WO2022044781A1

WO2022044781A1 - Gel composition

Info

Publication number: WO2022044781A1
Application number: PCT/JP2021/029367
Authority: WO
Inventors: 俊輔徳永; 陽子橋爪; 友紀奈倉田; 慶子平野
Original assignee: 日本コルマー株式会社; キユーピー株式会社
Priority date: 2020-08-28
Filing date: 2021-08-06
Publication date: 2022-03-03
Also published as: JP2022039549A; JP7104942B2

Abstract

The present invention pertains to a gel composition that contains 0.2 mass% or more of hyaluronic acid and/or a hyaluronic acid derivative or a salt thereof (A) and that has a viscosity of 15,000-60,000 mPa·s, said gel composition containing 0.1 mass% or more of an anionic polymer compound thickener (B) and 0.05 mass% or more of an associative thickener (C), wherein: the anionic polymer compound thickener (B) is an anionic polymer compound thickener other than the hyaluronic acid and/or a hyaluronic acid derivative or a salt thereof (A); and the ratio by mass of the anionic polymer compound thickener (B) to the associative thickener (C) is 5:1 - 0.15:1.

Description

Gel-like composition

The present invention relates to a gel-like composition.

Hyaluronic acid is a linear high molecular weight polysaccharide with a molecular weight of tens of thousands to millions, in which N-acetylglucosamine and D-glucuronic acid are alternately bound, which was isolated and identified from bovine vitreous by Meyer et al. In 1934. It is widely distributed in the living body and is present in connective tissues and organs such as skin, joint fluid, blood vessels, brain and cartilage. Hyaluronic acid has high water retention, is viscous due to its water retention capacity, exerts a cell retention function, and functions to maintain the flexibility of tissues. Utilizing this property, hyaluronic acid and hyaluronic acid derivatives are widely used as raw materials for pharmaceuticals, cosmetics, and foods. For example, cosmetics containing hyaluronic acid form a film containing water on the surface of the skin, have the effect of preventing the evaporation of water from the skin, and are useful for maintaining the moisturized state of the skin.

There are lotions, milky lotions, beauty essences, creams, etc. as basic cosmetics. In recent years, all-in-one makeup, which can cover these basic makeup with one cosmetic, has been attracting attention because it can be applied in a short time with the advancement of women into society.

From the above background, a highly viscous gel-like composition containing hyaluronic acid or the like having a high concentration of 0.2% by mass or more, which can be used as an all-in-one cosmetic and more positively utilizes the characteristics of hyaluronic acid. Is desired. However, the high-viscosity gel-like composition containing a high concentration of hyaluronic acid and the like has a problem that the stability over time is poor, the gel becomes non-uniform over time, and it is easy to be fooled.

Patent Document 1 contains 0.01% by mass or more and 5% by mass or less of a thickener, and 0.1 parts or more and 5 parts or more of modified hyaluronic acid containing a carboxymethyl group and / or a salt thereof with respect to 1 part of the thickener. The gel-like cosmetics containing less than a portion are described. However, since this gel-like cosmetic contains a high concentration of hyaluronic acid and the like, its stability over time is not sufficient, and there is the above problem.
Patent Documents 2 and 3 describe gel-like compositions containing hyaluronic acid and the like, using an associative thickener. However, the content of hyaluronic acid and the like in the gel-like composition is at most 0.02% by mass and 0.03% by mass, which are very low concentrations.
Further, Patent Documents 1 to 3 do not describe the use of an anionic polymer compound thickener and an associative thickener in combination as a thickener, and there are examples in which these are used in combination. do not do.

Japanese Unexamined Patent Publication No. 2016-199516 Japanese Unexamined Patent Publication No. 2018-08714 Japanese Unexamined Patent Publication No. 2017-036217

The subject of the present invention is hyaluronic acid having a high concentration of 0.2% by mass or more, which has stability over time, does not have gel inhomogeneity over time, is less likely to be fooled, and has an excellent usability. It is an object of the present invention to provide a highly viscous gel-like composition containing.

As a result of diligent studies using various thickeners in order to solve the above-mentioned problems of the present invention, the present inventors have made a case where only (B) anionic polymer compound thickener is used as the thickener. And (C) When only the associative thickener was used, the obtained gel-like composition containing a high concentration of hyaluronic acid and the like was not stable over time, but (B) was highly anionic. When the molecular compound thickener and the (C) associative thickener are combined in a mass ratio of 5: 1 to 0.15: 1, a high concentration of 0.2% by mass or more of hyaluronic acid or the like is contained. The present invention has been completed by finding that the gel-like composition having a viscosity unexpectedly has stability over time, does not cause non-uniformity of the gel over time, and is less likely to be fooled.

That is, the present invention is as follows.
[1] (A) A gel-like composition containing 0.2% by mass or more of hyaluronic acid and / or a hyaluronic acid derivative or a salt thereof and having a viscosity of 15,000 to 60,000 mPa · s.
The gel-like composition contains (B) anionic polymer compound thickener in an amount of 0.1% by mass or more and (C) an associative thickener in an amount of 0.05% by mass or more.
The (B) anionic polymer compound thickener is an anionic polymer compound thickener other than (A) hyaluronic acid and / or a hyaluronic acid derivative or a salt thereof.
A gel-like composition in which the mass ratio of the (B) anionic polymer compound thickener to the (C) associative thickener is 5: 1 to 0.15: 1.

[2] The gel-like composition according to [1], wherein the (C) associative thickener is hydrophobized modified alkyl cellulose.
[3] (A) At least one selected from hyaluronic acid and / or hyaluronic acid derivatives or salts thereof, containing 0.1% by mass or more having an average molecular weight of 500,000 to 2,000,000 [1]. ] Or the gel-like composition according to [2].
[4] (A) Among one or more selected from the group consisting of hyaluronic acid and / or hyaluronic acid derivatives or salts thereof, those having an average molecular weight of 500,000 to 2 million are contained in an amount of 0.1% by mass or more. The gelled composition according to [1] or [2], which contains 0.1% by mass or more of an average molecular weight of 10,000 or less.
[5] The gel-like composition according to any one of [1] to [4], which has a viscosity of 25,000 to 45,000 mPa · s.

The gel-like composition of the present invention has stability over time, does not have gel non-uniformity over time, is less likely to be fooled, spreads well on the skin, is not sticky, and is excellent in usability. There is.

1. 1. Gel-like composition The present invention is a gel-like composition containing (A) hyaluronic acid and / or a hyaluronic acid derivative or a salt thereof in an amount of 0.2% by mass or more and having a viscosity of 15,000 to 60,000 mPa · s. The gel-like composition contains (B) an anionic polymer compound thickener in an amount of 0.1% by mass or more, (C) an associative thickener in an amount of 0.05% by mass or more, and (B) an anionic polymer. The present invention relates to a gel-like composition in which the mass ratio of the compound thickener to the (C) associative thickener is 5: 1 to 0.15: 1.

<(A) Hyaluronic acid and / or hyaluronic acid derivative or salt thereof>
As the hyaluronic acid, those extracted from animal tissues, those produced by a fermentation method by culturing microorganisms, and the like are known, and commercially available hyaluronic acid may be appropriately used. For example, the average molecular weight is 500,000 to 3,000,000. Those having a high molecular weight, those having a high molecular weight, those having an average molecular weight of 10,000 or less, and the like can be used. Low-molecular-weight hyaluronic acid is produced, for example, by dissolving high-molecular-weight hyaluronic acid in a buffer solution, adding hyaluronidase, incubating for several days, inactivating the enzyme, and then producing (Japanese Patent Laid-Open No. 10-195107). It is produced by using a method of hydrolyzing hyaluronic acid with an acid or the like. The average molecular weight of hyaluronic acid and / or hyaluronic acid derivatives or salts thereof specified in the present invention can be measured by the following method.

First, a calibration curve is prepared from the retention time of a plurality of hyaluronic acids (reference substances) having known molecular weights by liquid chromatography analysis using a gel filtration column. Similarly, hyaluronic acid and / or hyaluronic acid derivatives or salts thereof to be measured are analyzed by liquid chromatography and the molecular weight is determined using the above calibration curve to obtain hyaluronic acid and / or hyaluronic acid derivatives or salts thereof. The molecular weight of can be determined.
Examples of the liquid chromatography analyzer that can be used for liquid chromatography analysis include Waters Alliance 2690 HPLC Separations Module (Waters), Waters Alliance 2695 HPLC Separations Module (Waters), 1200 Agilents. ). Examples of the column that can be used for liquid chromatography analysis include a column for ligand exchange chromatography manufactured by shodex (ligand exchange mode + size exclusion mode), model name "SUGAR KS-801", and the like. "SUGAR KS-802", "SUGAR KS-803", "SUGAR KS-804", "SUGAR KS-805", "SUGAR KS-806", "SUGAR KS-807", and TOSOH size exclusion chromatography columns, The model name "TSKgel GMPW" can be mentioned.

Examples of the hyaluronic acid derivative include derivatives obtained by etherifying, esterifying, acetylating, amidating, acetalizing, and ketalizing the hydroxyl group and carboxyl group of hyaluronic acid. Specifically, for example, a cationized hyaluronic acid having a quaternary ammonium group-containing group (WO2008 / 133267), a modified hyaluronic acid containing a glycerin skeleton-containing group (WO2011 / 102462), and a carboxymethyl group-containing modified hyaluronic acid (WO2016). / 159159 (Japanese Patent Laid-Open No. 2015-147945), low molecular weight cationized hyaluronic acid in which a part of the hydroxy group is replaced with a quaternary nitrogen-containing group (Japanese Patent Laid-Open No. 2016-108344) and the like can be mentioned.
The hyaluronic acid and the hyaluronic acid derivative may be salts such as sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt, basic amino acid salt and zinc salt.

As the hyaluronic acid and / or the hyaluronic acid derivative, a commercially available hyaluronic acid and / or the hyaluronic acid derivative may be appropriately used. Since a gel-like composition containing a high concentration of hyaluronic acid or the like can be stabilized over time, the hyaluronic acid and / or the hyaluronic acid derivative has an average molecular weight of 500,000 or more and 2 million or less. It is preferable to combine one or more hyaluronic acid derivatives and one or more hyaluronic acid or hyaluronic acid derivatives having an average molecular weight of 10,000 or less, and at least two or more types of hyaluronic acid and / or hyaluronic acid derivatives. The hyaluronic acid and / or the hyaluronic acid derivative includes two or more hyaluronic acid and / or hyaluronic acid derivatives having an average molecular weight of 500,000 or more and 2 million or less, and hyaluronic acid and / or hyaluronic acid derivatives having an average molecular weight of 10,000 or less. It is more preferable to combine at least 4 kinds of hyaluronic acid and / or hyaluronic acid derivatives of more than one kind.
The hyaluronic acid and / or hyaluronic acid derivative contains a medium-high molecular weight hyaluronic acid having an average molecular weight of 500,000 or more and 2 million or less, a low-molecular-weight hyaluronic acid having an average molecular weight of 10,000 or less, and / or a hyaluronic acid derivative, and a quaternary ammonium group. Catified hyaluronic acid derivative having an average molecular weight of 500,000 or more and 2 million or less, hyaluronic acid derivative containing a carboxymethyl group having an average molecular weight of 500,000 or more and 2 million or less, modified hyaluronic acid containing a glycerin skeleton-containing group, zinc hyaluronate, etc. However, a combination thereof is also preferable (Japanese Patent Laid-Open No. 2016-166133).
Hyaluronic acid and / or hyaluronic acid derivatives having an average molecular weight of 500,000 or more and 2 million or less have a property of staying on the skin surface and preventing water from evaporating from the skin surface, and thus exhibit a continuous skin moisturizing effect.

Examples of the low molecular weight hyaluronic acid and / or hyaluronic acid derivative having an average molecular weight of 10,000 or less include those having an average molecular weight of 800 or more and 10,000 or less and 1,000 or more and 10,000 or less. This low-molecular-weight hyaluronic acid and / or hyaluronic acid derivative has a high permeability to the skin and has a property of improving the moisturization of the stratum corneum, and thus exhibits a continuous skin moisturizing effect.
The cationized hyaluronic acid derivative having a quaternary ammonium group-containing group more preferably has a cationization degree of 0.15 to 0.6, and more preferably has a cationization degree of 0.15 to 0.4. Things can be mentioned. The degree of cationization refers to the number of quaternary ammonium group-containing groups per disaccharide, which is a constituent unit of hyaluronic acid, and is determined by a conventional method or a semi-micro Kjeldahl method. This cationized hyaluronic acid exerts a long-lasting moisturizing effect on the skin.

The "carboxymethyl group" of the modified hyaluronic acid derivative containing a carboxymethyl group means a group represented by "-CH ₂ ^- CO ₂ H" or "-CH ₂ -CO _2- ", and at least one. Hyaluronic acid in which a carboxymethyl group is introduced. The modified hyaluronic acid derivative containing a carboxymethyl group more preferably has a carboxymethylation rate of 5% or more and 200% or less with respect to the disaccharide unit constituting hyaluronic acid, and more preferably with respect to the disaccharide unit constituting hyaluronic acid. Examples thereof include those having a carboxymethylation rate of 60% or more and 200% or less.

The disaccharide unit constituting hyaluronic acid refers to one unit composed of adjacently bonded disaccharides (glucuronic acid and N-acetylglucosamine) constituting hyaluronic acid, and is a disaccharide unit constituting hyaluronic acid. The carboxymethylation rate with respect to 1 unit is the number of carboxymethyl groups contained in the 1 unit, and more specifically, when the 1 unit is 100%, the 1 unit is related to the 1 unit. The ratio (%) of the number of carboxymethyl groups contained in the unit. This modified hyaluronic acid derivative containing a carboxymethyl group exerts a long-lasting moisturizing effect on the skin.

The modified hyaluronic acid containing a glycerin skeleton-containing group is preferably of the formula: -O-CH ₂ -CHOH-CH ₂ -OR ¹ (where R ¹ represents a linear or branched alkyl or alkenyl). It is a modified hyaluronic acid containing a glycerin skeleton-containing group represented. This modified hyaluronic acid has the property of repairing the lamellar structure composed of the aqueous layer and the lipid layer and improving the barrier function repairing effect of the skin, and thus exerts a continuous skin moisturizing effect.
Zinc hyaluronic acid is a complex formed by the interaction of zinc ions with carboxyl ions derived from the carboxyl groups constituting hyaluronic acid. Preferred zinc hyaluronates have a zinc content of 55 to 100 mg per gram, more preferably 60 to 80 mg. Zinc hyaluronate exerts a long-lasting moisturizing effect on the skin.

The gel-like composition of the present invention contains 0.2% by mass or more of hyaluronic acid and / or a hyaluronic acid derivative. Preferred contents include 0.2 to 5% by mass, more preferably 0.25 to 3% by mass, and further preferably 0.3 to 2% by mass.
When 5% by mass or more of hyaluronic acid and / or a hyaluronic acid derivative is contained in the gel-like composition of the present invention, the viscosity of the gel-like composition becomes high, the stability over time becomes insufficient, and over time. Gel non-uniformity may occur.

Further, among one or more selected from the group consisting of hyaluronic acid and / or hyaluronic acid derivatives or salts thereof, those having an average molecular weight of 500,000 to 2,000,000 are preferably contained in an amount of 0.1% by mass or more. .. When it is contained in an amount of 0.1% by mass or more, it stays on the skin surface and has a property of preventing water from evaporating from the skin surface, so that a continuous skin moisturizing effect is exhibited. The more preferable content is 0.1 to 3% by mass, more preferably 0.1 to 1% by mass, and even more preferably 0.1 to 0.2% by mass.
Further, among one or more selected from the group consisting of aluronic acid and / or hyaluronic acid derivatives or salts thereof, those having an average molecular weight of 10,000 or less are preferably contained in an amount of 0.1% by mass or more. When it is contained in an amount of 0.1% by mass or more, it has a high permeability to the skin and has a property of improving the moisturization of the stratum corneum, so that a continuous skin moisturizing effect is exhibited. More preferable content is 0.1 to 3% by mass or more, further preferably 0.1 to 1% by mass, and even more preferably 0.1 to 0.25% by mass. ..

<(B) Anionic polymer compound thickener>
The anionic polymer compound thickener is an anionic polymer compound thickener other than (A) hyaluronic acid and / or a hyaluronic acid derivative or a salt thereof, and is, for example, from a carboxy group, a sulfo group, a phospho group, or the like. It is a polymer compound having a selected anionic group in the molecule, and may be a synthetic polymer or a natural polymer. Preferably, the anionic polymer compound thickener has a carboxy group in the molecule.

Examples of the anionic synthetic polymer compound thickener include unsaturated monocarboxylic acid-based monomers (acrylic acid, methacrylic acid, clonic acid, neutralized products of these acids, partially neutralized products, etc.) and unsaturated dicarboxylic acids. Acid-based monomers (maleic acid, fumaric acid, itaconic acid, citraconic acid, neutralized products of these acids, partially neutralized products, etc.), and unsaturated sulfonic acid-based monomers (vinyl sulfonic acid, allyl sulfonic acid, methacrylic sulfone, etc.) Acids, styrene sulfonic acids, 2-acrylamide-2-methyl propane sulfonic acids, sulfoethyl (meth) acrylates, sulfoethyl maleimides, 3-allyloxy-2-hydroxypropane sulfonic acids, neutralized and partially neutralized products of these acids. Etc.), homopolymers composed of monomers selected from the group consisting of the above-mentioned monomers, copolymers composed of arbitrary combinations of the above-mentioned monomers, copolymers of the above-mentioned monomers with other monomers commutable, and the like. Specifically, (Acrylate / alkyl acrylate (10 to 30 carbon atoms)) cross polymer, (acrylic acid / vinylpyrrolidone) cross polymer, (methyl vinyl ether / maleic acid) cross polymer, alkyl-modified carboxyvinyl polymer, carboxyvinyl Polymer, Alkyl Acrylic Acid / Steareth Methacrylate-20 Copolymer, Acrylic Copolymer, Acrylate / Steareth Methacrylate-20 Polymer, Acrylate / Steareth Itaconic Acid-20 Polymer, Polyacrylic Acid, Acrylate / Behenes methacrylate-25 Copolymer, Acrylate / Methacrylate Laureth -25 Copolymer, Acrylate / Vinyl Neodecanoate Cross Polymer, Alkyl Acrylic Acid / Steareth Methacrylate-20 Cross Polymer, Acrylate / Steareth Methacrylate-20 Cross Polymer, Methyl Vinyl Ether / Maleic Anhydrous / Decadien Cross Polymer, Acrylic Acid Examples thereof include alkyl methacrylate copolymers, vinylpyrrolidone / acrylate / lauryl methacrylate copolymers, acrylates copolymers, Na polyacrylate, Na alginate, (acryloyldimethyltaurine ammonium / Behenes-25 methacrylate) crosspolymers and the like.

Anionic natural polymer compound thickeners include pectic acid, alginic acid, agar, carrageenan, fucoidan, heparin, gellan gum, native gellan gum, xanthan gum, dextran gum, arabic rubber, carboxymethyl cellulose, carboxymethyl hydroxyethyl cellulose, carboxymethyl starch, Examples thereof include carboxymethyl dextran, polyglutamic acid, succinylated collagen, carboxymethyl chitin, succinylated chitosan, sodium cellulose sulfate, gelatin, mucin, dextran and the like.

Preferred anionic polymer compound thickeners include anionic synthetic polymer compound thickeners. More preferably, an acrylic acid-based anionic polymer compound thickener such as a (meth) acrylic acid / alkyl (meth) acrylic acid copolymer is mentioned, and more preferably, an acrylic acid / alkyl methacrylate copolymer is mentioned. And even more preferably (Acrylate / alkyl acrylate (10 to 30 carbon atoms)) crosspolymers.
The gel-like composition contains 0.1% by mass or more of an anionic polymer compound thickener. Preferred contents include 0.1 to 2% by mass, more preferably 0.15 to 1% by mass, and further preferably 0.2 to 0.5% by mass.

<(C) Associative thickener>
Associative thickeners are thickeners that contain both hydrophilic and hydrophobic areas. For example, a thickener having a hydrophobic region containing at least one _C8-36 fat chain and a hydrophilic region and at least one hydrophilic region can be mentioned. Associative thickeners include, for example, those defined in the Encyclopedia of Polymer Science and Engineering, 2nd Edition, 17, 772-779. Hydrophobic regions can bind to hydrophobic moieties and hydrophilic regions can bind to hydrophilic moieties. The associative thickener forms a network (network structure) by these bonds, that is, by associating the hydrophobic regions with each other, and further by associating the hydrophobic regions with other hydrophobic substances. , Thickening action is exhibited.

Examples of the associative thickener include those described in Special Table 2015-514788, Special Table 2017-310649, Special Table 2016-591159, Special Table 2005-500397, WO2011 / 162421, WO2018 / 088312 and the like.
Examples of associative thickeners include:
(A) Nonionic amphipathic polymer containing at least one _C8-36 fatty chain and at least one hydrophilic unit;
(B) An anionic amphipathic polymer containing at least one hydrophilic unit and at least one unit having a _C8-36 fatty chain;
(C) A cationic amphipathic polymer containing at least one hydrophilic unit and at least one unit having a _C8-36 fatty chain;
(D) An amphoteric amphoteric polymer containing at least one hydrophilic unit and at least one unit having a _C8-36 fatty chain.

Of these associated thickeners, (a) nonionic amphipathic polymers are preferred. Examples of the (a) nonionic amphipathic polymer include the following.
(1) Cellulose modified with a group having at least one _C8-36 fatty chain (hydrophobic modified alkyl cellulose);
(2) Urethane polyether (hydrophobic modified polyether urethane) containing at least one type of _C8-36 fat chain;
(3) Hydroxypropyl guar compound modified with a group having at least one _C8-36 fatty chain;
(4) Copolymer of vinylpyrrolidone and a hydrophobic monomer having a _C8-36 fatty chain;
(5) Copolymer of amphipathic monomer containing C _1-6 alkyl methacrylate or C _1-6 alkyl acrylate and at least one C _8-36 fatty chain;
(6) A copolymer of a hydrophobic monomer containing hydrophilic methacrylate or acrylate and at least one _C8-36 fatty chain.

Examples of the hydrophobized modified alkyl cellulose include those described in WO2011 / 162421, formula (1) :.

[In the formula, R ¹ , R ² and R ³ are the same or different, hydrogen atom, alkyl,-[CH ₂ CH _2-k (CH ₃ ) _k O] _m -H, or -CH ₂ CH (OH). ) CH ₂ OC _j H _{2j + 1} . However, -CH ₂ CH (OH) CH ₂ OC _j H _{2j + 1} is always included.
n is an integer of 100 to 10000.
k is 0 or 1.
m is an integer from 1 to 10.
j is an integer of 6 to 26. ]
It is an associative thickener represented by.

The hydrophobized modified alkyl cellulose is preferably
Alkyl is 10 to 50% by mass,
-[CH ₂ CH _2-k (CH ₃ ) _k O] _m -H is contained in an amount of 3 to 20% by mass, and -CH ₂ CH (OH) CH ₂ OC _j H _{2j + 1} is contained in an amount of 0.1 to 10% by mass. ..
The hydrophobized modified alkyl cellulose is more preferably one in which j is 18.
As the hydrophobized modified alkyl cellulose, hydroxypropylmethyl cellulose stearoxy ether (for example, Sangelose (registered trademark) (manufactured by Daido Kasei Kogyo Co., Ltd.)) and the like can be preferably used.

Examples of the hydrophobically modified polyether urethane include those described in WO2018 / 088312, and the formula (2):
R ¹ -{(OR ² ) _k -OCONH-R ³ [-NHCOO- (R ⁴ -O) _n -R ⁵ ] _h } _m
[In the formula, R ¹ , R ² and R ⁴ are each independently a hydrocarbon group having 2 to 4 carbon atoms.
R ³ is a hydrocarbon group having 1 to 10 carbon atoms which may have a urethane bond.
R5 is a hydrocarbon group having ⁸ to 36 carbon atoms.
m is a number of 2 or more.
h is a number of 1 or more.
k is a number from 1 to 500.
n is a number from 1 to 200. ]
It is an associative thickener represented by.

As the hydrophobically modified polyether urethane, a (PEG-240 / decyltetradeceth-20 / hexamethyldiisocyanate) copolymer (for example, Adecanol (registered trademark) GT-700 (manufactured by ADEKA)) or the like can be used.

Examples of the associative thickener include (a) a nonionic amphoteric polymer, more preferably a hydrophobic modified alkyl cellulose, a hydrophobic modified polyether urethane, and the like, and further preferably hydroxypropylmethyl cellulose steer. Examples thereof include rhoxyethers, (PEG-240 / decyltetradeceth-20 / hexamethyldiisocyanate) polymers, and even more preferably hydroxypropylmethylcellulose stearoxy ethers.

Even in a gel-like composition containing a high concentration of hyaluronic acid or the like, stability over time can be obtained. Therefore, 0.05% by mass or more of an associative thickener is contained in the gel-like composition. Preferred contents include 0.05 to 1% by mass, more preferably 0.06 to 0.5% by mass, and further preferably 0.07 to 0.3% by mass.
Since stability over time can be obtained even in a gel-like composition containing a high concentration of hyaluronic acid or the like, the mass ratio of (B) anionic polymer compound thickener to (C) associative thickener is It is 5: 1 to 0.15: 1. The mass ratio is preferably 4: 1 to 1: 1 and more preferably 3.5: 1 to 1.2: 1. When the mass ratio is in the above range, the gel of the gel-like composition of the present invention becomes uniform and the occurrence of unevenness is suppressed.

<Oil>
The gel-like composition of the present invention can contain 5% by mass or more and 20% by mass or less of oil in terms of enhancing the effect of improving skin compatibility. The oil content used in the gel-like composition of the present invention is not particularly limited as long as it is an oil-soluble raw material that can be used in cosmetics and the like. Squalane, Macademian oil, d-δ-tocopherol, trioctanoin, cetyl lactate, cetyl 2-ethylhexanate, phytosqualane, liquid paraffin, squalane, beeswax, vaseline, lanolin, carnauba wax, olive oil, avocado oil, camellia oil, jojoba Oil, horse oil, mink oil, ceramide, coenzyme Q10, retinol palmitate, pantenol, egg yolk lecithin, soy lecithin, hydrogenated lecithin, polysorbate-60, phytosterol, triethylhexanoin, glycerol monostearate, polyoxyethylene monostea Rate, stearyl alcohol, sorbitan stearate, cetostearyl alcohol, polyoxyethylene cetostearyl alcohol, polyoxyethylene fatty acid ester, polyglyceryl-10 stearate, polyoxyethylene hydrogenated castor oil derivative, glycerin caprylate, higher fatty acid (lauric acid, Behenic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, higher fatty acid salts, etc.), silicone and silicone derivatives (dimethylpolysiloxane, cyclic dimethylpolysiloxane, methylphenylpolysiloxane, silicone resin, polyether-modified silicone) , Amino-modified silicone, etc.) and the like.

<Other ingredients>
The gel-like composition of the present invention contains water as a solvent. Further, the gel-like composition of the present invention can contain, as other components, components generally blended in cosmetics and the like in an amount suitable for the purpose. Other components include, for example, surfactants (anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants), moisturizers, functional ingredients, natural product extracts, protein hydrolysis. Substances, amino acids, cationized polysaccharides, higher alcohols, polyhydric alcohols, amphoteric polymer resin compounds, cationic polymer resin compounds, preservatives, antioxidants, metal sequestering agents, UV absorbers, UV reflectors, pH adjustment Examples include agents, fragrances and pigments.

Examples of the anionic surfactant include alkylbenzene sulfonates, polyoxyalkylene alkyl ether sulfate esters, alkyl sulfate ester salts, olefin sulfonates, dialkyl sulfosuccinates and the like.
Examples of the nonionic surfactant include polyoxyethylene fatty acid ester, polyoxyethylene hydrogenated castor oil derivative and the like.
Examples of the cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkylpyridinium salt, stearyltrimethylammonium chloride and the like.
Examples of the amphoteric tenside include alkyl betaine, alkylamide propyl betaine, imidazolinium betaine, egg yolk lecithin, soybean lecithin and the like.
Examples of the moisturizer include diphytosteryl octyldodecyl lauroyl glutamate, phytoglycogen, hydrolyzed eggshell membrane, trehalose, atelocollagen, sorbitol, maltitol and the like.

Examples of the functional component include albutin, polyquaternium 51, elastin, platinum nanocolloid, allantin, sodium dilauroyl glutamate lysine, ascorbic magnesium phosphate, L-ascorbic acid 2-glucoside, ellagic acid, niacin, vitamin A oil, and the like. Retinol, retinol palmitate, innosit, pyridoxin hydrochloride, benzyl nicotinate, nicotinic acid amide, dl-α-tocopherol nicotinate, vitamin D2 (ergocasiferol), dl-α-tocopherol, dl-α-tocopherol acetate, pantothenic acid , Vitamins such as biotin, hormone allantin such as estradiol and ethynyl estradiol, anti-inflammatory agents such as tranexamic acid, glycyrrhetinic acid and azulene acid.

Natural product extracts include, for example, Kujin extract, Kazil extract, Seaweed extract, Eucalyptus extract, Royal jelly extract, Rosemary extract, Beech tree extract, Asenyaku extract, Bunanome extract, Ukon extract, Dokudami extract, Oubaku extract, Merilot extract, Odorikosou extract. , Kanzo extract, Shakuyaku extract, Sabonsou extract, Hechima extract, Kina extract, Yukinoshita extract, Clara extract, Kohone extract, Uikyo extract, Sakurasou extract, Rose extract, Dio extract, Lemon extract, Shikon extract, Aloe extract, Shobu root extract, Eucalyptus extract, Sugina extract, sage extract, thyme extract, tea extract, cucumber extract, butterfly extract, strawberry extract, melissa extract, carrot extract, carrot extract, marronnier extract, peach extract, peach leaf extract, kuwa extract, yagurumagiku extract, hamamelis extract, placenta extract, Chest line extract, silk extract and the like can be mentioned.

Examples of the protein hydrolyzate include keratin peptide, collagen peptide, soybean peptide, wheat peptide, milk peptide, silk peptide, egg white peptide, hydrolyzed eggshell membrane and the like.
Examples of amino acids include arginine, glutamic acid, glycine, alanine, hydroxyproline, cysteine, serine, L-theanine and the like.
Examples of the cationized polysaccharide include cationized hydroxyethyl cellulose, cationized guar gum, cationized starch, cationized locust bean gum, cationized dextran, cationized chitosan, cationized honey and the like.
Examples of the higher alcohol include cetyl alcohol, behenyl alcohol, isostearyl alcohol, bacillic alcohol and the like.
Examples of the polyhydric alcohol include propylene glycol, polyethylene glycol, pentylene glycol, caprylyl glycol, hexanediol, ethylhexyl gluserine, 1,3-butylene glycol, 1,3-propanediol, diglycerin, glycerin and the like. Be done.

Examples of the amphoteric polymer resin compound include betaineized dialkylaminoalkyl acrylate copolymers.
Examples of the cationic polymer resin compound include vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer cationized products, polydimethyldiallyl ammonium halide-type cationic polymers, and the like.
Examples of the preservative include methylparaben, ethylparaben, butylparaben, propylparaben, phenoxyethanol and the like.
Examples of the antioxidant include tocopherol, BHT and the like.
Examples of the metal sequestering agent include EDTA-2Na, EDTA-4Na, edetate, etidronate and the like.
Examples of the ultraviolet absorber include a benzophenone derivative, a para-aminobenzoic acid derivative, a methoxycinnamic acid derivative and the like.
Examples of the ultraviolet reflector include titanium oxide, zinc oxide and the like.

Examples of the pH adjuster include alkaline hydroxides such as sodium hydroxide and acids such as hydrochloric acid, sulfuric acid, phosphoric acid and methanesulfonic acid. The pH of the gelled composition of the present invention can be adjusted to preferably pH 5 to 7.5, more preferably pH 6 to 7, using a pH adjuster.

2. 2. Methods and Applications for Producing Gel-like Composition The gel-like composition of the present invention can be produced according to a conventional method. For example, it can be produced by mixing each of the above components with a thickener and gelling. The produced gel-like composition is filled and sealed in a container or the like according to the intended use.
The gel-like composition of the present invention can be suitably used as a high-viscosity cosmetic such as an all-in-one cosmetic and a hair cosmetic.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Examples 1 to 16 and Comparative Examples 1 to 4
<Preparation of gel-like composition>
Each component (mass%) shown in Tables 1 to 4 is added to ion-exchanged water (residual) and mixed, and if necessary, an aqueous sodium hydroxide solution is added to adjust the pH to 6 to 7.5. By doing so, the gel-like compositions of Examples 1 to 16 and Comparative Examples 1 to 4 were prepared.

The materials used in the above Examples and Comparative Examples are as shown below.
<Ingredient (A)>
Na hyaluronate: Hyaluronsan HA-LQ (manufactured by Kewpie), average molecular weight 850,000 to 1.6 million Hydrolyzed alkyl hyaluronate (C12-13) Glyceryl: Hyalo Repair (registered trademark) (manufactured by Kewpie), average molecular weight 10,000 or less Carboxy Na Methylhyaluronate: Hyalocatch (registered trademark) (manufactured by Kewpie), average molecular weight 800,000 to 1.2 million Hydrolyzed Na Na hyaluronate (registered trademark) (manufactured by Kewpie), average molecular weight 1000 to 3500
Hydroxypropyltrimonium hyaluronate: Hyalover-P (registered trademark) (manufactured by Kewpie), average molecular weight of 500,000 to 800,000 Hydrolyzed hyaluronic acid: hyalooligo (registered trademark) (manufactured by Kewpie), average molecular weight of 10,000 or less

<Ingredient (B)>
(Acrylate / Alkyl acrylate (C10-30)) Crosspolymer: Pemulen (registered trademark) TR-1 (manufactured by Lubrizol)
Acrylate Copolymer: Carbopol (R) Aqua SF-1 Polymer (manufactured by Lubrizol Advanced Material)
Sodium polyacrylate: Aronbis MX (manufactured by Toagosei Co., Ltd.)
(Acryloyldimethyltaurine ammonium methacrylate Behenes-25) Crosspolymer: Aristoflex HMB (manufactured by Clariant Japan)
Na alginate: Kimika algin I-3 (manufactured by Kimika)
Carboxymethyl Cellulose Na: CMC Daicel 1350 (manufactured by Daicel FineChem)
Carrageenan: GENUGEL (manufactured by CP Kelco)
Carbomer: CARBOPOL® (registered trademark) ULTREZ 10 (manufactured by Lubrizol Advanced Material)

<Ingredient (C)>
Hydroxypropyl Methyl Cellulose Stearoxy Ether: Sangelose (registered trademark) (manufactured by Daido Kasei Kogyo Co., Ltd.)
(PEG-240 / decyltetradeceth-20 / HDI) copolymer: Adecanol GT-700® (registered trademark) (manufactured by ADEKA)
<Oil>
As the oil content, squalane, ethylhexyl palmitate, macadamia seed oil and the like were used.
<Glycols>
Butylene glycol, pentylene glycol and glycerin were used as glycols.

Test Example <Evaluation of gel-like composition>
(viscosity)
The viscosity of the gel-like composition was measured the day after the gel-like composition was prepared. The viscosity (mPa · s) was determined by using a B-type viscometer (Viscometer BLII, manufactured by Toki Sangyo Co., Ltd.) to obtain Rotor No. At 4, the measurement was performed at 25 ° C. at 6 rpm for 60 seconds.
(PH)
The pH of the gel-like composition was measured the day after the gel-like composition was prepared. The pH was measured using a pH meter (manufactured by HORIBA).

(Stability)
The stability of the gel-like composition was evaluated according to the following index after 6 months had passed since the gel-like composition was prepared.
◯: Good △: Gel non-uniformity is confirmed a little ×: Gel is completely non-uniform and unevenness occurs

(Comprehensive usability)
The usability of the gel-like composition was comprehensively evaluated by 5 volunteers arbitrarily selected according to the following evaluation items and indicators.
・ Evaluation items Spread on the skin at the time of application, moderate thickness No stickiness after application ◎: Very good ○: Good △: Medium ×: Defective (Items that were defective are listed in the margin)

Table 5 shows the results of evaluation of the gelled compositions of Examples 1 to 16 and Comparative Examples 1 to 4.

As can be seen from Table 5, all of the gel-like compositions of Examples 1 to 16 were contained in the range of 15,000 to 60,000 mPa · s, and were highly viscous gel-like compositions. In Examples 1 to 9 and 14 to 16 in which an anionic synthetic polymer compound thickener is used as the component (B), the viscosity is 24000 to 42,500 mPa · s, which is more suitable than that it can be used as, for example, all-in-one cosmetics. Has a good viscosity. In Examples 10 to 12 using the anionic natural polymer compound thickener, the viscosity was as low as 17800 to 20500 mPa · s. As described above, it can be seen that the anionic synthetic polymer compound thickener is more preferable in the (B) anionic polymer compound thickener. Further, for example, by comparing Examples 1 to 4, it can be seen that the viscosity increases as the content of the component (B) increases.

Regarding stability, in Examples 1 to 16 in which the mass ratio of (B) anionic polymer compound thickener and (C) associative thickener is 5: 1 to 0.15: 1, it is good or slightly. The non-uniformity of the gel was confirmed, and it could be used as the gel-like composition of the present invention. On the other hand, in Comparative Examples 1 and 2 using only the (B) anionic polymer compound thickener and Comparative Examples 3 and 4 using only the (C) associative thickener, the gel became non-uniform and stable over time. The sex was unsatisfactory, and the feeling of use was also insufficient. Since the viscosities of Comparative Examples 1 and 3 were low, those in which the content of each thickener was increased were Comparative Examples 2 and 4, but the stability was also unsatisfactory, and the skin was spread and sticky. Was worse.

Regarding the feeling of use, the gelled compositions of Examples 1 to 6 using the (Acrylate / alkyl acrylate (C10-30)) crosspolymer as the component (B) gave favorable results in the comprehensive evaluation of the feeling of use. .. Therefore, it can be seen that in the (B) anionic polymer compound thickener, an acrylic acid-based anionic polymer compound thickener such as (Acrylate / alkyl acrylate (C10-30)) crosspolymer is more suitable. ..

The embodiments and examples disclosed this time are exemplary in all respects and are not restrictive. The scope of the present invention is shown by the scope of claims, not the above description, and includes all modifications within the meaning and scope equivalent to the scope of claims.

According to the present invention, it is in the form of a highly viscous gel containing hyaluronic acid or the like having a high concentration of 0.2% by mass or more, which has stability over time, does not cause non-uniformity of the gel over time, and is less likely to be fooled. The composition is provided.

Claims

(A) A gel-like composition containing 0.2% by mass or more of hyaluronic acid and / or a hyaluronic acid derivative or a salt thereof and having a viscosity of 15,000 to 60,000 mPa · s.
The gel-like composition contains (B) anionic polymer compound thickener (however, excluding (A) component) in an amount of 0.1% by mass or more, and (C) an associative thickener in an amount of 0.05% by mass. Contains more than
The (B) anionic polymer compound thickener is an anionic polymer compound thickener other than (A) hyaluronic acid and / or a hyaluronic acid derivative or a salt thereof.
A gel-like composition in which the mass ratio of the (B) anionic polymer compound thickener to the (C) associative thickener is 5: 1 to 0.15: 1.
(C) The gel-like composition according to claim 1, wherein the associative thickener is hydrophobized modified alkyl cellulose.
(A) Claimed to contain 0.1% by mass or more of one or more selected from the group consisting of hyaluronic acid and / or hyaluronic acid derivatives or salts thereof, having an average molecular weight of 500,000 to 2,000,000. Item 2. The gel-like composition according to Item 1 or 2.
(A) Among one or more selected from the group consisting of hyaluronic acid and / or hyaluronic acid derivatives or salts thereof, those having an average molecular weight of 500,000 to 2 million are contained in an average of 0.1% by mass or more. The gel-like composition according to claim 1 or 2, which contains 0.1% by mass or more of a composition having a molecular weight of 10,000 or less.
The gel-like composition according to any one of claims 1 to 4, which has a viscosity of 25,000 to 45,000 mPa · s.