Gel composition

Abstract

The present invention relates to [1] a gel composition containing aluminum ions, and when the dynamic viscoelasticity (frequency dependence) of the gel composition is measured under strain conditions in the linear region at 25°C, there exists a frequency in the frequency range of 0.001 to 100 rad / s where the loss elastic modulus G'' / storage elastic modulus G'(tanδ) is 1, and the storage elastic modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is 500 Pa or more; and [2] a topical skin agent comprising the above gel composition.

Description

[Technical Field]

[0001] This invention relates to a gel composition and a topical skin agent. [Previous Technology]

[0002] Gel compositions are widely used in various fields such as pharmaceuticals, quasi-pharmaceuticals, cosmetics, fragrances, coatings, adhesives, binders, packaging materials, emulsifiers, suspending agents, water-retaining agents, surfactants, fiber treatment agents, and paper processing agents. Regarding technologies related to gel compositions, for example, the technologies described in Patent Documents 1 and 2 are available.

[0003] Japanese Patent Application Publication No. 55-127311 (Patent Document 1) discloses a topical cosmetic, characterized in that: a sol obtained by adding a divalent metal lactate or chloride to an aqueous solution of polyvinyl alcohol is used as a first agent, and a sol obtained by adding borax to an aqueous solution of sodium salt, potassium salt or triethanolamine salt of alginic acid is used as a second agent, and a gel film of the first agent and the second agent is formed by combining the two; the above-mentioned topical cosmetic hardly changes over time even when applied to the skin for a long time, the peeling time can be freely changed, and it can always maintain a state of absorbing moisture, so it is extremely effective in terms of the physiological function and cosmetic effect of the skin.

[0004] Japanese Patent Application Publication No. 2020-152869 (Patent Document 2) discloses a polyvinyl alcohol-based gel molding material with a structure formed by crosslinking a polyvinyl alcohol-based polymer with a titanium chelate compound, which has excellent strength. Regarding the polyvinyl alcohol-based gel molding material of Patent Document 2, its main applications are envisioned as a carrier for microbial fixation, a water-retaining material, a cold-retaining material, a filter material, etc., and its use in cosmetics, fragrances, pharmaceuticals, quasi-pharmaceuticals, or as a gel-like skin care agent has not yet been envisioned.

[0005] Furthermore, regarding the technology concerning compositions containing polyvinyl alcohol, for example, there is the technology described in Japanese Patent Application Publication No. 11-1595 (Patent Document 3). Patent Document 3 describes an aqueous composition comprising (A) a modified polyvinyl alcohol containing 0.1 to 20 molars of carboxyl groups within its molecule and (B) a water-soluble aluminum compound, wherein the solid content ratio (A) / (B) is 100 / 0.01 to 100 / 50 by weight. The aqueous composition exhibits a significant increase in viscosity with water evaporation and demonstrates significantly superior initial adhesion. Regarding the aqueous composition of Patent Document 3, its primary applications are envisioned as adhesives for paper processing, woodworking, fiber treatment, bonding agents, and coatings, where it is cured after water evaporation. Its use in cosmetics, fragrances, pharmaceuticals, quasi-pharmaceuticals, or as a gel-like skincare agent is not yet envisioned. [Summary of the Invention]

[0006] The present invention relates to a gel composition containing aluminum ions, and when the dynamic viscoelasticity (frequency dependence) of the gel composition is measured under strain conditions in the linear region at 25°C, there exists a frequency in the frequency region of 0.001 to 100 rad / s where the loss elastic modulus G'' / storage elastic modulus G'(tanδ) is 1, and the storage elastic modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is 500 Pa or more.

Implementation Method

[0007] As a type of film product, such as a skin care film, there are sheet films made by impregnating a liquid in a non-woven fabric. However, such sheet films lack sufficient adhesion and spreadability to the skin, resulting in poor skin conformability. Here, the adhesion or spreadability of the gel compositions described in Patent Documents 1 and 2 or the polyvinyl alcohol-based materials described in Patent Document 3 to the skin has not been investigated. This invention relates to a gel composition and a topical skin agent that improves the balance between adhesion and spreadability.

[0008] The inventors discovered that a gel composition containing aluminum ions and having a frequency where the loss elastic modulus G'' / storage elastic modulus G' becomes 1, and where the storage elastic modulus G' is within a specific range at a specific frequency, can improve the balance between adhesion and spreadability, thereby completing the present invention.

[0009] That is, the present invention relates to the following [1] and [2]. [1] A gel composition containing aluminum ions, and when the dynamic viscoelasticity (frequency dependence) of the gel composition is measured under strain conditions in the linear region at 25°C, there exists a frequency in the frequency region of 0.001 to 100 rad / s where the loss elastic modulus G'' / storage elastic modulus G'(tanδ) is 1, and the storage elastic modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is 500 Pa or more. [2] A topical skin agent comprising the gel composition described in [1] above.

[0010] According to the present invention, a gel composition and a topical skin agent that improve the balance of adhesion and spreadability can be provided.

[0011] [Gel Composition] The gel composition of the present invention contains aluminum ions. When the dynamic viscoelasticity (frequency dependence) of the gel composition is measured under strain conditions in the linear region at 25°C, there exists a frequency in the frequency range of 0.001 to 100 rad / s where the loss elastic modulus G'' / storage elastic modulus G' (tanδ) is 1. At 25°C and a frequency of 62.8 rad / s, the storage elastic modulus G' of the gel composition is 500 Pa or more. Furthermore, in the present invention, the term "containing component X" is considered synonymous with "formulated from component X".

[0012] The gel composition of the present invention can improve the balance between adhesion and spreadability. Since the gel composition of the present invention has good adhesion to the skin, the skin is the preferred contact surface. Therefore, the gel composition of the present invention has particularly good skin adherence and is suitable for use in topical skin preparations. Topical skin preparations of the present invention refer to compositions applied to the skin in the fields of cosmetics, fragrances, pharmaceuticals, and quasi-pharmaceuticals.

[0013] While the reason why the gel composition of the present invention exhibits the effects of the present invention by having the above-described configuration is uncertain, it is speculated as follows. The gel composition of the present invention contains aluminum ions, and has a frequency in the frequency range of 0.001 to 100 rad / s where the loss modulus G'' / storage modulus G'(tanδ) is 1, and a storage modulus G' at 25°C and a frequency of 62.8 rad / s is 500 Pa or more. Aluminum ions can form a cross-linked gel through ion interactions. Moreover, if a frequency exists in the frequency range of 0.001 to 100 rad / s where the loss modulus G'' / storage modulus G'(tanδ) is 1, then it becomes a gel composition with the following special properties: stronger viscous properties on the low-frequency side (i.e., long-term action system) and stronger elastic properties on the high-frequency side (i.e., short-term action system). If it possesses these properties, the gel composition exhibits moderate softness and is easily stretched. Furthermore, if the storage modulus of elasticity G' is 500 Pa or higher, the gel composition exhibits moderate hardness and is not prone to flow. Because of its strong adhesive properties, the gel composition of the present invention is considered to have improved extensibility. Moreover, when in close contact with an object, in addition to possessing the adhesive force of a gel composition, it also has a moderate modulus of elasticity, thus the gel composition is not prone to flow. Through these properties, the gel composition of the present invention is considered to have improved adhesion.

[0014] <Component (A)> The gel composition of the present invention preferably contains a polymer as component (A). The polymer of component (A) forms the backbone of the gel composition. Component (A) is, for example, an anionic polymer, preferably an anionic polymer having anionic groups such as sulfonic acid group, sulfate group, carboxyl group, phosphate group, phosphonic acid group, etc., more preferably an anionic polymer having at least one anionic group of sulfonic acid group and carboxyl group, and even more preferably an anionic polymer having a carboxyl group. Examples of anionic polymers include: anionic polyvinyl alcohol, carboxylated vinyl polymers, (meth)acrylic acid / (meth)acrylate copolymers, etc., vinyl polymers having anionic groups; anionic polysaccharides such as anionic cellulose, etc. From the viewpoint of further improving the balance between adhesion and spreadability, component (A) is preferably anionic polyvinyl alcohol, more preferably polyvinyl alcohol having at least one anionic group of sulfonic acid group and carboxyl group, and even more preferably polyvinyl alcohol having a carboxyl group. In this specification, anionic groups refer to anionic groups or groups that can become anionic groups after ionization.

[0015] Examples of polyvinyl alcohol having a carboxyl group include: (1) obtained by graft polymerization or block polymerization of polyvinyl alcohol with an unsaturated monomer having a carboxyl group; (2) obtained by saponification after copolymerizing an ethylene ester compound with an unsaturated monomer having at least one selected from carboxyl and carboxylic ester groups; (3) obtained by saponification after polymerizing an ethylene ester compound using a chain transfer agent having a carboxyl group; and (4) obtained by reacting polyvinyl alcohol with a carboxylating agent.

[0016] Examples of unsaturated monomers having a carboxyl group used in methods (1) and (2) above, and unsaturated monomers having a carboxylic acid ester group used in method (2) above, include: ethylene unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itconic acid; ethylene unsaturated dicarboxylic acid monoesters such as maleic acid monoalkyl esters, fumaric acid monoalkyl esters, and itconic acid monoalkyl esters; ethylene unsaturated dicarboxylic acid diesters such as maleic acid dialkyl esters, fumaric acid dialkyl esters, and itconic acid dialkyl esters; ethylene unsaturated carboxylic acid anhydrides such as maleic anhydride and itconic anhydride; unsaturated monocarboxylic acids such as (meth)acrylic acid; and unsaturated monocarboxylic acid esters such as (meth)acrylate alkyl esters. Furthermore, salts of the above compounds can be used as unsaturated monomers having at least one selected from carboxyl and carboxylic acid ester groups. One of these compounds can be used alone, or two or more can be used in combination.

[0017] Examples of the vinyl ester compounds used in the methods (2) and (3) above include vinyl acetate, vinyl formate, vinyl propionate, vinyl terephthalate, vinyl pentanoate, etc. Of these, vinyl acetate is preferred from the viewpoint of reactivity during synthesis and ease of acquisition. One of these compounds may be used alone, or two or more may be used in combination.

[0018] Examples of carboxylating agents used in the method described in (4) above include: succinic anhydride, maleic anhydride, acetic anhydride, trimellitic anhydride, phthalic anhydride, pyromellitic anhydride, glutaric anhydride, hydrogenated phthalic anhydride, naphthalenedicarboxylic anhydride, and other carboxylic anhydrides. One of these may be used alone, or two or more may be used in combination.

[0019] Regarding the amount of anionic groups in anionized polyvinyl alcohol (derived from the ratio of monomers with anionic groups), from the viewpoint of further improving adhesion and enhancing water retention or gel strength, it is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, and even more preferably 1 mol% or more. From the viewpoint of further improving the balance between adhesion and spreadability, and enhancing water supply or moisturizing sensation when applied to the skin, it is preferably 10 mol% or less, more preferably 5 mol% or less, and even more preferably 3 mol% or less. The amount of anionic groups in anionized polyvinyl alcohol can be determined by analyzing the anionized polyvinyl alcohol before saponification using 1H-NMR (solvent: CDCl3).

[0020] Regarding the degree of saponification of anionized polyvinyl alcohol, from the viewpoint of further improving adhesion and enhancing water retention or gel strength, it is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 98 mol% or more. There is no particular upper limit to the above-mentioned degree of saponification; for example, it may be 100.0 mol% or less, preferably 99.9 mol% or less, and even more preferably 99.5 mol% or less. The degree of saponification of anionized polyvinyl alcohol was determined according to JIS K6726:1994.

[0021] Regarding the degree of polymerization of anionized polyvinyl alcohol, from the viewpoint of further improving the balance between adhesion and spreadability, and from the viewpoint of improving water retention or gel strength, it is preferably 100 or more, more preferably 500 or more, and even more preferably 1,000 or more. From the viewpoint of further improving the balance between adhesion and spreadability, it is preferably 200,000 or less, more preferably 10,000 or less, and even more preferably 4,000 or less. The degree of polymerization of anionized polyvinyl alcohol can be calculated from the relative viscosity of a fully saponified aqueous solution of polyvinyl alcohol to water (refer to JIS K6726:1994).

[0022] Specific examples of anionized polyvinyl alcohol include: KL-118, KL-318, KL-506, KM-118 and KM-618 manufactured by Kuraray Co., Ltd.; GOHSENX CKS50, GOHSENX T-330H, GOHSENX T-330 and GOHSENX T-350 manufactured by Mitsubishi Chemical Co., Ltd.; AP-17, AT-17 and AF-17 manufactured by JAPAN VAM & POVAL Co., Ltd.

[0023] Component (A) may be used alone or in combination with two or more.

[0024] Regarding the content of component (A) in the gel composition of the present invention, from the viewpoint of further improving the balance between adhesion and spreadability, and from the viewpoint of improving water retention or gel strength, it is preferably 1.0% by mass or more, more preferably 3.0% by mass or more, and even more preferably 5.0% by mass or more, and even more preferably 8.0% by mass or more. From the viewpoint of further improving the balance between adhesion and spreadability, it is preferably 30.0% by mass or less, more preferably 25.0% by mass or less, even more preferably 20.0% by mass or less, even more preferably 15.0% by mass or less, even more preferably 13.0% by mass or less, even more preferably 12.5% ​​by mass or less, and even more preferably 12.0% by mass or less.

[0025] <Component (B): Aluminum Ions> The gel composition of the present invention contains aluminum ions as component (B). The preferred source of the aluminum ions is an aluminum salt (B'). That is, the gel composition of the present invention preferably contains an aluminum salt (B'). The aluminum salt (B') is preferably water-soluble, and examples include salts of aluminum and inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, or organic acids such as acetic acid. Specific examples of aluminum salts (B') include aluminum chloride, aluminum nitrate, aluminum sulfate, and potassium aluminum sulfate. Among these, from the viewpoints of safety, availability, price, and gel properties, it is preferred to select at least one of aluminum chloride, aluminum sulfate, and potassium aluminum sulfate, and more preferably at least one of aluminum chloride and aluminum sulfate.

[0026] Aluminum salt (B') can be used alone or in combination with two or more types.

[0027] Regarding the content of aluminum salt (B') in the gel composition of the present invention, from the viewpoint of further improving the balance between adhesion and spreadability, and from the viewpoint of improving water retention or gel strength, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.10% by mass or more, further preferably 0.20% by mass or more, further preferably 0.23% by mass or more, and further preferably 0.25% by mass or more, from the viewpoint of further improving the balance between adhesion and spreadability, and from the viewpoint of improving water retention or gel strength, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and ... and further preferably 0.23% by mass or more, and further preferably 0.25% by mass or more, from the viewpoint of further improving the balance between adhesion and spreadability, and from the viewpoint of improving water retention or gel strength, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.10% by mass or more, more preferably 0.20% by mass or more, and further preferably 0.23% by mass or more, more preferably 0.25% by mass or more, and further preferably 0.25% by mass or more, from the viewpoint of further improving the balance between adhesion and spreadability, and from the viewpoint of improving water retention or gel strength, it is preferably 0.01 From the perspective of balancing adhesion and extensibility, it is preferable to be 10.0% or less by mass, more preferably 5.0% or less by mass, further preferably 2.0% or less by mass, further preferably 1.0% or less by mass, further preferably 0.80% or less by mass, further preferably 0.60% or less by mass, further preferably 0.50% or less by mass, further preferably 0.40% or less by mass, further preferably 0.36% or less by mass, and further preferably 0.34% or less by mass.

[0028] <Water> The gel composition of the present invention preferably contains water as component (C). Examples of water as component (C) include deionized water, distilled water, high-purity water, and ultrapure water.

[0029] The content of component (C) in the gel composition of the present invention is preferably the remaining amount excluding component (A), aluminum salt (B'), and other components described below. Regarding the content of component (C) in the gel composition of the present invention, from the viewpoint of adjusting the gel composition to an appropriate viscosity and improving the stability of the gel composition or the moisturizing sensation when applied to the skin, it is preferably 65.0% by mass or more, more preferably 70.0% by mass or more, further preferably 75.0% by mass or more, further preferably 78.0% by mass or more, further preferably 80.0% by mass or more, further preferably 83.0% by mass or more. Similarly, from the same viewpoint, it is preferably 98.99% by mass or less, more preferably 98.0% by mass or less, further preferably 96.0% by mass or less, further preferably 94.0% by mass or less.

[0030] <Ratio of each component> In the gel composition of the present invention, the mass ratio ((C) / (A)) of component (C) to component (A) is preferably 1.0 or more, more preferably 2.0 or more, more preferably 3.0 or more, more preferably 4.0 or more, from the viewpoint of further improving the balance of adhesion and spreadability, and from the viewpoint of improving water retention or gel strength, preferably 20.0 or less, more preferably 16.0 or less, more preferably 14.0 or less, more preferably 12.0 or less, more preferably 11.0 or less.

[0031] In the gel composition of the present invention, the mass ratio ((B') / (A)) of aluminum salt (B') to component (A) is preferably 0.001 or more, more preferably 0.005 or more, more preferably 0.010 or more, more preferably 0.020 or more, more preferably 0.025 or more, and more preferably 0.500 or less, more preferably 0.200 or less, more preferably 0.120 or less, more preferably 0.080 or less, more preferably 0.060 or less, and more preferably 0.040 or less, from the viewpoint of further improving the balance between adhesion and spreadability.

[0032] <Sulfate Ions> From the viewpoint of exhibiting better gel properties even after storage, the gel composition of the present invention may further contain sulfate ions. Sulfate ions may be ions derived from component (B'), or ions derived from sulfates or sulfuric acids other than component (B'). Examples of sulfates other than component (B') include sodium sulfate, potassium sulfate, magnesium sulfate, zinc sulfate, and ferric sulfate. In the gel composition of the present invention, regarding the molar ratio of sulfate ions to aluminum ions (SO42- / Al3+), from the viewpoint of adjusting the viscosity during storage, it is preferably 0.08 or more, more preferably 0.09 or more, further preferably 0.10 or more, further preferably 0.11 or more, further preferably 0.13 or more, further preferably 0.15 or more; and from the viewpoint of adjusting the viscosity during storage, it is preferably 1.45 or less, more preferably 0.50 or less, further preferably 0.45 or less, further preferably 0.35 or less, further preferably 0.27 or less, further preferably 0.25 or less, further preferably 0.23 or less, further preferably 0.20 or less. Here, the aforementioned aluminum ions are generally ions derived from component (B').

[0033] <Other Ingredients> The gel composition of the present invention may also contain other ingredients within a range that does not impair the purpose of the present invention. Examples of other ingredients include those commonly used in cosmetics, fragrances, pharmaceuticals, and quasi-pharmaceuticals. Examples of ingredients commonly used in such products include polymers other than anionized polymers, moisturizers, whitening agents, blood circulation promoters, anti-inflammatory agents, bactericides, ultraviolet absorbers, colorants, preservatives, antioxidants, fragrances, pH adjusters, chelating agents, water-retaining agents, pharmaceuticals, alcohols, etc.

[0034] <pH Value> Regarding the pH value of the gel composition of the present invention at 25°C, from the viewpoint of suppressing stickiness and improving water retention or gel strength, it is preferably 2.0 or higher, more preferably 2.5 or higher, and even more preferably 2.8 or higher, and even more preferably 3.0 or higher. From the viewpoint of improving adhesion, improving softness or elongation, and improving water supply or moisturizing sensation when applied to the skin, it is preferably 6.5 or lower, more preferably 6.0 or lower, even more preferably 5.5 or lower, and even more preferably 5.0 or lower. Specifically, the pH value of the gel composition of the present invention at 25°C can be measured by the method described in the examples.

[0035] <Dynamic Viscoelasticity> From the viewpoint of further improving the balance between adhesion and spreadability, the gel composition of the present invention preferably has a loss modulus G'' > storage modulus G' in the region where the frequency is lower than the frequency at which tanδ becomes 1, and a storage modulus G' > loss modulus G'' in the region where the frequency is higher than the frequency at which tanδ becomes 1. In the present invention, as shown below, the storage modulus G' and loss modulus G'' can be used at a frequency of 62.8 rad / s in the region where the frequency of the gel composition is higher than the frequency at which tanδ becomes 1 at 25°C, and at a frequency of 0.135 rad / s in the region where the frequency is lower than the frequency at which tanδ becomes 1.

[0036] In the gel composition of the present invention, regarding the frequency at which the above-mentioned tanδ becomes 1, from the viewpoint of further improving the balance between adhesion and spreadability, it is preferably 0.1 rad / s or more, more preferably 1.0 rad / s or more, and even more preferably 1.5 rad / s or more, and even more preferably 2.5 rad / s or more. From the same viewpoint, it is preferably 30.0 rad / s or less, more preferably 20.0 rad / s or less, even more preferably 15.0 rad / s or less, even more preferably 10.0 rad / s or less, even more preferably 8.0 rad / s or less, and even more preferably 6.5 rad / s or less.

[0037] Regarding the storage elastic modulus G' (25°C, frequency: 62.8 rad / s) of the gel composition of the present invention, from the viewpoint of improving the balance between adhesion and spreadability, and from the viewpoint of improving water retention or gel strength, it is 500 Pa or more, preferably 700 Pa or more, more preferably 900 Pa or more, and even more preferably 1,500 Pa or more, and even more preferably 1,800 Pa or more. From the viewpoint of further improving spreadability, it is preferably 15,000 Pa or less, more preferably 10,000 Pa or less, even more preferably 9,500 Pa or less, even more preferably 8,000 Pa or less, even more preferably 7,000 Pa or less, and even more preferably 6,500 Pa or less.

[0038] Regarding the ratio (G'' / G'(tanδ)) of the loss elastic modulus G'' (25°C, frequency: 62.8 rad / s) to the storage elastic modulus G' (25°C, frequency: 62.8 rad / s) of the gel composition of the present invention, from the viewpoint of further improving adhesion and further improving extensibility, it is preferably 0.10 or more, more preferably 0.15 or more, and even more preferably 0.20 or more, and even more preferably 0.25 or more. From the same viewpoint, it is preferably 1.0 or less, more preferably 0.70 or less, even more preferably 0.50 or less, even more preferably 0.40 or less, and even more preferably 0.35 or less.

[0039] Furthermore, regarding the ratio (G'' / G'(tanδ)) of the loss elastic modulus G'' (25°C, frequency: 0.135 rad / s) to the storage elastic modulus G' (25°C, frequency: 0.135 rad / s) of the gel composition of the present invention, from the viewpoint of further improving adhesion and improving extensibility, it is preferably 0.10 or more, more preferably 0.50 or more, more preferably 0.80 or more, more preferably 1.0 or more, more preferably 1.5 or more, more preferably 1.8 or more. From the same viewpoint, it is preferably 10.0 or less, more preferably 5.0 or less, more preferably 4.0 or less, more preferably 3.5 or less, more preferably 3.3 or less, more preferably 3.2 or less.

[0040] Regarding the storage elastic modulus G' (25°C, frequency: 0.135 rad / s) of the gel composition of the present invention, from the viewpoint of improving the balance between adhesion and spreadability, and from the viewpoint of improving water retention or gel strength, it is preferably 1 Pa or more, more preferably 5 Pa or more, more preferably 10 Pa or more, more preferably 15 Pa or more, more preferably 20 Pa or more. From the viewpoint of improving spreadability, it is preferably 5,000 Pa or less, more preferably 2,000 Pa or less, more preferably 1,000 Pa or less, more preferably 800 Pa or less, more preferably 500 Pa or less, more preferably 300 Pa or less, more preferably 200 Pa or less.

[0041] The storage elastic modulus G' and loss elastic modulus G'' of the gel composition of the present invention can be measured using a rheometer (fixture: 25 mm in diameter, made of PP, plate: parallel plate, 8 mm in diameter) under the conditions of temperature: 25°C, frequency: 10-3 to 102 rad / s, and strain: within the linear region. More specifically, they can be measured by the method described in the examples.

[0042] <Manufacturing Method> As a method for manufacturing the gel composition of the present invention, it can be manufactured, for example, by dissolving the polymer in water to prepare an aqueous solution (A), dissolving the aluminum salt (B') in water to prepare an aqueous solution (B) containing aluminum ions, and mixing the obtained aqueous solution (A) and aqueous solution (B) using a known stirring device or the like.

[0043] [Topical Skin Agents] The gel composition of the present invention is suitable for use as a topical skin agent. That is, the topical skin agent of the present invention comprises the gel composition of the present invention described above. The topical skin agent of the present invention is applied to the skin, preferably to any part of the face, torso, hands, feet, etc., other than the scalp. It can be freely stretched or expanded during use, has good adhesion to the skin, provides the user with a comfortable cooling sensation and feel, is non-sticky, and is easily peeled off from the skin after use. Even when filled into a portable container such as a tube or bag, the topical skin agent of the present invention is easy to remove without leaving any residue in the container.

[0044] The topical skin agent of the present invention is a composition applied to the skin in the fields of cosmetics, perfumes, pharmaceuticals, and quasi-pharmaceuticals, preferably a gel-like skin care agent, more preferably a skin care film, and even more preferably a skin care mask.

[0045] The method of using the gel composition of the present invention can be exemplified by the following method. First, the gel composition is stretched to an appropriate size and applied to the skin, or the gel composition is applied to the skin and then stretched to an appropriate size. Then, it is left on the skin for a certain period of time, preferably 1 minute to 8 hours, more preferably 5 minutes to 1 hour. Afterward, the gel composition is peeled off from the skin. The gel composition can be easily peeled off. This allows for a good skin care effect. Furthermore, the gel composition can be used while massaging, either directly with the hands or with a sponge or other tools.

[0046] Furthermore, the present invention provides a skin moisturizing method by applying the gel composition of the present invention to the skin to moisturize the skin. [Example]

[0047] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.

[0048] [Preparation of Gel Composition] Example 1 (1) Preparation of Polymer Aqueous Solution Anionized PVA (product name: GOHSENX (registered trademark) T-330H, manufactured by Mitsubishi Chemical Corporation, degree of polymerization = 2,000, degree of saponification > 99.0 moles, carboxylic acid modified) 19.0 g and 192.1 g of deionized water were added to a 2 L container and stirred at 90°C for more than 2 hours to obtain an 9% by mass anionized PVA aqueous solution.

[0049] (2) Preparation of aluminum salt aqueous solution: 144.9 g of aluminum(III) hexahydrate (manufactured by Fujifilm and Koko Pure Chemical Industries Co., Ltd.) and 1188.5 g of ion-exchanged water were added to a 2 L container and stirred at 50°C for more than 1 hour to obtain a 6% aluminum chloride aqueous solution by mass.

[0050] (3) Preparation of the gel composition: 60.0 g of 9% anionized PVA aqueous solution and 2.57 g of 6% aluminum chloride aqueous solution prepared at 25°C were added to a 100 mL container (for mixing). The mixture was stirred for 10 minutes using a mixing machine (name: HM-500, manufactured by Keyence Corporation) (rotation conditions: 2000 revolutions / 800 rotations, acceleration: 400 G) to obtain the gel composition.

[0051] Example 2 In the preparation of the gel composition in (3) of Example 1, “60.0 g of 10% by mass anionized PVA and 2.85 g of 6% by mass aluminum chloride aqueous solution” was used instead of “60.0 g of 9% by mass anionized PVA aqueous solution and 2.57 g of 6% by mass aluminum chloride aqueous solution”. Otherwise, the gel composition was obtained in the same manner as in Example 1.

[0052] Example 3 (1) Preparation of polymer aqueous solution 11% by mass of anionized PVA aqueous solution was obtained by the same method as in Example 1.

[0053] (2) Preparation of aluminum salt aqueous solution: 10.0 g of aluminum(III) hexahydrate (manufactured by Fujifilm and Koko Pure Chemical Industries Co., Ltd.) and 45.2 g of deionized water were added to a 100 mL container and stirred at 50°C for more than 1 hour to obtain a 10% aluminum chloride aqueous solution. 10.0 g of aluminum sulfate octahydrate (manufactured by SIGMA-ALDRICH) and 75.6 g of deionized water were added to a 100 mL container and stirred at 50°C for more than 1 hour to obtain a 6% aluminum sulfate aqueous solution. 29.0 g of the obtained 10% aluminum chloride aqueous solution and 10.0 g of the 6% aluminum sulfate aqueous solution were mixed to obtain an aluminum chloride / aluminum sulfate aqueous solution.

[0054] (3) Preparation of the gel composition In the preparation of the gel composition in Example 1 above (3), "60.0 g of 11% by mass anionized PVA aqueous solution and 2.18 g of aluminum chloride / aluminum sulfate aqueous solution" were used instead of "60.0 g of 9% by mass anionized PVA aqueous solution and 2.57 g of 6% by mass aluminum chloride aqueous solution". Otherwise, the gel composition was obtained in the same manner as in Example 1.

[0055] Example 4 In the preparation of the gel composition described in (3) of Example 1, “60.0 g of 11% by mass anionized PVA and 3.14 g of 6% by mass aluminum chloride aqueous solution” was used instead of “60.0 g of 9% by mass anionized PVA aqueous solution and 2.57 g of 6% by mass aluminum chloride aqueous solution”. Otherwise, the gel composition was obtained in the same manner as in Example 1.

[0056] Example 5 In the preparation of the gel composition in Example 1 (3) above, “60.0 g of 12% by mass anionized PVA and 3.42 g of 6% by mass aluminum chloride aqueous solution” was used instead of “60.0 g of 9% by mass anionized PVA aqueous solution and 2.57 g of 6% by mass aluminum chloride aqueous solution”. Otherwise, the gel composition was obtained in the same manner as in Example 1.

[0057] Example 6 In the preparation of the gel composition described in (3) of Example 1, “60.0 g of 13% by mass anionized PVA and 3.71 g of 6% by mass aluminum chloride aqueous solution” was used instead of “60.0 g of 9% by mass anionized PVA aqueous solution and 2.57 g of 6% by mass aluminum chloride aqueous solution”. Otherwise, the gel composition was obtained in the same manner as in Example 1.

[0058] Example 7 In the preparation of the gel composition in Example 1 (3) above, “60.0 g of 14% by mass anionized PVA and 3.99 g of 6% by mass aluminum chloride aqueous solution” was used instead of “60.0 g of 9% by mass anionized PVA aqueous solution and 2.57 g of 6% by mass aluminum chloride aqueous solution”. Otherwise, the gel composition was obtained in the same manner as in Example 1.

[0059] Example 8 In the preparation of the gel composition described in (3) of Example 1, “60.0 g of 15% by mass anionized PVA and 4.28 g of 6% by mass aluminum chloride aqueous solution” was used instead of “60.0 g of 9% by mass anionized PVA aqueous solution and 2.57 g of 6% by mass aluminum chloride aqueous solution”. Otherwise, the gel composition was obtained in the same manner as in Example 1.

[0060] Example 9 In the preparation of the gel composition described in (3) of Example 1, “60.0 g of 8% anionized PVA and 2.28 g of 6% aluminum chloride aqueous solution” was used instead of “60.0 g of 9% anionized PVA aqueous solution and 2.57 g of 6% aluminum chloride aqueous solution”. Otherwise, the gel composition was obtained in the same manner as in Example 1.

[0061] Example 10 In the preparation of the gel composition described in (3) of Example 1, “60.0 g of 7% anionized PVA and 2.00 g of 6% aluminum chloride aqueous solution” was used instead of “60.0 g of 9% anionized PVA aqueous solution and 2.57 g of 6% aluminum chloride aqueous solution”. Otherwise, the gel composition was obtained in the same manner as in Example 1.

[0062] Example 11 In the preparation of the gel composition in Example 1 (3), "60.0 g of 11% by mass anionized PVA aqueous solution, 0.78 g of 6% by mass aluminum chloride aqueous solution, and 0.52 mL of 1 mol / L hydrochloric acid (manufactured by Fujifilm and Koko Pure Chemical Industries, Ltd.)" was used instead of "60.0 g of 9% by mass anionized PVA aqueous solution and 2.57 g of 6% by mass aluminum chloride aqueous solution". Otherwise, the gel composition was obtained using the same method as in Example 1.

[0063] Comparative Example 1 In the preparation of the gel composition described in (3) of Example 1, “60.0 g of 6% anionized PVA and 1.71 g of 6% aluminum chloride aqueous solution” was used instead of “60.0 g of 9% anionized PVA aqueous solution and 2.57 g of 6% aluminum chloride aqueous solution”. Otherwise, the gel composition was obtained in the same manner as in Example 1.

[0064] Comparative Example 2 In the preparation of the gel composition described in (3) of Example 1, “60.0 g of 11% by mass anionized PVA and 0.78 g of 6% by mass aluminum chloride aqueous solution” was used instead of “60.0 g of 9% by mass anionized PVA aqueous solution and 2.57 g of 6% by mass aluminum chloride aqueous solution”. Otherwise, the gel composition was obtained in the same manner as in Example 1.

[0065] [Physical Property Measurement and Evaluation] The following physical properties were measured and evaluated for the gel compositions obtained in the Examples and Comparative Examples. The evaluation results are shown in Table 1. The amounts of each component in Table 1 are expressed as mass%.

[0066] <pH value of gel composition> A 100 mL container is filled with gel composition, and a glass electrode (manufactured by Horiba Manufacturing Co., Ltd., product name: 9681S-10D) is inserted into the gel composition at 25°C to measure the pH value of the gel composition at 25°C.

[0067] <Storage elastic modulus G' and loss elastic modulus G'' of the gel composition> The storage elastic modulus G' and loss elastic modulus G'' of the gel composition were determined using a rheometer under the following conditions. Machine: MRC302 (manufactured by Anton Paar) Fixture: PP25 (diameter: 24.985 mm) Plate: LOWER MEASURING PLATE L-PP08 / CTD, D: 8 mm FOR CTD450 / 600 / 1000 Temperature: 25℃ Frequency: 10⁻³~10² rad / s Strain: within the linear region (1% strain in this embodiment) Based on the measurement curves obtained under the above measurement conditions, the stored elastic modulus G' (frequency: 62.8 rad / s, 0.135 rad / s), loss elastic modulus G'' (frequency: 62.8 rad / s, 0.135 rad / s), tanδ (frequency: 62.8 rad / s, 0.135 rad / s), and the frequency at which tanδ becomes 1 were obtained.

[0068] <Evaluation of Skin Adhesion> The skin adhesion of the gel composition was evaluated by five professional sensory examiners. Specifically, 2 g / 9 cm² (3 cm × 3 cm) of the gel composition was applied to the back of the hand. The back of the hand was then rotated 180° for 120 seconds, and the dripping state of the gel composition was observed. The skin adhesion of the gel composition was evaluated based on the following evaluation criteria: (Evaluation Criteria) 1: Drips within 30 seconds 2: Drips within 120 seconds but more than 30 seconds 3: No dripping, but the gel composition flows slightly 4: No dripping at all The average values ​​of the evaluations obtained by the five sensory examiners are shown in Table 1.

[0069] <Evaluation of Spreadability> The spreadability of the gel composition was evaluated by 5 professional sensory inspectors. Specifically, the spreadability of the gel composition (2 g / 9 cm2 (3 cm × 3 cm)) was evaluated by holding both ends and stretching it, based on the following evaluation criteria: (Evaluation Criteria) 1: The gel composition cannot be held by hand (cannot be stretched) 2: The gel composition can be held by hand, and although it stretches, it breaks easily 3: The gel composition can be held by hand and stretches well 4: The gel composition can be held by hand and stretches very well The average value of the evaluations obtained by the 5 sensory inspectors is shown in Table 1.

[0070] [Table 1] Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Comparative Example 1 Comparative Example 2 A polymer type Carboxylated PVA Carboxylated PVA Carboxylated PVA Carboxylated PVA Carboxylated PVA Carboxylated PVA Carboxylated PVA Carboxylated PVA Carboxylated PVA Carboxylated PVA Carboxylated PVA Carboxylated PVA Carboxylated PVA Quantity (mass%) 8.6 9.5 10.6 10.5 11.4 12.2 13.1 14.0 7.7 6.8 10.8 5.8 10.9 B' Aluminum salts type Al chloride Al chloride Al chloride Al chloride Al chloride Al chloride Al chloride Al chloride Al chloride Al chloride Al chloride Al chloride Al chloride Quantity (mass%) 0.25 0.27 0.26 0.30 0.32 0.35 0.37 0.40 0.22 0.19 0.08 0.17 0.077 type - - Al sulfate - - - - - - - - - - Quantity (mass%) - - 0.05 - - - - - - - - - - C water Quantity (mass%) 91.1 90.2 89.1 89.2 88.3 87.4 86.5 85.6 92.1 93.0 89.2 94.0 89.1 C / A Water / polymer (mass ratio) 10.6 9.4 8.4 8.5 7.8 7.1 6.6 6.1 11.9 13.7 8.3 16.1 8.2 B' / A Aluminum salt / polymer (mass ratio) 0.029 0.029 0.030 0.029 0.029 0.029 0.029 0.029 0.029 0.029 0.007 0.029 0.007 G' (Pa, frequency 62.8 rad / s) 2188 3344 4356 4607 6005 8475 9832 10390 1337 847 685 469 1001 G''(Pa, frequency 62.8 rad / s) 743 1051 1367 1365 1696 2208 2523 2634 486 331 331 198 551 tanδ(G'' / G', frequency 62.8 rad / s) 0.34 0.31 0.31 0.30 0.28 0.26 0.26 0.25 0.36 0.39 0.48 0.42 0.55 G' (Pa, frequency 0.135 rad / s) 26 68 91 105 150 307 340 407 14 8 8 1 116 G'' (Pa, frequency 0.135 rad / s) 83 153 194 211 300 486 565 613 48 29 29 11 105 tanδ(G'' / G', frequency 0.135 rad / s) 3.1 2.3 2.1 2.0 2.0 1.6 1.7 1.5 3.5 3.5 3.5 7.5 0.9 The frequency (rad / s) of G' / G'' = 1 6.0 4.0 3.0 4.0 3.0 2.0 2.0 2.0 7.0 7.0 15.0 12.0 none pH adjuster - - - - - - - - - - hydrochloric acid - - pH value (gel) 4.1 4.1 4.1 4.1 4.1 4.1 4.1 4.0 4.1 4.2 4.5 4.2 5.1 evaluate skin contact 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 3.2 3.0 3.0 1.2 3.0 Scalability 4.0 4.0 4.0 4.0 4.0 3.6 3.4 2.4 3.8 3.8 3.4 1.8 1.2

[0071] As can be understood from Table 1, compared with the gel composition of the comparative example, the gel composition of the example improves the balance of skin adhesion and spreadability. That is, according to the present invention, it is possible to provide a gel composition and a topical skin agent that improves the balance of adhesion and spreadability.

Claims

1. A gel composition comprising the following components (A) to (C): (A) an anionized polymer at 5.0% to 20.0% by mass, (B) an aluminum salt as a source of aluminum ions at 0.05% to 0.50% by mass, and (C) water, wherein component (A) is a polyvinyl alcohol having a carboxyl group, the polyvinyl alcohol having a saponification degree of 90 mol% or more, a polymerization degree of 500 to 4000 or less, and a carboxyl group content of 0.1 mol% to 10 mol% or less, wherein when the above gel composition is subjected to dynamic viscoelasticity (frequency dependence) measurement under strain conditions in the linear region at 25°C, there exists a frequency in the frequency region of 0.001 to 100 rad / s where the loss elastic modulus G'' / storage elastic modulus G'(tanδ) is 1, and the storage elastic modulus G' of the above gel composition at 25°C and a frequency of 62.8 rad / s is 500 Pa or more.

2. The gel composition of claim 1, wherein the storage elastic modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is 15,000 Pa or less.

3. The gel composition of claim 1 or 2, wherein the mass ratio of water to the anionized polymer (water / anionized polymer) is 1.0 or more and 20.0 or less.

4. The gel composition of claim 1 or 2, wherein in the region of frequency below the frequency at which tanδ becomes 1, the loss modulus G'' > the storage modulus G', and in the region of frequency above the frequency at which tanδ becomes 1, the storage modulus G' > the loss modulus G''.

5. The gel composition of claim 1 or 2, wherein the frequency at which the above-mentioned tanδ becomes 1 is 0.1 rad / s or more and 30.0 rad / s or less.

6. The gel composition of claim 1 or 2, wherein the storage elastic modulus G' of the gel composition at 25°C and a frequency of 0.135 rad / s is more than 1 Pa and less than 5,000 Pa.

7. The gel composition of claim 1 or 2, further comprising sulfate ions.

8. The gel composition of claim 7, wherein the molar ratio (SO42- / Al3+) of the sulfate ions contained in the gel composition to the aluminum ions is 0.08 or more and 1.45 or less.

9. A topical skin preparation comprising a gel composition as claimed in any one of claims 1 to 8.