whitening agents, anti-wrinkle ingredients, anti-inflammatory agents, cell revitalizing agents, active oxygen scavengers, and moisturizers.

Antibacterial agents include, for example, benzoic acid, sodium benzoate, paraoxybenzoate ester, benzalkonium chloride, phenoxyethanol, and isopropyl methyl phenol.

Whitening agents have the effect of preventing the occurrence of darkening of the skin caused by suntanning, etc., and blemishes and freckles caused by pigmentation, and examples thereof include arbutin, ellagic acid, linoleic acid, vitamin C and derivatives, vitamin E and derivatives, glycyrrhizic acid and derivatives, glycyrrhetinic acid and derivatives, tranexamic acid, placental extracts, chamomile extracts, licorice extracts, rose hip extracts, goldenrod extracts, seaweed extracts, soybean extracts, Chinese juniper extracts, Acanthopanax extracts, rice bran extracts, wheat germ extracts, capsaicin extracts, hawthorn extracts, Chinese yam extracts, white lily extracts, peony extracts, schisandra chinensis extracts, soybean extracts, tea extracts, molasses extracts, white lotus extracts, grape extracts, hop extracts, quince extracts, cotton extracts, and rock aster extracts.

Anti-wrinkle ingredients include, but are not particularly limited to, retinoids such as retinol, retinoic acid, retinol acetate, and retinol palmitate; vitamin B types such as nicotinic acid and its derivatives; α-hydroxy acids such as citric acid, fruit acid, glycolic acid, and lactic acid; α-hydroxy acid cholesterol, rutin sugar derivatives, N-methylserine, elastin, collagen, sericin, Centella asiatica extract, and golden extract.

Anti-inflammatory agents have the effect of suppressing inflammation such as skin burning or erythema after sunburn, and examples thereof include sulfur and derivatives thereof, glycyrrhizic acid and derivatives thereof, glycyrrhetinic acid and derivatives thereof, althea extract, ashitaba extract, arnica extract, injinho extract, nettle extract, phellodendron extract, capsicum extract, chamomile extract, honeysuckle extract, watercress extract, comfrey extract, salvia extract, lily of the valley extract, perilla extract, birch extract, and gentian extract.

Cell revitalizing agents are used for the purpose of improving dermatitis, etc., and examples thereof include caffeine, cinnamon extracts, shell extracts, royal jelly, silk protein and its decomposition products or derivatives thereof, lactoferrin or its decomposition products, chondroitin sulfate, mucopolysaccharides such as hyaluronic acid or salts thereof, collagen, yeast extracts, lactic acid bacteria extracts, bifidobacteria extracts, fermented metabolic extracts, ginkgo extracts, barley extracts, bitter melon extracts, jujube extracts, carrot extracts, rosemary extracts, glycolic acid, citric acid, lactic acid, malic acid, tartaric acid, succinic acid, etc.

Active oxygen scavengers have the effect of inhibiting lipid peroxidation production, and examples thereof include superoxide dismutase, mannitol, quercetin, catechin and its derivatives, rutin and its derivatives, botanical extract, yarrow fruit extract, melissa extract, luohan fruit extract, retinol and its derivatives, carotenoids and other vitamin A types, thiamine and its derivatives, riboflavin and its derivatives, pyridoxine and its derivatives, nicotinic acid and its derivatives, other vitamin B types, tocopherol and its derivatives, other vitamin E types, dibutyl hydroxytoluene and butyl hydroxyanisole.

Moisturizers include, for example, proteins such as elastin and keratin or derivatives thereof, hydrolyzed substances and salts thereof, amino acids such as glycine, serine, aspartic acid, glutamic acid, arginine and theanine and derivatives thereof, trehalose, inositol, glucose, sucrose and derivatives thereof, dextrin and derivatives thereof, sugars such as honey, D-panthenol and derivatives thereof, urea, phospholipids, ceramides, coptis extract, calamus extract, rehmannia glutinosa extract, cnidium extract, malvaceae extract, thyme (Thymus vulgaris) extract, sasanqua extract, hamamelis extract, barley extract, horse chestnut extract, quince extract, etc.

＜2. Raw material composition of the skin-attaching gel sheet of the present invention and method for producing the skin-attaching gel sheet＞

The skin-attachment gel sheet of the present invention can be obtained by (i) preparing an O/W emulsion raw material composition containing the above components (a) to (f) and appropriately the above <optional component>, and (ii) forming the O/W emulsion composition into a sheet and drying it to a predetermined moisture content.

The manufacturing method for emulsifying the composition in the above (i) may utilize a known emulsifying method.

The O/W emulsion composition used in the present invention can be obtained by emulsifying the components (a) to (f) and the appropriate <optional component> by mixing or the like. More specifically, the O/W emulsion composition can be obtained by emulsifying an oil phase including at least component (d) a solid and/or semi-solid emulsion and component (e) a liquid emulsion, and an aqueous phase including at least component (a) polyvinyl alcohol, component (b) an acrylic acid polymer, component (c) a polyhydric alcohol, and (f) water.

In addition, as an example of a method for producing the O/W emulsion composition, the composition can be obtained by dissolving component (a) polyvinyl alcohol and component (b) acrylic acid polymer in an aqueous system containing component (c) polyhydric alcohol and component (f) water, and dispersing an emulsion containing solid oils of components (d) and (e) in the aqueous system. In this production process, an optional component such as a surfactant may be appropriately added to improve dispersibility, or a component expected to have an effect may be added.

In addition, as an example of a method for producing the O/W emulsion composition, a dispersion containing component (f) and a surfactant and an emulsion containing solid oils such as component (d) and component (e) are mixed and dispersed, and an aqueous system containing component (a) polyvinyl alcohol, component (b) acrylic acid polymer, component (c) polyhydric alcohol, and component (f) water is dispersed in the dispersion. In this production process, an arbitrary component such as a surfactant may be appropriately added to improve dispersibility, or a component expected to have an effect may be added.

In the O/W emulsion composition of the present invention, it is preferable to adjust the content or mass content ratio of each component (a) to (f) and appropriately the <optional component> so as to become the content or mass content ratio of each component of the skin-attaching gel sheet of the present invention described above.

In the O/W emulsion composition of the present invention, the content of each component in the composition (hereinafter also referred to as “O/W emulsion composition (excluding the amount of component (f))”) when the total amount of components other than component (f) water is 100 mass% is described below, but the present invention is not limited to this.

The content of component (a) polyvinyl alcohol in the above O/W emulsion composition (excluding the amount of component (f)) is not particularly limited, and is suitably 2 to 26 mass%, more suitably 3 to 20 mass%, and even more suitably 5 to 20 mass%.

In addition, the content of the component (b) acrylic acid polymer in the O/W emulsion composition (excluding the amount of component (f)) is not particularly limited, but is suitably 0.05 to 3 mass%, more suitably 0.1 to 2 mass%, even more suitably 0.1 to 1.5 mass%, and even more suitably 0.1 to 1.0 mass%.

In addition, the content of component (c) polyhydric alcohol in the O/W emulsion composition (excluding the amount of component (f)) is not particularly limited, but is suitably 35 to 94 mass%, more suitably 40 to 95 mass%, and even more suitably 50 to 80 mass%.

In addition, the content of the solid and/or semi-solid emulsion of component (d) in the O/W emulsion composition (excluding the amount of component (f)) is not particularly limited, but is suitably 0.08 to 19 mass%, more suitably 0.1 to 16 mass%, further suitably 0.5 to 15 mass%, and further suitably 1 to 15 mass%.

In addition, the content of the liquid emulsion of component (e) in the O/W emulsion composition (excluding the amount of component (f)) is not particularly limited, but is suitably 0.5 to 32 mass%, more suitably 1 to 30 mass%, and even more suitably 1 to 20 mass%.

In addition, the content of the surfactant component (g) in the O/W emulsion composition (excluding the amount of component (f)) is not particularly limited, but is suitably 0.1 to 3 mass%, more suitably 0.5 to 2 mass%.

In addition, the amount of water used in the O/W emulsion composition can be adjusted so as to be an amount capable of forming an O/W emulsion and also an amount capable of forming a gel sheet having a desired moisture content after drying. The amount of moisture is not particularly limited, but it is suitably adjusted to be 10 to 50 mass% in the O/W emulsion composition.

A more preferable numerical range of the mass ratio (a)/(b) in the above O/W emulsion composition is suitably 3 to 160, more suitably 4 to 150, more suitably 5 to 100, and even more suitably 6 to 70.

A more preferable numerical range of the mass ratio (a)/(c) in the above O/W emulsion composition is suitably 0.02 to 0.5, more suitably 0.03 to 0.4, and even more suitably 0.04 to 0.3.

A more preferable numerical range of the content mass ratio (d)/(e) in the above O/W emulsion composition is suitably 0.001 to 3.5, more suitably 0.003 to 3.1, more suitably 0.1 to 2.5, and even more suitably 0.5 to 2.

And, the skin attachment sheet of the present invention can be obtained by forming the O/W emulsion raw material composition into a sheet of a desired thickness and shape, and then drying and removing the moisture so that the moisture content is as desired by a known drying method (e.g., hot air drying, infrared drying, vacuum drying, suction drying, steam drying, hot plate drying, freeze drying, etc.).

As a method for forming the skin-attaching gel sheet of the present invention, for example, a method in which a composition for forming a gel sheet is spread on a peeling substrate film to a uniform thickness, and then heat-dried and cut to obtain a sheet of a predetermined shape (cast method); a method in which the composition is coated on a peeling substrate film to a desired thickness using a roll, a blade, a calendar, or the like, and then heat-dried and cut to obtain a sheet of a predetermined shape (coating method); a manufacturing method in which the composition is filled into a frame portion (tray) formed of a resin or the like, and then heat-dried to obtain a sheet of a predetermined shape; a manufacturing method in which a stencil in which holes corresponding to the shape of the gel sheet are formed are used, the composition is filled into the holes, the composition is printed on a peeling substrate film, and then heat-dried to obtain a sheet of a predetermined shape (stencil printing), etc., but any method can be used. In addition, the skin-attaching gel sheet of the present invention may be stored or sealed in a packaging container made of plastic or the like with a peeling substrate attached thereto. In addition, the peeling substrate is preferably a substrate from which the skin-attaching gel sheet of the present invention can be peeled off when in use, and is not particularly limited to a film, but may be a tray or the like, and the material thereof is not particularly limited.

Examples of materials for the peeling base film or tray used include polyethylene, polyethylene terephthalate, polybutylene terephthalate, polypropylene, polystyrene, polycarbonate, polyvinyl chloride, paper, etc. In addition, various coatings such as silicone or fluorine can be applied to the surface so that the skin-attaching gel sheet of the present invention can be easily peeled.

As for the shape of the gel sheet, it is best to choose an optimal shape so that it can be easily attached to the attachment target area, and it can be freely formed into a circle, oval, square, bead-shaped, face-shaped, etc.

As described above, the skin-attachable gel sheet obtained by the method for manufacturing the skin-attachable gel sheet has excellent moisturizing effects, usability (film strength, absence of film burden, solubility in water), and sheet moldability. In addition, the obtained skin-attachable gel sheet has excellent moisturizing properties as well as flexibility and strength, so that a support is unnecessary, and it has excellent usability, and due to its high water solubility, it can be easily dissolved in water and applied to the skin.

＜Method of using the skin-attaching gel sheet of the present invention＞

The method of using the skin-attaching gel sheet of the present invention includes using the sheet alone, and also using it by applying an appropriate amount of water or a composition containing water, such as a cosmetic, to the attached sheet after attaching the sheet to the skin and massaging the attached sheet. This allows the sheet to easily dissolve in water, and various ingredients, such as moisturizing ingredients and blended effective ingredients, can be effectively absorbed into the skin. The skin-attaching gel sheet of the present invention is easy to handle even without a support, and is easy to dissolve in water, so it is easy to apply to various usage methods.

The skin-attachable gel sheet of the present invention is composed of component (a) polyvinyl alcohol, component (b) acrylic acid-based polymer, component (c) polyhydric alcohol, and component (f) water and other appropriate optional components, and the emulsions of component (d) and component (e) are dispersed and present in the gel, so that the gel is softened by the plasticizing effect of the emulsions. In addition, the skin-attachable gel sheet of the present invention has the major characteristics of being remarkably easy to dissolve in water and not forming fragments when melted when massaged, compared to conventional gel sheets that do not contain an emulsifier.

In addition, in order to better achieve the film strength, moisturizing effect, and solubility in water, it is also effective to adjust the film thickness of the skin-attaching gel sheet of the present invention. At this time, the film thickness is preferably 50 to 2000 μm, and more preferably 100 to 1000 μm.

In addition, the thickness of the film of the gel sheet in the present invention is a value measured using a digital micrometer (MDE-25MJ manufactured by Mitutoyo Corporation) after the gel has dried.

The present invention may adopt the following configuration.

[1] The following components (a) to (f);

(a) polyvinyl alcohol

(b) Acrylic acid polymer

(c) Polyhydric alcohol 40 to 93 mass%

(d) 0.1 to 16 mass% of solid and/or semi-solid emulsion at 25°C

(e) 1.0 to 30 mass% of liquid emulsion at 25°C

(f) Water 10 mass% or less

A gel sheet for skin application containing:

[2] A gel sheet for skin attachment as described in [1], wherein the thickness of the gel sheet is 50 to 2000 μm.

[3] A gel sheet for skin attachment as described in [1] or [2], wherein the mass ratio (a)/(b) of the components (a) and (b) is 3 to 160. Preferably, (a)/(b) is 4.0 to 150.

[4] A gel sheet for skin attachment according to any one of [1] to [3], wherein the mass ratio (a)/(c) of the components (a) and (c) is 0.02 to 0.5.

[5] A gel sheet for skin attachment according to any one of [1] to [4], wherein the mass ratio (d)/(e) of the components (d) and (e) is 0.001 to 3.5. Preferably, (d)/(e) is 0.003 to 3.0.

[6] The skin-attaching gel sheet according to any one of [1] to [5], wherein the component (c) is glycerin and/or 1,3-butylene glycol.

[7] The skin-attachable gel sheet according to any one of [1] to [6], wherein the component (b) is a polymer obtained by polymerizing or copolymerizing one or more raw material monomers selected from acrylic acid, methacrylic acid, alkyl acrylic acid ester, alkyl methacrylic acid ester, and acryloyldimethyl taurine. The amount of a structural unit derived from acrylic acid in the polymer is preferably 40 mol% or more.

[8] The skin-attachable gel sheet according to any one of [1] to [7], wherein the component (b) is one or a combination of two or more selected from a carboxyvinyl polymer, an alkyl-modified carboxyvinyl polymer, a cross-linked copolymer of acrylamide and 2-acrylamide-2-methylpropane sulfonic acid, and a sodium acrylate-acryloyldimethyl taurine copolymer.

[9] A gel sheet for skin attachment as described in any one of [1] to [8], wherein the saponification degree of the component (a) is 70 to 90 mol%. Preferably, the saponification degree is 80 to 90 mol%.

[10] The gel sheet for skin attachment described in any one of [1] to [9] above, wherein the content of the above component (a) is 1.5 to 29 mass%, preferably 3.0 to 25 mass%.

[11] The gel sheet for skin attachment described in any one of [1] to [10] above, wherein the content of the above component (b) is 0.03 to 4.5 mass%, preferably 0.1 to 2.0 mass%.

[12] The skin-attachable gel sheet according to any one of [1] to [11] above, wherein the degree of polymerization of the component (a) polyvinyl alcohol is 100 to 4000.

[13] The skin-attachment gel sheet according to any one of [1] to [12], wherein the weight average molecular weight of the acrylic acid polymer of the above component (b) is suitably 500 or more and 5 million or less.

[14] The skin-attachable gel sheet according to any one of the above [1] to [13], wherein the polyhydric alcohol (c) is an alcohol having a structure having two or more hydroxyl groups in the skeleton. Preferably, the polyhydric alcohol is one or two or more selected from 1,3-butylene glycol, dipropylene glycol, tripropylene glycol, glycerin, diglycerin, propylene glycol, and 1,2-pentane diol.

[15] A gel sheet for skin attachment, according to any one of [1] to [14], further comprising a surfactant component (g). Preferably, the content is 0.1 to 3 mass%.

[16] A method of using a gel sheet for skin attachment, comprising attaching the gel sheet for skin attachment described in any one of [1] to [15] above to the skin, or adding water or a composition containing water to the attached gel sheet after attachment to the skin to adapt the gel sheet to the skin.

[17] A method of using the skin-attaching gel sheet of the above-mentioned [16], which uses the gel sheet without requiring a support.

[18] An O/W emulsion composition comprising components (a) polyvinyl alcohol, (b) an acrylic acid polymer, (c) a polyhydric alcohol, (d) an emulsion that is solid and/or semi-solid at 25°C, (e) an emulsion that is liquid at 25°C, and component (f) water, for manufacturing a gel sheet for skin attachment.

When the total amount of components other than water (f) is 100 mass%, the polyhydric alcohol (c) is 40 to 93 mass%, the emulsion that is solid and/or semi-solid at 25°C is 0.1 to 16 mass%, and the emulsion that is liquid at 25°C is 1.0 to 30 mass%.

An O/W emulsion composition for producing a gel sheet for skin attachment.

More suitably, when the total amount of components other than component (f) water is 100 mass%, the content of component (a) is 1.5 to 29 mass%, and/or the content of component (b) is 0.03 to 4.5 mass%.

[19] A gel sheet for skin attachment or a method for producing a gel sheet for skin attachment, obtained by forming the O/W emulsion composition of the above [18] into a sheet shape and drying it to a predetermined moisture content.

Example

The present invention is described in more detail below by way of examples, but the present invention is not limited thereto.

＜Examples 1 to 12 and Comparative Examples 1 to 15: Gel sheets for skin attachment＞

Gel sheets for skin attachment having the compositions shown in Tables 1 to 5 were prepared according to the manufacturing method below, and each of the items of “moisturizing effect,” “film strength,” “no burden on film,” “solubility in water,” and “formability of sheet” was evaluated and judged according to the evaluation methods and judgment criteria shown below, and the results were shown together in Tables 1 to 5.

*1: Resinol S-10 (manufactured by Nikko Chemicals Co., Ltd.)

*2: Nikkol SMT (manufactured by Nikko Chemicals Co., Ltd.)

*3: PERFORMALENE 500 (manufactured by New Phase Technologies)

*4: T.I.O (manufactured by Nisshin OilliO Group, Ltd.)

*5: CARBOPOL 980 (carboxyvinyl polymer) (manufactured by Lubrizol Advanced Materials)

*6: CARBOPOL 1382 (Acrylates/Alkyl acrylate (C10-30)) cross polymer) (Lubrizol Advanced Materials)

*7: SIMULGEL EG (Na acrylate/Na acryloyldimethyl taurine) copolymer (manufactured by SEPPIC)

*8: METOLOSE 65SH4000 (manufactured by Shin-Etsu Chemical Co., Ltd.)

*9: KELTROL (CPKelco)

*10: PVA-205 (made by Kuraray Co. Ltd.)

*11: PVA-105 (made by Kuraray Co. Ltd.)

In addition, among the ingredients (d) in the table of solid and/or semi-solid emulsions at 25°C, No. 3 polyethylene wax, No. 4 cetostearyl alcohol, and No. 5 petrolatum, a gel hardness (maximum load applied to the decompressor shaft when the decompressor shaft is pushed in to a depth of 5 mm in a penetration test at a specimen storage temperature of 25°C, a needle diameter of a decompressor (adapter) of 10 mmφ, and a penetration speed of 60 mm/min) is 15 gf or more.

In addition, No. 6 liquid paraffin, No. 7 tri-2-ethylhexanoic acid glyceryl, and No. 9 dimethyl polysiloxane in the table are liquid emulsions at 25°C (component (e)).

In addition, the weight average molecular weight of No. 10 carbomer, No. 11 acrylic acid-methacrylic acid copolymer, and No. 12 (acrylic acid Na/acryloyldimethyl taurine Na) copolymer in the table is 500 or more and 5 million or less in GPC analysis (standard polystyrene as a standard material).

(Manufacturing method)

A: Add 10% water to components (1) to (2), heat to 70℃, and mix and dissolve evenly.

B: Heat components (3) to (9) to 90℃ and mix and dissolve evenly.

C: Add 30% water to components (10) to (22), heat to 70℃, and mix and dissolve evenly.

D: Add B to A and mix evenly at 70℃.

E: Add C while stirring D at 70℃ to emulsify, then cool to room temperature to obtain an O/W emulsified raw material composition.

F: E was uniformly formed onto a polyethylene terephthalate film having a thickness of 50 μm with a doctor blade, heated and dried in a 60°C blower dryer for 1 hour, and cooled to room temperature, thereby obtaining a skin-attachment gel sheet having a film thickness of 300 μm. The water content in the skin-attachment gel sheet obtained at this time is assumed to be 0 mass% assuming that "water has completely evaporated." In addition, in the <Method for Measuring Water Content: Karl Fischer Method>, the water content in the gel sheets of Examples 1 to 9 and Comparative Examples 1 to 11 is less than 1 mass%, and in this specification, less than 1 mass% is considered to be 0 mass%.

In addition, the amount of component (f) water in Example 10 and Comparative Example 12 was adjusted to a predetermined amount by shortening the drying time.

[Moisturizing effect]

First, the initial moisture content of the skin on the inner side of the forearm to which nothing was applied was measured with SKICON-200EX (manufactured by IBS), and each gel sheet of Examples 1 to 12 and Comparative Examples 1 to 15, cut into a square with a side of 2 cm, was attached to the inner side of the forearm, and the skin moisture content was measured 6 hours after attachment. Each sample was measured on 5 normal subjects, and when the initial moisture content was taken as 100, the moisture content after 6 hours was calculated as a relative value, and the moisturizing effect was evaluated according to the following 4-step judgment criteria by the average moisture content of the relative value of each panel.

4-step evaluation criteria

(Evaluation)　　　　　　　　　　　　　　　　　　: (Judging criteria)

The average moisture content relative to the initial moisture content is 150% or more

: ◎(Excellent)

The average moisture content relative to the initial moisture content is less than 150% and more than 130%

: ○(Good)

The relative average moisture content of the initial moisture content is less than 130% and more than 110%

: △(slightly defective)

The average moisture content relative to the initial moisture content is less than 110%

: ×(bad)

[Strength]

For each sheet of Examples 1 to 12 and Comparative Examples 1 to 15, the strength of the sheet when peeled from the polyethylene terephthalate film as the substrate was evaluated by one expert evaluator according to the following four-stage evaluation criteria. In addition, one film used in the evaluation criteria means a state in which the sheet can be handled as one film without being torn when peeling the gel sheet from the substrate film.

4-step evaluation criteria

(Evaluation)　　　　　　　　　　　　　　　　　　　: (Judging criteria)

It can be peeled off as a single sheet without any cracks in the sheet.

: ◎(Excellent)

There are some cracks in the sheet, but it can be peeled off as a single sheet of film, so there is no problem in using it: ○ (Good)

The sheet is torn during peeling and cannot be peeled as a single film.

: △(slightly defective)

The sheet is not hardened and cannot be peeled off as a single film.

: ×(bad)

[No burden of curtain]

For each sheet of Examples 1 to 12 and Comparative Examples 1 to 15, a usage test was conducted by five expert panelists. Each sheet cut into a 4 cm x 8 cm square shape was attached to the area under the eyes by each panelist, and immediately thereafter, a score was given according to the evaluation criteria below, and an average value was calculated from the sum of the scores of all panelists, and a comprehensive judgment was made according to the judgment criteria below.

＜Evaluation criteria＞

(Rating): (Evaluation)

4 points: Follows the movement or shape of the skin flexibly and does not feel pulling.

3 points: The skin lifts slightly when moved, but does not feel tight.

2 points: When the skin moves, a slight pulling is felt

1 point: The membrane is hard, so you feel a strong pull when it is attached.

＜Judging criteria＞

(Judgment): (Average of scores)

◎(Excellent)　　: 3.5 points or higher

○(Good)　　　: 2.5 points or more but less than 3.5 points

△(Slightly bad): 1.5 points or more but less than 2.5 points

×(bad): less than 1.5 points

In the present invention, it is determined that a judgment of ○ or more is appropriate.

[Solubility in water]

Each gel sheet of Examples 1 to 12 and Comparative Examples 1 to 15, cut into a square with a side size of 2 cm, was attached to the inner side of the forearm, 1 mL of water was added, and the solubility of the sheet in water when massaged with a finger was evaluated by one expert evaluator according to the following four-step evaluation criteria.

4-step evaluation criteria

(Evaluation)　　　　　　　　　　　　　　　　　　　　　: (Judging criteria)

Without massaging, it quickly swells with the addition of water and becomes creamy.

: ◎(Excellent)

After adding water and massaging with your fingers, it swells completely and becomes creamy: ○ (good)

Even after adding water and massaging with your fingers, it does not swell completely and pieces of the sheet remain: △ (slightly bad)

Even after adding water and massaging with your fingers, it does not swell completely and maintains the shape of the sheet: × (bad)

[Formability of the sheet]

When preparing the gel sheets of Examples 1 to 12 and Comparative Examples 1 to 15, a process was taken in which an O/W emulsion type raw material composition was uniformly molded onto a polyethylene terephthalate film having a thickness of 50 μm as a substrate using a doctor blade, and then heated and dried in a 60°C blower dryer for 1 hour. However, whether or not the molded raw material composition bounced off the substrate, shrank, or deformed was evaluated by one expert evaluator according to the following four-step judgment criteria.

4-step evaluation criteria

(Evaluation)　　　　　　　　　　　　　　　　　　　　　: (Judging criteria)

After the molding, it maintains its shape completely without being bounced off the substrate even after being left at room temperature for 10 minutes. : ◎(Excellent)

After pre-molding, when left at room temperature for 10 minutes, uniform shrinkage of less than 4 mm occurs at the end, but the shape is maintained. : ○ (Good)

After the full molding, if left to stand at room temperature for 10 minutes, the shrinkage is unevenly greater than 4 mm and less than 10 mm from the end, and the shape cannot be maintained. : △ (slightly defective)

After the full-form molding, if left to stand at room temperature for 10 minutes, the shrinkage is unevenly greater than 10 mm from the end and the product is significantly deformed. : × (defective)

As is clear from Tables 1 to 5, the skin-attachment gel sheets of Examples 1 to 12 of the present invention were excellent in all items of “moisturizing effect”, “film strength”, “no burden of film”, “solubility in water”, and “formability of sheet”. On the other hand, Comparative Examples 1 and 2 in which (a) the blending amount of polyvinyl alcohol was smaller than the preferred range were particularly inferior in film strength and sheet formability. Conversely, Comparative Example 3 in which (a) the blending amount of polyvinyl alcohol was larger than the preferred range was particularly inferior in water solubility and sheet formability. In addition, Comparative Examples 4 and 5 in which (b) the blending amount of the acrylic acid-based polymer was smaller than the preferred range were particularly inferior in film strength and sheet formability. Conversely, Comparative Example 6 in which (b) the blending amount of the acrylic acid-based polymer was larger than the preferred range was particularly inferior in no burden of film and solubility in water.

In addition, Comparative Example 7, in which (c) the amount of polyhydric alcohol was smaller than the preferred range, and furthermore, the amount of (d) the solid or semi-solid emulsion at 25°C and (e) the liquid emulsion at 25°C was larger than the preferred range, had difficulty in maintaining the film state due to the excessive amount of emulsion, and the film strength and solubility in water were particularly poor. In contrast, Comparative Examples 10 and 11, in which (c) the amount of polyhydric alcohol was larger than the preferred range, and furthermore, the amount of (d) the solid or semi-solid emulsion at 25°C and (e) the liquid emulsion at 25°C were smaller than the preferred range, had particularly poor moisturizing effects and sheet formability.

Regarding the balance of the emulsion, Comparative Example 8, in which the ratio (d)/(e) of (d) and (e) was larger than the preferred range, had particularly poor membrane burden and water solubility. Conversely, Comparative Example 9, in which (d)/(e) was smaller than the preferred range, had particularly poor membrane strength and sheet formability. In addition, Comparative Example 13, in which (a) polyvinyl alcohol had a high degree of saponification, had particularly poor membrane burden and water solubility. In addition, Comparative Examples 14 and 15, in which hydroxypropyl methyl cellulose or xanthan gum was used instead of the acrylic acid polymer of (b), the membrane formability was significantly reduced, and the membrane strength and sheet formability were particularly poor. In addition, Comparative Example 12, which contained 10% or more of water, also had low membrane formability, and the membrane strength and sheet formability were particularly poor.

In this way, an O/W emulsion composition was prepared by mixing and dispersing an aqueous solution containing a polyhydric alcohol, a polyvinyl alcohol having excellent film-forming ability and flexibility, an acrylic acid-based polymer having excellent film-forming ability and strength, and an emulsion containing a solid oil or semi-solid oil and a liquid oil, and then spreading the composition into a sheet, and then drying the sheet by evaporating a specific amount of water, thereby obtaining a gel sheet for skin attachment having excellent usability. Since this gel sheet for skin attachment has excellent moisturizing property, flexibility, and strength, it can be used without requiring a support. In addition, since this gel sheet for skin attachment has excellent usability, excellent sheet formability, and high solubility in water, the sheet easily collapses with water or a composition containing water, thereby easily allowing the active ingredient to be applied to the skin.

In addition, in Example 16, a skin-attachment gel sheet having a moisture content of 2 mass% was obtained in the same manner as Example 1, except that the water content and glycerin content of Example 1 were set to 2 mass% and 70.84 mass%, respectively.

In Example 17, a skin-attachment gel sheet having a moisture content of 5 mass% was obtained in the same manner as in Example 1, except that the water content and glycerin content of Example 1 were set to 5 mass% and 87.84 mass%, respectively.

As in Example 1, each evaluation was conducted. As a result, the skin-attachment gel sheets of Examples 16 and 17 (water contents of 2 mass% and 5 mass%, respectively) were excellent in all aspects of “moisturizing effect,” “film strength,” “no burdensome film,” “solubility in water,” and “formability of sheet.” In addition, after attaching the gel sheet and massaging it with a commercially available toner 10 minutes later to allow adaptation, the duration of the skin’s moisturizing effect was excellent.

In this way, a gel sheet for skin attachment was obtained that had excellent moisturizing effect, usability (film strength, absence of film burden, solubility in water), and sheet formability even when the water content was more than 0 mass% and less than 10 mass%.

Example 13: Gel sheet for skin application

(Ingredients)　　　　　　　　　　　　　　　　　　　　　　　　　(%)

1. Hydrogenated lecithin *1 1.0

2. Stearoylmethyltaurine Na　*2　　　　　　　　　 0.3

3. Beeswax (melting point 60 ~ 67℃) *12 3.0

4. Behenyl alcohol (melting point 65 ~ 73℃)　　　　　　　　　 2.0

5. Dimer dilinoleic acid (phytosteryl/isostearyl/cetyl/stearyl/behenyl) (melting point 35 ~ 38℃) *13 1.0

6. (Dimethicone/Vinyl Dimethicone) Crosspolymer (Dimethicone Melt) *14　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　 1.0

7. Isopropyl myristate *15 2.0

8. 2-Ethylhexanoate cetyl *16 1.0

9. Octyldodecanol *17 1.0

10. Dimethyl polysiloxane　　　　　　　　　　　　　　　 0.2

11. 40% dispersion of crosslinked copolymer of acrylamide and 2-acrylamide-2-methylpropane sulfonic acid *18 1.0

12. Polyvinyl alcohol (degree of saponification 88 mol%, degree of polymerization 2400) *19 6.0

13. Glycerin Remaining Amount

14. 1,3-Butylene glycol　　　　　　　　　　　 　10.0

15. Dipropylene glycol　　　　　　　　　　　　　　 20.0

16. L-ascorbic acid 2-glucoside　　　　　　　　　　 2.0

17. Citric acid　　　　　　　　　　　　　　　　　　　　　0.03

18. Sodium citrate　　　　　　　　　　　　　　　　　 0.2

19. Sodium hydroxide 　　　　　　　　　　　　　　　　　　 0.3

20. Methylparaben　　　　　　　　　　　　　　　　　　　 0.05

21. Fragrance　　　　　　　　　　　　　　　　　　　　　0.1

*12: WHITE BEES WAX (manufactured by MIKI CHEMICAL INDUSTRIES Co., Ltd.)

*13: PLANDOOL-S (manufactured by Nippon Fine Chemical)

*14: KSG-16 (manufactured by Shin-Etsu Chemical Co., Ltd.)

*15: IPM-EX (manufactured by NIPPON SURFACTANT INDUSTRIES CO., LTD.)

*16: SALACOS 816T (manufactured by Nisshin OilliO Group, Ltd.)

*17: RISONOL 20SP (manufactured by KOKYU ALCOHOL KOGYO CO., LTD.)

*18: SEPIGEL 305 (manufactured by SEPIC)

*19: PVA-224 (made by Kuraray Co. Ltd.)

(Manufacturing method)

A: Add 10% water to components (1) to (2), heat to 70℃, and mix and dissolve evenly.

B: Heat components (3) to (10) to 90℃ and mix and dissolve evenly.

C: Add 30% water to components (11) to (21) and heat to 70℃ to mix and dissolve evenly.

D: Add B to A and mix evenly at 70℃.

E: Add C while stirring D at 70℃ to emulsify, then cool to room temperature to obtain an O/W emulsified raw material composition.

F: E was heat-dried and molded into a uniform thickness on a polypropylene film having a thickness of 50 μm using a caster, and then cut into a 400 μm thick gel sheet for skin attachment.

The gel sheet for skin attachment of Example 13 was excellent in all aspects of “moisturizing effect,” “film strength,” “no burdensome film,” “solubility in water,” and “formability of sheet.” In addition, after attaching the gel sheet and massaging it with commercially available toner 10 minutes later to allow adaptation, the skin’s moisturizing effect was excellently sustained.

Example 14: Gel sheet for skin application

(Ingredients)　　　　　　　　　　　　　　　　　　　　　　　　　　(%)

1. Hydrogenated lecithin *1 1.0

2. Stearoylmethyltaurine Na * 2 0.3

3. Microcrystalline wax (melting point 76 ~ 83℃) *20

　　　　　　　　　　　　　　　　　　　　　　　　 　　　　1.0

4. Paraffin wax (melting point 61 ~ 65℃)　　　　　　　　 2.0

5. Cetostearyl alcohol (melting point 50 ~ 63℃) 3.0

6. Di(octyl dodecyl/phytosteryl/behenyl) lauroyl glutamate (melting point 33℃) *22 1.0

7. (Dimethicone/polyglycerin-3) cross polymer (dimethicone soluble) *23 1.0

8. Polybutene (viscosity at 30℃: 400,000 ㎟/s) 1.0

9. Polyglyceryl diisostearate 2 * 24 1.0

10. Isotridecyl isononanoate *25 2.0

11. Decyltetradecanol *26 1.0

12. Dimethyl polysiloxane　　　　　　　　　　　　　 0.2

13. (Acrylic acid/alkyl acrylate (C10-30)) copolymer *27　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　 0.4

14. Polyvinyl alcohol (saponification degree 88 mol%, 4% aqueous solution viscosity at 20℃ 5.4 mPa s) *28 10.0

15. Glycerin Remaining Amount

16. 1,3-Butylene glycol　　　　　　　　　　　　10.0

17. Diglycerin　　　　　　　　　　　　　 3.0

18. Tripropylene Glycol　　　　　　　　　　 5.0

19. Nicotinamide　　　　　　　　　　　　　　　　　　　 5.0

20. Sodium hydroxide　　　　　　　　　　　　　　　　　　 0.2

21. 1,2-Pentanediol　　　　　　　　　　　　　　 0.5

22. Fragrance　　　　　　　　　　　　　　　　　　　　　　　　　 0.1

*20: MULTIWAX W445 (made by SONNEBORN)

*21: PARACERA P (manufactured by PARAMELT)

*22: ELDEW PS-306 (made by AJINOMOTO CO., INC.)

*23: KSG-710 (manufactured by Shin-Etsu Chemical Co., Ltd.)

*24: Cosmol 43V (manufactured by Nisshin OilliO Group, Ltd.)

*25: SALACOS 913 (manufactured by Nisshin OilliO Group, Ltd.)

*26: RISONOL 24SP (manufactured by KOKYU ALCOHOL KOGYO CO., LTD.)

*27: PEMUREN TR-1 (manufactured by LUBRIZOL ADVANCED MATERIALS)

*28: GOHSENOL EG-05 (manufactured by Nippon Synthetic Chem Industry Co., Ltd.)

(Manufacturing method)

A: Add 10% water to components (1) to (2), heat to 70℃, and mix and dissolve evenly.

B: Heat components (3) to (12) to 90℃ and mix and dissolve evenly.

C: Add 30% water to components (13) to (22), heat to 70℃, and mix and dissolve evenly.

D: Add B to A and mix evenly at 70℃.

E: Add C while stirring D at 70℃ to emulsify, then cool to room temperature to obtain an O/W emulsified raw material composition.

F: Using a metal mask with holes in the shape of a sphere, E was printed on a polyvinyl chloride substrate having a thickness of 50 μm, and then vacuum-dried to obtain a gel sheet for skin attachment having a thickness of 400 μm.

The gel sheet for skin attachment of Example 14 was excellent in all aspects of “moisturizing effect,” “film strength,” “no burdensome film,” “solubility in water,” and “formability of sheet.” In addition, after attaching the gel sheet and massaging it with commercially available toner 10 minutes later to allow adaptation, the skin’s moisturizing effect was excellently sustained.

Example 15: Gel sheet for skin application

(Ingredients)　　　　　　　　　　　　　　　　　　　　　　　　　　(%)

1. Hydrogenated lecithin *1 　　　　　　　　　　　　 　　　　 1.0

2. Stearoylmethyltaurine Na　*2　　　　　　　　　 0.3

3. Synthetic wax (melting point 80 ~ 88℃) *29 3.0

4. Ethylene-propylene copolymer (melting point 95℃) *30 2.0

5. Cetostearyl alcohol (melting point 50 ~ 63℃) 3.0

6. Paraffin (melting point 56 ~ 61℃) *3 1.0

7. Macadamia nut fatty acid phytosterol (melting point 35 ~ 38℃) *32

　　　　　　　　　　　　　　　　　　　　　　　　　　　　 0.5　

8. Tribehenin (melting point 57 ~ 65℃) *33 1.0

9. (Caprylic/caprin/myristin/stearic acid) Triglyceryl (melting point 35 ~ 45℃) *34 0.5

10. Bisdiglyceryl polyacyladipate-2 (melting point 39℃) *35

　　　　　　　　　　　　　　　　　　　　　　　　　　　　 0.5

11. Diphenyl dimethicone *36 1.0

12. Diisostearyl malate *37 1.0

13. Isononyl isononanoate *38 2.0

14. Cetyl lactate *39 2.0

15. Dimethyl polysiloxane　　　　　　　　　　　　　　　 0.2

16. (Acrylic acid/alkyl acrylate (C10-30)) copolymer *26　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　 0.4

17. Polyvinyl alcohol (saponification degree 88 mol%, 4% aqueous solution viscosity at 20℃ 44.0 mPa s) * 40 6.0

18. Glycerin Remaining Amount

19. 1,3-Butylene glycol　　　　　　　　　　　　 10.0

20. Dipotassium glycyrrhizinate　　　　　　　　　　　　　 0.1

21. Sodium hydroxide　　　　　　　　　　　　　　　　　　 0.2

22. 1,2-Pentanediol　　　　　　　　　　　　　　 0.5

23. Fragrance　　　　　　　　　　　　　　　　　　　　　　　　　 0.1

*29: CIREBELLE 108 (manufactured by CIREBELLE)

*30: EP-700 (made by BakerPetrolite)

*31: PARACERA 256 (manufactured by PARAMELT)

*32: PLANDOOL-MAS (manufactured by Nippon Fine Chemical)

*33: SYNCROWAX HRC (made by Croda Japan K.K.)

*34: SALACOS　334 (manufactured by Nisshin OilliO Group, Ltd.)

*35: SOFTISAN 649 (manufactured by SASOL GERMANY GMBH)

*36: KF-54 (manufactured by Shin-Etsu Chemical Co., Ltd.)

*37: Cosmol 222 (manufactured by Nisshin OilliO Group, Ltd.)

*38: SALACOS 99 (manufactured by Nisshin OilliO Group, Ltd.)

*39: CERAPHYL 28 (manufactured by ASHLAND SPECIALITY INGREDIENTS)

*40: GOHSENOL EG-40 (manufactured by Nippon Synthetic Chem Industry Co., Ltd.)

(Manufacturing method)

A: Add 10% water to components (1) to (2), heat to 70℃, and mix and dissolve evenly.

B: Heat components (3) to (15) to 90℃ and mix and dissolve evenly.

C: Add 30% water to components (16) to (23), heat to 70℃, and mix and dissolve evenly.

D: Add B to A and mix evenly at 70℃.

E: Add C while stirring D at 70℃ to emulsify, then cool to room temperature to obtain an O/W emulsified raw material composition.

D: E was poured into a polystyrene tray having a concave portion in the shape of a sphere, heated and dried at 60°C for 1 hour, and a gel sheet for skin attachment having a thickness of 400 μm was obtained.

The gel sheet for skin attachment of Example 15 was excellent in all aspects of “moisturizing effect,” “film strength,” “no burdensome film,” “solubility in water,” and “formability of sheet.” In addition, after attaching the gel sheet and massaging it with commercially available toner 10 minutes later to allow adaptation, the skin’s moisturizing effect was excellently sustained.

Claims (13)

The following components (a) to (f);
(a) 1.5 to 26 mass% of polyvinyl alcohol having a saponification degree of 70 to 90 mol%;
(b) 0.06 to 3 mass% of acrylic acid polymer
(c) 40 to 93 mass% of polyhydric alcohol
(d) 0.1 to 16 mass % of solid and/or semi-solid emulsion at 25°C;
(e) 1.0 to 30 mass% of liquid emulsion at 25°C
(f) Water 10 mass% or less
A gel sheet for skin application, containing: In the first paragraph,
A gel sheet for skin attachment, wherein the thickness of the gel sheet is 50 to 2000 μm. In paragraph 1 or 2,
A gel sheet for skin attachment, wherein the mass ratio (a)/(b) of the components (a) and (b) above is 3 to 160. In paragraph 1 or 2,
A gel sheet for skin attachment, wherein the mass ratio (a)/(c) of the components (a) and (c) above is 0.02 to 0.5. In paragraph 1 or 2,
A gel sheet for skin attachment, wherein the mass ratio (d)/(e) of the components (d) and (e) contained therein is 0.001 to 3.5. In paragraph 1 or 2,
A gel sheet for skin application, wherein the above component (c) is glycerin and/or 1,3-butylene glycol. In paragraph 1 or 2,
The above component (b) is a skin-attachment gel sheet, which is a polymer obtained by polymerizing or copolymerizing one or more raw material monomers selected from acrylic acid, methacrylic acid, alkyl acrylic acid ester, alkyl methacrylic acid ester, and acryloyldimethyl taurine. In paragraph 1 or 2,
The above component (b) is a gel sheet for skin attachment, which is one or a combination of two or more selected from a carboxyvinyl polymer, an alkyl-modified carboxyvinyl polymer, a cross-linked copolymer of acrylamide and 2-acrylamide-2-methylpropane sulfonic acid, and a sodium acrylate-acryloyldimethyl taurine copolymer. A gel sheet for skin attachment as described in claim 1 or claim 2,
A method of using a gel sheet for skin attachment, which comprises attaching the gel sheet to the skin or, after attachment to the skin, adding water or a composition containing water to the attached gel sheet to adapt the gel sheet to the skin. In Article 9,
A method of using a gel sheet for skin attachment, which uses a gel sheet without requiring a support. delete delete delete