Cosmetic modifier and cosmetic

Abstract

To provide a cosmetic modifier that enables production of a cosmetic exhibiting superior makeup durability and usability.SOLUTION: A cosmetic modifier comprises a polymer (A) having a carboxyl group and / or -COO- and exhibiting a viscosity of 10 mPa s or more at 25°C when prepared as a 1 mass% aqueous solution (excluding hyaluronic acid and a neutralized product thereof), and a polymer (B) having a functional group capable of forming a hydrogen bond with the carboxyl group (excluding the polymer (A)), the cosmetic modifier forming a hydrogel upon contact with moisture.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a cosmetic modifier and a cosmetic, and more particularly to a cosmetic modifier that forms a hydrogel upon contact with water. [Background technology]

[0002] In cosmetics such as makeup cosmetics, nail care cosmetics, skin care cosmetics, and hair cosmetics, water-soluble polymers are primarily used as film-forming agents, which are one of the ingredients in cosmetics, taking environmental and hygienic considerations into account. Furthermore, in order to provide sustained skin care or coverage in daily life, or for daily UV protection, cosmetics are desired to have high water resistance and oil resistance (sebum resistance) and excellent durability of cosmetic effects (hereinafter also referred to as "cosmetic durability"). However, because water-soluble polymers have poor moisture resistance and water resistance, aqueous polymer emulsions have been widely used as film-forming agents in recent years.

[0003] In order to improve the water resistance, oil resistance, and cosmetic durability of cosmetics, for example, Patent Document 1 proposes the use of an aqueous, emulsifier-free polymerized resin emulsion in which no emulsifier is used during polymerization. Patent Document 2 also proposes the use of an aqueous polymer emulsion in which a plasticizer or film-forming aid is used during polymerization. Patent Document 3 proposes a method of incorporating organopolysiloxane particles (Patent Document 3). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 54-49338 [Patent Document 2] Special Publication No. 8-18950 [Patent Document 3] Japanese Patent Application Laid-Open No. 2000-355532 Summary of the Invention [Problem to be solved by the invention]

[0005] Aqueous polymer emulsions usually contain trace amounts of volatile organic compounds, such as unreacted monomers and decomposition products generated during polymerization. Therefore, there is room for improvement in terms of odor, etc. Therefore, the development of new materials for cosmetic use is considered. However, considering that they are used in cosmetics, they are required to be compatible with the skin, have a good feel when used, and have a long-lasting cosmetic effect.

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a cosmetic modifier that can provide a cosmetic that has excellent cosmetic durability and a good feeling when used. [Means for solving the problem]

[0007] The present inventors conducted extensive research to solve the above problems and discovered that the above problems can be solved by using a combination of multiple specific polymers, which led to the completion of the present invention. Specifically, the present invention provides the following cosmetic modifier and cosmetic.

[0008] [1] Carboxyl group and / or "-COO - " and contains a polymer (A) (excluding hyaluronic acid or its neutralized products) having a viscosity of 10 mPa·s or more at 25°C when made into a 1% by mass aqueous solution, and a polymer (B) (excluding the polymer (A)) having a functional group capable of forming a hydrogen bond with a carboxyl group, and which forms a hydrogel upon contact with water.

[0009] [2] The cosmetic modifier according to [1], wherein the polymer (A) is a crosslinked polymer. [3] The cosmetic modifier according to [1] or [2], wherein the polymer (A) is poly(meth)acrylic acid. [4] The cosmetic modifier according to [1], wherein the polymer (A) is at least one selected from the group consisting of polysaccharides, polypeptides, and neutralized products thereof. [5] The cosmetic modifier according to [4], wherein the polymer (A) is at least one selected from the group consisting of oxidized cellulose, carboxyalkyl cellulose, pectin, polyglutamic acid, polyaspartic acid, alginic acid, and neutralized products thereof. [6] The cosmetic modifier according to any one of [1] to [3], wherein the polymer (B) has an amide group. [7] The cosmetic modifier according to [6], wherein the polymer (B) is at least one selected from the group consisting of polyvinylpyrrolidone and poly(meth)acrylamide. [8] The cosmetic modifier according to any one of [1] to [7], which is in powder form. [9] The cosmetic modifier according to any one of [1] to [8], which is a dried product obtained by contacting a film-like solid containing one of the polymers (A) and (B) with a solution containing the other polymer and drying the resulting product, and the hydrogel formed by contact with water has adhesive properties to biological tissue.

[10] A cosmetic comprising the cosmetic modifier according to any one of [1] to [9]. [Effects of the Invention]

[0010] According to the present invention, by blending the above polymer (A) and polymer (B) in combination in a cosmetic, it is possible to obtain a cosmetic that is excellent in cosmetic durability and feeling in use. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below. In this specification, "(meth)acrylic" means acrylic and / or methacrylic. "(meth)acrylate" means acrylate and / or methacrylate. "(meth)acrylo" means acrylo and / or methacrylo.

[0012] Cosmetic modifier The cosmetic modifier of the present invention (hereinafter simply referred to as "cosmetic modifier") is incorporated into cosmetics to improve or change the properties and performance of the cosmetics. The cosmetic modifier forms a hydrogel upon contact with water and exhibits adhesive properties to biological tissue in the hydrogel state. Such cosmetic modifiers are particularly useful as components (base materials or additives) incorporated into cosmetics to improve the feel and long-lasting effect of the cosmetics.

[0013] Specifically, the cosmetic modifier contains the following polymer (A) and polymer (B). Polymer (A): Carboxyl group and / or —COO - " and a polymer (excluding hyaluronic acid or its neutralized products) that has a viscosity of 10 mPa·s or more at 25°C when made into a 1% by mass aqueous solution. Polymer (B): A polymer having a functional group capable of forming a hydrogen bond with a carboxyl group (hereinafter also referred to as "functional group E") (excluding polymer (A)).

[0014] Here, the cosmetic modifier is in a dry state before coming into contact with water, and when it comes into contact with water, it absorbs water and swells, becoming a hydrogel (i.e., a swollen body). Furthermore, when it changes from a dry state to a swollen state upon contact with water, it exhibits adhesiveness to biological tissue. This does not limit the present invention, but in the cosmetic modifier, the carboxyl groups of the polymer (A) or the "-COO" of the polymer (A) are bonded to the carboxyl groups of the polymer (A). - M + " (However, M + is a counter ion) comes into contact with water, and the carboxyl groups generated instantaneously form hydrogen bonds with the functional group E of polymer (B). In particular, when polymer (A) contains carboxyl groups, the remaining free carboxyl groups in polymer (A) in the cosmetic modifier are also thought to contribute to the cosmetic modifier's excellent adhesiveness to biological tissues upon contact with water. Water includes water, water-soluble organic solvents (ethanol, etc.), body fluids (blood, tissue fluid, etc.), and mixtures of these.

[0015] Below, we will explain the components contained in the cosmetic modifier and the components that are optionally blended as needed. Unless otherwise specified, each component may contain one type alone or two or more types in combination. When describing a numerical range, the notation "a to b" means a to b, unless otherwise specified. For example, "0 to 5% by mass" means "0% by mass to 5% by mass."

[0016] <Polymer (A)> When polymer (A) is prepared into an aqueous solution containing 1% by mass of polymer (A), the viscosity of the aqueous solution at 25°C (hereinafter also referred to as "aqueous solution viscosity of polymer (A)") is 10 mPa·s or more. If the aqueous solution viscosity of polymer (A) is less than 10 mPa·s, when the cosmetic modifier comes into contact with water and becomes a hydrogel, it does not blend well with the skin, resulting in a poor cosmetic feel. Furthermore, when a cosmetic containing the cosmetic modifier is applied to the skin, the cosmetic is likely to peel off from the skin during daily life, and sufficient cosmetic durability cannot be ensured. Note that, in this specification, hyaluronic acid or its neutralized products is not included in polymer (A).

[0017] From the viewpoint of enhancing the effects of improving the feel of use and cosmetic longevity of the cosmetic preparation, the aqueous solution viscosity of polymer (A) is preferably 15 mPa·s or more, more preferably 20 mPa·s or more, and even more preferably 25 mPa·s or more. From the viewpoint of improving the handleability of the cosmetic preparation modifier, the upper limit of the aqueous solution viscosity of polymer (A) is preferably 30,000 mPa·s or less, more preferably 25,000 mPa·s or less, even more preferably 20,000 mPa·s or less, and particularly preferably 15,000 mPa·s or less. The aqueous solution viscosity of polymer (A) is a value measured at 25°C using a Brookfield viscometer. Details of the measurement method follow the method described in the Examples below.

[0018] As the polymer (A) having a viscosity of 10 mPa·s or more at 25°C when made into a 1% by mass aqueous solution, a crosslinked polymer, a polymer having a weight-average molecular weight of 1.8 million or more (hereinafter also referred to as a "high molecular weight polymer (AH)"), or at least one selected from the group consisting of polysaccharides, polypeptides and neutralized products thereof (hereinafter also referred to as a "bio-derived polymer (AO)") can be preferably used. Each polymer is described in detail below.

[0019] Cross-linked polymer / high molecular weight polymer (AH) When the polymer (A) is a crosslinked polymer and / or a high-molecular-weight polymer (AH), the polymer (A) (hereinafter also referred to as "polymer (A1)") is preferably a polymer primarily composed of structural units derived from an ethylenically unsaturated monomer having a carboxyl group (hereinafter also referred to as "unsaturated monomer (ma)"), from the viewpoint of ensuring that the cosmetic modifier exhibits excellent adhesive properties to biological tissues when the cosmetic modifier is brought into contact with moisture and enhancing the sustained curing of that adhesive property.

[0020] Specific examples of the unsaturated monomer (ma) include (meth)acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, cinnamic acid, succinic acid monohydroxyethyl (meth)acrylate, ω-carboxy-caprolactone mono(meth)acrylate, β-carboxyethyl (meth)acrylate, 4-carboxystyrene, etc. The unsaturated monomer (ma) is preferably (meth)acrylic acid, since it can provide a cosmetic modifier with excellent adhesiveness to biological tissues.

[0021] In polymer (A1), the content of structural units derived from unsaturated monomer (ma) is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and even more preferably 90% by mass or more, based on the total structural units of polymer (A1). When the structural units derived from unsaturated monomer (ma) in polymer (A1) are within the above range, a hydrogel can be obtained that has higher and more persistent adhesiveness to biological tissues. The unsaturated monomer (ma) constituting polymer (A1) may be of one type or two or more types.

[0022] Among them, poly(meth)acrylic acid can be preferably used as the polymer (A1). Poly(meth)acrylic acid is a polymer mainly composed of (meth)acrylic acid, and specifically, it contains structural units derived from (meth)acrylic acid in an amount of 95% by mass or more, preferably 97% by mass or more, and more preferably 99% by mass or more, based on the total structural units of the poly(meth)acrylic acid. Furthermore, in terms of superior swelling properties in contact with water and adhesive properties to biological tissues, the polymer (A1) is preferably a crosslinked polymer, and particularly preferably crosslinked poly(meth)acrylic acid.

[0023] The method for producing the crosslinked polymer is not particularly limited, and examples of the method for producing the crosslinked polymer include the following methods (1) and (2). Method (1): A method of copolymerizing an ethylenically unsaturated monomer having a crosslinkable functional group (hereinafter also referred to as "unsaturated monomer (mb)") with an unsaturated monomer (ma). Method (2): Synthesize a polymer with reactive functional groups and, if necessary, add a crosslinking agent to crosslink it. Among these, method (1) is preferred because the procedure is simple and the degree of crosslinking can be easily controlled.

[0024] Examples of the unsaturated monomer (mb) include polyfunctional polymerizable monomers having two or more ethylenically unsaturated groups, and self-crosslinking monomers having a self-crosslinkable functional group (e.g., a hydrolyzable silyl group). Specific examples of polyfunctional polymerizable monomers include polyfunctional (meth)acrylate compounds, polyfunctional alkenyl compounds, and compounds having both a (meth)acryloyl group and an alkenyl group. Of these, polyfunctional polymerizable monomers are preferably polyfunctional alkenyl compounds, as they are more likely to produce a uniform crosslinked structure.

[0025] Specific examples of polyfunctional alkenyl compounds include polyfunctional allyl ether compounds such as trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl ether, tetraallyloxyethane, and polyallylsucrose; polyfunctional allyl compounds such as diallyl phthalate; polyfunctional vinyl compounds such as divinylbenzene; and alkenyl group-containing (meth)acrylic acid compounds such as allyl (meth)acrylate, isopropenyl (meth)acrylate, butenyl (meth)acrylate, pentenyl (meth)acrylate, and 2-(2-vinyloxyethoxy)ethyl (meth)acrylate. Among these polyfunctional alkenyl compounds, polyfunctional allyl ether compounds having multiple allyl ether groups in the molecule are particularly preferred.

[0026] Specific examples of the self-crosslinking monomer include hydrolyzable silyl group-containing vinyl monomers, etc. Examples of the hydrolyzable silyl group-containing vinyl monomers include vinyl silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, and vinyldimethylmethoxysilane; silyl group-containing (meth)acrylic acid esters such as trimethoxysilylpropyl (meth)acrylate, triethoxysilylpropyl (meth)acrylate, and methyldimethoxysilylpropyl (meth)acrylate; trimethoxysilylpropyl vinyl ether; and vinyl trimethoxysilylundecanoate.

[0027] When the polymer (A1) contains structural units derived from the unsaturated monomer (mb), the amount of the structural units derived from the unsaturated monomer (mb) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, based on the total structural units of the polymer (A1). The amount of the structural units derived from the unsaturated monomer (mb) is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less, based on the total structural units of the polymer (A1). The unsaturated monomer (mb) constituting the polymer (A1) may be one type or two or more types.

[0028] The polymer (A1) may further have a structural unit derived from a monomer different from the unsaturated monomer (ma) and the unsaturated monomer (mb) (hereinafter, "other monomer (mc)"), within the scope that does not impair the effects of the present disclosure. Examples of the other monomer (mc) include (meth)acrylic acid alkyl esters, aliphatic cyclic (meth)acrylic acid esters, aromatic (meth)acrylic acid esters, (meth)acrylic acid alkoxyalkyl esters, (meth)acrylic acid hydroxyalkyl esters, and polyalkylene glycol mono(meth)acrylates.

[0029] Specific examples of these include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, hexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0030] Specific examples of the aliphatic cyclic esters of (meth)acrylic acid include cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyl (meth)acrylate, etc. Specific examples of the aromatic esters of (meth)acrylic acid include phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, and 3-phenoxypropyl (meth)acrylate, etc.

[0031] Specific examples of (meth)acrylic acid alkoxyalkyl esters include methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, n-propoxyethyl (meth)acrylate, n-butoxyethyl (meth)acrylate, methoxypropyl (meth)acrylate, ethoxypropyl (meth)acrylate, n-propoxypropyl (meth)acrylate, n-butoxypropyl (meth)acrylate, methoxybutyl (meth)acrylate, ethoxybutyl (meth)acrylate, n-propoxybutyl (meth)acrylate, and n-butoxybutyl (meth)acrylate.

[0032] Specific examples of the (meth)acrylic acid hydroxyalkyl ester include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate, etc. Examples of the polyalkylene glycol mono(meth)acrylate include polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and polyethylene glycol-polypropylene glycol mono(meth)acrylate, etc.

[0033] In the polymer (A1), the content of structural units derived from the other monomer (mc) is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less, based on the total structural units of the polymer (A1). The other monomer (mc) constituting the polymer (A1) may be one type or two or more types.

[0034] When a high molecular weight polymer (AH) is used as the polymer (A1), the weight average molecular weight (Mw) of the high molecular weight polymer (AH) is preferably 1.8 × 10 6 From the viewpoint of ease of handling, the Mw of the high molecular weight polymer (AH) is preferably 5×10 7 or less, and more preferably 3×10 7 or less, and more preferably 1×10 7 The molecular weight of the high molecular weight polymer (AH) is a polystyrene-equivalent value measured by gel permeation chromatography (GPC) using a tetrahydrofuran eluent after methylating the carboxyl group with trimethylsilyldiazomethane.

[0035] The polymerization method for producing the polymer (A1) is not particularly limited. The polymer (A1) can be obtained by polymerizing the monomers using a known polymerization method such as solution polymerization, suspension polymerization, emulsion polymerization, or bulk polymerization. In the case of solution polymerization, for example, an organic solvent and the monomers are charged into a reactor, a polymerization initiator (e.g., an azo compound) is added, and the mixture is heated to 40 to 250°C to polymerize, thereby obtaining the target polymer.

[0036] The method for obtaining the polymer (A1) is not limited to a method of polymerizing a monomer containing the unsaturated monomer (ma). For example, the polymer (A1) may be obtained by polymerizing a (meth)acrylic acid ester monomer and then hydrolyzing the polymer. Alternatively, the polymer (A1) may be obtained by polymerizing a nitrogen-containing monomer such as (meth)acrylamide or (meth)acrylonitrile and then treating the polymer with a strong alkali, or by reacting a polymer having a hydroxyl group with an acid anhydride.

[0037] Commercially available polymers (A1) may also be used, such as those listed under trade names as JURYMER (registered trademark) AC-10SHP, JUNRON (registered trademark) PW-120, JUNRON PW-121, and JUNRON PW-312S (all manufactured by Toagosei Co., Ltd.).

[0038] Biopolymers (AO) When polymer (A) is a biopolymer (AO), one or more of various polysaccharides, polypeptides, and neutralized products thereof can be used as polymer (A) (hereinafter also referred to as "polymer (A2)"). Polymer (A2) is preferably at least one selected from the group consisting of oxidized cellulose, carboxyalkyl cellulose, pectin, polyglutamic acid, polyaspartic acid, alginic acid, and neutralized products thereof, because when a cosmetic containing the cosmetic modifier is applied to biological tissue, the cosmetic modifier quickly exhibits adhesiveness to the biological tissue, thereby allowing for the production of a cosmetic that is well-compatible with biological tissue.

[0039] Oxidized cellulose is cellulose obtained by oxidizing a cellulosic raw material with an oxidizing agent. The cellulosic raw material may be any material primarily composed of cellulose, such as pulp, natural cellulose, regenerated cellulose, or fine cellulose obtained by depolymerizing cellulose through mechanical treatment. Commercially available cellulosic raw materials, such as crystalline cellulose made from pulp, can also be used as they are. Examples of oxidizing agents include 2,2,6,6-tetramethyl-1-piperidine-N-oxy radical (TEMPO), hypochlorous acid, or a salt thereof. The oxidation treatment of the cellulosic raw material can be carried out by appropriately adopting a known method.

[0040] Oxidized cellulose may be fibrous cellulose obtained by oxidizing a cellulosic raw material with an oxidizing agent (i.e., oxidized cellulose before defibration), or it may be nanocellulose obtained by defibrating and nano-sizing fibrous cellulose obtained by oxidizing a cellulosic raw material with an oxidizing agent (i.e., oxidized cellulose after defibration). Nanocellulose includes cellulose nanofibers, cellulose nanocrystals, etc.

[0041] Commercially available oxidized cellulose or its neutralized products can also be used, such as Aronfibro (registered trademark) (manufactured by Toagosei Co., Ltd.), Cellenpia TEMPO oxidized CNF (manufactured by Nippon Paper Industries Co., Ltd.), and Leocrysta (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

[0042] Examples of carboxyalkyl cellulose include carboxymethyl cellulose and carboxypropyl cellulose. Carboxymethyl cellulose (CMC) is a cellulose-based water-soluble polymer in which carboxymethyl groups have been introduced into some or all of the hydroxyl groups of the glucose units that constitute cellulose. Commercially available carboxymethyl cellulose products include Cellogen (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.); CMC Daicel 1110, 1120, 1130, 1140, 1150, and 1160 (all manufactured by Daicel Miraize Co., Ltd.).

[0043] Pectin is a polysaccharide contained in plant tissues (e.g., cell walls and mesophyll), and is a polygalacturonic acid having galacturonic acid units and galacturonic acid methyl ester units in which a portion of the galacturonic acid is methyl-esterified. Pectin can be obtained by acid extraction from citrus fruits, apples, beet pulp, etc. Commercially available pectin products include HM pectin and LM pectin manufactured by Sumitomo Pharma Food & Chemical Co., Ltd.; the GENU pectin series (manufactured by CP Kelco); and the UNIPECTINE series (manufactured by Unitec Foods).

[0044] Examples of polyglutamic acid include α-polyglutamic acid and γ-polyglutamic acid. Polyglutamic acid may be composed of either D-glutamic acid or L-glutamic acid, or may be composed of both. Polyglutamic acid can be obtained, for example, by isolating it from the products of various strains of bacteria or microorganisms (e.g., Bacillus subtilis var. natto and microorganisms of the genus Bacillus). Commercially available polyglutamic acid or its neutralized products include Meiji Polyglutamic Acid (manufactured by Meiji Food Materials Co., Ltd.).

[0045] Polyaspartic acid can be obtained by thermal polymerization or phosphorus-catalyzed polymerization of aspartic acid. Polyaspartic acid may be composed of either D-aspartic acid or L-aspartic acid, or may be composed of both. Commercially available polyaspartic acid or its neutralized product includes poly-(α,β)-DL-aspartic acid sodium salt P3418 (manufactured by Sigma-Aldrich).

[0046] Alginic acid is a polysaccharide found in seaweed such as brown algae and red algae, and can be obtained, for example, by treating seaweed with an acid, heating it in the presence of alkali, and then extracting it. Examples of seaweed that can be used as raw materials include kelp and duckweed. Commercially available alginic acid or its neutralized products can also be used. Examples of commercially available alginic acid products include Chimica Algin IL-2, IL-6, I-1, I-3, and I-5 (all manufactured by Chimica Co., Ltd.).

[0047] The polymer (A2) may be an unneutralized polymer having a carboxyl group, or may be a partially neutralized product in which a part of the carboxyl groups in a multifunctional polymer having two or more carboxyl groups has been neutralized. The polymer (A2) may also be a fully neutralized product in which all of the carboxyl groups in the multifunctional polymer have been neutralized. In the neutralized product, "-COO -Counter ions of " include various cations such as lithium ion, sodium ion, potassium ion, magnesium ion, calcium ion, aluminum ion, and ammonium ion. Considering that the compound is to be used in cosmetics, among these, alkali metal ions are preferred, sodium ions or potassium ions are more preferred, and sodium ions are even more preferred.

[0048] When the polymer (A2) is a neutralized product, the degree of neutralization of the polymer (A2) is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, still more preferably 40 mol% or more, and even more preferably 50 mol% or more, from the viewpoint of ensuring solubility in aqueous solvents. The degree of neutralization of the polymer (A2) can be calculated from the acid value (mgKOH / g) of the polymer obtained by titrating the polymer solution with a potassium hydroxide solution.

[0049] The weight-average molecular weight of polymer (A2) is not particularly limited. The weight-average molecular weight of polymer (A2) is, for example, 1.8 million or less, and may be 1.5 million or less. The weight-average molecular weight of polymer (A2) may also be 1.2 million or less, 800,000 or less, 500,000 or less, or 300,000 or less. The lower limit of the weight-average molecular weight of polymer (A2) is also not particularly limited, as long as the aqueous solution viscosity of polymer (A2) is 10 mPa s or more.

[0050] <Polymer (B)> Polymer (B) has a functional group (functional group E) capable of forming a hydrogen bond with a carboxyl group, and is a polymer different from polymer (A). Examples of functional group E include amide groups, cyano groups, carbonyl groups, amino groups, and hydroxyl groups. Polymer (B) may have one type of functional group E, or two or more types of functional groups E. Among these, amide groups and / or hydroxyl groups are preferred, with amide groups being particularly preferred, in that they can provide excellent water-swelling properties to the cosmetic modifier.

[0051] Specific examples of the polymer (B) include amide group-containing polymers containing structural units derived from ethylenically unsaturated monomers having amide groups. Specific examples include polymers obtained using monomers such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N-methyl(meth)acrylamide, N-vinyl-2-pyrrolidone, and 1-vinyl-4-methyl-2-pyrrolidone. Of these, the amide group-containing polymer is preferably at least one selected from the group consisting of polyvinylpyrrolidone and poly(meth)acrylamide.

[0052] Examples of hydroxyl group-containing polymers include polyethylene glycol (commercially available products such as Macrogol 4000, Macrogol 6000, and Macrogol 20000 manufactured by NOF Corporation), polyoxyethylene hydrogenated castor oil (commercially available products such as Cremophor RH40 manufactured by BASF and HCO-40 and HCO-60 manufactured by Nikko Chemicals), polyoxyethylene polyoxypropylene glycol (commercially available products such as Pluronic (registered trademark) F68 manufactured by ADEKA Corporation), and polyvinyl alcohol. Of these, polyethylene glycol is preferred as the hydroxyl group-containing polymer.

[0053] Among the above, polymer (B) is preferably at least one selected from the group consisting of polyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyvinyl alcohol, and polymers having an amide group. From the viewpoint of obtaining a cosmetic modifier that rapidly develops adhesiveness to biological tissue upon contact with moisture, polymer (B) is preferably an amide group-containing polymer, and more preferably at least one selected from the group consisting of polyvinylpyrrolidone and poly(meth)acrylamide. Among these, polymer (B) is preferably polyvinylpyrrolidone and / or polyacrylamide, in view of the excellent polymerizability of the constituent monomers and the ease of production of polymer (B).

[0054] Polyvinylpyrrolidone is typically a polymer made of N-vinyl-2-pyrrolidone. However, it may contain structural units derived from monomers other than N-vinyl-2-pyrrolidone (hereinafter also referred to as "other monomers"), provided that the effects of the present disclosure are not impaired. Examples of other monomers include (meth)acrylic acid alkyl esters, aliphatic cyclic (meth)acrylic acid esters, aromatic (meth)acrylic acid esters, (meth)acrylic acid alkoxyalkyl esters, (meth)acrylic acid hydroxyalkyl esters, and polyalkylene glycol mono(meth)acrylates.

[0055] In polyvinylpyrrolidone, the content of structural units derived from other monomers is preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, based on all structural units constituting polyvinylpyrrolidone.

[0056] Similarly, polyacrylamide is typically a polymer made of acrylamide. However, it may contain structural units derived from monomers other than acrylamide, as long as the effects of the present disclosure are not impaired. Specific examples of monomers other than acrylamide include the compounds exemplified above as other monomers. In polyacrylamide, the content of structural units derived from monomers other than acrylamide is preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, based on the total structural units constituting the polyacrylamide.

[0057] Polymethacrylamide is typically a polymer made of methacrylamide. However, it may contain structural units derived from a monomer other than methacrylamide, as long as the effects of the present disclosure are not impaired. Specific examples of monomers other than methacrylamide include the compounds exemplified above as other monomers. In polymethacrylamide, the content of structural units derived from monomers other than methacrylamide is preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, based on the total structural units constituting the polymethacrylamide.

[0058] As the polymer (B), at least one of a crosslinked polymer and a polymer having a weight-average molecular weight of 6,000 or more (hereinafter also referred to as a "high molecular weight polymer (BH)") can be preferably used, since it can provide a hydrogel with excellent adhesiveness to biological tissues. The polymer (B) is more preferably a high molecular weight polymer (BH).

[0059] When a high molecular weight polymer (BH) is used as polymer (B), the weight-average molecular weight (Mw) of the high molecular weight polymer (BH) is preferably 10,000 or more, more preferably 30,000 or more, and even more preferably 50,000 or more, from the viewpoint of ensuring the mechanical strength and thickening effect of the hydrogel and obtaining a hydrogel with excellent adhesiveness to biological tissue. Furthermore, from the viewpoint of the handleability of the polymer and polymer solution, the Mw of the high molecular weight polymer (BH) is preferably 100,000,000 or less, more preferably 50,000,000 or less, and even more preferably 30,000,000 or less. The weight-average molecular weight of polymer (B) is a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

[0060] The polymerization method for producing the polymer (B) is not particularly limited. The polymer (B) can be obtained by polymerizing the monomers using a known polymerization method such as solution polymerization, suspension polymerization, emulsion polymerization, or bulk polymerization. In the case of solution polymerization, for example, an organic solvent and the monomers are charged into a reactor, a polymerization initiator (e.g., an azo compound) is added, and the mixture is heated to 40 to 250°C to polymerize, thereby obtaining the target polymer.

[0061] Cosmetic modifiers can be produced by appropriately combining one or more of the polymers (A) described above with one or more of the polymers (B). From the viewpoints of availability of raw materials and ease of production of the polymers, preferred embodiments of the combination of polymer (A) and polymer (B) include the following embodiments (1) and (2). Aspect (1): Aspect in which the polymer (A) is a crosslinked polymer and the polymer (B) is at least one selected from the group consisting of polyvinylpyrrolidone and poly(meth)acrylamide. Aspect (2): An aspect in which the polymer (A) is at least one selected from the group consisting of polysaccharides, polypeptides, and neutralized products thereof, and the polymer (B) is at least one selected from the group consisting of polyvinylpyrrolidone and poly(meth)acrylamide. These cosmetic modifiers are useful in that they are not bioabsorbable and are highly safe.

[0062] The total content of polymer (A) and polymer (B) contained in the cosmetic modifier is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more, based on the total amount of the cosmetic modifier, from the viewpoint of obtaining a hydrogel that easily swells upon contact with water and has excellent adhesive properties to biological tissue.

[0063] The content of each polymer in the cosmetic modifier is preferably adjusted so that the content of polymer (B) is 20 to 500 parts by mass per 100 parts by mass of polymer (A). When the contents of polymer (A) and polymer (B) are within the above ranges, it is advantageous in that a hydrogel can be formed that maintains adhesion to biological tissue for a long period of time. From this perspective, the content of each of polymer (A) and polymer (B) in the cosmetic modifier is preferably adjusted so that the content of polymer (B) is 30 to 400 parts by mass per 100 parts by mass of polymer (A), more preferably 50 to 300 parts by mass, even more preferably 50 to 200 parts by mass, and even more preferably 75 to 150 parts by mass.

[0064] <Other ingredients> The cosmetic modifier may further contain other components, such as hyaluronic acid or its neutralized products.

[0065] When the cosmetic modifier contains hyaluronic acid or a neutralized product thereof, the content of hyaluronic acid or a neutralized product thereof is preferably 0.01 to 20 parts by mass per 100 parts by mass of the combined total of polymer (A) and polymer (B). By setting the content of hyaluronic acid or a neutralized product thereof within the above range, it is possible to further enhance the water retention of the hydrogel while maintaining good flexibility of the cosmetic modifier. From this perspective, the content of hyaluronic acid or a neutralized product thereof is more preferably 0.1 parts by mass or more, and even more preferably 0.5 parts by mass or more, per 100 parts by mass of the combined total of polymer (A) and polymer (B). The upper limit of the content of hyaluronic acid or a neutralized product thereof is more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of the combined total of polymer (A) and polymer (B).

[0066] In addition to the above, other components that may be contained in the cosmetic modifier include various additives such as antibacterial agents, antioxidants, etc. The content of the other components can be appropriately selected depending on each component, as long as the effects of the present invention are not impaired.

[0067] The shape of the cosmetic modifier is not particularly limited. Examples of the shape of the cosmetic modifier include film (including sheet), sponge, and powder. The size is also not particularly limited. For example, when the cosmetic modifier is in film form, its thickness is approximately 0.1 to 50,000 μm.

[0068] From the perspective of blending it into various cosmetics, the cosmetic modifier is preferably in powder form. The cosmetic modifier of the present invention, even in powder form, is capable of adhering to biological tissue upon contact with water to form a film on the surface of biological tissue, and furthermore, has a highly sustained adhesive property to biological tissue. This makes it useful for cosmetics. When the cosmetic modifier is in powder form (i.e., powder), the shape of the particles constituting the powder is not particularly limited, and examples include spherical, acicular, and plate-like shapes. From the perspective of balancing dispersibility when blended into cosmetics and ease of handling of the cosmetic modifier, the average particle size of the cosmetic modifier is preferably 0.1 μm or more and 20 μm or less in mass-based median diameter. When the cosmetic modifier is in powder form, the average particle size is a value measured by laser diffraction / scattering particle size measurement.

[0069] <Method for manufacturing cosmetic modifier> The method for producing the cosmetic modifier of the present invention is not particularly limited. The cosmetic modifier of the present invention can be produced, for example, by drying a mixture of polymer (A) and polymer (B) in a wet state and shaping the resulting dried product into a desired shape as needed. Specific examples of methods for producing the cosmetic modifier of the present invention include the following methods [1], [2], and [3].

[0070] Method [1]: A method in which a film-like solid containing one of the polymers (A) and (B) is brought into contact with a solution containing the other polymer, and then dried. Method [2]: A method of mixing a solution containing polymer (A) and a solution containing polymer (B) in the presence of hyaluronic acid or a neutralized product thereof, and then removing the solvent. Method [3]: A method of mixing an alcohol solution containing polymer (A) with an alcohol solution containing polymer (B) and removing the solvent.

[0071] Here, if an aqueous solution of polymer (A) and an aqueous solution of polymer (B) are simply mixed, hydrogen bonds between the functional groups of polymer (A) and polymer (B) are formed very quickly. In this case, fibrous aggregates are formed, and a hydrogel may not be obtained. Furthermore, even if a hydrogel is obtained, the obtained hydrogel has insufficient water-swelling properties and poor adhesiveness to biological tissue. In contrast, according to the above-mentioned methods [1], [2], and [3], the hydrogel rapidly absorbs water upon contact with water and becomes a hydrogel, thereby rapidly exhibiting adhesiveness to biological tissue.

[0072] (Regarding Method 1) In method [1], first, a film-like solid material containing one of polymer (A) and polymer (B) (hereinafter also referred to as "first polymer") is produced. Methods for producing a film-like solid material include, for example, solution drying and heat pressing. Among these, solution drying is preferred because it can suppress the generation of bubbles and produce a smooth film. When producing a film-like solid material by solution drying, it is preferable to prepare a polymer solution (hereinafter also referred to as "first polymer solution") by dissolving the first polymer in a solvent, and then coat the first polymer solution on a support and dry it. The first polymer constituting the film-like solid material may be polymer (A) or polymer (B).

[0073] Examples of the solvent for dissolving the first polymer include water, a mixture of a water-soluble organic solvent and water, and an organic solvent that is soluble in water. Examples of the organic solvent that is soluble in water include methanol, ethanol, and acetone. Of these, the solvent for dissolving the first polymer is preferably water, ethanol, or a mixture of water and ethanol. The polymer concentration in the first polymer solution is not particularly limited, but is, for example, 0.01 to 10% by mass, and preferably 0.1 to 5% by mass.

[0074] The method for forming a film-like solid on a support is not particularly limited, and known film-forming methods can be appropriately adopted. For example, a film-like solid containing the first polymer can be formed on a support by applying a first polymer solution to the support and preferably heating it to remove the solvent. When heat treatment is performed, the heating temperature is, for example, 50 to 120°C, and the heating time is, for example, 0.1 to 30 hours. The heat treatment may be performed under reduced pressure or under airflow. The thickness of the film-like solid formed on the support is, for example, 1 to 5,000 μm. The moisture content of the film-like solid is, for example, 10% by mass or less.

[0075] Subsequently, the film-like solid formed on the support is brought into contact with a polymer solution (hereinafter also referred to as the "second polymer solution") obtained by dissolving a polymer (A) and a polymer (B) different from the first polymer (hereinafter also referred to as the "second polymer") in a solvent. Examples of the solvent for dissolving the second polymer include the same solvents as those exemplified as the solvent for dissolving the first polymer. The solvent for dissolving the second polymer may be the same as or different from the solvent for dissolving the first polymer. The polymer concentration in the second polymer solution is, for example, 0.1 to 30% by mass, and preferably 1 to 20% by mass.

[0076] The method for contacting a solid film containing a first polymer with a second polymer solution is not particularly limited. Examples of methods for contacting a solid film with a second polymer solution include applying, dripping, or spraying the second polymer solution onto the surface of the solid film; and immersing the solid film in the second polymer solution. A preferred embodiment involves dripping the second polymer solution onto the surface of the solid film to form a liquid layer of the second polymer solution on the solid film, followed by allowing the solid film to stand for a predetermined period of time (e.g., 10 to 180 minutes). The thickness of the liquid layer is not particularly limited, but is, for example, 0.1 to 50,000 μm. This allows the first polymer in the solid film to gradually dissolve in the second polymer solution, forming a hydrogel.

[0077] When the film-like solid material containing the first polymer is brought into contact with the second polymer solution, the amount of the second polymer solution to be brought into contact with the film-like solid material is preferably selected so that a crosslinked structure is appropriately formed in the resulting hydrogel. Specifically, the carboxyl groups and "-COO" groups contained in the polymer (A) are preferably selected so that the crosslinked structure is appropriately formed in the resulting hydrogel. - It is preferable to adjust the amounts of the film-like solid and the second polymer solution and the polymer concentration so that the number of moles of functional group E in polymer (B) is preferably 0.1 to 10 moles, more preferably 0.2 to 8 moles, and even more preferably 0.5 to 2 moles per mole of the total of ".

[0078] When obtaining a dried product containing hyaluronic acid or its neutralized product as a cosmetic modifier, the hyaluronic acid or its neutralized product may be contained in either the film-like solid or the second polymer solution. From the viewpoint of favorable hydrogel formation, it is preferable that the second polymer solution contains hyaluronic acid or its neutralized product. Furthermore, when the second polymer solution contains hyaluronic acid or its neutralized product, the hyaluronic acid or its neutralized product may be previously blended into the second polymer solution, and the second polymer solution containing hyaluronic acid or its neutralized product may be contacted with the film-like solid. Alternatively, the film-like solid may be contacted with the second polymer solution, and then the hyaluronic acid or its neutralized product may be added to the second polymer solution. From the viewpoint of favorable hydrogel formation by contact between the film-like solid containing the first polymer and the second polymer solution, it is preferable that the second polymer solution previously containing hyaluronic acid or its neutralized product be contacted with the film-like solid.

[0079] When contacting a film-like solid with a second polymer solution containing hyaluronic acid or its neutralized product, the content of hyaluronic acid or its neutralized product in the second polymer solution is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and even more preferably 0.5 to 15 parts by mass, per 100 parts by mass of the second polymer.

[0080] Thereafter, a gel-like product (hereinafter also referred to as "hydrogel product") obtained by contacting the film-like solid containing the first polymer with the second polymer solution can be dried to obtain a dried product. There are no particular restrictions on the method for drying the hydrogel product, and any known drying method can be used as appropriate.

[0081] For example, when drying a hydrogel product by a solution drying method, freeze-drying is preferred. In this case, the hydrogel product is placed in a mold and frozen, and the resulting frozen product is freeze-dried to obtain a dried product having a desired shape. In the freeze-drying process, the freezing temperature is, for example, -70°C to -5°C, and preferably -60°C to -5°C. The drying process by freeze-drying is preferably carried out at room temperature under reduced pressure. The pressure during freeze-drying is, for example, 50 Pa or less, preferably 20 Pa or less, and more preferably 10 Pa or less.

[0082] When producing a sponge-like dried product, the freeze-drying process may be performed by supercooling the hydrogel product and then freezing it. In this case, it is preferable to cool the hydrogel product through multiple steps at different cooling temperatures. This method makes it possible to obtain, in a relatively simple manner, a dried product that, when used as a cosmetic modifier, exhibits excellent adhesiveness to biological tissue in a water-swollen state.

[0083] Specifically, the first cooling step preferably involves first cooling the hydrogel product to a temperature below 0°C and above -10°C to put the hydrogel product into a supercooled state, followed by the second cooling step of freezing the hydrogel product by cooling it to a temperature lower than -10°C. In this regard, in the first cooling step, it is preferable to gradually lower the temperature in order to efficiently create a supercooled state. In the second cooling step, the cooling temperature is preferably set to -15°C or below, more preferably -20°C or below, and even more preferably -25°C or below, in order to obtain a dried product that exhibits excellent adhesiveness to biological tissue in a water-swollen state. The cooling times for the first and second cooling steps are not particularly limited and can be set appropriately, for example, between 3 minutes and 5 hours. The first and / or second cooling steps may be performed in multiple steps with different cooling temperatures.

[0084] In this specification, the term "dry" refers to a state in which moisture is completely removed, as well as a state in which moisture remains during the drying process. The moisture content of the dried product obtained by the drying treatment is, for example, 10% by mass or less, preferably 5% by mass or less, and more preferably 2% by mass or less.

[0085] In this way, a film-like solid containing one of polymers (A) and (B) is contacted with a solution containing the other polymer, and the resulting hydrogel product is dried to obtain a dried product. The resulting dried product may be used as a cosmetic modifier as is, or may be used as a powdered cosmetic modifier after being subjected to a process such as pulverization.

[0086] (Regarding Method 2) In method [2], a solution containing polymer (A) is mixed with a solution containing polymer (B) in the presence of hyaluronic acid or its neutralized product, and then the solvent is removed from the resulting mixture to produce a dried product.

[0087] In the solution containing polymer (A) (hereinafter also referred to as "polymer solution A") and the solution containing polymer (B) (hereinafter also referred to as "polymer solution B"), examples of the solvent for dissolving the polymer include the same solvents as those exemplified as the solvent for dissolving the first polymer. Of these, it is preferable to use water alone from the viewpoint of efficient drying treatment. In polymer solution A and polymer solution B, the polymer concentration is, for example, 0.001 to 5% by mass, and preferably 0.01 to 1% by mass.

[0088] The amounts and concentrations of polymer solution A and polymer solution B are preferably adjusted so that the content of polymer (B) in each of polymer solution A and polymer solution B is 20 to 500 parts by mass per 100 parts by mass of polymer (A). The amounts of polymer (A) and polymer (B) are more preferably 30 to 400 parts by mass, and even more preferably 50 to 300 parts by mass, per 100 parts by mass of polymer (A).

[0089] In the method [2], the amount of hyaluronic acid or its neutralized product used is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 30 parts by mass, and even more preferably 0.5 to 20 parts by mass, relative to 100 parts by mass of the polymer (A).The hyaluronic acid or its neutralized product is preferably used as an aqueous solution.

[0090] Subsequently, the mixed liquid containing the polymer (A), the polymer (B), and hyaluronic acid or its neutralized product obtained as described above is subjected to a drying treatment to remove the solvent, thereby obtaining a dried product. The drying treatment is preferably freeze-drying. Freeze-drying can be carried out according to a conventional method. For example, the mixed liquid is placed in a mold, frozen, and the resulting frozen product is freeze-dried to obtain a dried product having the desired shape. The freeze-drying treatment is preferably carried out by a method in which the hydrogel product is supercooled and then frozen. Details of this method are as described in Method [1]. The obtained dried product may be used as a cosmetic modifier as is, or may be used as a cosmetic modifier after being subjected to a process such as pulverization.

[0091] (Regarding Method 3) In method [3], the alcohol solution containing polymer (A) is mixed with the alcohol solution containing polymer (B), and then the solvent is removed from the resulting mixture to obtain a dried product.Method [3] is useful in that it can obtain a high-quality dried product in the presence of hyaluronic acid or its neutralized product without mixing the polymer solutions.

[0092] In the alcohol solution containing polymer (A) (hereinafter also referred to as "alcohol solution A") and the alcohol solution containing polymer (B) (hereinafter also referred to as "alcohol solution B"), a linear or branched alcohol having 1 to 5 carbon atoms is preferably used as the alcohol. The alcohols used to prepare alcohol solution A and alcohol solution B may be the same or different. When preparing each of alcohol solution A and alcohol solution B, one type of alcohol may be used alone, or two or more types of alcohols may be used in combination.

[0093] From the viewpoint of obtaining a hydrogel with superior adhesiveness to biological tissues, the alcohol used in preparing alcohol solution A and alcohol solution B is preferably a linear or branched alcohol having 1 to 3 carbon atoms among the above. Furthermore, considering application to cosmetic applications, at least one selected from the group consisting of ethanol, n-propanol, and isopropanol is preferred, with ethanol being particularly preferred. The polymer concentration in alcohol solution A and alcohol solution B is, for example, 0.1 to 30% by mass, preferably 0.5 to 20% by mass.

[0094] The amounts and concentrations of the alcoholic solutions A and B are preferably adjusted so that the content of the polymer (A) and the polymer (B) is 20 to 500 parts by mass per 100 parts by mass of the polymer (A). The amounts of the polymer (A) and the polymer (B) are more preferably 30 to 400 parts by mass, and even more preferably 50 to 300 parts by mass, per 100 parts by mass of the polymer (A). Furthermore, when obtaining a dried product containing hyaluronic acid or a neutralized product thereof, it is preferable to add hyaluronic acid or a neutralized product thereof to at least one of the alcoholic solutions A and B. The content of hyaluronic acid or a neutralized product thereof in the alcoholic solutions A and / or B is, for example, 0.01 to 15 parts by mass per 100 parts by mass of the polymer.

[0095] Subsequently, the mixed liquid containing the polymer (A), the polymer (B), and the alcohol obtained above is subjected to a drying treatment to remove the solvent, thereby obtaining a dried product. The drying method is not particularly limited, and may be, for example, natural drying, heating, air blowing, or a combination thereof, or freeze-drying. Details of the freeze-drying treatment are as described in Method [1]. The obtained dried product may be used as a cosmetic modifier as is, or may be used as a cosmetic modifier after being subjected to a treatment such as pulverization.

[0096] <Cosmetics> The cosmetic of the present invention contains the cosmetic modifier described above. The components to be blended into the cosmetic together with the cosmetic modifier are not particularly limited, and known cosmetic components used in cosmetic formulations can be used as appropriate. Examples of cosmetic components include thickeners, film-forming aids, plasticizers, moisturizers, UV absorbers, fatty acid soaps, fats and oils, waxes, hydrocarbon oils, ester oils, powders, polymeric compounds, preservatives, antioxidants, pH adjusters, chelating agents, and colorants. The cosmetic of the present invention can be prepared by blending at least one of these components.

[0097] Examples of thickeners include alkali swelling thickeners, associative polyurethanes, carboxyvinyl polymers, thickening polysaccharides, and clay minerals.

[0098] Examples of the film-forming aid and plasticizer include cellosolves such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; carbitols such as carbitol, dimethyl carbitol, diethyl carbitol, butyl carbitol, and dibutyl carbitol; carbonates such as ethylene carbonate, diethylene carbonate, and propylene carbonate; acetates such as cellosolve acetate, butyl cellosolve acetate, butyl carbitol acetate, and sucrose acetate; Examples of the alcohol include ethanol, propanol, butanol, pentanol, hexanol, benzyl alcohol, and 2-phenylethanol alcohol; diols such as ethylene glycol, propylene glycol, butylene glycol, and hexylene glycol; esters such as phthalic acid diester, adipic acid diester, succinic acid diester, sebacic acid diester, and abieticitric acid ester; benzoic acid esters such as sucrose benzoate; and diethylbenzene.

[0099] Examples of moisturizing agents include sorbitol, xylitol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, glycerin, diglycerin, polyethylene glycol, hyaluronic acid, chondroitin sulfate, pyrrolidone carboxylate, and DL-pyrrolidone carboxylate.

[0100] Examples of ultraviolet absorbers include benzophenone derivatives such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sodium sulfonate, dihydromethoxybenzophenone, dihydroxymethoxybenzophenone-sodium sulfonate, 2,4-dihydroxybenzophenone, and tetrahydroxybenzophenone; benzoic acid derivatives such as para-aminobenzoic acid, ethyl para-aminobenzoate, glyceryl para-aminobenzoate, amyl para-dimethylaminobenzoate, and octyl para-dimethylaminobenzoate; and ethyl para-methoxycinnamate, isopropyl para-methoxycinnamate, octyl para-methoxycinnamate, and 2-ethoxyethyl para-methoxycinnamate. methoxycinnamic acid derivatives such as ethyl paramethoxycinnamate, sodium paramethoxycinnamate, potassium paramethoxycinnamate, and glycerin paramethoxycinnamate mono-2-ethylhexanoate; salicylic acid derivatives such as octyl salicylate, phenyl salicylate, homomenthyl salicylate, dipropylene glycol salicylate, ethylene glycol salicylate, myristyl salicylate, and methyl salicylate; urocanic acid, ethyl urocanate, ethyl urocanate, 4-tert-butyl-4'-methoxybenzoylmethane, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-phenyl-5-methylbenzoxazole, methyl anthranilate, and 2-ethylhexyl dimethoxybenzylidene dioxoimidazolidinepropionate.

[0101] Examples of fatty acid soaps include alkali salts of C6-24 higher fatty acids. The fatty acids may be saturated or unsaturated, and examples include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid, behenic acid, oleic acid, isooleic acid, linoleic acid, linolenic acid, and arachidonic acid. The alkali used to neutralize the fatty acid is not particularly limited, and may be any alkali commonly used in the production of soap, such as potassium hydroxide, sodium hydroxide, triethanolamine, N-methyltaurine, and ammonia.

[0102] Examples of fats and oils include avocado oil, camellia oil, evening primrose oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, camellia oil, castor oil, linseed oil, safflower oil, cottonseed oil, perilla oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, Chinese tung oil, Japanese tung oil, jojoba oil, germ oil, triglycerin, glycerin trioctanoate, glycerin triisopalmitate, cacao butter, coconut oil, hydrogenated coconut oil, palm oil, palm kernel oil, Japan wax kernel oil, hydrogenated oil, hydrogenated castor oil, and polyoxyethylene adducts thereof.

[0103] Examples of waxes include whale wax, beeswax, high acid value beeswax, shellac, mink wax, lanolin, lanolin acetate, liquid lanolin, carnauba wax, candelilla wax, rice bran wax, rice bran wax, Japan wax, cotton wax, bayberry wax, ivory wax, montan wax, Kabocha wax, jojoba wax, sugarcane wax, ivory wax, lanolin fatty acid isopropyl, hexyl laurate, reduced lanolin, hard lanolin, shellac wax, polyoxyethylene lanolin alcohol ether, polyoxyethylene lanolin alcohol acetate, polyoxyethylene cholesterol ether, lanolin fatty acid polyethylene glycol, and polyoxyethylene hydrogenated lanolin alcohol ether.

[0104] Examples of hydrocarbon oils include paraffin, liquid paraffin, ozokerite, squalene, bristle, ceresin, vaseline, and microcrystalline wax.

[0105] Examples of ester oils include myristate esters such as isopropyl myristate, butyl myristate, myristyl myristate, isocetyl myristate, octyldodecyl myristate, and 2-hexyldecyl myristate; palmitate esters such as isopropyl palmitate, cetyl palmitate, isostearyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, and 2-heptylundecyl palmitate; butyl stearate, isocetyl stearate, cholesteryl stearate; Stearic acid esters such as isocetyl tearate, cholesteryl 12-hydroxystearate, and N-alkyl glycol isostearate; lauric acid esters such as isopropyl laurate and hexyl laurate; linoleic acid esters such as ethyl linoleate and isopropyl linoleate; octanoic acid esters such as cetyl octanoate, hexyldecyl dimethyloctanoate, octyldodecyl dimethyloctanoate, and cetyl isooctanoate; oleic acid esters such as decyl oleate and oleic acid oil; sorbitan monolaurate sorbitan fatty acid ester oils such as sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquistearate, sorbitan tristearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, sorbitan monoisostearate, and sorbitan sesquiisostearate; polyoxyethylene sorbitan monococonut oil fatty acid, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monoisostearate; Polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan stearate and polyoxyethylene sorbitan monooleate, polyoxyethylene sorbit monolaurate, polyoxyethylene sorbit hexastearate, polyoxyethylene sorbit tetrastearate and polyoxyethylene sorbit tetraoleate, polyoxyethylene sorbit fatty acid esters such as cetyl lactate and myristyl lactate, malic acid esters such as diisostearyl malate, diisobutyl adipate,Adipic acid esters such as di-2-heptylundecyl adipate and 2-hexyldecyl adipate, sebacate esters such as di-2-ethylhexyl sebacate and diisopropyl sebacate, succinic acid esters such as 2-ethylhexyl succinate, citric acid esters such as triethyl citrate, triisocetyl citrate, triisoarachyl citrate, triisooctyl citrate, acetyltriethyl citrate and acetyltributyl citrate, ethylene glycol di-2-ethylhexanoate, propylene glycol monocaprate, propylene glycol dicaprate, propylene glycol didecanoate, glyceryl tri-2-ethylhexanoate, caprylic / capric triglyceride, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexanoate, glyceryl tri-2-ethylhexanoate, trimili Examples of the glyceryl stearate include polyhydric alcohol esters such as glyceryl stearate, decaglyceryl decaglyceryl, decaglyceryl decaisostearate, glyceryl di-2-heptylundecanoate, polyoxyethylene glyceryl monostearate, polyethylene glycol glyceryl monooleate, diglyceryl monostearate, diglyceryl monoisostearate, diglyceryl monooleate, tetraglyceryl monostearate, polyglyceryl monooleate, polyglyceryl tristearate, polyglyceryl pentastearate, polyglyceryl pentaoleate, and neopentyl glycol dicaprate; lanolin acetate, dipentaerythritol fatty acid esters, tri-2-heptylundecanoic acid glyceride, castor oil fatty acid methyl esters, acetoglyceride, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, and ethyl laurate.

[0106] There are no particular limitations on the powder, so long as it is one that is normally used in combination with cosmetic resins. Powders can be used regardless of particle shape (e.g., spherical, acicular, plate-like, etc.), particle size (aerosol, fine particles, pigment-grade, etc.), particle structure (porous, non-porous, etc.), etc.

[0107] Examples of inorganic powders include titanium oxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, synthetic mica, mica, kaolin, sericite, muscovite, phlogopite, lepidolite, biotite, lithia mica, silicic acid, anhydrous silicic acid, aluminum silicate, magnesium silicate, aluminum magnesium silicate, calcium silicate, barium silicate, strontium silicate, metal tungstate, hydroxyapatite, vermiculite, higilite, bentonite, montmorillonite, hecrite, zeolite, ceramic powder, dibasic calcium phosphate, alumina, aluminum hydroxide, boron nitride, boron nitride, and silica.

[0108] Examples of organic powders include starch powder, polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane powder, benzoguanamine powder, polymethylbenzoguanamine powder, tetrafluoroethylene powder, polymethyl methacrylate powder, cellulose, silk powder, nylon powder, nylon 12, nylon 6, styrene-acrylic acid copolymer, divinylbenzene-styrene copolymer, vinyl resin, urea resin, phenolic resin, fluororesin, silicone resin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin, microcrystalline fiber powder, rice starch, and lauroyl lysine.

[0109] The polymeric compound is not particularly limited as long as it is a polymer that is typically used in combination with cosmetic resins and is different from polymer (A), polymer (B), and hyaluronic acid or a salt thereof. Examples of polymeric compounds include natural polymeric compounds such as gum arabic, tragacanth gum, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, cannabinol, quince seed (quince), and alkecoid (gassow extract); and synthetic polymeric compounds such as polyvinyl methyl ether, carboxyvinyl polymer (carbobol), polyoxyethylene polymers such as polyethylene glycol 2000, 4000, and 6000, polyoxyethylene-polyoxypropylene copolymer polymers, vinyl acetate polymers, polyethyleneimine, and cationic polymers. These polymeric compounds may be in any form, such as a solution or particles (including microparticles).

[0110] Examples of preservatives include alkyl parahydroxybenzoates, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, and dehydroacetic acid, as well as salts thereof. Examples of antioxidants include tocopherol, butylhydroxyanisole, and dibutylhydroxytoluene. Examples of pH adjusters include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, dl-malic acid, potassium carbonate, sodium bicarbonate, and ammonium bicarbonate. Examples of chelating agents include alanine, sodium edetate, sodium polyphosphate, sodium metaphosphate, and phosphoric acid. Examples of coloring materials include organic pigments, inorganic pigments, dyes, polymer powders, and natural dyes.

[0111] By appropriately selecting the components to be blended together with the cosmetic modifier described above, the cosmetic of the present invention can be applied to various parts of the body, such as the scalp, face (skin, eyebrows, eyes, lips, cheeks, etc.), neck, fingers, nails, feet, etc., or to the entire body. The form of these cosmetics is not particularly limited, and examples include solid, semi-solid, paste, powder, solution, emulsion, gel, mousse, spray, film, and sheet. Furthermore, the cosmetic may be provided in the form of a sheet in which a substrate such as a nonwoven fabric is impregnated with the cosmetic.

[0112] For example, the cosmetic of the present invention can be used as various cosmetics such as makeup cosmetics, skin cosmetics, and hair cosmetics. Specific examples of makeup cosmetics include eyeliner, eyeshadow, eyebrow pencil, mascara, nail polish, blush, foundation (powder foundation, liquid foundation, etc.), lipstick, etc. Examples of skin cosmetics include face packs, sunscreens, emulsions, creams, lotions, etc. Examples of hair cosmetics include hair dyes, hair dyes, perm solutions, bleaching agents, hair foams, shampoos, conditioners, etc. Furthermore, the cosmetic of the present invention can also be used in antiperspirants such as deodorants, UV protection agents such as sunscreen creams, etc.

[0113] In a specific example of an application form, a powdered cosmetic modifier is blended with powders such as pigments and oils and fats during the production of foundation. When applying the foundation to the face, for example, the foundation can be applied to skin that has been moistened with water beforehand, or by applying the foundation to the skin with a water-soaked puff, thereby enhancing the adhesion of the foundation to the skin with the cosmetic modifier. This reduces the tendency of the foundation to float on the skin, providing a pleasant feel in use and improving the longevity of the makeup. Similarly, the cosmetic modifier can be applied to point makeup such as lipstick, eye shadow, and eyebrow makeup, or as a second skin, improving the feel in use and the longevity of the makeup. The cosmetic modifier described above is also useful in that it is not bioabsorbable, does not irritate the skin, and is highly safe. [Example]

[0114] The present disclosure will be specifically described below based on examples, but the present invention is not limited to these examples. In the following, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

[0115] 1. Manufacturing of cosmetic modifiers Example 1 A silicone rubber sheet (10 mm thick) with a 10 mm x 10 mm opening was placed on a 50 mm x 50 mm polypropylene substrate. 0.86 mL of a 1.2 wt% highly cross-linked polyacrylic acid (Toagosei Co., Ltd., Junlon PW-120, hereinafter referred to as "PAA1") (polymer (A)) aqueous solution was cast into the opening of the silicone rubber sheet and dried at 70 °C for 20 hours to produce a PAA1 film. Next, 0.86 mL of a mixed solution of 0.6 mL of a 4.6 wt% polyvinylpyrrolidone (polymer (B), hereinafter referred to as "PVP") aqueous solution and 0.9 mL of a 0.4 wt% sodium hyaluronate (hereinafter referred to as "HA") aqueous solution was dropped onto the surface of the PAA1 film and allowed to stand for 60 minutes. After cooling (pre-cooling) at 0 °C for 0.5 h and then -4 °C for 0.5 h, the film was frozen at -35 °C for 1 h. The frozen product was freeze-dried at room temperature under reduced pressure (5 Pa) to obtain a sponge-like cosmetic modifier. The resulting sponge was pulverized for 10 seconds using a Wonder Blender (Osaka Chemical Co., Ltd., WB-1) to obtain a powdered cosmetic modifier. The polymer blend ratio was PAA1:PVP:HA = 1:1.53:0.1 (mass ratio).

[0116] Example 3 2.0 g of PVP (polymer (B)) and 0.26 g of HA were diluted with water to a total volume of 50 mL to prepare 45 mL of a mixed aqueous solution. 45 mL of this mixed aqueous solution was mixed with 51 mL of a 4.63 mass% aqueous solution of 90 mol% neutralized PGluNa (polymer (A)) to obtain a mixed solution (referred to as mixed solution PS2). A silicone rubber sheet (10 mm thick) with a 10 mm x 10 mm opening was placed on a 50 mm x 50 mm polypropylene substrate. 0.2 mL of the mixed solution PS2 was cast into the opening of the silicone rubber sheet, and the sheet was cooled (pre-cooled) at 0°C for 0.5 h and then at -4°C for 0.5 h, and then frozen at -35°C for 1 h. The frozen product was freeze-dried at room temperature under reduced pressure (5 Pa) to obtain a sponge-like cosmetic modifier. The resulting sponge was pulverized for 10 seconds using a Wonder Blender (Osaka Chemical Co., Ltd., WB-1) to obtain a powdered cosmetic modifier. The polymer blend ratio was 90 mol% neutralized PGluNa:PVP:HA = 1:0.75:0.1 (mass ratio).

[0117] <Example 2 and Comparative Example 1> A powdered cosmetic modifier was obtained in the same manner as in Example 1, except that the types of raw materials were as shown in Table 1.

[0118] 2. Cosmetic production and evaluation Cosmetics were produced using the cosmetic modifiers of Examples 1 to 3 and Comparative Example 1, and the feel of use and cosmetic durability of the cosmetics were evaluated. The evaluation results are shown in Table 1. Cosmetic manufacturing 30 mg of each cosmetic modifier was thoroughly mixed with 270 mg of titanium oxide (manufactured by Sakai Chemical Industry Co., Ltd., STR-100N), and this was used as the cosmetic to be evaluated. Evaluation of usability and makeup durability Three male subjects wet their faces with water and applied each cosmetic product for evaluation. The sensation of use upon application (how well the cosmetic product blended with the skin) was checked. Each subject scored the sensation of use on a three-point scale of 1, 2, or 3 according to the following evaluation criteria. Furthermore, after applying the cosmetic products to their faces and going about their daily lives as normal for 8 hours, the subjects checked how much of each cosmetic product remained on their skin. Each subject scored the results on a 3-point scale of 1, 2, or 3 according to the following evaluation criteria to evaluate the cosmetic longevity. The average scores of the three subjects for ease of use and makeup durability are shown in Table 1. (Evaluation criteria for usability) 3 points: Good 2 points: Fairly good 1 point: Bad (Evaluation criteria for makeup durability) 3 points: More than 80% of the product remains on the skin 2 points: 30% to less than 80% of the product remains on the skin 1 point: Less than 30% of the product remains on the skin

[0119] [Table 1]

[0120] Details of the compounds in Table 1 are shown below. (Carboxyl group / -COO - (containing polymer) PAA1: Highly cross-linked polyacrylic acid (Toagosei Co., Ltd., Junron PW-120, viscosity of 1% by mass aqueous solution at 25°C = 600 mPa s) PAA2: Medium-crosslinked polyacrylic acid (Toagosei Co., Ltd., Junron PW-121, viscosity of 1% by weight aqueous solution at 25°C = 13,500 mPa s) PAA3: Uncrosslinked polyacrylic acid (Toagosei Co., Ltd., Jurimer AC-10LHPK) Weight-average molecular weight: 1.5 million, viscosity of 1% by mass aqueous solution at 25°C: 2 mPa·s 90 mol% neutralized PGluNa: sodium polyglutamate (Meiji Food Materials Co., Ltd., Meiji polyglutamic acid, viscosity of 1% by mass aqueous solution at 25°C = 25 mPa s) (Polymer (B)) PVP: Polyvinylpyrrolidone (BASF, Kollidon 90F, polystyrene equivalent weight average molecular weight = 320,000 (dimethylformamide eluent)) (Other ingredients) HA: Sodium hyaluronate (Kewpie Corporation, Hyaluronsan HA-LQH)

[0121] Each carboxyl group / -COO - The viscosity of the contained polymer was measured by the following method. Carboxyl group / -COO -Viscosity measurement method for contained polymer 1.0 mass% carboxyl group / -COO - The aqueous polymer solution was allowed to stand overnight at room temperature of 25°C, and the viscosity (mPa·s) was measured using a Brookfield viscometer (Tokyo Keiki Seisakusho, model: BM).

[0122] 3. Evaluation Results As is clear from the results in Table 1, the carboxyl group and / or "-COO - Cosmetics (Examples 1 to 3) prepared using a cosmetic modifier containing a polymer (A) having a viscosity of 10 mPa·s or more at 25°C when made into a 1% by mass aqueous solution, and a polymer (B) different from polymer (A) having a functional group capable of forming a hydrogen bond with a carboxyl group, were excellent in feel during use and cosmetic long-lasting properties. These results demonstrate that the cosmetic modifiers of Examples 1 to 3 function as ingredients that improve the properties of cosmetics (particularly feel during use and cosmetic long-lasting properties).

[0123] In contrast, carboxyl groups and / or "-COO - A cosmetic modifier (Comparative Example 1) produced using PAA3 (2 mPa·s), which has a viscosity of less than 10 mPa·s at 25°C when made into a 1% by mass aqueous solution, instead of polymer (A) as the polymer having the formula "," was inferior to Examples 1 to 3 in both feel during use and cosmetic durability.

Claims

1. Carboxyl group and / or "-COO － " and a polymer (A) (excluding hyaluronic acid or a neutralized product thereof) having a viscosity of 10 mPa s or more at 25°C when made into a 1% by mass aqueous solution; a polymer (B) having a functional group capable of forming a hydrogen bond with a carboxyl group (excluding the polymer (A)); Contains A cosmetic modifier that forms a hydrogel upon contact with water.

2. 2. The cosmetic modifier according to claim 1, wherein the polymer (A) is a crosslinked polymer.

3. 3. The cosmetic modifier according to claim 2, wherein the polymer (A) is poly(meth)acrylic acid.

4. 2. The cosmetic modifier according to claim 1, wherein the polymer (A) is at least one selected from the group consisting of polysaccharides, polypeptides, and neutralized products thereof.

5. 5. The cosmetic modifier according to claim 4, wherein the polymer (A) is at least one selected from the group consisting of oxidized cellulose, carboxyalkyl cellulose, pectin, polyglutamic acid, polyaspartic acid, alginic acid, and neutralized products thereof.

6. The cosmetic modifier according to claim 1 , wherein the polymer (B) has an amide group.

7. 7. The cosmetic modifier according to claim 6, wherein the polymer (B) is at least one selected from the group consisting of polyvinylpyrrolidone and poly(meth)acrylamide.

8. 10. The cosmetic modifier according to claim 1, which is in powder form.

9. a dried body obtained by bringing a film-like solid material containing one of the polymers (A) and (B) into contact with a solution containing the other polymer, and drying the resulting solid material; 2. The cosmetic modifier according to claim 1, wherein the hydrogel formed upon contact with water has adhesive properties to biological tissue.

10. A cosmetic comprising the cosmetic modifier according to any one of claims 1 to 9.

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