JP7104942B2 - gel composition - Google Patents

Description

Application of Article 30, Paragraph 2 of the Patent Act (1) Date of interview: September 5, 2019 Place of interview: Large hall on the 2nd floor of Kewpie Corporation Shibuya Headquarters Building (1-4-13 Shibuya, Shibuya-ku, Tokyo) (2) Distribution date: September 5, 2019 Distribution location: Kewpie Co., Ltd. Shibuya Headquarters Building 2nd floor large hall (1-4-13 Shibuya, Shibuya-ku, Tokyo) (3) Website publication date: September 5, 2019 Website address: 1) https://www. kewpie. com/newsrelease/2019/1475/ 2) https://www. kewpie. com/newsrelease/items/2019/items/pdf/2019/newsrelease_20190905_73. pdf 3) https://www. kewpie. co. jp/products/skincare/skincare/hyalo_one/ (4) Website publication date and sales date: October 1, 2020 Sales location and website address: 1) Kewpie Ohata Net Shop http://www. blue flag. co. jp/sp/supplement/category/002004/list/http://kewpie. blue flag. co. jp/lp/n_hyaloone_01/ 2) Kewpie Aohata Rakuten Ichiba https://item. rakuten. co. jp/kewpie-blueflag/34161/ 3) Kewpie Aohata PayPay Mall store https://paypaymall. Yahoo. co. jp/store/kewpie-blueflag/item/y-28937/

Article 30, Paragraph 2 of the Patent Act applies 4) Amazon. co. jp https://www. amazon. co. jp/%E3%82%AD%E3%83%A6%E3%83%BC%E3%83%94%E3%83%BC-%E3%82%AA%E3%83%BC%E3%83% AB%E3%82%A4%E3%83%B3%E3%83%AF%E3%83%B3%E3%82%B8%E3%82%A7%E3%83%AB-%E3%83%92 %E3%82%A2%E3%83%AB%E3%83%AD%E3%83%B3%E9%85%B8-%E3%82%AA%E3%83%BC%E3%83%AB% E3%82%A4%E3%83%B3%E3%83%AF%E3%83%B3%E3%82%B2%E3%83%AB-%E3%83%92%E3%82%A2%E3 %83%AD%E3%83%A2%E3%82%A4%E3%82%B9%E3%83%81%E3%83%A3%E3%83%BC/dp/B07YG3L29F/ref=pd_lpo_194_img_2/357 -4685241-7128307? ＿ｅｎｃｏｄｉｎｇ＝ＵＴＦ８＆ｐｄ＿ｒｄ＿ｉ＝Ｂ０７ＹＧ３Ｌ２９Ｆ＆ｐｄ＿ｒｄ＿ｒ＝ｄｆ１２８０ｆｂ－６２２５－４０ｆ１－ａ３ｂ３－７ｂ２６２ｃｃ０ｃｃ３ｅ＆ｐｄ＿ｒｄ＿ｗ＝ＩａｒｍＤ＆ｐｄ＿ｒｄ＿ｗｇ＝ｗＱ６ｃｗ＆ｐｆ＿ｒｄ＿ｐ＝４ｂ５５ｄ２５９－ｅｂｆ０－４３０６－９０５ａ－７７６２ｄ１ｂ９３７４０＆ｐｆ＿ｒｄ＿ｒ＝８ＱＷＪＲ９Ｗ０５１７３Ｚ３ＫＫ７９ＪＺ＆ｐｓｃ＝１＆ｒｅｆＲＩＤ＝８ＱＷＪＲ９Ｗ０５１７３Ｚ３ＫＫ７９ＪＺ（５）公開日 ：令和１年１２月１０日 刊行Material: Asahi Shimbun December 10, 2019 morning edition (6) Publication date: January 26, 2020 Publication: Asahi Shimbun January 26, 2020 morning edition

The present invention relates to gel compositions. More specifically, the present invention relates to a gel composition containing hyaluronic acid or the like at a high concentration of 0.2% by mass or more.

Hyaluronic acid is a linear high-molecular-weight polysaccharide consisting of alternating bonds of N-acetylglucosamine and D-glucuronic acid, isolated and identified from bovine vitreous by Meyer et al. in 1934. It is widely distributed in vivo and is present in connective tissues and organs such as skin, synovial fluid, blood vessels, brain and cartilage. Hyaluronic acid has a high water retention capacity, has viscosity due to its ability to retain water, exhibits a cell retention function, and works to maintain tissue flexibility. Taking advantage of 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 moisture-containing film on the surface of the skin, which has the effect of preventing evaporation of moisture from the skin and is useful for keeping the skin moist.

There are lotions, milky lotions, beauty essences, creams, etc. as basic cosmetics, but in recent years, all-in-one cosmetics that can cover all of these basic cosmetics have become popular in a short period of time with the advancement of women into society. It is gaining attention because it can be done.

Based on the above background, a high-viscosity gel composition containing hyaluronic acid at a high concentration of 0.2% by mass or more, etc., which can be used as an all-in-one cosmetic and more actively utilizes the properties of hyaluronic acid. is desired. However, a high-viscosity gel composition containing a high concentration of hyaluronic acid or the like has a problem of poor stability over time, causing the gel to become non-uniform over time and easily forming lumps.

Patent Document 1 contains 0.01% by mass or more and 5% by mass or less of a thickening agent, and 0.1 part or more of a carboxymethyl group-containing modified hyaluronic acid and / or a salt thereof per 1 part of the thickening agent. A gel cosmetic containing 1 part or less is described. However, since this gel-like cosmetic contains hyaluronic acid and the like at a high concentration, it is not stable over time and has the above-mentioned problems.
Patent Documents 2 and 3 describe a gel composition containing hyaluronic acid and the like using an associative thickener. However, the content of hyaluronic acid and the like is 0.02% by mass and 0.03% by mass at most, which is a very low concentration.
In addition, Patent Documents 1 to 3 do not describe the use of a combination of an anionic polymer compound thickener and an associative thickener as thickeners, and there are examples in which these are used in combination. do not do.

JP 2016-199516 A JP 2018-087148 A JP 2017-036217 A

An object of the present invention is to provide a high-concentration hyaluronic acid of 0.2% by mass or more, which has stability over time, does not cause uneven gel over time, does not easily form lumps, and has excellent usability. To provide a highly viscous gel composition containing

In order to solve the above-mentioned problems of the present invention, the present inventors have made intensive studies using various thickeners, and as a result, only the (B) anionic polymer compound thickener was used as the thickener. and (C) when only an associative thickener was used, the resulting gel composition containing a high concentration of hyaluronic acid and the like had no stability over time, but (B) anionic When the polymer compound thickener and (C) the associative thickener are combined at a mass ratio of 5:1 to 0.15:1, it contains hyaluronic acid at a high concentration of 0.2% by mass or more. The inventors have found that a high-viscosity gel composition has unexpectedly long-term stability, does not become non-uniform over time, and is less likely to clump, thus completing the present invention.

That is, the present invention is as follows.
[1] (A) A gel 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 composition contains (B) 0.1% by mass or more of an anionic polymer compound thickener and (C) 0.05% by mass or more of an associative thickener,
(B) the anionic polymer compound thickener is (A) an anionic polymer compound thickener other than hyaluronic acid and/or hyaluronic acid derivatives or salts thereof;
A gel composition in which the mass ratio of (B) anionic polymer compound thickener and (C) associative thickener is 5:1 to 0.15:1.

[2] The gel composition of [1], wherein (C) the associative thickener is hydrophobized modified alkylcellulose.
[3] (A) contains 0.1% by mass or more of at least one selected from hyaluronic acid and/or hyaluronic acid derivatives or salts thereof having an average molecular weight of 500,000 to 2,000,000, [1 ] or the gel composition according to [2].
[4] (A) Contains 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 and having an average molecular weight of 500,000 to 2,000,000 and the gel composition according to [1] or [2], which contains 0.1% by mass or more of those having an average molecular weight of 10,000 or less.
[5] The gel composition according to any one of [1] to [4], which has a viscosity of 25,000 to 45,000 mPa·s.

The high-viscosity gel composition containing hyaluronic acid or the like at a high concentration of 0.2% by mass or more of the present invention has stability over time, does not become uneven over time, and does not clump. It is hard to become, spreads well on the skin, has no stickiness, and has an excellent feeling of use.

1. The gel composition of the present invention includes (A) a gel 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 composition contains (B) 0.1% by mass or more of an anionic polymer compound thickener, (C) 0.05% by mass or more of an associative thickener, and (B) an anionic high It relates to a gel composition, wherein the mass ratio of the molecular compound thickener and (C) associative thickener is 5:1 to 0.15:1.

<(A) Hyaluronic Acid and/or Hyaluronic Acid Derivatives or Their Salts>
As hyaluronic acid, those extracted from animal tissues, those produced by fermentation by culturing microorganisms, and the like are known, and commercially available hyaluronic acid may be used as appropriate. For example, the average molecular weight is 500,000 to 3,000,000. , higher molecular weight ones, lower molecular weight ones having an average molecular weight of 10,000 or less, and the like can be used. Low-molecular-weight hyaluronic acid, for example, after dissolving high-molecular-weight hyaluronic acid in a buffer, adding hyaluronidase and incubating for several days to inactivate the enzyme, a method of generating (JP-A-10-195107), polymer It is produced 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 defined in the present invention can be measured by the following method.

Using a gel filtration column, multiple hyaluronic acids (reference substances) with known molecular weights are analyzed by liquid chromatography, and a calibration curve is created from their retention times. 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 calibration curve, hyaluronic acid and / or hyaluronic acid derivatives or salts thereof can be determined.
Liquid chromatography analyzers that can be used for the liquid chromatography analysis include, for example, Waters Alliance 2690 HPLC Separations Module (manufactured by Waters), Waters Alliance 2695 HPLC Separations Module (manufactured by Waters), 1200 Series (Agilent made). Further, columns that can be used for liquid chromatography analysis include, for example, a column for ligand exchange chromatography (ligand exchange mode + size exclusion mode) manufactured by shodex, model name "SUGAR KS-801";"SUGARKS-802","SUGARKS-803","SUGARKS-804","SUGARKS-805","SUGARKS-806","SUGARKS-807", TOSOH size exclusion chromatography column, A type name "TSKgel GMPW" is mentioned.

Examples of hyaluronic acid derivatives include derivatives obtained by etherifying, esterifying, acetylating, amidating, acetalizing, and ketalizing hydroxyl groups, carboxyl groups, etc. of hyaluronic acid. Specifically, for example, cationized hyaluronic acid having a quaternary ammonium group-containing group (WO2008/133267), modified hyaluronic acid containing a glycerin skeleton-containing group (WO2011/102462), modified hyaluronic acid containing a carboxymethyl group (WO2016 / 159159, JP 2015-147945), low molecular weight cationized hyaluronic acid in which a part of the hydroxy group is substituted with a quaternary nitrogen-containing group (JP 2016-108344), and the like.
Hyaluronic acid and hyaluronic acid derivatives may be salts such as sodium salts, potassium salts, calcium salts, magnesium salts, ammonium salts, basic amino acid salts, zinc salts and the like.

As hyaluronic acid and/or hyaluronic acid derivatives, commercially available hyaluronic acid and/or hyaluronic acid derivatives may be used as appropriate. Therefore, one or more hyaluronic acid or hyaluronic acid derivatives having an average molecular weight of 500,000 to 2,000,000 and one or more hyaluronic acid or hyaluronic acid derivatives having an average molecular weight of 10,000 or less, at least two types of hyaluronic acid and/or a combination of hyaluronic acid derivatives. Two or more hyaluronic acid and/or hyaluronic acid derivatives with an average molecular weight of 500,000 to 2,000,000 and two or more hyaluronic acid and/or hyaluronic acid derivatives with an average molecular weight of 10,000 or less, at least four or more types of hyaluronic acid and/or a combination of hyaluronic acid derivatives is more preferred.
In addition, hyaluronic acid and/or hyaluronic acid derivatives include medium/high molecular weight hyaluronic acid with an average molecular weight of 500,000 to 2,000,000, low molecular weight hyaluronic acid and/or hyaluronic acid derivatives with an average molecular weight of 10,000 or less, and quaternary ammonium. Cationic hyaluronic acid derivative having an average molecular weight of 500,000 to 2,000,000 having a group-containing group, hyaluronic acid derivative containing a carboxymethyl group having an average molecular weight of 500,000 to 2,000,000, modified hyaluronic acid containing a glycerin skeleton-containing group, hyaluronic acid Zinc and the like are included, and a combination thereof is also preferable (JP-A-2016-166133).
Hyaluronic acid and/or hyaluronic acid derivatives with an average molecular weight of 500,000 or more and 2,000,000 or less have the property of staying on the skin surface and preventing moisture from evaporating from the skin surface, so they exhibit a continuous moisturizing effect.

The low-molecular-weight hyaluronic acid and/or hyaluronic acid derivative having an average molecular weight of 10,000 or less preferably has an average molecular weight of 800 or more and 10,000 or less, and more preferably 1,000 or more and 10,000 or less. This low-molecular-weight hyaluronic acid and/or hyaluronic acid derivative exhibits a long-lasting moisturizing effect on the skin because it has high skin permeability and has the property of improving the moisture content of the stratum corneum.
The cationic hyaluronic acid derivative having a group containing a quaternary ammonium group preferably has a degree of cationization of 0.15 to 0.6, and more preferably 0.15 to 0.4. things are 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 the semi-micro Kjeldahl method in a conventional manner. This cationic hyaluronic acid exerts a long-lasting moisturizing effect on the skin.

The “carboxymethyl group” of the modified hyaluronic acid derivative containing a carboxymethyl group refers to a group represented by “—CH ₂ —CO ₂ H” or “—CH ₂ —CO ₂ ^— ”, and at least one It refers to hyaluronic acid in which a carboxymethyl group has been introduced into the part. The modified hyaluronic acid derivative containing a carboxymethyl group is more preferably one having a carboxymethylation rate of 5% or more and 200% or less with respect to the disaccharide unit constituting hyaluronic acid, and still 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 the disaccharide unit constituting hyaluronic acid. The carboxymethylation rate for the unit is the number of carboxymethyl groups contained in the unit, and more specifically, when the unit is 100%, the 1 Refers to the ratio (%) of the number of carboxymethyl groups contained in a unit. Modified hyaluronic acid derivatives containing this carboxymethyl group exert a long-lasting moisturizing effect on the skin.

Modified hyaluronic acid containing a glycerin skeleton-containing group preferably has the formula: —O—CH ₂ —CHOH—CH ₂ —OR ¹ (wherein R ¹ represents linear or branched alkyl or alkenyl). It is a modified hyaluronic acid containing a glycerin backbone-containing group as shown. This modified hyaluronic acid has the property of repairing the lamellar structure consisting of the water layer and the lipid layer and improving the effect of repairing the barrier function of the skin, so that it exerts a sustained moisturizing effect on the skin.
Zinc hyaluronate is a complex formed by interaction between zinc ions and carboxyl ions derived from the carboxyl groups that constitute hyaluronic acid. Preferable zinc hyaluronate has a zinc content of 55 to 100 mg per gram, more preferably 60 to 80 mg per gram. Zinc hyaluronate exerts a long-lasting moisturizing effect on the skin.

The gel composition of the present invention contains 0.2% by mass or more of hyaluronic acid and/or hyaluronic acid derivative. A preferable content is 0.2 to 5% by mass, more preferably 0.25 to 3% by mass, still more preferably 0.3 to 2% by mass.
When the gel composition of the present invention contains 5% by mass or more of hyaluronic acid and/or a hyaluronic acid derivative, the viscosity of the gel composition increases, the stability over time becomes insufficient, and over time Gel non-uniformity may occur.

In addition, it is preferable 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 and having an average molecular weight of 500,000 to 2,000,000. . When the content is 0.1% by mass or more, it stays on the skin surface and has the property of preventing moisture from evaporating from the skin surface, so that a sustained skin moisturizing effect is exhibited. A 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.
In addition, it is preferable to contain 0.1% by mass or more of one or more selected from the group consisting of arronic acid and/or hyaluronic acid derivatives and salts thereof, having an average molecular weight of 10,000 or less. By containing 0.1% by mass or more, it has high permeability into the skin and has the property of improving the moisture of the stratum corneum, so that a sustained skin moisturizing effect is exhibited. A more preferable content is 0.1 to 3% by mass or more, more 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 (A) an anionic polymer compound thickener other than hyaluronic acid and/or hyaluronic acid derivatives or salts thereof. 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 polymeric compound thickener has a carboxy group in the molecule.

Anionic synthetic polymer compound thickeners include, for example, unsaturated monocarboxylic acid-based monomers (acrylic acid, methacrylic acid, crotonic acid, neutralized products of these acids, partially neutralized products, etc.), 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 (vinylsulfonic acid, allylsulfonic acid, methacrylsulfone acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, sulfoethyl (meth)acrylate, sulfoethylmaleimide, 3-allyloxy-2-hydroxypropanesulfonic acid, neutralized products of these acids, and partially neutralized products etc.), a copolymer composed of any combination of the above-mentioned monomers, a copolymer of the above-mentioned monomers and other copolymerizable monomers, and the like. Specifically, (acrylates/alkyl acrylate (C10-30)) crosspolymer, (acrylic acid/vinylpyrrolidone) crosspolymer, (methyl vinyl ether/maleic acid) crosspolymer, alkyl-modified carboxyvinyl polymer, carboxyvinyl Polymers, Alkyl Acrylates/Steareth-20 Methacrylate Copolymers, Acrylic Copolymers, Acrylates/Steareth-20 Methacrylates Copolymers, Acrylates/Steareth-20 Itaconates Copolymers, Polyacrylic Acids, Acrylates/Beheneth-25 Methacrylates Copolymers, Acrylates/Methacrylics Laureth-25 acid copolymer, acrylates/vinyl neodecanoate cross-copolymer, alkyl acrylate/steareth-20 methacrylate cross-polymer, acrylates/steareth-20 methacrylate cross-copolymer, methyl vinyl ether/maleic anhydride/decadiene cross-polymer, acrylic acid Alkyl methacrylate copolymer, vinylpyrrolidone/acrylate/lauryl methacrylate copolymer, acrylates copolymer, sodium polyacrylate, sodium alginate, (ammonium acryloyldimethyltaurate/beheneth-25 methacrylate) crosspolymer, and the like.

Anionic natural polymer compound thickeners include pectic acid, alginic acid, agar, carrageenan, fucoidan, heparin, gellan gum, native gellan gum, xanthan gum, dehydroxanthan gum, gum arabic, carboxymethylcellulose, carboxymethylhydroxyethylcellulose, carboxymethylstarch, Carboxymethyldextran, polyglutamic acid, succinylated collagen, carboxymethylchitin, succinylated chitosan, sodium cellulose sulfate, gelatin, mucin, dextran and the like.

Preferred anionic polymeric compound thickeners include anionic synthetic polymeric compound thickeners. More preferably, acrylic acid-based anionic polymer thickeners such as (meth)acrylic acid/alkyl (meth)acrylate copolymers are mentioned, and more preferably acrylic acid/alkyl methacrylate copolymers are mentioned. and still more preferably an (acrylates/alkyl acrylate (10 to 30 carbon atoms)) crosspolymer.
The gel composition contains 0.1% by mass or more of the anionic polymer thickener. A preferable content is 0.1 to 2% by mass, more preferably 0.15 to 1% by mass, and still more preferably 0.2 to 0.5% by mass.

<(C) Associative thickener>
Associative thickeners are thickeners that contain both hydrophilic and hydrophobic regions. Examples thereof include thickeners having a hydrophobic region containing at least one _C8-36 fatty chain or the like and at least one hydrophilic region. Associative thickeners include, for example, those defined in the Encyclopedia of Polymer Science and Engineering, 2nd Edition, 17, 772-779. Hydrophobic regions can be associated with hydrophobic moieties and hydrophilic regions can be associated with hydrophilic moieties. The associative thickener forms a network (mesh 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. , a thickening action is expressed.

Examples of associative thickeners include those described in JP2015-514788, JP2017-31064, JP2016-519159, JP2005-500397, WO2011/162421, WO2018/088312, and the like.
Associative thickeners are exemplified below.
(a) a nonionic amphiphilic polymer containing at least one _C8-36 fatty chain and at least one hydrophilic unit;
(b) an anionic amphiphilic polymer containing at least one hydrophilic unit and at least one unit having a _C8-36 fatty chain;
(c) a cationic amphiphilic polymer containing at least one hydrophilic unit and at least one unit having a _C8-36 fatty chain;
(d) an amphoteric amphiphilic polymer containing at least one hydrophilic unit and at least one unit having a _C8-36 fatty chain.

Among these associative thickeners, (a) nonionic amphiphilic polymers are preferred. The (a) nonionic amphiphilic polymer is exemplified below.
(1) cellulose modified with at least one group having a _C8-36 fatty chain (hydrophobized modified alkyl cellulose);
(2) urethane polyethers containing at least one _C8-36 fatty chain (hydrophobic modified polyether urethane);
(3) hydroxypropyl guar compounds modified with at least one group having a _C8-36 fatty chain;
(4) copolymers of vinylpyrrolidone and hydrophobic monomers with _C8-36 fatty chains;
(5) Copolymers of C _1-6 alkyl methacrylates or C _1-6 alkyl acrylates and at least one amphiphilic monomer containing a C _8-36 fatty chain;
(6) Copolymers of hydrophilic methacrylates or acrylates and at least one hydrophobic monomer containing a _C8-36 fatty chain.

〔式中、Ｒ^１、Ｒ^２及びＲ^３は、同一又は異なって、水素原子、アルキル、－［ＣＨ_２ＣＨ_２－ｋ（ＣＨ_３）_ｋＯ］_ｍ－Ｈ、又は－ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２ＯＣ_ｊＨ_２ｊ＋１を表す。ただし、－ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２ＯＣ_ｊＨ_２ｊ＋１が必ず含まれる。
ｎは１００～１００００の整数である。
ｋは０又は１である。
ｍは１～１０の整数である。
ｊは６～２６の整数である。〕
で表される会合性増粘剤である。 Examples of hydrophobized modified alkyl cellulose include those described in WO2011/162421, and the formula (1):

[Wherein, R ¹ , R ² and R ³ are the same or different, and are hydrogen atom, alkyl, -[CH ₂ CH _2-k (CH ₃ ) _k O] _m -H, or -CH ₂ CH(OH ) represents _{CH2OCjH2j + 1} . However, -CH ₂ CH(OH)CH ₂ OC _j H _2j+1 is always included.
n is an integer from 100 to 10,000.
k is 0 or 1;
m is an integer from 1 to 10;
j is an integer from 6 to 26; ]
is an associative thickener represented by

The hydrophobized modified alkyl cellulose is preferably
10 to 50% by mass of alkyl,
-[CH ₂ CH _2-k (CH ₃ ) _k O] _m -H in an amount of 3 to 20% by mass and -CH ₂ CH(OH)CH ₂ OC _j H _2j+1 in an amount of 0.1 to 10% by mass. .
More preferably, the hydrophobized modified alkyl cellulose is one in which j is 18.
Hydroxypropyl methylcellulose stearoxy ether (for example, Sangelose (registered trademark) (manufactured by Daido Kasei Kogyo Co., Ltd.)) and the like can be suitably used as hydrophobized modified alkyl cellulose.

Hydrophobic modified polyether urethanes include those described in WO2018/088312 and have 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.
R ⁵ 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; ]
is an associative thickener represented by

(PEG-240/decyltetradeceth-20/hexamethyldiisocyanate) copolymer (eg, Adekanol (registered trademark) GT-700 (manufactured by ADEKA)) and the like can be used as the hydrophobically modified polyether urethane.

The associative thickener preferably includes (a) a nonionic amphipathic polymer, more preferably hydrophobized modified alkyl cellulose, hydrophobic modified polyether urethane and the like, and still more preferably hydroxypropylmethyl cellulose stir oxyether, (PEG-240/decyltetradeceth-20/hexamethyldiisocyanate) copolymer, etc., and more preferably hydroxypropylmethylcellulose stearoxyether.

Even a gel composition containing hyaluronic acid or the like at a high concentration is stable over time. A preferable content is 0.05 to 1% by mass, more preferably 0.06 to 0.5% by mass, still more preferably 0.07 to 0.3% by mass.
Even a gel composition containing a high concentration of hyaluronic acid or the like can provide stability over time. , 5:1 to 0.15:1. The weight ratio is preferably 4:1 to 1:1, more preferably 3.5:1 to 1.2:1. When the mass ratio is within the above range, the gel of the gel composition of the present invention becomes uniform and the occurrence of unevenness is suppressed.

<Oil content>
The gel composition of the present invention can contain 5% or more and 20% or less of oil in order to enhance the effect of improving familiarity with the skin. The oil used in the gel 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, macadamian oil, d-delta-tocopherol, trioctanoin, cetyl lactate, cetyl 2-ethylhexanoate, phytosqualane, liquid paraffin, squalane, beeswax, petrolatum, lanolin, carnauba wax, olive oil, avocado oil, camellia oil, jojoba Oil, horse oil, mink oil, ceramide, coenzyme Q10, retinol palmitate, panthenol, egg yolk lecithin, soy lecithin, hydrogenated lecithin, polysorbate-60, phytosterol, triethylhexanoin, glycerol monostearate, polyoxyethylene monostearate rate, stearyl alcohol, sorbitan stearate, cetostearyl alcohol, polyoxyethylene cetostearyl alcohol, polyoxyethylene fatty acid ester, polyglyceryl-10 stearate, polyoxyethylene hydrogenated castor oil derivative, glyceryl caprylate, higher fatty acids (lauric acid, behenic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, higher fatty acid salts, etc.), silicones and silicone derivatives (dimethylpolysiloxane, cyclic dimethylpolysiloxane, methylphenylpolysiloxane, silicone resin, polyether-modified silicone , amino-modified silicone, etc.).

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

Examples of anionic surfactants include alkylbenzenesulfonates, polyoxyalkylene alkyl ether sulfates, alkyl sulfates, olefinsulfonates, and dialkylsulfosuccinates.
Examples of nonionic surfactants include polyoxyethylene fatty acid esters and polyoxyethylene hydrogenated castor oil derivatives.
Examples of cationic surfactants include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylpyridinium salts, stearyltrimethylammonium chloride and the like.
Examples of amphoteric surfactants include alkyl betaine, alkylamidopropyl betaine, imidazolinium betaine, egg yolk lecithin, soybean lecithin and the like.
Moisturizers include, for example, diphytosteryloctyldodecyl lauroylglutamate, phytoglycogen, hydrolyzed eggshell membrane, trehalose, atelocollagen, sorbitol, maltitol and the like.

Examples of functional ingredients include arbutin, polyquaternium 51, elastin, platinum nanocolloid, allantoin, sodium lysine dilauroyl glutamate, magnesium ascorbyl phosphate, L-ascorbic acid 2-glucoside, ellagic acid, kojic acid, vitamin A oil, Retinol, retinol palmitate, inosit, pyridoxine hydrochloride, benzyl nicotinate, nicotinamide, dl-α-tocopherol nicotinate, vitamin D2 (ergocaciferol), dl-α-tocopherol, dl-α-tocopherol acetate, pantothenic acid , biotin and other vitamins, estradiol, ethinyl estradiol and other hormones allantoin, tranexamic acid, glycyrrhetinic acid, and azulenic acid anti-inflammatory agents.

Natural product extracts include, for example, ragweed extract, kasil extract, seaweed extract, eucalyptus extract, royal jelly extract, rosemary extract, beech tree extract, ashenyak extract, beech tree extract, turmeric extract, houttuynia cordata extract, Phellodendron bark extract, mellot extract, dead nettle extract , licorice extract, peony extract, soapwort extract, loofah extract, cinchona extract, saxifrage extract, clara extract, kuhone extract, fennel extract, primrose extract, rose extract, rhubarb extract, lemon extract, licorice extract, aloe extract, calamus root extract, eucalyptus extract, horsetail extract, sage extract, thyme extract, tea extract, cucumber extract, clove extract, raspberry extract, melissa extract, carrot extract, carrot extract, horse chestnut extract, peach extract, peach leaf extract, mulberry extract, cornflower extract, hamamelis extract, placenta extract, Thymus extract, silk extract and the like can be mentioned.

Examples of protein hydrolysates include keratin peptides, collagen peptides, soybean peptides, wheat peptides, milk peptides, silk peptides, egg white peptides, hydrolyzed eggshell membranes, and the like.
Amino acids include, for example, arginine, glutamic acid, glycine, alanine, hydroxyproline, cysteine, serine, L-theanine and the like.
Examples of cationic polysaccharides include cationic hydroxyethyl cellulose, cationic guar gum, cationic starch, cationic locust bean gum, cationic dextran, cationic chitosan, and cationic honey.
Higher alcohols include, for example, cetyl alcohol, behenyl alcohol, isostearyl alcohol, and batyl alcohol.
Examples of polyhydric alcohols include propylene glycol, polyethylene glycol, pentylene glycol, caprylyl glycol, hexanediol, ethylhexylglycerin, 1,3-butylene glycol, 1,3-propanediol, diglycerin, and glycerin. be done.

Examples of amphoteric polymer resin compounds include betainated dialkylaminoalkyl acrylate copolymers.
Examples of the cationic polymer resin compound include cationized vinylpyrrolidone/dimethylaminoethyl methacrylate copolymer and polydimethyldiallylammonium halide type cationic polymer.
Examples of antiseptics include methylparaben, ethylparaben, butylparaben, propylparaben, phenoxyethanol and the like.
Examples of antioxidants include tocopherol and BHT.
Examples of sequestering agents include EDTA-2Na, EDTA-4Na, edetate, etidronate and the like.
Examples of ultraviolet absorbers include benzophenone derivatives, para-aminobenzoic acid derivatives, methoxycinnamic acid derivatives and the like.
Ultraviolet reflectors include, for example, titanium oxide and zinc oxide.

Examples of pH adjusters include alkali hydroxides such as sodium hydroxide, and acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and methanesulfonic acid. A pH adjuster can be used to adjust the pH of the gel composition of the present invention to preferably pH 5 to 7.5, more preferably pH 6 to 7.

2. Production method and use of gel composition The gel 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 together with a thickening agent to form a gel. The produced gel composition is filled and sealed in a container or the like depending on the application.
The gel composition of the present invention can be suitably used as high-viscosity cosmetics such as all-in-one cosmetics, hair cosmetics, and the like.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these.

Examples 1-16 and Comparative Examples 1-4
<Preparation of gel composition>
Each component (% by mass) listed in Tables 1 to 4 is added to ion-exchanged water (remainder) and mixed, and if necessary, an aqueous sodium hydroxide solution is added to adjust the pH to 6 to 7.5. By doing so, gel 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 shown below.
<(A) Component>
Hyaluronic acid Na: Hyaluronic acid HA-LQ (manufactured by Kewpie), average molecular weight 850,000 to 1,600,000 Hydrolyzed alkyl hyaluronate (C12-13) glyceryl: Hyalorepair (registered trademark) (manufactured by Kewpie), average molecular weight 10,000 or less carboxy Methyl hyaluronic acid Na: Hyalocatch (registered trademark) (manufactured by Kewpie Corporation), average molecular weight 800,000 to 1,200,000 Hydrolyzed hyaluronic acid Na: HAbooster (registered trademark) (manufactured by Kewpie Corporation), average molecular weight 1000 to 3500
Hydroxypropyltrimonium hyaluronate: Hyalobel-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

<(B) Component>
(Acrylates/alkyl acrylate (C10-30)) crosspolymer: Pemulen (registered trademark) TR-1 (manufactured by Lubrizol)
Acrylates copolymer: Carbopol (R) Aqua SF-1 Polymer (manufactured by Lubrizol Advanced Materials)
Polyacrylic acid Na: Aronbis MX (manufactured by Toagosei Co., Ltd.)
(Acryloyldimethyltaurate ammonium methacrylate beheneth-25) Crosspolymer: Aristoflex HMB (manufactured by Clariant Japan)
Sodium alginate: Kimika Algin I-3 (manufactured by Kimica)
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)

<(C) Component>
Hydroxypropyl methylcellulose stearoxy ether: Sangelose (registered trademark) (manufactured by Daido Kasei Kogyo Co., Ltd.)
(PEG-240/decyltetradeceth-20/HDI) copolymer: ADEKA NOL GT-700 (registered trademark) (manufactured by ADEKA)
<Oil content>
Squalane, ethylhexyl palmitate, macadamia seed oil and the like were used as the oil.
<Glycols>
Butylene glycol, pentylene glycol and glycerin were used as glycols.

Test Example <Evaluation of gel composition>
(viscosity)
The viscosity of the gel composition was measured the day after the gel composition was prepared. Viscosity (mPa·s) was measured by Rotor No. using a Brookfield viscometer (Viscometer BLII, manufactured by Toki Sangyo Co., Ltd.). 4 at 6 rpm for 60 seconds at 25°C.
(pH)
The pH of the gel composition was measured on the next day after preparing the gel composition. The pH was measured using a pH meter (manufactured by HORIBA).

(Stability)
The stability of the gel composition was evaluated according to the following indices after the gel composition was prepared and kept at room temperature for 6 months.
○: Good △: A little non-uniformity of the gel is confirmed ×: The gel is completely non-uniform and unevenness occurs

(Comprehensive usability)
The feeling of use of the gel composition was comprehensively evaluated by 5 arbitrarily selected volunteers according to the following evaluation items and indexes.
・Evaluation items Spreading on the skin at the time of application, moderate thickness Absence of stickiness after application ・Index ◎: Extremely good ○: Good △: Moderate ×: Poor (items that were poor are described in the margin)

Table 5 shows the evaluation results of the gel compositions of Examples 1-16 and Comparative Examples 1-4.

As can be seen from Table 5, the viscosities of the gel compositions of Examples 1 to 16 were all within the range of 15,000 to 60,000 mPa·s, indicating high viscosity gel compositions. In Examples 1 to 9 and 14 to 16 using an anionic synthetic polymer compound thickener as the component (B), the viscosity is 24000 to 42500 mPa s, which is more suitable for use as an all-in-one cosmetic, for example. has a high viscosity. In Examples 10 to 12 using the anionic natural polymer compound thickener, the viscosity was as low as 17,800 to 20,500 mPa·s. Thus, it can be seen that in (B) the anionic polymer compound thickener, the anionic synthetic polymer compound thickener is more preferable. Further, for example, by comparing Examples 1 to 4, it can be seen that the viscosity increases as the content of component (B) increases.

Regarding stability, in Examples 1 to 16 in which the mass ratio of (B) the anionic polymer compound thickener and (C) the associative thickener was 5:1 to 0.15:1, good or little The degree of non-uniformity of the gel was confirmed, and it could be used as the gel composition of the present invention. On the other hand, in (B) Comparative Examples 1 and 2 using only the anionic polymer compound thickener and (C) Comparative Examples 3 and 4 using only the associative thickener, the gel became non-uniform and remained stable over time. The properties were unsatisfactory, and the feeling of use was also unsatisfactory. In addition, since the viscosity was low in Comparative Examples 1 and 3, the content of each thickener was increased in Comparative Examples 2 and 4, but the stability was similarly unsatisfactory, and the spread and stickiness on the skin got worse.

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

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

According to the present invention, a high-viscosity gel containing hyaluronic acid at a high concentration of 0.2% by mass or more, which has stability over time, does not become uneven over time, and does not easily form lumps. A composition is provided.

Claims (5)

(A) 0.2 mass of hyaluronic acid, a hyaluronic acid derivative obtained by etherification, esterification, acetylation, amidation, acetalization, or ketalization of the hydroxyl group or carboxyl group of hyaluronic acid, or a salt thereof % or more and has a viscosity of 15000 to 60000 mPa s,
The gel composition contains 0.1% by mass or more of (B) an anionic polymer compound thickener (excluding component (A)) and 0.05% by mass of (C) an associative thickener. contains more than
(B) The anionic polymer compound thickener is obtained by etherifying, esterifying, acetylating, amidating, acetalizing, or ketalizing (A) hyaluronic acid and the hydroxyl group or carboxyl group of hyaluronic acid. An anionic polymer compound thickener other than a hyaluronic acid derivative or a salt thereof,
The content of the (B) anionic polymer compound thickener in the gel composition is 0.24% by mass or more and 0.8% by mass or less,
A gel composition wherein the mass ratio of (B) an anionic polymer compound thickener and (C) an associative thickener is 4.44:1 to 1.33:1. 2. The gel composition according to claim 1, wherein (C) the associative thickener is hydrophobized modified alkylcellulose. (A) selected from the group consisting of hyaluronic acid and hyaluronic acid derivatives obtained by etherification, esterification, acetylation, amidation, acetalization, or ketalization of the hydroxyl group or carboxyl group of hyaluronic acid, or salts thereof; 3. The gel composition according to claim 1 or 2, which contains 0.1% by mass or more of one or more compounds having an average molecular weight of 500,000 to 2,000,000. (A) selected from the group consisting of hyaluronic acid and hyaluronic acid derivatives obtained by etherification, esterification, acetylation, amidation, acetalization, or ketalization of the hydroxyl group or carboxyl group of hyaluronic acid, or salts thereof; 0.1% by mass or more of those having an average molecular weight of 500,000 to 2,000,000 and 0.1% by mass or more of those having an average molecular weight of 10,000 or less among the one or more 3. The gel composition according to 1 or 2. The gel composition according to any one of claims 1 to 4, which has a viscosity of 25,000 to 45,000 mPa·s.