CN117412736A - Gel composition - Google Patents

Gel composition Download PDF

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Publication number
CN117412736A
CN117412736A CN202280039118.8A CN202280039118A CN117412736A CN 117412736 A CN117412736 A CN 117412736A CN 202280039118 A CN202280039118 A CN 202280039118A CN 117412736 A CN117412736 A CN 117412736A
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China
Prior art keywords
gel composition
mass
component
gel
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CN202280039118.8A
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Chinese (zh)
Inventor
伊森洋一郎
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Kao Corp
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Kao Corp
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Publication of CN117412736A publication Critical patent/CN117412736A/en
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/02Inorganic compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/34Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/06Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00Drugs for dermatological disorders
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00Drugs for dermatological disorders
    • A61P17/16Emollients or protectives, e.g. against radiation
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin

Abstract

The present invention relates to [1] a gel composition comprising (A) an anionized polyvinyl alcohol, (B) a metal salt of 3 valence, and (C) water, and having a pH of 3.0 to 5.0 at 25 ℃; [2] a skin external agent comprising the above gel composition; and [3] a method for forming a gel composition comprising a step of gelling (A) an anionized polyvinyl alcohol, (B) a metal salt of 3 valence, and (C) water by mixing them before use, wherein the pH of the gel composition at 25 ℃ is 3.0 to 5.0.

Description

Gel composition
Technical Field
The present invention relates to a gel composition, an external preparation for skin, and a method for forming the gel composition.
Background
Polyvinyl alcohol materials are widely used in various fields such as pharmaceuticals, quasi drugs, cosmetics, paints, adhesives, binders, packaging materials, emulsifiers, suspending agents, water-retaining agents, surfactants, fiber treatment agents, and paper processing agents by utilizing their hydrophilicity.
As a technique for a polyvinyl alcohol material, for example, the techniques described in patent documents 1 to 3 below are known.
Japanese patent application laid-open No. 55-127311 (patent document 1) discloses a facial mask cosmetic characterized in that: the above-mentioned facial mask cosmetic is extremely effective in view of physiological effects and cosmetic effects of skin, because it is free from change with time even if it is applied to skin for a long period of time, and can maintain a state of moisture absorption at all times, because a sol obtained by adding lactate or chloride of a divalent metal to an aqueous solution of polyvinyl alcohol is used as a first agent, 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 both the first agent and the second agent is formed by a combination of both agents.
JP-A11-1595 (patent document 2) discloses an aqueous composition comprising (A) a modified polyvinyl alcohol having 0.1 to 20 mol% of carboxyl groups in the molecule and (B) a water-soluble aluminum compound, wherein the solid formation/distribution ratio (A)/(B) on a weight basis is 100/0.01 to 100/50, the aqueous composition has a large viscosity rise due to evaporation of water, and the initial adhesion is remarkably excellent.
The aqueous composition of patent document 2 is mainly intended for use after the evaporation of water and solidification of a paper processing binder, a woodworking binder, a fiber treating agent, an adhesive, a paint, etc., and has not been intended for use in the fields of cosmetics, pharmaceuticals, quasi drugs, etc., or as a gel-like skin care agent.
Japanese patent application laid-open No. 2020-152869 (patent document 3) discloses a polyvinyl alcohol gel-forming article having a structure in which a polyvinyl alcohol polymer is crosslinked with a titanium chelate compound, which is excellent in strength.
The polyvinyl alcohol gel molded product of patent document 3 is mainly used as a carrier for immobilizing microorganisms, a water-retaining material, a cold-retaining material, a filter medium, and the like, and has not been used in the fields of cosmetics, pharmaceuticals, quasi drugs, and the like or as a gel-like skin care agent.
Disclosure of Invention
The present invention relates to a gel composition comprising the following components (A) to (C) and having a pH of 3.0 to 5.0 at 25 ℃,
(A) Anionizing polyvinyl alcohol;
(B) A 3-valent metal salt;
(C) And (3) water.
Detailed Description
Examples of the film product such as skin care film include a sheet-like film in which a nonwoven fabric is impregnated with a liquid. However, such a sheet-like film has poor moisture retention and a sticky feel due to liquid, because of insufficient adhesion to the skin, i.e., adhesiveness. Here, the polyvinyl alcohol materials described in patent documents 1 to 3 have not been studied for adhesion to skin or sticky feeling.
The present invention relates to a gel composition, an external preparation for skin, and a method for forming the gel composition, which improve the balance of sticky feel and adhesiveness.
The present inventors have found that a gel composition comprising (a) an anionized polyvinyl alcohol, (B) a 3-valent metal salt, and (C) water, the pH of which is in a specific range, can promote a balance of a sticky feel and adhesion, and have completed the present invention.
That is, the present invention relates to the following [1] to [3].
[1] A gel composition comprising the following components (A) to (C) and having a pH of 3.0 to 5.0 at 25 ℃,
(A) Anionizing polyvinyl alcohol;
(B) A 3-valent metal salt;
(C) And (3) water.
[2] A skin external preparation comprising the gel composition according to the above [1 ].
[3] A method for forming a gel composition comprising the step of mixing the following component (A), the following component (B) and the following component (C) to gel the components before use,
the pH value of the gel composition at 25 ℃ is 3.0-5.0,
(A) Anionizing polyvinyl alcohol;
(B) A 3-valent metal salt;
(C) And (3) water.
According to the present invention, a gel composition, a skin external preparation, and a method for forming a gel composition, which have improved balance between sticky feel and adhesiveness, can be provided.
[ gel composition ]
The gel composition of the present invention comprises the following components (A) to (C), and has a pH of 3.0 to 5.0 at 25 ℃.
(A) Anionized polyvinyl alcohol
(B) 3-valent metal salt
(C) Water and its preparation method
In the present invention, the term "comprising the component X" is understood to mean the same meaning as "blending the component X".
The gel composition of the present invention may be a gel composition obtained by mixing the components (a) to (C) before use.
That is, the gel composition of the present invention may be a gel composition obtained by mixing the components (a) to (C) before use, and the pH of the gel composition obtained by gelling the components (a) to (C) may be 3.0 to 5.0 at 25 ℃.
The gel composition of the present invention can improve the balance between the sticky feeling and the adhesiveness. The gel composition of the present invention has good adhesion to the skin, and therefore, the object to be adhered is preferably the skin. Thus, the gel composition of the present invention is particularly suitable for use in external preparations for skin. The external skin preparation of the present invention is a composition to be applied to the skin in the fields of cosmetics, pharmaceuticals, quasi drugs, etc.
The reason why the effect of the present invention is exerted by the above-described constitution of the gel composition of the present invention is not specified, but is presumed as follows.
The gel composition of the present invention contains an anionic polyvinyl alcohol as component (A), a 3-valent metal salt as component (B), and water as component (C), and has a pH value of 3.0 to 5.0 at 25 ℃.
The component (a) as the anionized polyvinyl alcohol and the component (B) as the 3-valent metal salt can form a crosslinked gel by ionic interaction.
Further, it is considered that by setting the pH value to be within the above range, an optimum crosslinked structure is formed by ion interaction and entanglement of polymer chains, and a gel composition having moderate adhesion can be formed.
That is, it is considered that when the gel composition is touched by hand, the sticky feeling of the gel is suppressed, and the adhesive property is improved without dripping when the gel composition is applied to an object.
From the above, it is considered that the gel composition of the present invention is a gel composition having particular viscoelasticity by combining the components (a) to (C) and optimizing the pH range, and thus, the balance of the sticky feel and the adhesiveness can be improved.
< component (A): anionized polyvinyl alcohol
The gel composition of the present invention contains an anionized polyvinyl alcohol as the component (A).
The component (A) is, for example, polyvinyl alcohol having an anionic group such as a sulfonic acid group, a sulfuric acid group, a carboxyl group, a phosphoric acid group, or a phosphonic acid group.
From the viewpoint of further suppressing the sticky feeling and further improving the adhesion, the component (a) is preferably a polyvinyl alcohol having at least 1 anionic group of a sulfonic acid group and a carboxyl group, more preferably a polyvinyl alcohol having a carboxyl group.
Herein, in the present specification, an anionic group means an anionic group or a group which can be an anionic group by ionization.
Examples of the polyvinyl alcohol having a carboxyl group include: (1) Polyvinyl alcohol having a carboxyl group obtained by graft polymerization or block polymerization of polyvinyl alcohol with an unsaturated monomer having a carboxyl group; (2) Polyvinyl alcohol having a carboxyl group obtained by copolymerizing a vinyl ester compound with an unsaturated monomer having at least 1 selected from the group consisting of a carboxyl group and a carboxylic acid ester group, and then performing saponification; (3) Polyvinyl alcohol having a carboxyl group obtained by performing saponification after polymerizing a vinyl ester compound using a chain transfer agent having a carboxyl group; and (4) a polyvinyl alcohol having a carboxyl group obtained by reacting a polyvinyl alcohol with a carboxylating agent.
Examples of the unsaturated monomer having a carboxyl group used in the methods (1) and (2) and the unsaturated monomer having a carboxylate group used in the method (2) include: ethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, and the like; monoesters of ethylenically unsaturated dicarboxylic acids such as monoalkyl maleates, monoalkyl fumarates, and monoalkyl itaconates; ethylenically unsaturated dicarboxylic acid diesters such as dialkyl maleates, dialkyl fumarates, and dialkyl itaconates; ethylene unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; unsaturated monocarboxylic acids such as (meth) acrylic acid; unsaturated monocarboxylic acid esters such as alkyl (meth) acrylate, and the like. In addition, as the unsaturated monomer having at least 1 selected from the group consisting of a carboxyl group and a carboxylate group, salts of the above-mentioned compounds may also be used.
These compounds may be used singly or in combination of 1 kind or 2 or more kinds.
Examples of the vinyl ester compound used in the methods (2) and (3) include: vinyl acetate, vinyl formate, vinyl propionate, vinyl neodecanoate, vinyl pivalate, and the like. Among these, vinyl acetate is preferable from the viewpoints of reactivity at the time of synthesis and easiness of acquisition.
These compounds may be used singly or in combination of 1 kind or 2 or more kinds.
Examples of the carboxylating agent used in the method (4) include: succinic anhydride, maleic anhydride, acetic anhydride, trimellitic anhydride, phthalic anhydride, pyromellitic anhydride, glutaric anhydride, hydrogenated phthalic anhydride, naphthalene dicarboxylic anhydride, and other carboxylic anhydrides.
These may be used singly or in combination of 1 kind or 2 or more kinds.
The amount of anionic groups (derived from the ratio of the monomer having anionic groups) in the anionic polyvinyl alcohol is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, still more preferably 1 mol% or more from the viewpoint of further suppressing the sticky feeling, and improving the water holding power and gel strength, and is preferably 10 mol% or less, more preferably 5 mol% or less, still more preferably 3 mol% or less from the viewpoint of further improving the adhesion, and the amount of water to be supplied and the moisturizing feeling when applied to the skin.
The amount of anionic groups in the anionized polyvinyl alcohol can be controlled by using 1 H-NMR (solvent: CDCl) 3 ) The anionic polyvinyl alcohol before saponification was analyzed to obtain the product.
The degree of saponification of the anionic polyvinyl alcohol is preferably 90 mol% or more, more preferably 95 mol% or more, further preferably 98 mol% or more, from the viewpoint of further suppressing the sticky feeling, and improving the water retention and gel strength, and the upper limit of the degree of saponification is not particularly limited, and is, for example, 100.0 mol% or less, preferably 99.9 mol% or less, more preferably 99.5 mol% or less.
The degree of saponification of the anionized polyvinyl alcohol was in accordance with JIS K6726: 1994.
The polymerization degree of the anionic polyvinyl alcohol is preferably 100 or more, more preferably 500 or more, further preferably 1,000 or more from the viewpoint of further suppressing a sticky feeling, and improving the retention of water and gel strength, and is preferably 20 ten thousand or less, more preferably 1 ten thousand or less, further preferably 4,000 or less from the viewpoint of further improving adhesion, and improving flexibility and elongation.
The degree of polymerization of the anionic polyvinyl alcohol can be calculated from the relative viscosity of the aqueous solution of the completely saponified polyvinyl alcohol and water (see JIS K6726:1994).
Specific examples of the anionic polyvinyl alcohol include: KL-118, KL-318, KL-506, KM-118, KM-618 manufactured by Kuraray co., ltd; GOHSENX CKS50, GOHSENX T-330H, GOHSENX T-330, and GOHSENX T-350 manufactured by Mitsubishi chemical corporation; AP-17, AT-17, AF-17, etc. of JAPAN VAM & POVAL co.
The component (A) may be used alone or in combination of 1 or more than 2.
The content of the component (a) in the gel composition of the present invention is preferably 3.0% by mass or more, more preferably 5.0% by mass or more, still more preferably 8.0% by mass or more, still more preferably 9.0% by mass or more, still more preferably 10.0% by mass or more, from the viewpoint of further suppressing the sticky feeling, and from the viewpoint of improving the water retention and the gel strength, preferably 30.0% by mass or less, more preferably 25.0% by mass or less, still more preferably 22.0% by mass or less, and still more preferably 20.0% by mass or less.
< component (B): 3 valence metal salt >)
The gel composition of the present invention contains a 3-valent metal salt as the component (B).
The metal salt having a valence of 3 is preferably water-soluble, that is, a metal salt which becomes a valence of 3 when dissolved in water, and examples thereof include: salts of organic acids such as inorganic acids selected from hydrochloric acid, nitric acid and sulfuric acid, and organic acids such as acetic acid, with 3-valent metals selected from titanium, manganese, iron, cobalt, nickel, aluminum, and the like. In addition, hydroxides of these 3-valent metals and the like may also be used. The metal 3 is preferably aluminum from the viewpoints of safety, ease of acquisition, price, gel properties, etc. That is, as the 3-valent metal salt, an aluminum salt is preferable.
Specific examples of the 3-valent metal salt include: metal chlorides such as titanium chloride, manganese chloride, ferric chloride, cobalt chloride, nickel chloride, and aluminum chloride; metal nitrates such as titanium nitrate, manganese nitrate, iron nitrate, cobalt nitrate, nickel nitrate, and aluminum nitrate; metal sulfates such as titanium sulfate, manganese sulfate, iron sulfate, cobalt sulfate, nickel sulfate, aluminum sulfate, and aluminum potassium sulfate; etc. Among these, aluminum salts are preferable, at least one selected from aluminum chloride and aluminum sulfate is more preferable, at least one selected from aluminum chloride, aluminum sulfate and aluminum potassium sulfate is more preferable, and at least one selected from aluminum chloride and aluminum sulfate is more preferable from the viewpoints of safety, ease of acquisition, price, gel property and the like.
The component (B) may be used alone or in combination of 1 or more than 2.
The content of the component (B) in the gel composition of the present invention is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, still more preferably 0.10 mass% or more, still more preferably 0.23 mass% or more, still more preferably 0.26 mass% or more, still more preferably 0.28 mass% or more, and from the viewpoint of further improving the adhesion and from the viewpoint of improving the flexibility and elongation, preferably 5.0 mass% or less, more preferably 2.0 mass% or less, still more preferably 1.0 mass% or less, still more preferably 0.80 mass% or less, still more preferably 0.60 mass% or less, and still more preferably 0.55 mass% or less.
< component (C): water >
The gel composition of the present invention contains water as the component (C).
Examples of the water as the component (C) include deionized water, distilled water, high-purity water, and ultrapure water.
The content of the component (C) in the gel composition of the present invention is preferably the remaining amount excluding the component (a), the component (B), and the other components described later.
The content of the component (C) in the gel composition of the present invention is preferably 65.0% by mass or more, more preferably 70.0% by mass or more, still more preferably 75.0% by mass or more, still more preferably 78.0% by mass or more, still more preferably 80.0% by mass or more, still more preferably 81.0% by mass or more, and from the viewpoint of adjusting the gel composition to an appropriate viscosity, and from the viewpoint of improving the stability of the gel composition and the moisturizing feel when applied to the skin, preferably 98.0% by mass or less, still more preferably 95.0% by mass or less, still more preferably 91.5% by mass or less, still more preferably 90.5% by mass or less.
< ratio of ingredients >
In the gel composition of the present invention, the mass ratio ((C)/(a)) of the component (C) to the component (a) is preferably 4.0 or more, more preferably 4.2 or more, still more preferably 4.3 or more from the viewpoint of further improving the adhesion, the amount of water to be supplied, and the moisture retention when applied to the skin, and is preferably 13.0 or less, more preferably 12.0 or less, still more preferably 11.0 or less, still more preferably 10.0 or less, and still more preferably 9.0 or less from the viewpoint of further suppressing the sticky feel, and the retention of water and the gel strength.
In the gel composition of the present invention, the mass ratio ((B)/(a)) of the component (B) to the component (a) is preferably 0.001 or more, more preferably 0.005 or more, still more preferably 0.010 or more, still more preferably 0.020 or more, still more preferably 0.025 or more, from the viewpoint of further suppressing the sticky feeling, and from the viewpoint of improving the water retention and the gel strength, preferably 0.500 or less, more preferably 0.200 or less, still more preferably 0.120 or less, still more preferably 0.080 or less, and still more preferably 0.060 or less, from the viewpoint of further improving the adhesion, and from the viewpoint of improving the flexibility and the elongation.
< other Components >)
The gel composition of the present invention may contain other components as appropriate within a range that does not impair the object of the present invention.
Examples of the other components include components commonly used in cosmetics, pharmaceuticals, quasi drugs, and the like.
Examples of the components commonly used in these products include: polymers other than the component (a), moisturizers, whitening agents, blood circulation promoters, anti-inflammatory agents, bactericides, ultraviolet absorbers, colorants, preservatives, antioxidants, fragrances, pH adjusters, chelating agents, water-retaining agents, medicaments, alcohols, and the like.
< pH value >
The pH of the gel composition of the present invention is 3.0 or more, preferably 3.3 or more, more preferably 3.5 or more, still more preferably 3.8 or more from the viewpoint of further suppressing a sticky feeling and improving the retention and gel strength of water, and is 5.0 or less, preferably 4.5 or less, more preferably 4.3 or less from the viewpoint of improving the adhesion, improving the softness and elongation, and improving the water supply amount and moisturizing feeling when applied to the skin.
The pH of the gel composition of the present invention at 25℃can be specifically measured by the method described in examples.
< storage modulus and loss modulus >
The ratio (G "/G '(tan δ)) of the loss modulus G" (25 ℃, frequency: 62.8 rad/s) to the storage modulus G' (25 ℃, frequency: 62.8 rad/s) of the gel composition of the present invention is preferably 0.10 or more, more preferably 0.15 or more, still more preferably 0.20 or more from the viewpoint of further improving the adhesion property and the flexibility and elongation, and is preferably 1.0 or less, more preferably 0.70 or less, more preferably 0.50 or less, more preferably 0.35 or less, more preferably 0.33 or less from the viewpoint of further suppressing the sticky feeling, and from the viewpoint of improving the retention and the gel strength of water.
The storage modulus G' (25 ℃ C., frequency: 62.8 rad/s) of the gel composition of the present invention is preferably 300Pa or more, more preferably 500Pa or more, still more preferably 1000Pa or more, still more preferably 1500Pa or more, still more preferably 3500Pa or more, still more preferably 4000Pa or more, from the viewpoint of further suppressing the sticky feeling and from the viewpoint of improving the water retention and the gel strength, and is preferably 50000Pa or less, more preferably 40000Pa or less, still more preferably 30000Pa or less from the viewpoint of further improving the adhesion and from the viewpoint of improving the flexibility and elongation.
The ratio (G "/G '(tan δ)) of the loss modulus G" (25 ℃ at a frequency of 0.135 rad/s) to the storage modulus G' (25 ℃ at a frequency of 0.135 rad/s) of the gel composition of the present invention is preferably 0.10 or more, more preferably 0.50 or more, still more preferably 0.80 or more, still more preferably 1.0 or more, from the viewpoint of further improving the adhesion property and the flexibility and elongation, and is preferably 10.0 or less, more preferably 5.0 or less, still more preferably 3.8 or less, still more preferably 3.2 or less, still more preferably 2.6 or less, and still more preferably 2.2 or less, from the viewpoint of further suppressing the sticky feeling and the retention of water and the gel strength.
The storage modulus G' (25 ℃ C., frequency: 0.135 rad/s) of the gel composition of the present invention is preferably 1Pa or more, more preferably 5Pa or more, still more preferably 10Pa or more, still more preferably 20Pa or more, still more preferably 45Pa or more, still more preferably 75Pa or more, from the viewpoint of further suppressing a sticky feeling, and from the viewpoint of improving flexibility and elongation, preferably 10000Pa or less, more preferably 5000Pa or less, still more preferably 3000Pa or less, still more preferably 2000Pa or less, and still more preferably 1500Pa or less.
The gel compositions of the invention can have a storage modulus G 'and a loss modulus G' using rheometers (clamps: diameter 25mm, PP-made, plates: parallel plates, diameter 8 mm), at temperature: 25 ℃, frequency: 10 -3 ~10 2 rad/s, strain: the measurement is performed under conditions in the linear region, and more specifically, the measurement can be performed by the method described in examples.
< viscosity >
Regarding the viscosity (25 ℃ C., shear rate 0.1 s) of the gel composition of the present invention -1 ) From the viewpoint of further suppressing the sticky feeling and from the viewpoint of improving the water retention and gel strength, it is preferably 300pa·s or more, more preferably 600pa·s or more, further preferably 900pa·s or more, and from the viewpoint of further improving the adhesion, and from the viewpoint of improving the flexibility and elongation, it is preferably 15000pa·s or less, more preferably 10000pa·s or less, further preferably 5000pa·s or less.
The viscosity of the gel composition of the present invention can be specifically measured by the following method.
(method for measuring viscosity of gel composition)
The shear viscosity of the gel composition was measured using a rheometer under the following conditions.
Machine: MRC302 (manufactured by Anton Paar Co., ltd.)
And (3) clamping: CP25-2 (diameter: 24.978 mm)
A plate: LOWER MEASURING PLATE L-PP08/CTD, D:8mm FOR CTD450/600/1000
Temperature: 25 DEG C
Shear rate: 0.1s -1
< manufacturing method >)
The gel composition of the present invention can be produced, for example, by dissolving the component (a) in water to prepare an aqueous solution (a), dissolving the component (B) in water to prepare an aqueous solution (B), and mixing the aqueous solution (a) and the aqueous solution (B) obtained using a known stirring device or the like.
[ skin external preparation ]
The gel composition of the present invention can be suitably used for external preparations for skin. That is, the external skin preparation of the present invention comprises the gel composition of the present invention.
The external skin preparation of the present invention is preferably applied to any part of the face, body, hands and feet other than the scalp, can be freely stretched or expanded during use, has good adhesion to the skin, gives a pleasant cooling sensation and feeling of use to the user, has no sticky feeling, and is easily peeled off from the skin after use.
The external skin preparation of the present invention is easy to take out even when filled in a container which is easy to carry, such as a tube or a bag, and does not remain in the container.
The external skin preparation of the present invention is a composition to be applied to the skin in the fields of cosmetics, pharmaceuticals, quasi drugs, etc., and is preferably a gel-like skin care agent, more preferably a skin care film, and even more preferably a skin care mask.
[ method of Forming gel composition ]
The method for forming a gel composition of the present invention comprises a step of gelling the gel composition by mixing the following component (A), the following component (B), and the following component (C) before use, wherein the pH of the gel composition at 25 ℃ is 3.0 to 5.0,
(A) Anionizing polyvinyl alcohol;
(B) A 3-valent metal salt;
(C) And (3) water.
According to the method for forming a gel composition of the present invention, a gel composition having an improved balance of sticky feel and adhesiveness can be obtained before use. The reason why the gel composition obtained by the method for forming a gel composition of the present invention exerts the effects of the present invention is not defined, but the reason is considered to be the same as the reason why the above-described gel composition of the present invention exerts the effects of the present invention.
The components (a) to (C) in the method for forming a gel composition of the present invention and the preferred embodiments and preferred uses of the obtained gel composition are the same as those of the gel composition of the present invention.
The method for forming a gel composition of the present invention also includes a method for using a gel composition, which includes a step of mixing the component (a), the component (B), and the component (C) before using to gel the components.
Other embodiments
The method of using the gel composition of the present invention includes, for example, the following methods. First, the gel composition is stretched to a proper size and then applied to the skin, or the gel composition is stretched to a proper size and then applied to the skin. Then, the skin is kept on for a certain period of time, preferably 1 minute to 8 hours, more preferably 5 minutes to 1 hour. Thereafter, the gel composition is peeled from the skin. The gel composition can be easily peeled off. Thereby, a good skin care effect can be obtained. The gel composition may be used for massage, either by direct massage by hand or by a prop such as a sponge.
Further, the present invention provides a skin moisturizing method for moisturizing skin by applying the gel composition of the present invention to skin.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[ preparation of gel composition ]
Example 1
(1) Preparation of an aqueous solution of anionized polyvinyl alcohol (PVA)
Into a 2L container, 150.0g of anionic PVA (product name: GOHSENX (registered trademark) T-330H, manufactured by Mitsubishi chemical Co., ltd., polymerization degree=2,000, saponification degree > 99.0 mol%, carboxylic acid modification) and 1213.6g of ion-exchanged water were charged, and stirred at 90℃for 2 hours or more to obtain an 11 mass% anionic PVA aqueous solution.
(2) Preparation of a salt solution of a metal of valence 3
144.9g of aluminum (III) chloride hexahydrate (manufactured by Fuji photo-pure chemical Co., ltd.) and 1188.5g of ion-exchanged water were put into a 2L container, and stirred at 50℃for 1 hour or more, whereby a 6 mass% aluminum chloride aqueous solution was obtained.
(3) Preparation of gel compositions
A100 mL container (dedicated to a mixer) was charged with 60.0G of an 11% by mass aqueous solution of anionic PVA and 3.14G of a 6% by mass aqueous solution of aluminum chloride prepared at 25℃and stirred for 10 minutes using a mixer (apparatus name: HM-500, manufactured by Kabushiki Kaisha Co., ltd.) (rotation conditions: revolution 2000/rotation 800, acceleration: 400G), thereby obtaining a gel composition.
Example 2
In the preparation of the above-mentioned (3) gel composition, a gel composition was obtained in the same manner as in example 1, except that "12 mass% of the anionized PVA 60.0g, 6 mass% of the aqueous aluminum chloride solution 3.42g" was used instead of "11 mass% of the anionized PVA 60.0g, 6 mass% of the aqueous aluminum chloride solution 3.14 g".
Example 3
In the preparation of the above-mentioned gel composition (3), a gel composition was obtained in the same manner as in example 1, except that "60.0 g of 13 mass% anionic PVA and 3.71g of 6 mass% aqueous aluminum chloride solution" were used instead of "60.0 g of 11 mass% anionic PVA and 3.14g of 6 mass% aqueous aluminum chloride solution".
Example 4
In the preparation of the gel composition (3) above, a gel composition was obtained in the same manner as in example 1, except that "15 mass% of the anionic PVA 60.0g and 6 mass% of the aqueous aluminum chloride solution 4.28g" were used instead of "11 mass% of the anionic PVA 60.0g and 6 mass% of the aqueous aluminum chloride solution 3.14 g".
Example 5
In the preparation of the gel composition (3) above, a gel composition was obtained in the same manner as in example 1, except that "60.0 g of 20 mass% anionic PVA and 5.70g of 6 mass% aqueous aluminum chloride solution" were used instead of "60.0 g of 11 mass% anionic PVA and 3.14g of 6 mass% aqueous aluminum chloride solution".
Example 6
In the preparation of the above-mentioned gel composition (3), a gel composition was obtained in the same manner as in example 1, except that "60.0 g of 10 mass% anionic PVA and 2.85g of 6 mass% aqueous aluminum chloride solution" were used instead of "60.0 g of 11 mass% anionic PVA and 3.14g of 6 mass% aqueous aluminum chloride solution".
Example 7
In the preparation of the above-mentioned gel composition (3), a gel composition was obtained in the same manner as in example 1, except that "60.0 g of 9 mass% anionic PVA and 2.57g of 6 mass% aqueous aluminum chloride solution" were used instead of "60.0 g of 11 mass% anionic PVA and 3.14g of 6 mass% aqueous aluminum chloride solution".
Example 8
In the preparation of the above-mentioned gel composition (3), a gel composition was obtained in the same manner as in example 1, except that "60.0 g of 8 mass% anionic PVA, 2.28g of 6 mass% aqueous aluminum chloride solution" was used instead of "60.0 g of 11 mass% anionic PVA, 3.14g of 6 mass% aqueous aluminum chloride solution".
Example 9
In the preparation of the gel composition (3) of example 1, a gel composition was obtained in the same manner as in example 1, except that "60.0 g of 7 mass% anionic PVA, 2.00g of 6 mass% aqueous aluminum chloride solution" was used instead of "60.0 g of 11 mass% aqueous anionic PVA, 3.14g of 6 mass% aqueous aluminum chloride solution".
Example 10
(1) Preparation of anionic PVA aqueous solution
An 11 mass% aqueous solution of an anionized PVA was obtained by the same method as in example 1.
(2) Preparation of a salt solution of a metal of valence 3
10.0g of aluminum potassium sulfate (manufactured by Fuji photo-pure chemical Co., ltd.) and 156.7g of ion-exchanged water were added to a 100mL container, and the mixture was stirred at 50℃for 1 hour or more, thereby obtaining a 6 mass% aqueous aluminum potassium sulfate solution.
(3) Preparation of gel compositions
A gel composition was obtained in the same manner as in (3) of example 1, except that "3.14 g of a 6 mass% aqueous aluminum chloride solution" was changed to "6.07 g of a 6 mass% aqueous aluminum potassium sulfate solution".
Example 11
In the preparation of the gel composition (3) of example 1, a gel composition was obtained in the same manner as in example 1 except that 3.14g of "6 mass% aqueous aluminum chloride solution" was changed to 0.78g of "6 mass% aqueous aluminum chloride solution", and 0.52mL of "1mol/L hydrochloric acid (manufactured by Fuji photo-co. Co., ltd.) was further added.
Example 12
In the preparation of the gel composition (3) of example 1, a gel composition was obtained in the same manner as in example 1, except that "6 mass% aluminum chloride aqueous solution 10.98g" was used instead of "6 mass% aluminum chloride aqueous solution 3.14 g".
Comparative example 1
In the preparation of the gel composition (3) of example 1, a gel composition was obtained in the same manner as in example 1, except that "6 mass% aluminum chloride aqueous solution 0.78g" was used instead of "6 mass% aluminum chloride aqueous solution 3.14 g".
[ measurement and evaluation of physical Properties ]
The following physical properties were measured and evaluated for the gel compositions obtained in examples and comparative examples, respectively. The evaluation results are shown in table 1. The amounts of the components in table 1 represent mass%.
< pH value of gel composition >
A100 mL container was filled with the gel composition, and a glass electrode (manufactured by horiba manufacturing Co., ltd., product name: 9681S-10D) was inserted into the gel composition at 25℃to measure the pH of the gel composition at 25 ℃.
Storage modulus G' and loss modulus G ">, of gel composition
The storage modulus G 'and loss modulus G' of the gel composition were measured using a rheometer under the following conditions.
Machine: MRC302 (manufactured by Anton Paar Co., ltd.)
And (3) clamping: PP25 (diameter: 24.985 mm)
A plate: LOWER MEASURING PLATE L-PP08/CTD, D:8mm FOR CTD450/600/1000
Temperature: 25 DEG C
Frequency: 10 -3 ~10 2 rad/s
Strain: in the linear region (strain 1% in this example)
Based on the measurement curves obtained under the above measurement conditions, physical property values of storage modulus G' (frequencies: 62.8rad/s, 0.135 rad/s) and loss modulus G "(frequencies: 62.8rad/s, 0.135 rad/s) were obtained.
< evaluation of skin adhesion >
The adhesion of the gel composition to the skin was evaluated by a professional evaluator of 5 persons.
Specifically, the gel composition was applied to the back of the hand at a rate of 2g/9cm 2 (3 cm. Times.3 cm). Thereafter, the back of the hand was turned over for 180 ° for 120 seconds, and the dripping state of the gel composition was observed, and the adhesion of the gel composition to the skin was evaluated based on the following evaluation criteria.
(evaluation criterion)
1: dripping within 30 seconds
2: dripping within more than 30 seconds and 120 seconds
3: not drip, but the gel composition slightly flows
4: completely not drip down
The average value of the evaluations of the obtained 5 person skilled in the art is shown in table 1.
< evaluation of sticky feel >)
The evaluation of the sticky feel of the gel composition was performed by a professional evaluation staff of 5 persons.
Specifically, the gel composition was applied to the back of the hand at a rate of 2g/9cm 2 (3 cm. Times.3 cm), the sticky feel when the surface of the coated article of the gel composition was touched with a hand was evaluated based on the following evaluation criteria.
(evaluation criterion)
1: very sticky
2: sticky and greasy
3: slightly sticky
4: non-sticky and greasy
The average value of the evaluations of the obtained 5 person skilled in the art is shown in table 1.
TABLE 1
TABLE 1
Example 13
(1) Preparation of anionic PVA aqueous solution
An 11 mass% aqueous solution of an anionized PVA was obtained by the same method as in example 1.
(2) Preparation of a salt solution of a metal of valence 3
To a 1L container were added 46.7g of aluminum sulfate octadecahydrate (manufactured by SIGMA-ALDRICH Co., ltd.) and 353.3g of ion exchange water, and the mixture was stirred at 50℃for 1 hour or more, whereby a 6 mass% aluminum sulfate aqueous solution was obtained.
(3) Preparation of gel compositions
A gel composition was obtained in the same manner as in (3) of example 1, except that "3.14 g of a 6 mass% aqueous aluminum chloride solution" was changed to "4.02 g of a 6 mass% aqueous aluminum sulfate solution".
Regarding the composition of the obtained gel composition, the carboxypva as component (a) was 10.3 mass%, the aluminum sulfate as component (B) was 0.38 mass%, the water as component (C) was 89.3 mass%, the (C)/(a) was 8.7, the (B)/(a) was 0.037, and the ph was 4.1. The adhesion to the skin was 4.0, and the sticky feeling was 4.0.
It can be understood from table 1 and example 13 that the gel compositions of examples have a balanced and improved sticky feel and adhesion to the skin as compared with the gel compositions of comparative examples. That is, it can be understood that the present invention provides a gel composition, a skin external preparation, and a method for forming a gel composition, which can improve the balance between the sticky feeling and the adhesiveness.

Claims (11)

1. A gel composition, wherein,
comprises the following components (A) - (C) and has a pH of 3.0-5.0 at 25 ℃,
(A) Anionizing polyvinyl alcohol;
(B) A 3-valent metal salt;
(C) And (3) water.
2. The gel composition of claim 1, wherein,
the mass ratio (C)/(A) of the component (C) to the component (A) is 4.0 to 13.0.
3. The gel composition according to claim 1 or 2, wherein,
the component (A) contains a polyvinyl alcohol having a carboxyl group.
4. The gel composition according to claim 1 to 3,
the saponification degree of the component (A) is 90 mol% or more.
5. The gel composition according to claim 1 to 4,
the component (B) is water-soluble.
6. The gel composition according to claim 1 to 5,
the component (B) contains an aluminum salt.
7. The gel composition according to claim 1 to 6,
the mass ratio (B)/(A) of the component (B) to the component (A) is 0.001 to 0.500.
8. The gel composition according to claim 1 to 7,
the content of the component (A) is 3.0 to 30.0 mass%.
9. The gel composition according to claim 1 to 8, wherein,
the content of the component (B) is 0.01 to 5.0 mass%.
10. A skin external preparation, wherein,
a gel composition comprising any one of claims 1 to 9.
11. A method of forming a gel composition, wherein,
comprises a step of mixing the following component (A), the following component (B) and the following component (C) before use to gel the components,
the pH value of the gel composition at 25 ℃ is 3.0-5.0,
(A) Anionizing polyvinyl alcohol;
(B) A 3-valent metal salt;
(C) And (3) water.
CN202280039118.8A 2021-06-04 2022-04-18 Gel composition Pending CN117412736A (en)

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