O / W type cosmetic containing polymer containing cationic groups

Abstract

To provide a novel cosmetic composition comprising a cationic group-containing polymer and is stable over time.SOLUTION: There is provided a cosmetic composition comprising: (a) a cationic group-containing polymer; and (b) an α-gel containing a nonionic surfactant.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to cosmetics. More specifically, it relates to a cosmetic composition containing a polymer containing a cationic group and α-gel, which is used in skin cosmetics, topical skin preparations, hair cosmetics, etc. [Background technology]

[0002] Polymers containing cationic groups are often used in cosmetics. For example, Patent Document 1 describes an oil-in-water emulsion composition containing (A) a solid hydrocarbon oil, (B) waxes, (C) polyoxyethylene cetyl ether (15-25EO), and (D) a cationic polymer. It describes the use of a copolymer of methylvinylimidazolinium, a polymer containing amino groups, and vinylpyrrolidone as the cationic polymer (D), and also describes the use of a carboxyl vinyl polymer as a thickener. For example, Patent Document 2 describes an oil-in-water emulsion composition emulsified with a polyion complex formed from a polymer containing a cationic group and carboxymethyl cellulose. It describes that O-[2-hydroxy-3-(trimethylammonio)propyl]hydroxyethyl cellulose chloride is used as the polymer containing a cationic group. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-102258 [Patent Document 2] Japanese Patent Application Laid-Open No. 2011-32249 Summary of the Invention [Problem to be solved by the invention]

[0004] As described above, the use of cationic group-containing polymers as cosmetic raw materials has been proposed, and in order to stabilize or thicken O / W cosmetic compositions containing cationic group-containing polymers, they are commonly used in combination with anionic polymers such as carboxyvinyl polymers and carboxymethyl cellulose. Such cosmetic compositions often exhibit insufficient storage stability, such as the formation of aggregates. Therefore, an object of the present invention is to provide a novel cosmetic composition that contains a cationic group-containing polymer and has good stability over time. [Means for solving the problem]

[0005] The present inventors have conducted various studies to achieve the above object and have arrived at the present invention. That is, the present invention comprises: (a) a polymer containing a cationic group; (b) an α-gel containing a nonionic surfactant. [Effects of the Invention]

[0006] The cosmetic composition of the present disclosure has excellent storage stability over time, and can therefore be preferably used as a cosmetic ingredient for skin care and hair care, for example. [Brief explanation of the drawings]

[0007] [Figure 1] 1 is a chart showing the results of XRD (small angle) measurement of the compositions obtained in Production Example 1, Comparative Production Example 1, Production Example 7, and Comparative Production Example 2. [Figure 2] 1 is a chart showing the results of XRD (wide angle) measurement of the compositions obtained in Production Example 1, Comparative Production Example 1, Production Example 7, and Comparative Production Example 2. [Figure 3] 1 is a chart showing the results of XRD (small angle) measurement of the compositions obtained in Production Example 8 and Comparative Production Example 3. [Figure 4] 1 is a chart showing the results of XRD (wide angle) measurement of the compositions obtained in Production Example 8 and Comparative Production Example 3. DETAILED DESCRIPTION OF THE INVENTION

[0008] The present disclosure will be described in detail below. Note that a combination of two or more of the individual preferred embodiments of the present disclosure described below is also a preferred embodiment of the present disclosure.

[0009] <Polymer containing cationic groups> In the present disclosure, a cationic group-containing polymer refers to a polymer containing a cationic group in its structure. Examples include homopolymers polymerized using a cationic group-containing monomer, copolymers of a cationic group-containing monomer with another monomer not containing a cationic group, and compounds obtained by reacting a polymer with a cationic group-containing compound. In the case of a copolymer, the cationic group-containing monomer preferably accounts for 30% by mass or more of the entire copolymer, more preferably 40% by mass or more, particularly preferably 50% by mass or more, and most preferably 60% by mass or more. In the case of a compound obtained by reacting a polymer with a cationic group-containing compound, the cationic group-containing portion preferably accounts for 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the compound (100% by mass). Polymers containing cationic groups may have antibacterial properties. Antibacterial properties refer to the ability to kill microorganisms (kill microorganisms), bacteriostasis (suppress the growth of microorganisms), sterilize, disinfect, inhibit bacteria, eliminate bacteria, and prevent mold. Microorganisms that are the subject of the present disclosure include, but are not limited to, Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Candida, and Aspergillus niger. For example, polymers containing cationic groups exhibit antibacterial properties against the above-mentioned bacteria. In the present disclosure, the amount of the polymer containing a cationic group is preferably 0.0001 part by mass or more, and more preferably 0.0002 part by mass or more, relative to 100% by mass of the α-gel containing the nonionic surfactant described below.

[0010] <Cationic group> In the present disclosure, a cationic group refers to a group having a cation or a group that generates a cation, and is not particularly limited, but examples thereof include primary to tertiary amino groups, quaternary ammonium bases, etc. Of the primary to tertiary amino groups and quaternary ammonium bases, the cationic group is preferably a tertiary amino group or a quaternary ammonium base.

[0011] <Primary to tertiary amino groups> Examples of the primary to tertiary amino group include those represented by the following formula (1):

[0012] [ka] (wherein R1 and R2 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.) The hydrocarbon group is preferably an alkyl group, an alkenyl group, or an aryl group, more preferably an alkyl group or an alkenyl group, and even more preferably an alkyl group. The hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, particularly preferably 1 to 5 carbon atoms, and most preferably 1 to 2 carbon atoms. At least one of R1 and R2 is preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably both R1 and R2 are hydrocarbon groups having 1 to 12 carbon atoms. Among primary to tertiary amino groups, a tertiary amino group is preferred. As the tertiary amino group, a dimethylamino group or a diethylamino group is preferred.

[0013] <Quaternary ammonium base> The quaternary ammonium base is represented by the following formula (2):

[0014] [ka] (wherein R3 to R5 are the same or different and represent a hydrocarbon group having 1 to 12 carbon atoms.) The hydrocarbon group is preferably an alkyl group, an alkenyl group, or an aryl group, more preferably an alkyl group or an alkenyl group, and even more preferably an alkyl group. The number of carbon atoms in R3 to R5 is more preferably 1 to 10, even more preferably 1 to 7, and particularly preferably 1 to 5. The hydrocarbon groups of R3 to R5 are most preferably methyl or ethyl groups.

[0015] <Method for producing polymer containing cationic groups> In the present disclosure, the method for producing a polymer containing a cationic group is not particularly limited, but it can usually be produced by polymerizing a monomer containing a cationic group. In the present disclosure, examples of a monomer containing a cationic group include those having at least one ethylenically unsaturated group and one cationic group. For example, a polymer can be produced by polymerizing a monomer containing a primary to tertiary amino group and a quaternary ammonium salt group alone, or, if necessary, by polymerizing it with other monomers that do not contain a cationic group. In addition to production methods using other ethylenically unsaturated groups, for example, a cellulose-based polymer containing a cationic group can be produced by reacting the alcohol group of cellulose with an etherifying agent such as ethylene oxide to form a cellulose ether, which can then be reacted with a glycidyl group having a cationic group. For example, polyaminoalkylbiguanide can be produced by reacting dicyandiamide with an alkyl-containing diamine. Other cationic-containing polymers can be produced by known production methods.

[0016] <Monomer containing a cationic group> In the present disclosure, the monomer containing the cationic group includes, for example, the monomer containing the primary to tertiary amino groups in the structure, and the monomer containing a quaternary ammonium salt group in the structure.Specifically, N,N-dialkylamino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate, as well as monomers obtained by adding a quaternizing agent to the above monomers, or neutralized products thereof with an acid such as hydrochloric acid or acetic acid; N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N, N,N-dialkylamino group-containing (meth)acrylamides such as N-dimethylaminopropyl (meth)acrylamide and N,N-diethylaminopropyl (meth)acrylamide, and monomers obtained by adding a quaternizing agent to the above monomers, or products thereof neutralized with an acid such as hydrochloric acid; monoalkylamino group-containing (meth)acrylates such as monomethylaminoethyl (meth)acrylate, monoethylaminoethyl (meth)acrylate, monomethylaminopropyl (meth)acrylate, monoethylaminopropyl (meth)acrylate, 2-(tert-butylamino)ethyl (meth)acrylate, and products thereof neutralized with an acid such as hydrochloric acid; monoalkylamino group-containing (meth)acrylamides such as monomethylaminoethyl (meth)acrylamide, monoethylaminoethyl (meth)acrylamide, monomethylaminopropyl (meth)acrylamide, monoethylaminopropyl (meth)acrylamide, and products thereof neutralized with an acid such as hydrochloric acid; esters of (meth)acrylic acid and alkanolamines such as 2-aminoethyl (meth)acrylate, and products thereof or a neutralized product thereof with an acid such as hydrochloric acid; N,N-diallylmethylamine and a monomer obtained by adding a quaternizing agent thereto, or a neutralized product thereof with an acid such as hydrochloric acid; allylamine and a neutralized product thereof with an acid such as hydrochloric acid; an addition reaction product of an unsaturated monomer having a cyclic ether-containing group having 2 to 8 carbon atoms, such as 1-allyloxy-3-dibutylamino-2-ol or 1-allyloxy-3-diethanolamino-2-ol, with an amine compound having 1 to 24 carbon atoms, and a monomer obtained by adding a quaternizing agent thereto, or a neutralized product thereof with an acid such as hydrochloric acid.Particularly preferred are N,N-dialkylamino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate, as well as monomers obtained by adding a quaternizing agent to the above-mentioned monomers, or neutralized products thereof with an acid such as hydrochloric acid or acetic acid.

[0017] <Other monomers> In the present disclosure, the other monomer that can be copolymerized with the above-mentioned monomer containing a cationic group is a monomer that does not contain a cationic group, and is not particularly limited as long as it is a monomer that can be copolymerized with the monomer containing a cationic group. vinyl halides such as vinyl chloride; alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; addition reaction products of unsaturated monomers having a cyclic ether-containing group with a carbon number of 2 to 8, such as 1-allyloxy-3-butoxypropan-2-ol, with alcohols having a carbon number of 1 to 20; alkylene oxide adducts of unsaturated alcohols having a carbon number of 2 to 20, such as an ethylene oxide adduct of allyl alcohol, an ethylene oxide adduct of methallyl alcohol, and an ethylene oxide adduct of isoprenol, and terminally hydrophobically modified products thereof; and cyclic vinyl monomers such as N-vinylpyrrolidone.

[0018] In order to adjust the viscosity, a monomer having two or more ethylenically unsaturated groups may be included. Examples of the monomer having two or more ethylenically unsaturated groups include esters of (meth)acrylic acid with di- or more substituted hydroxyl groups of polyols such as ethylene glycol, propylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, glycerin, polyglycerin, trimethylolpropane, pentaerythritol, sucrose, sorbitol, and 1,4-butanediol; di- or more substituted methacrylic acid esters of the above polyols; ethers of di- or more substituted hydroxyl groups of the above polyols with unsaturated alcohols such as allyl alcohol and vinyl alcohol; diallyl phthalate, triallyl phosphate, allyl methacrylate, tetraallyloxyethane, triallyl cyanurate, divinyl adipate, vinyl crotonate, 1,5-hexadiene, and divinylbenzene. These other monomers may be used alone or in combination of two or more. Among these, monomers containing an alkyl group having two or more carbon atoms are preferred because they have the effect of enhancing antibacterial properties, and ethyl (meth)acrylate and butyl (meth)acrylate are particularly preferred.

[0019] <α Gel containing nonionic surfactant>

[0020] <α Gel> In this disclosure, α-gel has a layered structure called a lamellar structure, in which surfactants are packed in a hexagonal crystal structure. It is in a hydrated crystalline state, with a large amount of water retained between the layers. Therefore, in X-ray diffraction measurements, peaks indicating a specific period due to the lamellar structure can usually be observed in small-angle X-ray scattering, while sharp peaks due to the crystalline structure can be observed in wide-angle X-ray scattering. The cosmetic composition of the present disclosure preferably has at least one peak in X-ray diffraction (wide angle) at a diffraction angle (2θ) of around 20° to 24°, and more preferably at around 21° to 22°. The half-width (deg) of the peak observed in the X-ray diffraction (wide angle) is preferably 0.17 to 2.0, more preferably 0.19 to 0.8, and particularly preferably 0.20 to 0.8. The crystallinity of α-gel is calculated using the following formula from the diffraction intensity of the crystalline portion in X-ray diffraction around 2θ = 21° to 22° and the diffraction intensity of the amorphous portion in 2θ = 10° to 50°. Crystallinity (%) = area of ​​the sharp peak near 21° to 22° ÷ (area of ​​the sharp peak near 21° to 22° + peak area of ​​the amorphous portion at 10° to 50°) × 100. In the present disclosure, the crystallinity is preferably 0.3% or more, and particularly preferably 1.0% or more. Within the above numerical range, the formed α-gel has high crystallinity, and the stability of the cosmetic composition tends to be improved. The α-gel of the present disclosure contains a nonionic surfactant and preferably contains water. The amount of water contained in the α-gel of the present disclosure is preferably 500% by mass or more, more preferably 600% by mass or more, even more preferably 700% by mass or more, and particularly preferably 800% by mass or more, relative to 100% by mass of the nonionic surfactant.

[0021] <Nonionic surfactants> In the present disclosure, a nonionic surfactant is a compound that does not exhibit ionic properties when dissolved in water but has surface-active properties. For example, ester types include esters of fatty acids and alcohols, and esters of fatty acids and sugars. Examples include glycerin fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, and polyglycerin fatty acid esters. Fatty acids are carboxylic acids having a hydrocarbon group, and the hydrocarbon group preferably has 2 to 25 carbon atoms, more preferably 8 to 22 carbon atoms, and particularly preferably 8 to 18 carbon atoms. For example, ether types include alkyl polyalkylene glycols, which are compounds in which alkylene oxide is added to a long-chain alcohol, such as alkyl polyethylene glycols and polyoxyethylene alkyl phenyl ethers.

[0022] In one preferred embodiment of the nonionic surfactant of the present disclosure, two or more types of nonionic surfactants with different HLB (Hydrophilic-Lipophilic Balance) values ​​can be used. The HLB (Hydrophilic-Lipophilic Balance) value indicates the degree of affinity of a surfactant for water and oil. For example, if the HLB value is 8 to 16, the surfactant will be stably dispersed in water and can be suitably used as an O / W type emulsifier. If the HLB value is 3 to 6, the surfactant will have low solubility in water but can be slightly dispersed, and can be suitably used as a W / O type emulsifier. When two or more surfactants with different HLB values ​​are used, at least one selected from nonionic surfactants with an HLB value of 8 to 16 and one selected from nonionic surfactants with an HLB value of 3 to 6 are used. By using two nonionic surfactants with different HLB values, the bilayer membrane structure that constitutes α-gel is fixed, forming a strong bilayer membrane, and the strength and stability of the formed oil droplets are increased. For example, a nonionic surfactant with an HLB value of 8 to 16 is a polyglycerol fatty acid ester, and polyglyceryl stearate 5 is particularly preferred. For example, a nonionic surfactant with an HLB value of 3 to 6 is a glycerol fatty acid ester, and glyceryl stearate is particularly preferred. When using one or more nonionic surfactants with an HLB value of 8 to 16 and one or more nonionic surfactants with an HLB value of 3 to 6, the proportion of the one or more nonionic surfactants with an HLB value of 8 to 16 relative to the total mass % of the nonionic surfactants is preferably 30% to 90% by mass. This range stabilizes the crystalline structure of α-gel. When mixing two or more surfactants with different HLB values ​​as described above, a higher alcohol may also be used as needed. The higher alcohol is an alcohol having a hydrocarbon group with 8 or more carbon atoms, and the hydrocarbon group may be linear or branched. It is particularly preferable to use a combination of one or more surfactants with 14 to 22 carbon atoms.

[0023] Another preferred embodiment of the nonionic surfactant of the present disclosure is when a nonionic surfactant with an HLB value of 8 to 16 is used, and when one or more nonionic surfactants selected from those with an HLB value of 3 to 6 are not used, it is preferable to use a higher alcohol. By using such a nonionic surfactant with a high HLB value and a higher alcohol, the bilayer membrane structure that constitutes α-gel is fixed, forming a strong bilayer membrane, and the formed oil droplets are strengthened and stable. The higher alcohol is an alcohol having a hydrocarbon group with 8 or more carbon atoms, and the hydrocarbon group may be linear or branched. It is particularly preferable to use a combination of one or more surfactants with 14 to 22 carbon atoms.

[0024] <Water> In the present disclosure, examples of water include purified water, distilled water, ion-exchanged water, pure water, soft water, hard water, natural water, deep sea water, alkaline ionized water, and purified water obtained by various other methods. The cosmetic composition of the present disclosure preferably contains water at 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on 100% by mass of the total cosmetic composition. Meanwhile, the cosmetic composition of the present disclosure preferably contains water at 99% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less, based on 100% by mass of the total cosmetic composition. Within the above ranges, the cosmetic composition of the present disclosure tends to have improved usability and storage stability.

[0025] <Other constituent substances> The cosmetic composition of the present disclosure may contain substances other than the above-mentioned (a) polymer containing a cationic group and (b) α-gel containing a nonionic surfactant and water. Examples include alcohol, thickener, powder component, pH adjuster, anionic surfactant, cationic surfactant, amphoteric surfactant, oil, moisturizer, water-soluble polymer, antioxidant, UV absorber, chelating agent, preservative, antibacterial agent, colorant, fragrance, etc. Any substance typically incorporated into cosmetics can be appropriately incorporated. The content of the above other components is not particularly limited as long as it does not impair the stability of the cosmetic composition, but it is preferably 0 to 50% by mass relative to 100% by mass of the cosmetic composition.

[0026] [Physical properties of cosmetic compositions containing the cationic group-containing polymer of the present disclosure] A cosmetic composition containing a polymer containing a cationic group according to the present disclosure (hereinafter also referred to as the cosmetic composition of the present disclosure) preferably has a viscosity suitable for use in cosmetic applications, preferably 1000 mPa·s or greater. The cosmetic composition of the present disclosure exhibits excellent long-term storage stability under normal storage conditions. The cosmetic composition of the present disclosure preferably has a pH in the range of 2.0 to 8.0. A cosmetic composition within this range can be used appropriately for cosmetic applications. The cosmetic composition of the present disclosure has a feel similar to or superior to that of an α-gel containing a nonionic surfactant. In cases where the cationic group-containing polymer has antibacterial properties against various bacteria, the cosmetic composition of the present disclosure can be used as a cosmetic composition while maintaining the antibacterial properties of the cationic group-containing polymer. For these reasons, a cosmetic composition containing a polymer containing a cationic group according to the present disclosure can be used appropriately for cosmetic applications.

[0027] [Method for producing a cosmetic composition containing a polymer containing a cationic group according to the present disclosure] Cosmetic compositions containing the cationic group-containing polymer of the present disclosure are not particularly limited and can be produced by mixing a cationic group-containing polymer with an α-gel containing a nonionic surfactant. A solvent can be selected appropriately based on the characteristics of the cationic group-containing polymer used. Solvents commonly used in cosmetics can be selected, such as water, alcohols, specifically ethanol, polyhydric alcohols, etc., with water being preferred. The device used to mix the cationic polymer and the α-gel containing a nonionic surfactant is not particularly limited, and commonly used stirring devices can be used. Examples include a homomixer, a homodisper, and a three-one motor, with a homomixer being preferred. The temperature conditions during mixing are not particularly limited, but it is preferable to mix the cationic group-containing polymer and the α-gel containing a nonionic surfactant at a temperature that enhances their miscibility, such as 40°C or higher, 60°C or higher, and 90°C or lower.

[0028] [Uses of cosmetic compositions containing the cationic group-containing polymer of the present disclosure] A cosmetic composition containing a polymer containing a cationic group according to the present disclosure can exhibit high storage stability in cosmetic applications and can be preferably used as a cosmetic composition for use in skin cosmetics, topical skin preparations, hair cosmetics, and the like. Cosmetics in the present disclosure refer to cosmetics and quasi-drugs that are applied directly to human skin, and specifically include skin cosmetics, topical skin preparations, skin cleansers, hair cosmetics, topical hair preparations, hair cleansers, etc. Cosmetic compositions containing the cationic group-containing polymer of the present disclosure are excellent in feel during use and have high storage stability, and are therefore preferably applicable to skin care cosmetic applications, hair care cosmetic applications, etc. A cosmetic composition containing the cationic group-containing polymer of the present disclosure can be preferably applied to the various uses described above because the antibacterial properties are maintained when the cationic group-containing polymer has antibacterial properties. [Example]

[0029] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass."

[0030] <Weight average molecular weight (Mw) measurement> Equipment: Tosoh EcoSEC HLC-8320GPC Detector: Differential Refractometer (RI) detector Column: Tosoh TSKgel α-M, α-2500 Column temperature: 40℃ Flow rate: 0.4mL / min Injection volume: 20 μL (eluent preparation solution with sample concentration of 0.4 wt%) Calibration curve: Polyethylene glycol manufactured by GL Sciences Eluent: 0.5 M acetic acid + 0.2 M Na nitrate / acetonitrile = 50 / 50 (v / v) <Compatibility> Those that were uniformly mixed were marked with a ◯, and those that were not uniformly mixed were marked with an ×. <Viscosity measurement>Measured using a B-type viscometer (model: BMII, manufactured by Toki Sangyo Co., Ltd.) under the conditions of rotor No. 4, rotation speed (α gel: 12 rpm, O / W type cream: 6 rpm), measurement time 60 seconds, and temperature 25°C. <pH measurement> Measured using a pH meter LAQUA pH / ION METER F-72 manufactured by HORIBA. The measurement temperature was 25°C. <Storage stability>Stored in an incubator at room temperature, 5°C, and 50°C for one month. ○: The state where there is no separation or precipitate <Use feeling>Evaluated the use feeling by 5 professional panelists ○: Based on the use feeling when there is no polymer having a cationic group, it is equal to or better than that. ×: The use feeling is inferior compared to ○. <Storage efficacy test> According to the method described in the Japanese Pharmacopoeia, the storage efficacy test of the composition of the present disclosure was carried out. The target bacteria used were Escherichia coli and Staphylococcus aureus. The bacterial survival rate was measured 4 hours, 3 days, and 7 days after inoculation. The determination of antibacterial property was defined as ○ (with antibacterial property) when the bacterial survival rate 4 hours after inoculation was 1% or less of the inoculated bacterial count and the bacterial count continuously decreased 3 days and 7 days after inoculation, and × (without antibacterial property) otherwise. <XRD measurement> Apparatus: Smart Lab (manufactured by Rigaku Corporation) X-ray source: Cu K-α (1.5405 Å) Tube voltage: 45 kV Tube current: 200 mA Figures 1 and 3 are charts of XRD (small angle) measurement, and Figures 2 and 4 are charts of XRD (wide angle) measurement.

[0031] <Raw materials used> Sunsoft α-C (manufactured by Sun Chemical Co., Ltd.): A mixture of polyglyceryl-5 stearate and glyceryl stearate Alpha Pure HSG (Sanyo Chemical Industries, Ltd.): Polyoxyethylene polyoxypropylene cetyl ether (12EO, 2EO) Kalcol 6850 (Kao Corporation): Cetearyl alcohol (a mixture of cetanol (45-55%) and stearyl alcohol (45-55%)) COSMOCIL CQ (Lonza): A mixture of polyaminopropyl biguanide and water MERQUAT 550PR (Lubrizol): A mixture of polyquaternium-7 and water CEH (Kyukyu Alcohol Kogyo Co., Ltd.): Cetyl ethylhexanoate KF-96A-100CS (Shin-Etsu Chemical Co., Ltd.): Dimethicone TAISET 50-C (Taiyo Chemical Co., Ltd.): A mixture of glyceryl behenate and polyglyceryl-6 octastearate Sangelose 60L (manufactured by Daido Chemical Industry Co., Ltd.): Hydroxypropyl methylcellulose stearoxy ether

[0032] [Synthesis Example - Synthesis of Polymer Containing Cationic Groups] <Synthesis Example 1> A separable glass flask equipped with a thermometer, reflux condenser, and stirrer was charged with 29.4 g of pure water and 100.0 g of 1,3-butanediol (KH Neochem Co., Ltd.), and the temperature was raised to 90°C under stirring. Next, with stirring, into the polymerization reaction system, which was kept at a constant temperature of 80°C, a monomer solution 1 consisting of 60.0 g of 2-(dimethylamino)ethyl methacrylate (N,N-dimethylaminoethyl methacrylate) (Kyoeisha Chemical Co., Ltd., hereinafter referred to as DAM), a monomer solution 2 consisting of 40.0 g of ethyl methacrylate (Kyoeisha Chemical Co., Ltd., hereinafter referred to as EMA), and an initiator aqueous solution consisting of 18.3 g of a 10% aqueous solution of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (Fujifilm Wako Pure Chemical Co., Ltd., hereinafter referred to as V-50) were each added dropwise from separate dropping nozzles. The addition of Monomer Solutions 1 and 2 and the aqueous initiator solution began simultaneously, with Monomer Solution 1 added over 180 minutes, Monomer Solution 2 added over 170 minutes, and the aqueous initiator solution added over 210 minutes. After all additions were complete, the reaction solution was maintained at 80°C for an additional 30 minutes to mature and complete the polymerization. Then, 55.2 g of pure water and 205.5 g of 1,3-butanediol were added to obtain Copolymer 1. The solids content of the obtained Copolymer 1 was 19.7%, the pH was 9.0, and the weight-average molecular weight was 30,000. [Synthesis Example 2] A separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 90.0 g of 1,3-butanediol and 22.6 g of water, and the temperature was raised to 80°C while stirring. Next, with stirring, into the polymerization reaction system kept at a constant temperature of 80°C, monomer solution 1 consisting of 117.5 g of DAM, monomer solution 2 consisting of 13.5 g of EMA, monomer solution 3 consisting of 23.2 g of an 18% aqueous acrylic acid solution (manufactured by Nippon Shokubai Co., Ltd.), and an aqueous initiator solution consisting of 22.6 g of a 10% aqueous solution of V-50 were each added dropwise from separate dropping nozzles. The addition of monomer solutions 1 and 2 and the aqueous initiator solution began simultaneously, with the monomer solutions added over 150 minutes and the initiator solution added over 180 minutes. After the addition was complete, the reaction solution was maintained at 80°C for an additional 60 minutes to mature the mixture. After the polymerization was completed, 53.9 g of pure water was added to obtain copolymer 2. The solids content of the resulting copolymer 2 was 39.3%, the pH was 9.0, and the weight-average molecular weight was 38,000. [Synthesis Example 3] Copolymer 3 was obtained by the method described in Synthesis Example 2, except that DAM was changed from 117.5 g to 101.4 g, EMA was changed from 13.5 g to 27.0 g, and 18% acrylic acid aqueous solution was changed from 23.2 g to 37.6 g. The solid content of the obtained copolymer 3 was 38.0%, pH was 9.0, and weight average molecular weight was 31,000. [Synthesis Example 4] Copolymer 4 was obtained by the method described in Synthesis Example 1, except that DAM was changed from 60.0 g to 80.0 g and EMA was changed from 40.0 g to 20.0 g of butyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., hereinafter referred to as BA). The solids content of the obtained copolymer 4 was 34.8%, pH was 9.0, and weight average molecular weight was 29,000.

[0033] [Manufacturing Example - Preparation of α-gel-containing composition] <Production Example 1> 89.5 parts of ion-exchanged water and 10.0 parts of Sunsoft α-C (Taiyo Kagaku Co., Ltd.) were mixed and stirred at 2500 rpm for 10 minutes in a homomixer (Labo-lution, Primix Corporation) while heating to 80°C ± 5°C. The resulting homogeneously dissolved mixture was then cooled to 35°C. Meanwhile, citric acid was added to Copolymer 1 to adjust the pH to 6, yielding an aqueous solution with a solids concentration of 2%. 0.5 parts of the aqueous solution of Copolymer 1 was mixed with the mixture while stirring, yielding the α-gel composition of Production Example 1. The results of the XRD (small angle) measurement are shown in Figure 1, and the results of the XRD (wide angle) measurement are shown in Figure 2. The peak half width in the wide angle measurement was 0.39 deg, and the crystallinity was 4.43%. <Production Example 2> The α-gel composition of Production Example 2 was prepared in the same manner as Production Example 1, except that Copolymer 1 was changed to Copolymer 2. <Production Example 3> The α-gel composition of Production Example 3 was obtained in the same manner as Production Example 1, except that Copolymer 1 was changed to Copolymer 3. <Production Example 4> The α-gel composition of Production Example 4 was prepared in the same manner as Production Example 1, except that Copolymer 1 was changed to Copolymer 4. <Production Example 5> The α-gel composition of Production Example 5 was prepared in the same manner as Production Example 1, except that 89.5 g of ion-exchanged water was changed to 89.95 g and 0.5 parts of the Copolymer 1 aqueous solution was changed to 0.05 parts of COSMOCIL CQ. <Production Example 6> The α-gel composition of Production Example 6 was prepared in the same manner as Production Example 1, except that 89.5 g of ion-exchanged water was changed to 89.9 g and 0.5 parts of the Copolymer 1 aqueous solution was changed to 0.1 parts of MERQUAT 550PR. <Production Example 7> The α-gel composition of Production 7 was prepared in the same manner as in Production Example 1, except that 89.5 parts of ion-exchanged water was changed to 79.5 parts, and 10.0 parts of Sunsoft α-C was replaced with 10.0 g of Alpha Pure HSG (manufactured by Sanyo Chemical Industries, Ltd.) and 10.0 g of Kalcol 6850 (manufactured by Kao Corporation). The results of the XRD (small angle) measurement are shown in Figure 1, and the results of the XRD (wide angle) measurement are shown in Figure 2. The peak half width in the wide angle measurement was 0.30 deg, and the crystallinity was 6.40%. <Comparative Manufacturing Example 1> The α-gel of Comparative Production Example 1 was obtained by the method described in Production Example 1, except that 90.0 parts of ion-exchanged water was used and Copolymer 1 was not used. The results of the XRD (small angle) measurement are shown in Figure 1, and the results of the XRD (wide angle) measurement are shown in Figure 2. The peak half width in the wide angle measurement was 0.37 deg, and the crystallinity was 2.18%. <Comparative Manufacturing Example 2> The α-gel of Comparative Production Example 2 was obtained by the method described in Production Example 7, except that 80.0 parts of ion-exchanged water was used and Copolymer 1 was not used. The results of the XRD (small angle) measurement are shown in Figure 1, and the results of the XRD (wide angle) measurement are shown in Figure 2. The peak half width in the wide angle measurement was 0.20 deg, and the crystallinity was 9.01%.

[0034] 2, the X-ray diffraction measurement results show that the composition of Production Example 1 has a sharp peak between 21° and 22° in the wide-angle region, and that the crystalline structure is maintained even after the polymer containing cationic groups of the present disclosure is mixed with the α-gel of Comparative Production Example 1 to form a composition. The composition of Production Example 7 has a sharp peak between 21° and 22° in the wide-angle region, and that the crystalline structure is maintained even after the polymer containing cationic groups of the present disclosure is mixed with the α-gel of Comparative Production Example 2 to form a composition.

[0035] The initial blendability, pH measurement, initial viscosity measurement, and storage stability were evaluated for Production Examples 1 to 7 and Comparative Production Examples 1 and 2. The results are shown in Table 1.

[0036] [Table 1] As shown in Table 1, Production Examples 1 to 7, which used polymers containing cationic groups, were found to be compatible with α-gel and also had excellent storage stability. Regarding the feel when used, Production Examples 1 to 5 and 7 were the same as α-gel alone, even when a polymer containing cationic groups was blended. Production Example 6 exhibited stringiness, resulting in an undesirable feel when used. This is thought to be due to the high molecular weight of the polymer containing cationic groups.

[0037] [Manufacturing Example - Preparation of O / W type cream containing α-gel-containing composition] <Production Example 8> (1) Mix 55.9 parts of ion-exchanged water, 10.0 parts of Sunsoft α-C (manufactured by Taiyo Kagaku Co., Ltd.), 5.0 parts of 1,3-butylene glycol-P (manufactured by KH Neochem Co., Ltd.), and 8.0 parts of concentrated cosmetic glycerin (manufactured by Sakamoto Pharmaceutical Industry Co., Ltd.), heat to 80°C ± 5°C with stirring, and dissolve until homogeneous. (2) Olive squalane (manufactured by Kokyu Alcohol Kogyo Co., Ltd.) (3) (1) was heated to 80°C ± 5°C while stirring with a homogenous mixer (Labo-lution, Primix Corporation) at 5000 rpm, and (2) was added in small portions over 5 minutes to emulsify and obtain a homogenous mixture. The mixture was then cooled to 35°C. (4) (3) was mixed with 0.1 parts of an aqueous solution of copolymer 1, which had been adjusted to pH 6 with citric acid to give a 2% solids concentration, and stirred to obtain an O / W cream of Production Example 7. The results of the XRD (small angle) measurement are shown in Figure 3, and the results of the XRD (wide angle) measurement are shown in Figure 4. The peak half width in the wide angle measurement was 0.31 deg, and the crystallinity was 4.65%. <Production Example 9> The same procedure as in Production Example 7 was repeated, except that 55.9 parts of ion-exchanged water was changed to 55.5 parts, and 0.1 parts of the copolymer 1 aqueous solution was changed to 0.5 parts of the copolymer 1 aqueous solution, to obtain an O / W type cream of Production Example 8. <Production Example 10> The same procedure as in Production Example 7 was repeated, except that 55.9 parts of ion-exchanged water was changed to 51 parts, and 0.1 parts of the copolymer 1 aqueous solution was changed to 5.0 parts of the copolymer 1 aqueous solution, to obtain an O / W type cream of Production Example 9. <Production Example 11> An O / W type cream of Production Example 10 was prepared in the same manner as in Production Example 8, except that 0.5 parts of the aqueous solution of Copolymer 1 was changed to 0.5 parts of the aqueous solution of Copolymer 2. <Production Example 12> An O / W type cream of Production Example 11 was prepared in the same manner as in Production Example 8, except that 0.5 parts of the aqueous solution of Copolymer 1 was changed to 0.5 parts of the aqueous solution of Copolymer 3. <Production Example 13> An O / W type cream of Production Example 12 was prepared in the same manner as in Production Example 8, except that 0.5 parts of the aqueous solution of Copolymer 1 was changed to 0.5 parts of the aqueous solution of Copolymer 4. <Production Example 14> An O / W type cream of Production Example 13 was prepared in the same manner as in Production Example 7, except that 55.9 parts of ion-exchanged water was changed to 55.95 parts, and 0.1 parts of the copolymer 1 aqueous solution was changed to 0.05 parts of COSMOCIL CQ. <Production Example 15> An O / W type cream of Production Example 14 was prepared in the same manner as in Production Example 7, except that 0.1 parts of the aqueous solution of Copolymer 1 was changed to 0.1 parts of MERQUAT 550PR. <Comparative Manufacturing Example 3> The same preparation as in Production Example 7 was carried out, except that the amount of ion-exchanged water was changed from 55.9 parts to 55.5 parts, 1.3-butylene glycol-P from 5.0 parts to 6.0 parts, and concentrated cosmetic glycerin (manufactured by Sakamoto Pharmaceutical Industry Co., Ltd.) from 8.0 parts to 5.0 parts, and no aqueous solution of Copolymer 1 was used, to obtain an O / W type cream as Comparative Production Example 10. The results of the XRD (small angle) measurement are shown in Figure 3, and the results of the XRD (wide angle) measurement are shown in Figure 4. The peak half width in the wide angle measurement was 0.30 deg, and the crystallinity was 3.34%.

[0038] The X-ray diffraction measurement results in Figure 4 show that the O / W cream of Production Example 8 has a sharp peak in the wide-angle region between 21° and 22°, and it was revealed that the crystalline structure was maintained even after the polymer containing cationic groups of the present disclosure was mixed with the O / W cream made of α-gel of Comparative Production Example 3 to form a composition.

[0039] The initial blendability, pH measurement, initial viscosity measurement, storage stability, feel in use, and preservative effectiveness tests were performed on Production Examples 8 to 15 and Comparative Production Example 3. The results are shown in Table 2.

[0040] [Table 2] As shown in Table 2, Production Examples 8 to 15, which used polymers containing cationic groups, were found to have good blendability when formulated into O / W creams and also to have excellent storage stability. Regarding the feel when used, Production Examples 8 to 14, even when blended with polymers containing cationic groups, were the same as α-gel alone. Production Example 15 exhibited stringiness, which made the feel when used undesirable. This is thought to be due to the high molecular weight of the polymers containing cationic groups. In the preservative effectiveness test, Production Examples 8 to 15, which contained a polymer containing cationic groups, were found to have antibacterial properties against both Escherichia coli and Staphylococcus aureus. In the preservative effectiveness test after 3 and 7 days, no increase in bacterial count was observed, demonstrating that antibacterial properties were maintained over the long term. Since Comparative Production Example 3, which was formulated with only α Gel, had no antibacterial properties, it was found that the polymer containing cationic groups imparted antibacterial properties to α Gel, and also provided excellent storage stability and usability.

[0041] [Manufacturing Example - Preparation of O / W type emulsion containing α-gel-containing composition] <Production Examples 16 to 21> An O / W emulsion containing an α-gel-containing composition was prepared according to the formulation shown in Table 3.

[0042] [Table 3] An O / W emulsion was prepared using the blending amounts shown in Table 3 according to the procedure described below. (1) Parts A and B were mixed uniformly at 80-85°C. (2) While stirring Part A, Part B was gradually added, and the mixture was emulsified at 5000 rpm for approximately 5 minutes using a homomixer (Labo-Lution, manufactured by Primix Corporation). The mixture was then gradually cooled to 50°C, and Part C, which had been previously mixed uniformly, was added and mixed uniformly. (3) 0.5 parts, 1.0 parts, and 5.0 parts of Part D (a solution of Copolymer 1 or Copolymer 2 prepared by adding citric acid to Copolymer 1 or 2 to adjust the pH to 6 and then adjusting the solids concentration to 2%) were added to (2) and mixed uniformly to prepare the O / W emulsions of Production Examples 16 to 21. The prepared O / W emulsion had an excellent feel when applied to the skin.

Claims

1. (a) a polymer containing a cationic group; (b) an α-gel containing a nonionic surfactant, the (a) cationic group-containing polymer is a copolymer of a monomer having a cationic group and another monomer not containing a cationic group, The (a) cationic group-containing polymer contains 30 mass % or more of a monomer having a cationic group based on the total mass of the copolymer, the (a) cationic group-containing polymer is a polymer containing primary to tertiary amino groups, The primary to tertiary amino groups are represented by the following formula (1): 【Chemistry 1】 (In the formula, R1 and R2 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.) the other monomer is at least one selected from the group consisting of an ester of (meth)acrylic acid and an alcohol which may have a substituent ((meth)acrylate); an unsaturated monocarboxylic acid (salt); an aromatic vinyl monomer; an olefin monomer; an ester of an unsaturated alcohol and a carboxylic acid; a vinyl halide; an alkyl vinyl ether; an addition reaction product of an unsaturated monomer having a cyclic ether-containing group of 2 to 8 carbon atoms and an alcohol having 1 to 20 carbon atoms; an alkylene oxide adduct of an unsaturated alcohol having 2 to 20 carbon atoms and a terminally hydrophobically modified product thereof; and a cyclic vinyl monomer; The oil-in-water cosmetic composition includes one or more nonionic surfactants having an HLB value of 8 to 16 and one or more nonionic surfactants having an HLB value of 3 to 6, and the proportion of the one or more nonionic surfactants selected from the group consisting of nonionic surfactants having an HLB value of 8 to 16 is 30% by mass to 90% by mass relative to the total mass of the nonionic surfactants.

2. (a) a polymer containing a cationic group, a nonionic surfactant, and water, which has at least one peak in X-ray diffraction at a diffraction angle (2θ) of 20° to 24°, wherein the polymer (a) containing a cationic group is a copolymer of a monomer having a cationic group and another monomer not containing a cationic group; The (a) cationic group-containing polymer contains 30 mass % or more of a monomer having a cationic group based on the total mass of the copolymer, the (a) cationic group-containing polymer is a polymer containing primary to tertiary amino groups, The primary to tertiary amino groups are represented by the following formula (1): 【Chemistry 1】 (In the formula, R1 and R2 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.) the other monomer is at least one selected from the group consisting of an ester of (meth)acrylic acid and an alcohol which may have a substituent ((meth)acrylate); an unsaturated monocarboxylic acid (salt); an aromatic vinyl monomer; an olefin monomer; an ester of an unsaturated alcohol and a carboxylic acid; a vinyl halide; an alkyl vinyl ether; an addition reaction product of an unsaturated monomer having a cyclic ether-containing group of 2 to 8 carbon atoms and an alcohol having 1 to 20 carbon atoms; an alkylene oxide adduct of an unsaturated alcohol having 2 to 20 carbon atoms and a terminally hydrophobically modified product thereof; and a cyclic vinyl monomer; The oil-in-water cosmetic composition includes one or more nonionic surfactants having an HLB value of 8 to 16 and one or more nonionic surfactants having an HLB value of 3 to 6, and the proportion of the one or more nonionic surfactants selected from the group consisting of nonionic surfactants having an HLB value of 8 to 16 is 30% by mass to 90% by mass relative to the total mass of the nonionic surfactants.

3. 3. The O / W cosmetic composition according to claim 1, wherein the (a) polymer containing a cationic group is present in an amount of 0.0001 parts by mass or more relative to 100% by mass of the α-gel containing the (b) nonionic surfactant.

4. The O / W cosmetic composition according to claim 1 , further comprising an alcohol having a hydrocarbon group having 8 or more carbon atoms.

5. The O / W cosmetic composition according to claim 1 , wherein the nonionic surfactant comprises a polyglycerol fatty acid ester.

6. The O / W cosmetic composition according to claim 1 , wherein the nonionic surfactant comprises a glycerin fatty acid ester.

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