Gel composition

Abstract

The present invention relates to [1] a gel composition and [2] a skin external preparation containing the same. The gel composition contains aluminum ions, and when dynamic viscoelasticity measurement (frequency dependence) is performed on the gel composition in a linear region at 25°C under a strain condition, there is a frequency at which the loss modulus G" / the storage modulus G' (tan δ) is 1 in the range of 0.001 to 100 rad / s, and the storage modulus G' of the gel composition at 25°C at a frequency of 62.8 rad / s is 500 Pa or more.

Description

Technical Field

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

[0002] Gel compositions have been widely used in various fields such as pharmaceuticals, quasi-drugs, cosmetics, fragrances, coatings, adhesives, bonding agents, packaging materials, emulsifiers, suspending agents, water-retaining agents, surfactants, fiber treatment agents, and paper processing agents.

[0003] As a technology involving gel compositions, there are, for example, the technologies described in Patent Documents 1 and 2.

[0004] Japanese Patent Application Publication No. 55-127311 (Patent Document 1) discloses a facial mask cosmetic, characterized by: a sol obtained by adding a divalent metal lactate or chloride to an aqueous solution of polyvinyl alcohol as a first agent, and a sol obtained by adding borax to an aqueous solution of sodium, potassium, or triethanolamine salts of alginate as a second agent. By combining the two, a gel film of the first and second agents is formed. This facial mask cosmetic hardly changes over time even when applied to the skin for a long time, and the peeling time can be freely changed. It can also maintain a state of continuous adsorption of moisture. Therefore, it is very effective from the perspective of skin physiology and cosmetic effect.

[0005] Japanese Patent Application Publication No. 2020-152869 (Patent Document 2) discloses a polyvinyl alcohol gel molded article having a structure formed by crosslinking a polyvinyl alcohol polymer with a titanium chelate compound, which has excellent strength.

[0006] Patent Document 2's polyvinyl alcohol gel molded articles are mainly envisioned for use as carriers for microbial fixation, water-retaining materials, cold-retaining materials, and filter materials, and are not envisioned for use in cosmetics, fragrances, pharmaceuticals, quasi-drugs, or as gel-like skin care agents.

[0007] In addition, as a technology involving compositions containing polyvinyl alcohol, there is, for example, the technology described in Japanese Patent Application Publication No. 11-1595 (Patent Document 3).

[0008] Patent document 3 describes an aqueous composition consisting of (A) a modified polyvinyl alcohol containing 0.1 to 20 mol% of carboxyl groups and (B) a water-soluble aluminum compound, wherein the solid component ratio (A) / (B) is 100 / 0.01 to 100 / 50 by weight. The aqueous composition exhibits a significant increase in viscosity as water evaporates, and has significantly superior initial adhesion.

[0009] The aqueous composition in Patent Document 3 is primarily envisioned for use as a paper processing adhesive, woodworking adhesive, fiber treatment agent, binder, coating, etc., where it is cured by evaporating water. It is not envisioned for use in cosmetics, fragrances, pharmaceuticals, quasi-drugs, or as a gel-like skin care agent. Summary of the Invention

[0010] This invention relates to a gel composition containing aluminum ions. When the dynamic viscoelasticity (frequency-dependent) of the gel composition is measured under strain conditions in a linear region at 25°C, there exists a frequency in the frequency range of 0.001 to 100 rad / s where the loss modulus G” / storage modulus G’ (tanδ) is 1. The storage modulus G’ of the gel composition at 25°C and a frequency of 62.8 rad / s is 500 Pa or more. Detailed Implementation

[0011] As for film products such as skin care films, there are sheet films made by permeating liquid into non-woven fabrics. However, such sheet films do not have sufficient adhesion and stretchability to the skin, resulting in poor skin fit. Here, the gel compositions described in Patent Documents 1 and 2 and the polyvinyl alcohol materials described in Patent Document 3 have not been studied regarding their adhesion and stretchability to the skin.

[0012] This invention relates to a gel composition and a topical skin agent that achieves an improved balance between adhesion and stretchability.

[0013] The inventors of this invention discovered that a gel composition containing aluminum ions, and a frequency at which the loss modulus G” / storage modulus G’ is 1, and a gel composition with a storage modulus G’ within a specific range at a specific frequency, can improve the balance between adhesion and tensile strength, thus completing this invention.

[0014] That is, the present invention relates to the following [1] and [2].

[0015] [1] A gel composition, wherein the gel composition contains aluminum ions, and when the dynamic viscoelasticity (frequency dependence) of the gel composition is measured under strain conditions in a linear region at 25°C, there exists 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 the storage modulus G’ of the gel composition at 25°C and a frequency of 62.8 rad / s is 500 Pa or more.

[0016] [2] A topical skin preparation comprising the gel composition described in [1] above.

[0017] According to the present invention, a gel composition and a topical skin agent with an improved balance of adhesion and stretchability can be provided.

[0018] [Gel Composition]

[0019] The gel composition of the present invention is a gel composition containing aluminum ions, wherein, when the dynamic viscoelasticity (frequency dependence) of the above gel composition is measured under strain conditions in the linear region at 25°C, there is 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 the storage modulus G’ of the above gel composition at 25°C and a frequency of 62.8 rad / s is 500 Pa or more.

[0020] In this invention, "containing ingredient X" is considered to have the same meaning as "formed by combining ingredient X".

[0021] The gel composition of the present invention improves the balance between adhesion and stretchability. The gel composition of the present invention exhibits good adhesion to the skin; therefore, the skin is the preferred target for adhesion. Consequently, the gel composition of the present invention has particularly good skin adhesion and is suitable for topical skin applications. Topical skin applications of the present invention refer to compositions suitable for use on the skin in the fields of cosmetics, fragrances, pharmaceuticals, and quasi-drugs.

[0022] The effects of the present invention are achieved by using the gel composition of the present invention with the above-described structure. The reason for this is not yet certain, but it is speculated as follows.

[0023] 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 the storage modulus G’ at 25°C and a frequency of 62.8 rad / s is 500 Pa or more.

[0024] Aluminum ions can form cross-linked gels through ion interactions.

[0025] Furthermore, within the frequency range of 0.001–100 rad / s, when the loss modulus G” / storage modulus G’ (tanδ) is 1, the gel composition exhibits the following unique properties: at low frequencies (i.e., during prolonged operation), it exhibits stronger viscous properties; at high frequencies (i.e., during short-term operation), it exhibits stronger elastic properties. With these properties, the gel composition achieves appropriate softness and is easily stretched. Additionally, when the storage modulus G’ is 500 Pa or higher, the gel composition achieves appropriate hardness and is less prone to flow.

[0026] It is believed that gel compositions possessing such special properties have strong adhesiveness, thus improving the stretchability of the gel compositions of the present invention. Furthermore, when bonded to an object, in addition to the adhesive force of the gel composition, it also possesses an appropriate elastic modulus, therefore, the gel composition is not prone to flow. It is believed that due to these properties, the adhesiveness of the gel compositions of the present invention is improved.

[0027] <Ingredients (A)>

[0028] 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.

[0029] Component (A) is, for example, an anionized polymer, preferably an anionized polymer having anionized groups such as sulfonic acid group, sulfuric acid group, carboxyl group, phosphoric acid group, phosphonic acid group, etc., more preferably an anionized polymer having at least one anionized group among sulfonic acid group and carboxyl group, and even more preferably an anionized polymer having carboxyl group.

[0030] Examples of anionized polymers include anionized polyvinyl alcohol, carboxylated vinyl polymers, (meth)acrylic acid / (meth)acrylate copolymers, and other vinyl polymers with anionic groups; anionized cellulose and other anionized polysaccharides.

[0031] From the viewpoint of further improving the balance between tightness and tensile strength, component (A) is preferably anionic polyvinyl alcohol, more preferably polyvinyl alcohol having at least one anionic group among sulfonic acid group and carboxyl group, and even more preferably polyvinyl alcohol having carboxyl group.

[0032] In this specification, an anionic group refers to an anionic group or a group that can become an anionic group through ionization.

[0033] Examples of polyvinyl alcohols containing carboxyl groups include: (1) polyvinyl alcohols containing carboxyl groups obtained by graft polymerization or block polymerization of polyvinyl alcohol with an unsaturated monomer containing a carboxyl group; (2) polyvinyl alcohols containing carboxyl groups obtained by saponification after copolymerizing a vinyl ester compound with an unsaturated monomer having at least one of a carboxyl group and a carboxylic acid ester group; (3) polyvinyl alcohols containing carboxyl groups obtained by saponification after polymerizing a vinyl ester compound using a chain transfer agent containing a carboxyl group; and (4) polyvinyl alcohols containing carboxyl groups obtained by reacting a carboxylating agent with polyvinyl alcohol.

[0034] 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), include olefinic unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; olefinic unsaturated dicarboxylic acid monoesters such as monoalkyl maleate, monoalkyl fumaric acid, and monoalkyl itaconic acid; olefinic unsaturated dicarboxylic acid diesters such as dialkyl maleate, dialkyl fumaric acid, and dialkyl itaconic acid; olefinic unsaturated carboxylic anhydrides such as maleic anhydride and itaconic anhydride; unsaturated monocarboxylic acids such as (meth)acrylic acid; and unsaturated monocarboxylic acid esters such as (meth)acrylate. Additionally, salts of the above-mentioned compounds can be used as unsaturated monomers having at least one of a carboxyl group and a carboxylic acid ester group.

[0035] These compounds can be used alone or in combination of two or more.

[0036] Examples of vinyl ester compounds used in methods (2) and (3) above include vinyl acetate, vinyl formate, vinyl propionate, vinyl tert-carbonate, and vinyl neopentanoate. Among these, vinyl acetate is preferred from the viewpoint of reactivity during synthesis and ease of acquisition.

[0037] These compounds can be used alone or in combination of two or more.

[0038] As the carboxylating agent used in the method described above (4), examples include succinic anhydride, maleic anhydride, acetic anhydride, trimellitic anhydride, phthalic anhydride, pyromellitic anhydride, glutaric anhydride, hydrogenated phthalic anhydride, naphthalenedicarboxylic anhydride, and other carboxylic anhydrides.

[0039] These can be used individually or in combination with two or more.

[0040] Regarding the amount of anionic groups in anionic polyvinyl alcohol (the proportion of monomers having anionic groups), from the viewpoint of further improving adhesion and improving water retention and 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 stretchability, as well as improving water supply and 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.

[0041] The amount of anionic groups in anionized polyvinyl alcohol can be determined by using 1 The determination was made by analyzing the anionized polyvinyl alcohol before saponification using 1H-NMR (solvent: CDCl3).

[0042] From the viewpoint of further improving the adhesion and the water retention and gel strength, the degree of saponification of the anionized polyvinyl alcohol is 90 mol% or more, more preferably 95 mol% or more, and even more preferably 98 mol% or more. The upper limit of the above-mentioned degree of saponification is not particularly limited, for example, it is 100.0 mol% or less, preferably 99.9 mol% or less, and more preferably 99.5 mol% or less.

[0043] The degree of saponification of anionized polyvinyl alcohol was determined according to JIS K6726:1994.

[0044] Regarding the degree of polymerization of anionic polyvinyl alcohol, from the viewpoint of further improving the balance between adhesion and stretchability, as well as improving water retention and 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 stretchability, it is preferably 200,000 or less, more preferably 10,000 or less, and even more preferably 4,000 or less.

[0045] The degree of polymerization of anionized polyvinyl alcohol can be calculated using the relative viscosity of a fully saponified aqueous solution of polyvinyl alcohol to water (refer to JIS K6726:1994).

[0046] 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 Corporation; and AP-17, AT-17 and AF-17 of JAPAN VAM&POVAL CO.,LTD.

[0047] Component (A) can be used alone or in combination with two or more.

[0048] 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 stretchability, as well as improving water retention and gel strength, it is preferably 1.0% by mass or more, more preferably 3.0% by mass or more, even more preferably 5.0% by mass or more, even more preferably 8.0% by mass or more. From the viewpoint of further improving the balance between adhesion and stretchability, 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, even more preferably 12.0% by mass or less.

[0049] <Component (B): Aluminum ions>

[0050] The gel composition of the present invention contains aluminum ions as a 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').

[0051] The aluminum salt (B') is preferably water-soluble, and examples include salts of aluminum with inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid, or organic acids such as acetic acid.

[0052] 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 preferable 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.

[0053] Aluminum salts (B') can be used alone or in combination with two or more.

[0054] 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 stretchability, as well as improving water retention and gel strength, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.10% by mass or more, even more preferably 0.20% by mass or more, even more preferably 0.23% by mass or more, even more preferably 0.25% by mass or more. From the viewpoint of further improving the balance between adhesion and stretchability, it is preferably 10.0% by mass or less, more preferably 5.0% by mass or less, even more preferably 2.0% by mass or less, even more preferably 1.0% by mass or less, even more preferably 0.80% by mass or less, even more preferably 0.60% by mass or less, even more preferably 0.50% by mass or less, even more preferably 0.40% by mass or less, even more preferably 0.36% by mass or less, even more preferably 0.34% by mass or less.

[0055] <Water>

[0056] The gel composition of the present invention preferably contains water as a component (C).

[0057] Water as component (C) can be categorized as, for example, deionized water, distilled water, high-purity water, ultrapure water, etc.

[0058] The content of component (C) in the gel composition of the present invention is preferably the balance after deducting component (A), aluminum salt (B') and other components described later.

[0059] 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 and 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. 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, and further preferably 94.0% by mass or less.

[0060] <Ratio of each component>

[0061] 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, further preferably 3.0 or more, and even more preferably 4.0 or more, from the viewpoint of further improving the balance between adhesion and stretchability, as well as improving water retention and gel strength. It is preferably 20.0 or less, more preferably 16.0 or less, even more preferably 14.0 or less, even more preferably 12.0 or less, and even more preferably 11.0 or less, from the viewpoint of further improving the balance between adhesion and stretchability, as well as improving water retention and gel strength.

[0062] 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, even more preferably 0.010 or more, even more preferably 0.020 or more, even more preferably 0.025 or more, and preferably 0.500 or less, more preferably 0.200 or less, even more preferably 0.120 or less, even more preferably 0.080 or less, even more preferably 0.060 or less, even more preferably 0.040 or less, from the viewpoint of further improving the balance between adhesion and stretchability.

[0063] <Sulfate ion>

[0064] From the viewpoint that the gel composition of the present invention exhibits preferred gel properties even after storage, it may also contain sulfate ions.

[0065] Sulfate ions can be ions from component (B') or ions 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.

[0066] In the gel composition of the present invention, the molar ratio of sulfate ions to aluminum ions (SO4) is... 2- / Al 3+ From the viewpoint of adjusting the viscosity during storage, it is preferably 0.08 or more, more preferably 0.09 or more, even more preferably 0.10 or more, even more preferably 0.11 or more, even more preferably 0.13 or more, even more preferably 0.15 or more. From the viewpoint of adjusting the viscosity during storage, it is preferably 1.45 or less, more preferably 0.50 or less, even more preferably 0.45 or less, even more preferably 0.35 or less, even more preferably 0.27 or less, even more preferably 0.25 or less, even more preferably 0.23 or less, even more preferably 0.20 or less.

[0067] The aluminum ions mentioned above are usually ions from component (B').

[0068] <Other Ingredients>

[0069] The gel composition of the present invention may appropriately contain other ingredients without prejudice to the purpose of the present invention.

[0070] Other ingredients include those commonly used in cosmetics, fragrances, pharmaceuticals, and quasi-drugs.

[0071] Commonly used ingredients in these products include, for example, 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.

[0072] <pH>

[0073] Regarding the pH of the gel composition of the present invention at 25°C, from the viewpoint of suppressing stickiness and improving water retention and gel strength, it is preferably 2.0 or higher, more preferably 2.5 or higher, even more preferably 2.8 or higher, and even more preferably 3.0 or higher. From the viewpoint of improving adhesion, improving softness and elongation, and improving water supply and 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.

[0074] The pH of the gel composition of the present invention at 25°C can be specifically determined using the method described in the examples.

[0075] <Dynamic Viscoelasticity>

[0076] From the viewpoint of further improving the balance between adhesion and tensile strength, the gel composition of the present invention preferably has a loss modulus G' > storage modulus G' in a frequency region lower than the frequency of tanδ 1, and a storage modulus G' > loss modulus G' in a frequency region higher than the frequency of tanδ 1. In the present invention, as described below, the storage modulus G' and loss modulus G' at a frequency of 62.8 rad / s can be used as the frequency region of the gel composition at 25°C that is higher than the frequency of tanδ 1, and the storage modulus G' and loss modulus G' at a frequency of 0.135 rad / s can be used as the frequency region lower than the frequency of tanδ 1.

[0077] In the gel composition of the present invention, regarding the frequency of tanδ=1, from the viewpoint of further improving the balance between adhesion and tensile strength, it is preferably 0.1 rad / s or more, more preferably 1.0 rad / s or more, even more preferably 1.5 rad / s or more, 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, even more preferably 6.5 rad / s or less.

[0078] Regarding the storage 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 tensile strength, as well as improving water retention and gel strength, it is 500 Pa or more, preferably 700 Pa or more, more preferably 900 Pa or more, further preferably 1,500 Pa or more, and even more preferably 1,800 Pa or more. From the viewpoint of further improving tensile strength, 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.

[0079] Regarding the ratio (G” / G’(tanδ)) of the loss modulus G” (25°C, frequency: 62.8 rad / s) to the storage 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 tensile strength, it is preferably 0.10 or more, more preferably 0.15 or more, even more preferably 0.20 or more, 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, even more preferably 0.35 or less.

[0080] Furthermore, regarding the ratio (G” / G’(tanδ)) of the loss modulus G” (25°C, frequency: 0.135 rad / s) to the storage 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 tensile strength, it is preferably 0.10 or more, more preferably 0.50 or more, even more preferably 0.80 or more, even more preferably 1.0 or more, even more preferably 1.5 or more, even more preferably 1.8 or more. From the same viewpoint, it is preferably 10.0 or less, more preferably 5.0 or less, even more preferably 4.0 or less, even more preferably 3.5 or less, even more preferably 3.3 or less, even more preferably 3.2 or less.

[0081] Regarding the storage 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 tensile strength, as well as improving water retention and gel strength, it is preferably 1 Pa or more, more preferably 5 Pa or more, further preferably 10 Pa or more, further preferably 15 Pa or more, and further preferably 20 Pa or more. From the viewpoint of improving tensile strength, it is preferably 5,000 Pa or less, more preferably 2,000 Pa or less, further preferably 1,000 Pa or less, further preferably 800 Pa or less, further preferably 500 Pa or less, further preferably 300 Pa or less, and further preferably 200 Pa or less.

[0082] The storage modulus G' and loss modulus G" of the gel composition of the present invention can be determined using a rheometer (clamp: 25 mm diameter, PP; plate: parallel plate, 8 mm diameter) at a temperature of 25°C and a frequency of 10... -3 ~10 2 Rad / s, strain: measured under conditions within the linear region, or more specifically, measured using the methods described in the examples.

[0083] <Manufacturing Method>

[0084] As a method for manufacturing the gel composition of the present invention, for example, a polymer is dissolved in water to prepare an aqueous solution (A), an aluminum salt (B') is dissolved in water to prepare an aqueous solution (B) containing aluminum ions, and the obtained aqueous solution (A) and aqueous solution (B) are mixed using a known stirring device or the like, thereby enabling the manufacture.

[0085] [Topical skin medication]

[0086] The gel composition of the present invention is suitable for use in topical skin preparations. That is, the topical skin preparations of the present invention contain the above-described gel composition of the present invention.

[0087] The topical skin agent of the present invention is used by adhering it to the skin, preferably to any part of the face, body, hands and feet other than the scalp. When in use, it can be freely stretched or unfolded, has good adhesion to the skin, can give the user a pleasant cooling sensation and feel, has no stickiness, and is easy to peel off from the skin after use.

[0088] The topical skin agent of the present invention is easy to remove even when filled into a portable container such as a tube or bag, and will not leave any residue in the container.

[0089] The topical skin agent of the present invention is a composition suitable for the skin in the fields of cosmetics, perfumes, pharmaceuticals, and quasi-drugs. It is preferably a gel-like skin care agent, more preferably a skin care film, and even more preferably a skin care mask.

[0090] The method of using the gel composition of the present invention can be exemplified by the following steps. First, the gel composition is stretched to an appropriate size and then applied to the skin, or the gel composition is applied to the skin and then stretched to an appropriate size. Next, 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. Thus, a good skin care effect can be obtained. Alternatively, the gel composition can be used while massaging, which can be done directly with the hands or using a sponge or other tools.

[0091] The present invention also provides a skin moisturizing method for applying the gel composition of the present invention to the skin to moisturize the skin.

[0092] Example

[0093] The present invention will be specifically described below using examples, but the present invention is not limited to these examples in any way.

[0094] [Preparation of the gel composition]

[0095] Example 1

[0096] (1) Preparation of polymer aqueous solution

[0097] Add 19.0 g of anionized PVA (product name: GOHSENX (registered trademark) T-330H, manufactured by Mitsubishi Chemical Corporation, degree of polymerization = 2,000, degree of saponification > 99.0 mol%, carboxylic acid modified) and 192.1 g of deionized water to a 2 L container, and stir at 90 °C for more than 2 hours to obtain a 9% by mass anionized PVA aqueous solution.

[0098] (2) Preparation of aluminum salt aqueous solution

[0099] 144.9 g of aluminum(III) hexahydrate (manufactured by Fujifilm and Koh Genuine Chemicals Co., Ltd.) and 1188.5 g of deionized water were added to a 2 L container and stirred at 50 °C for more than 1 hour to obtain a 6% by mass aluminum chloride aqueous solution.

[0100] (3) Preparation of gel composition

[0101] Add 60.0 g of the prepared 9% by mass anionized PVA aqueous solution and 2.57 g of 6% by mass aluminum chloride aqueous solution to a 100 mL container (for a mixer) at 25°C, and stir for 10 minutes using a mixer (HM-500, manufactured by Keyence Corporation) (rotation conditions: 2000 revolutions / 800 rotations, acceleration: 400G) to obtain a gel composition.

[0102] Example 2

[0103] In the preparation of the gel composition described in Example 1 (3), “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 operation was the same as in Example 1 to obtain the gel composition.

[0104] Example 3

[0105] (1) Preparation of polymer aqueous solution

[0106] An 11% by mass aqueous solution of anionized PVA was obtained using the same method as in Example 1.

[0107] (2) Preparation of aluminum salt aqueous solution

[0108] Add 10.0 g of aluminum(III) hexahydrate (manufactured by Fujifilm and Koh Genuine Chemicals Co., Ltd.) and 45.2 g of deionized water to a 100 mL container, and stir at 50 °C for more than 1 hour to obtain a 10% by mass aluminum chloride aqueous solution.

[0109] Add 10.0 g of aluminum sulfate octahydrate (manufactured by SIGMA-ALDRICH) and 75.6 g of deionized water to a 100 mL container, and stir at 50 °C for more than 1 hour to obtain a 6% by mass aluminum sulfate aqueous solution.

[0110] 29.0 g of the obtained 10% by mass aluminum chloride aqueous solution and 10.0 g of 6% by mass aluminum sulfate aqueous solution were mixed to obtain aluminum chloride / aluminum sulfate aqueous solution.

[0111] (3) Preparation of gel composition

[0112] In the preparation of the gel composition described in (3) of Example 1, “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 operation was the same as in Example 1 to obtain the gel composition.

[0113] Example 4

[0114] In the preparation of the gel composition described in (3) of Example 1, “60.0g of 11% by mass anionized PVA and 3.14g of 6% by mass aluminum chloride aqueous solution” was used instead of “60.0g of 9% by mass anionized PVA aqueous solution and 2.57g of 6% by mass aluminum chloride aqueous solution”. Otherwise, the operation was the same as in Example 1 to obtain the gel composition.

[0115] Example 5

[0116] In the preparation of the gel composition described in (3) of Example 1, “60.0g of 12% by mass anionized PVA and 3.42g of 6% by mass aluminum chloride aqueous solution” was used instead of “60.0g of 9% by mass anionized PVA aqueous solution and 2.57g of 6% by mass aluminum chloride aqueous solution”. Otherwise, the operation was the same as in Example 1 to obtain the gel composition.

[0117] Example 6

[0118] In the preparation of the gel composition described in (3) of Example 1, “60.0g of 13% by mass anionized PVA and 3.71g of 6% by mass aluminum chloride aqueous solution” was used instead of “60.0g of 9% by mass anionized PVA aqueous solution and 2.57g of 6% by mass aluminum chloride aqueous solution”. Otherwise, the operation was the same as in Example 1 to obtain the gel composition.

[0119] Example 7

[0120] In the preparation of the gel composition described in (3) of Example 1, “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 operation was the same as in Example 1 to obtain the gel composition.

[0121] Example 8

[0122] In the preparation of the gel composition described in (3) of Example 1, “60.0g of 15% by mass anionized PVA and 4.28g of 6% by mass aluminum chloride aqueous solution” was used instead of “60.0g of 9% by mass anionized PVA aqueous solution and 2.57g of 6% by mass aluminum chloride aqueous solution”. Otherwise, the operation was the same as in Example 1 to obtain the gel composition.

[0123] Example 9

[0124] In the preparation of the gel composition described in (3) of Example 1, “60.0g of 8% by mass anionized PVA and 2.28g of 6% by mass aluminum chloride aqueous solution” was used instead of “60.0g of 9% by mass anionized PVA aqueous solution and 2.57g of 6% by mass aluminum chloride aqueous solution”. Otherwise, the operation was the same as in Example 1 to obtain the gel composition.

[0125] Example 10

[0126] In the preparation of the gel composition described in (3) of Example 1, “60.0g of 7% by mass anionized PVA and 2.00g of 6% by mass aluminum chloride aqueous solution” was used instead of “60.0g of 9% by mass anionized PVA aqueous solution and 2.57g of 6% by mass aluminum chloride aqueous solution”. Otherwise, the operation was the same as in Example 1 to obtain the gel composition.

[0127] Example 11

[0128] 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 Kohden Chemical Co., 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.

[0129] Comparative Example 1

[0130] In the preparation of the gel composition described in (3) of Example 1, “60.0g of 6% anionized PVA and 1.71g of 6% aluminum chloride aqueous solution” was used instead of “60.0g of 9% anionized PVA aqueous solution and 2.57g of 6% aluminum chloride aqueous solution”. Otherwise, the operation was the same as in Example 1 to obtain the gel composition.

[0131] Comparative Example 2

[0132] 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 operation was the same as in Example 1 to obtain the gel composition.

[0133] [Physical Property Measurement and Evaluation]

[0134] The gel compositions obtained in the examples and comparative examples were subjected to the following physical property tests and evaluations. The evaluation results are shown in Table 1. The amounts of each component in Table 1 are expressed as mass%.

[0135] <pH of the gel composition>

[0136] A 100 mL container was filled with the gel composition, and a glass electrode (manufactured by Horiba Corporation, product name: 9681S-10D) was inserted into the gel composition at 25°C to measure the pH of the gel composition at 25°C.

[0137] <Storage modulus G' and loss modulus G” of the gel composition>

[0138] The storage modulus G' and loss modulus G of the gel composition were determined using a rheometer under the following conditions.

[0139] Equipment: MRC302 (manufactured by Anton Paar);

[0140] Fixture: PP25 (diameter: 24.985mm);

[0141] Plate: LOWER MEASURING PLATE L-PP08 / CTD, D: 8mm FOR CTD450 / 600 / 1000;

[0142] Temperature: 25℃;

[0143] Frequency: 10 -3 ~10 2 rad / s;

[0144] Strain: within the linear region (in this embodiment, the strain is 1%).

[0145] Based on the measurement graphs obtained under the above measurement conditions, the energy storage modulus G' (frequency: 62.8 rad / s, 0.135 rad / s), loss 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 is 1 were obtained.

[0146] <Evaluation of skin adhesion>

[0147] Five professional evaluators were used to evaluate the skin adhesion of the gel composition.

[0148] Specifically, the gel composition was prepared at 2g / 9cm 2 Apply a 3cm x 3cm gel to the back of the hand. Then, rotate the back of the hand 180° within 120 seconds and observe the sagging state of the gel composition. Evaluate the skin adhesion of the gel composition based on the following evaluation criteria.

[0149] (Evaluation Criteria)

[0150] 1: The penis droops within 30 seconds;

[0151] 2: The drooping lasts for more than 30 seconds but less than 120 seconds;

[0152] 3: It does not sag, but the gel composition flows slightly;

[0153] 4. It does not sag at all.

[0154] The average value of the evaluations from the five professional evaluators is shown in Table 1.

[0155] <Evaluation of Stretchability>

[0156] The tensile properties of the gel composition were evaluated using a panel of five professional evaluators.

[0157] Specifically, grasp the gel composition (2g / 9cm) 2 The stretchability of the gel composition was evaluated based on the following evaluation criteria after stretching both ends of a (3cm×3cm) gel composition.

[0158] (Evaluation Criteria)

[0159] 1: The gel composition cannot be grasped by hand (it cannot be stretched);

[0160] 2: The gel composition can be stretched by hand, but it breaks easily;

[0161] 3: Able to grasp the gel composition by hand and stretch it fully;

[0162] 4: The gel composition can be grasped by hand and stretched very fully.

[0163] The average value of the evaluations from the five professional evaluators is shown in Table 1.

[0164]

[0165] As can be understood from Table 1, the gel composition of the embodiments improves the balance between skin adhesion and stretchability compared to the gel composition of the comparative examples. That is, it can be understood that, according to the present invention, a gel and topical skin agent with improved balance between adhesion and stretchability can be provided.

Claims

1. A gel composition, wherein, The gel composition contains: (A) Anionized polymer, 5.0% by mass or more and 20.0% by mass or less; (B) The content of aluminum ions as aluminum salts is more than 0.25% by mass and less than 0.32% by mass; as well as (C) Water, Component (A) is a polyvinyl alcohol containing carboxyl groups, with a saponification degree of 90 mol% or more, a polymerization degree of 500 or more but less than 4000, and a carboxyl group content of 0.1 mol% or more but less than 10 mol%. When the dynamic viscoelasticity of the gel composition was measured under strain conditions at 25°C within the linear region, There exists a frequency range of 0.001–100 rad / s where the loss modulus G'' / storage modulus G' is 1, where the loss modulus G'' / storage modulus G' is tanδ. The storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is 500 Pa or more and 15,000 Pa or less.

2. The gel composition of claim 1, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is 500 Pa or more and 10,000 Pa or less.

3. The gel composition of claim 1, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is between 500 Pa and 9,500 Pa.

4. The gel composition according to any one of claims 1 to 3, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is between 500 Pa and 8,000 Pa.

5. The gel composition according to any one of claims 1 to 3, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is between 500 Pa and 7,000 Pa.

6. The gel composition according to any one of claims 1 to 3, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is 500 Pa or more and 6,500 Pa or less.

7. The gel composition of claim 1, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is 700 Pa or more and 15,000 Pa or less.

8. The gel composition of claim 2, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is 700 Pa or more and 10,000 Pa or less.

9. The gel composition of claim 3, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is 700 Pa or more and 9,500 Pa or less.

10. The gel composition of claim 1, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is 900 Pa or more and 15,000 Pa or less.

11. The gel composition of claim 2, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is 900 Pa or more and 10,000 Pa or less.

12. The gel composition of claim 3, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is 900 Pa or more and 9,500 Pa or less.

13. The gel composition of claim 1, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is between 1,500 Pa and 15,000 Pa.

14. The gel composition of claim 2, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is between 1,500 Pa and 10,000 Pa.

15. The gel composition of claim 3, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is above 1,500 Pa and below 9,500 Pa.

16. The gel composition of claim 1, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is above 1,800 Pa and below 15,000 Pa.

17. The gel composition of claim 2, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is above 1,800 Pa and below 10,000 Pa.

18. The gel composition of claim 3, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is above 1,800 Pa and below 9,500 Pa.

19. The gel composition according to any one of claims 1 to 3, wherein, The mass ratio of water to the anionized polymer is 1.0 or more and 20.0 or less, calculated as water / anionized polymer.

20. The gel composition according to any one of claims 1 to 3, wherein, In the frequency region lower than the frequency where tanδ is 1, the loss modulus G'' > the storage modulus G'. In the frequency region higher than the frequency where tanδ is 1, the energy storage modulus G' > the loss modulus G''.

21. The gel composition according to any one of claims 1 to 3, wherein, The frequency at which tanδ is 1 is between 0.1 rad / s and 30.0 rad / s.

22. The gel composition according to any one of claims 1 to 3, wherein, The frequency at which tanδ is 1 is between 1.0 rad / s and 100 rad / s.

23. The gel composition according to any one of claims 1 to 3, wherein, The frequency at which tanδ is 1 is between 1.5 rad / s and 100 rad / s.

24. The gel composition according to any one of claims 1 to 3, wherein, The frequency with tanδ = 1 is above 2.5 rad / s and below 100 rad / s.

25. The gel composition according to any one of claims 1 to 3, wherein, The frequency at which tanδ is 1 is between 0.001 rad / s and 20.0 rad / s.

26. The gel composition according to any one of claims 1 to 3, wherein, The frequency at which tanδ is 1 is between 0.001 rad / s and 15.0 rad / s.

27. The gel composition according to any one of claims 1 to 3, wherein, The frequency at which tanδ is 1 is between 0.001 rad / s and 10.0 rad / s.

28. The gel composition according to any one of claims 1 to 3, wherein, The frequency at which tanδ is 1 is between 0.001 rad / s and 8.0 rad / s.

29. The gel composition according to any one of claims 1 to 3, wherein, The frequency at which tanδ is 1 is between 0.001 rad / s and 6.5 rad / s.

30. The gel composition according to any one of claims 1 to 3, wherein, The storage 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.

31. The gel composition according to any one of claims 1 to 3, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 0.135 rad / s is greater than 5 Pa.

32. The gel composition according to any one of claims 1 to 3, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 0.135 rad / s is greater than 10 Pa.

33. The gel composition according to any one of claims 1 to 3, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 0.135 rad / s is greater than 20 Pa.

34. The gel composition according to any one of claims 1 to 3, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 0.135 rad / s is less than 2,000 Pa.

35. The gel composition according to any one of claims 1 to 3, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 0.135 rad / s is less than 1,000 Pa.

36. The gel composition according to any one of claims 1 to 3, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 0.135 rad / s is below 800 Pa.

37. The gel composition according to any one of claims 1 to 3, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 0.135 rad / s is less than 500 Pa.

38. The gel composition according to any one of claims 1 to 3, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 0.135 rad / s is less than 300 Pa.

39. The gel composition according to any one of claims 1 to 3, wherein, The storage modulus G' of the gel composition at 25°C and a frequency of 0.135 rad / s is less than 200 Pa.

40. The gel composition according to any one of claims 1 to 3, wherein, It also contains sulfate ions.

41. The gel composition of claim 40, wherein, The gel composition contains sulfate ions in a molar ratio to aluminum ions of SO42-. 2- / Al 3＋ The value is calculated as 0.08 or higher and 1.45 or lower.

42. The gel composition according to any one of claims 1 to 3, wherein, The pH is above 2.0 at 25°C.

43. The gel composition according to any one of claims 1 to 3, wherein, The pH is above 2.5 at 25°C.

44. The gel composition according to any one of claims 1 to 3, wherein, The pH is above 2.8 at 25°C.

45. The gel composition according to any one of claims 1 to 3, wherein, The pH is above 3.0 at 25°C.

46. ​​The gel composition according to any one of claims 1 to 3, wherein, The pH is below 6.5 at 25°C.

47. The gel composition according to any one of claims 1 to 3, wherein, The pH is below 6.0 at 25°C.

48. The gel composition according to any one of claims 1 to 3, wherein, The pH is below 5.5 at 25°C.

49. The gel composition according to any one of claims 1 to 3, wherein, The pH is below 5.0 at 25°C.

50. The gel composition according to any one of claims 1 to 3, wherein, The ratio of the loss modulus G'' to the storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is greater than 0.10, where G'' / G' is tanδ.

51. The gel composition according to any one of claims 1 to 3, wherein, The ratio of the loss modulus G'' to the storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is greater than 0.15, where G'' / G' is tanδ.

52. The gel composition according to any one of claims 1 to 3, wherein, The ratio of the loss modulus G'' to the storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is greater than 0.20, where G'' / G' is tanδ.

53. The gel composition according to any one of claims 1 to 3, wherein, The ratio of the loss modulus G'' to the storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is greater than 0.25, where G'' / G' is tanδ.

54. The gel composition according to any one of claims 1 to 3, wherein, The ratio of the loss modulus G'' to the storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is less than 1.0, where G'' / G' is tanδ.

55. The gel composition according to any one of claims 1 to 3, wherein, The ratio of the loss modulus G'' to the storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is less than 0.70, where G'' / G' is tanδ.

56. The gel composition according to any one of claims 1 to 3, wherein, The ratio of the loss modulus G'' to the storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is less than 0.50, where G'' / G' is tanδ.

57. The gel composition according to any one of claims 1 to 3, wherein, The ratio of the loss modulus G'' to the storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is less than 0.40, where G'' / G' is tanδ.

58. The gel composition according to any one of claims 1 to 3, wherein, The ratio of the loss modulus G'' to the storage modulus G' of the gel composition at 25°C and a frequency of 62.8 rad / s is less than 0.35, where G'' / G' is tanδ.

59. A topical skin agent, wherein, A gel composition comprising any one of claims 1 to 58.

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