JP7489919B2 - Emulsion cosmetic and its manufacturing method - Google Patents

Description

The present invention relates to an emulsion cosmetic, and more specifically to an emulsion cosmetic containing an oil phase containing a water-soluble cationic polymer and an aqueous phase containing a water-soluble anionic polymer, and a method for producing the same.

In recent years, the demand for functional cosmetics has been increasing, and various functional cosmetics have been developed according to the purpose of use. For example, there are cosmetics that are given the function of preventing hair from frizzing during the day when humidity is high, and foundations and sunscreens with high ultraviolet protection properties that protect the skin from UVA (long-wavelength ultraviolet rays with wavelengths of 320-400 nm) and UVB (medium-wavelength ultraviolet rays with wavelengths of 290-320 nm). Many of these cosmetics achieve their functionality by forming a coating film on the skin or hair.

However, it was known that the coating film formed when cosmetics were applied would fall off over time, causing a decrease in functionality. This was particularly evident when the product was subjected to physical friction, when sweating, or when bathing in a pool or the ocean, so there was a demand for the development of cosmetics whose functionality would not easily decrease.

In response to this, various technologies have been developed, including a technology in which silicic anhydride is selected as a gelling agent to solidify a coating film containing hydrophobically treated zinc oxide particles and an oil-based component containing an oil-soluble UV absorber, thereby imparting high water resistance (e.g., JP 2018-76313 A); a technology in which metal oxide particles whose surfaces are coated with a specific compound are dispersed in an oil phase together with a specific partially crosslinked organopolysiloxane polymer and polyhydroxystearic acid, and combined with a (sodium acrylate/sodium acryloyldimethyltaurate) copolymer to form an oil-in-water emulsion cosmetic, thereby forming a soft and uniform cosmetic film and imparting water resistance (e.g., JP 2017-137300 A); and a technology in which a stable oil-in-water emulsion composition is obtained by using a polyion complex formed from a specific combination of cationic polymers and anionic polymers as an emulsifier, which allows various oils to be blended, and in which the obtained oil-in-water emulsion exhibits excellent water resistance (e.g., JP 2011-32249 A).

However, the above technology had issues such as poor feel as a cosmetic product and insufficient water resistance and abrasion resistance.

Therefore, the objective of the present invention is to provide an emulsion cosmetic that forms a coating film that is excellent in water resistance and abrasion resistance, and further has formulation stability and good usability.

In view of this situation, the present inventors have attempted to blend a cationic polymer and an anionic polymer in the same phase. The present inventors have found that blending a cationic polymer and an anionic polymer in the same phase causes aggregation and makes the formulation unusable. As a result of intensive research, the present inventors have found that by incorporating a water-soluble cationic polymer in the oil phase and a water-soluble anionic polymer in the water phase, the formulation is stable, and further, the water-soluble cationic polymer and the water-soluble anionic polymer aggregate during application to form a strong coating film, improving the water resistance and abrasion resistance of the coating film and providing a good feel when used, and have completed the present invention.

That is, the present invention provides:
(1) An emulsion cosmetic comprising (a) an oil phase containing a water-soluble cationic polymer, and (b) an aqueous phase containing a water-soluble anionic polymer.

(2) (c) An emulsion cosmetic as described in (1) containing at least one of a metal oxide or a plate-like powder.

(3) (d) An emulsion cosmetic described in (1) or (2) containing inulin stearate.

(4) An emulsion cosmetic described in any one of (1) to (3), in which the mass ratio (a)/(b) is 0.05 to 20.

(5) (a) An emulsion cosmetic according to any one of (1) to (4), wherein the water-soluble cationic polymer is one or more selected from the group consisting of dimethyldiallylammonium chloride-acrylamide copolymer, O-[2-hydroxy-3-(trimethylammonio)propyl]hydroxyethylcellulose chloride, and O-[2-hydroxy-3-(trimethylammonio)propyl]guar gum chloride.

(6) (b) An emulsion cosmetic according to any one of (1) to (5), wherein the water-soluble anionic polymer is one or more selected from the group consisting of carboxyvinyl polymer, acrylic acid/alkyl methacrylate copolymer, and sodium acrylate/sodium acryloyldimethyltaurate copolymer.

(7) An emulsion cosmetic described in any one of (1) to (6) which is an oil-in-water emulsion cosmetic.

(8) (e) An emulsion cosmetic described in any one of (1) to (7) containing dimethicodimethyi benzalmalonate.

(9) A method for producing an emulsion cosmetic comprising (a) an oil phase containing a water-soluble cationic polymer and (b) an aqueous phase containing a water-soluble anionic polymer.

Preferred embodiments of the present invention are described in detail below. However, the present invention is not limited to the following preferred embodiments, and can be freely modified within the scope of the present invention. In this specification, "to" means a range including the numerical values before and after it. Furthermore, unless otherwise specified, operations and measurements of physical properties are performed under conditions of room temperature (20-25°C) and relative humidity of 40-50% RH.

The emulsion cosmetic of the present invention contains a water-soluble cationic polymer in the oil phase and a water-soluble anionic polymer in the aqueous phase, and thus can provide an emulsion cosmetic that is highly water-resistant, resistant to friction (highly resistant to friction), has an excellent feel when used (e.g., has a fresh feel without a sticky or slimy feel) and is highly stable.

(Emulsion cosmetics)
The emulsion cosmetic of the present invention is an emulsion cosmetic in which either an oil phase containing component (a) a water-soluble cationic polymer or an aqueous phase containing component (b) a water-soluble anionic polymer exists as emulsion droplets, and may contain other components as long as the effects of the present invention are not impaired.

The component (a) water-soluble cationic polymer (hereinafter also simply referred to as component (a)) used in the present invention is a polymer having a cationic group in the molecule. The component (a) water-soluble cationic polymer is not particularly limited as long as it is one that is normally used in cosmetics, but it is preferable that the component (a) contains an amino group or ammonium group bonded to the polymer chain, or contains dimethyldiallylammonium halide as a constituent unit, in terms of excellent feel and water resistance when a coating film is formed with the water-soluble anionic polymer.

Component (a) is not particularly limited, but examples thereof include vinylpyrrolidone/N,N-dimethylaminoethyl methacrylic acid copolymer diethyl sulfate, dimethyldiallylammonium chloride/acrylamide copolymer, acrylamide/acrylic acid/dimethyldiallylammonium chloride copolymer, dimethyldiallylammonium chloride/acrylic acid copolymer, polydimethylmethylenepiperidinium chloride, O-[2-hydroxy-3-(trimethylammonio)propyl]hydroxyethylcellulose chloride, O-[2-hydroxy-3-(trimethylammonio)propyl]guar gum chloride, vinylpyrrolidone/N,N-dimethylaminoethyl methacrylic acid copolymer diethyl sulfate, O-[2-hydroxy-3-(trimethylammonio)propyl]guar gum chloride, 2-methacryloyloxyethyl phosphorylcholine/2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride copolymer, O-(2-hydroxy-3-(trimethylammonio)propyl)locust bean gum chloride, hydroxypropyltrimonium starch chloride, vinylpyrrolidone/N,N-dimethylaminoethyl methacrylate/stearyl acrylate/tripropylene glycol diacrylate copolymer, hydroxypropyltrimonium hyaluronate, and the like can be mentioned, and one or more of these can be used. Among these, from the viewpoint of the water resistance and abrasion resistance of the coating film to be formed, dimethyldiallylammonium chloride/acrylamide copolymer, O-[2-hydroxy-3-(trimethylammonio)propyl]hydroxyethylcellulose chloride, and O-[2-hydroxy-3-(trimethylammonio)propyl]guar gum chloride are particularly preferred, and dimethyldiallylammonium chloride/acrylamide copolymer is most preferred.

Commercially available examples of component (a) in the present invention include, for example, polyquaternium-10, such as O-[2-hydroxy-3-(trimethylammonio)propyl]hydroxyethylcellulose chloride, such as Leoguard GP (manufactured by Lion Corporation) and Catinal HC-100 (manufactured by Toho Chemical Industry Co., Ltd.), and aqueous solutions of polyquaternium-7, such as dimethyldiallylammonium chloride-acrylamide copolymers, such as Lipoflow MN (manufactured by Lion Corporation), MERQUAT 550PR, and MERQUAT 740. Examples of the copolymer include MERQUAT POLYMER (manufactured by Lubrizol Nippon Co., Ltd.), MERQUAT 3331PR (manufactured by Lubrizol Nippon Co., Ltd.), which is an aqueous solution of polyquaternium-39 as an acrylamide-acrylic acid-dimethyldiallylammonium chloride copolymer, MERQUAT 295 Polymer (manufactured by Lubrizol Nippon Co., Ltd.), which is an aqueous solution of polyquaternium-22 as an acrylamide-acrylic acid-dimethyldiallylammonium chloride-acrylic acid copolymer, JAGUAR C-14S(C) (manufactured by Solvay Corporation) as an O-[2-hydroxy-3-(trimethylammonio)propyl]guar gum chloride, SENSOMER CI50 (manufactured by Lubrizol Nippon Co., Ltd.), which is an aqueous solution of hydroxypropyltrimonium starch chloride, and Hyalobell P (manufactured by Kewpie Corporation), which is hydroxypropyltrimonium hyaluronate.

The content of component (a) in the present invention is not particularly limited, but can be 0.001 to 3% by mass (hereinafter simply abbreviated as "%") in the emulsion cosmetic, with 0.001 to 1% being preferred, 0.01 to 1% being more preferred, 0.01 to 0.5% being even more preferred, and 0.1 to 0.3% being particularly preferred. Within this range, excellent stability can be achieved, and water resistance and abrasion resistance can be imparted while maintaining a good feel when used.

During the manufacturing process, component (a) can be contained in the oil phase by dissolving or dispersing component (a) in the oil phase.

The component (b) water-soluble anionic polymer (hereinafter also referred to as component (b)) used in the present invention is a polymer having an anionic group in the molecule. The component (b) water-soluble anionic polymer is not particularly limited as long as it is one that is usually used in cosmetics, but from the viewpoint of excellent feel, water resistance, and abrasion resistance when a coating film is formed with a water-soluble cationic polymer, for example, carboxyvinyl polymer, acrylic acid-alkyl methacrylate copolymer, sodium acrylate-sodium acryloyldimethyltaurate copolymer, alkyl acrylate-alkyl methacrylate-polyoxyethylene stearyl ether methacrylate (20E.O.) copolymer, and other acrylic acid-based water-soluble polymers, anionic polysaccharides, anionic polyamino acids, etc., can be mentioned, and one or more of these can be used. Among these, from the viewpoint of the water resistance and abrasion resistance of the coating film to be formed, the water-soluble anionic polymer of component (b) is preferably one or more selected from the group consisting of carboxyvinyl polymer, acrylic acid-alkyl methacrylate copolymer, and sodium acrylate-sodium acryloyldimethyltaurate copolymer, and is preferably an acrylic acid-based water-soluble polymer, more preferably an acrylic acid-alkyl methacrylate copolymer (preferably, acrylates/alkyl acrylate (C10-C30) crosspolymer), or more preferably a sodium acrylate-sodium acryloyldimethyltaurate copolymer. Furthermore, from the viewpoint of excellent water resistance and abrasion resistance, it is particularly preferable to use an acrylic acid-alkyl methacrylate copolymer and a sodium acrylate-sodium acryloyldimethyltaurate copolymer in combination. When an acrylic acid-alkyl methacrylate copolymer and a sodium acrylate-sodium acryloyldimethyltaurate copolymer are used in combination, the content mass ratio is, for example, acrylic acid-alkyl methacrylate copolymer:sodium acrylate-sodium acryloyldimethyltaurate copolymer=1:0.1-50, and preferably 1:5-40, from the viewpoint of excellent water resistance and abrasion resistance.

Commercially available products of component (b) include, for example, CARBOPOL 940, 941, 980, 981 (carbomer; manufactured by Lubrizol Advanced Materials Inc.), PEMULEN TR-1, TR-2, CARBOPOL POLYMER, 1342 POLYMER, 1382 POLYMER (acrylates/alkyl acrylate (C10-C30)) crosspolymer; manufactured by Lubrizol Advanced Materials Inc. Examples of suitable copolymers include SIMULGEL EG (sodium acrylate/sodium acryloyldimethyltaurate copolymer; manufactured by SEPPIC Corporation), ACULYN 22 (alkyl acrylate/steareth-20 methacrylate copolymer; manufactured by ROHM GMBH), and the like.

The content of component (b) in the present invention is not particularly limited, but is preferably 0.001 to 2% in the emulsion cosmetic, more preferably 0.001 to 1%, even more preferably 0.01 to 0.8%, and particularly preferably 0.01 to 0.5%. Within this range, the cosmetic composition is excellent in stability and can be imparted with water resistance and abrasion resistance while maintaining a good feel when used.

During the manufacturing process, component (b) can be contained in the aqueous phase by dissolving or dispersing component (b) in the aqueous phase.

In the present invention, the mass ratio (a)/(b) of component (a) to component (b) is not particularly limited, but is preferably 0.05 to 20, and more preferably 0.1 to 10. Within this range, the stability of the formulation and the water resistance and abrasion resistance of the resulting coating film are improved.

In the present invention, it is preferable to further contain component (c) metal oxide and/or plate-like powder (hereinafter also simply referred to as component (c)). By blending component (c) metal oxide and/or plate-like powder, water resistance, abrasion resistance, and formulation stability are further improved. Component (c) can be blended in either the aqueous phase or the oil phase, but it is particularly preferable to blend it in the oil phase. This is because by blending it in the oil phase, component (a) can be stably blended in the oil phase, further improving formulation stability.

The metal oxide component (c) used in the present invention is not particularly limited in terms of shape (spherical, plate-like, needle-like, etc.), particle size (aerosol, fine particles, pigment-grade, etc.), particle structure (porous, non-porous, etc.), etc., so long as it is a metal oxide normally used in cosmetics, any of them can be used. Examples of the metal oxide component (c) include zinc oxide, titanium oxide, cerium oxide, zirconium oxide, iron oxide, etc., and one or more of these can be used in combination, and may be further composited. From the viewpoint of improving water resistance and abrasion resistance, zinc oxide or titanium oxide is preferred, and zinc oxide is particularly preferred. In addition, the particle size of the metal oxide is not particularly limited, but from the viewpoint of stability in the oil phase of component (a), it is preferable that the average primary particle size is in the range of 1 to 100 nm. In addition, in the present invention, the average particle size refers to the average value of the width and length of the powder measured in a dispersed state in water using a laser diffraction/scattering type particle size distribution measuring device (average particle size value at 50% of the cumulative volume). If necessary, the surface may be treated by a known method using a silicone compound, a fluorine compound, a metal soap, collagen, a hydrocarbon, a higher fatty acid, lecithin, a higher alcohol, an ester, a wax, a surfactant, a trialkoxysilane, or the like, or a composite of these may be used.

The plate-like powder component (c) used in the present invention can be blended in either the water phase or the oil phase, but is particularly preferably blended in the oil phase. There are no particular limitations on the plate-like powder as long as it is a plate-like powder that is commonly used in cosmetics, and examples include body powders such as mica, sericite, boron nitride, synthetic phlogopite, synthetic sericite, aluminum silicate, magnesium silicate, barium sulfate, aluminum magnesium silicate, cleaved talc, plate-like silicic acid anhydride, plate-like kaolin, plate-like boron nitride, plate-like cellulose, titanium mica, and bismuth oxychloride, and one or more of these can be used in combination. Among these, from the viewpoint of emulsion stability when component (a) is blended in the oil phase, it is preferable to use sericite or boron nitride, and it is more preferable to use sericite. The average particle size of the plate-like powder component (c) used in the present invention is not particularly limited, but it is preferable to use one having an average particle size of 1 to 100 μm, and it is more preferable to use one having an average particle size of 1 to 50 μm. The aspect ratio is preferably 5 to 500, and more preferably 10 to 100. In the present invention, the average particle size refers to the average value of the width and length of the powder measured in a dispersed state in water using a laser diffraction/scattering type particle size distribution measuring device (average particle size value at 50% of the cumulative volume). These plate-like powders may be surface-treated with one or more of fluorine-based compounds, silicone-based compounds, metal soaps, lecithin, hydrogenated lecithin, collagen, hydrocarbons, higher fatty acids, higher alcohols, esters, waxes, surfactants, trialkoxysilanes, etc.

Examples of silicone compounds used in the surface treatment of component (c) include linear silicones such as low-polymerization dimethylpolysiloxane, high-polymerization dimethylpolysiloxane, methylhydrogenpolysiloxane, and methylphenylpolysiloxane; modified silicones such as silicone phosphate triester, amino-modified silicones such as amodimethicone, alkyl-modified silicones, and alkoxy-modified silicones; silicone resins such as trimethylsiloxysilicate and acrylate silicone; silicone rubbers; partially or fully crosslinked organopolysiloxanes; and various silylating agents.

The trialkoxyalkylsilane in the trialkoxyalkylsilane treatment is a compound in which three alkoxy groups and one alkyl group are bonded to a silicon atom, and the alkoxy group reacts with hydroxyl groups on the powder surface to chemically coat the powder surface. In the trialkoxyalkylsilane, the alkoxy group is preferably a methoxy, ethoxy, propoxy, etc. having 1 to 3 carbon atoms. In addition, the alkyl group in the trialkoxyalkylsilane is preferably a hexyl group, octyl group, decyl group, octadecyl group, etc. having 6 to 18 carbon atoms. Examples of such trialkoxyalkylsilanes include trimethoxyhexylsilane, trimethoxyoctylsilane, trimethoxydecylsilane, trimethoxyoctadecylsilane, triethoxyhexylsilane, triethoxyoctylsilane (triethoxycaprylylsilane), triethoxydecylsilane, and triethoxyoctadecylsilane.

The amount of surface treatment is preferably 0.5 to 30% by mass of the powder, and more preferably 1 to 20% by mass.

The component (c) used in the present invention can be a combination of one or two of the metal oxide and the plate-like powder, but from the viewpoint of emulsion stability in the oil phase of the component (a), it is preferable to use two of them in combination, and it is more preferable to use a combination of the metal oxide and the plate-like powder. When the metal oxide and the plate-like powder are used in combination, the mixing ratio of the two is not particularly limited, but for example, metal oxide: plate-like powder = 1: 0.1 to 10 (mass ratio). A particularly preferred combination is zinc oxide that may be surface-treated and sericite that may be surface-treated, such as surface-treated zinc oxide and surface-treated sericite. When the two types are used in combination, a composite such as titanium dioxide-coated mica, titanium dioxide-coated synthetic phlogopite, titanium dioxide-coated bismuth oxychloride, iron oxide titanium mica, titanium dioxide-coated glass powder, etc. may be used.

The content of component (c) in the present invention is not particularly limited, but is preferably 1 to 30% in the emulsion cosmetic, and more preferably 5 to 20%. Within this range, a formulation with excellent water resistance, abrasion resistance, and stability can be provided.

In the present invention, it is preferable to further include component (d) inulin fatty acid ester (hereinafter also simply referred to as component (d)). By including inulin fatty acid ester, adhesion to the skin is improved, and water resistance, friction resistance, usability (particularly non-stickiness), and formulation stability are further improved. Component (d) can be incorporated into either the aqueous phase or the oil phase, but it is particularly preferable to incorporate it into the oil phase. By incorporating it into the oil phase, the thickening effect of the oil phase further improves water resistance, friction resistance, usability (particularly non-stickiness), and formulation stability.

The inulin fatty acid ester component (d) used in the present invention is an ester compound of inulin and a linear or branched, saturated or unsaturated fatty acid having 8 to 32 carbon atoms, and is contained in the oil phase. There are no particular limitations on the inulin as long as it is one that is normally incorporated into cosmetics, but inulin is preferably one that is composed of a chain of β-1,2-bonded furanoid fructose units and has a structure having α-D-glucose bonded to sucrose at the reducing end, with about 2 to 60 furanoid fructose units. Hydrolyzed inulin may also be used. Component (d) is preferably inulin stearate. Commercially available products include Leopearl ISK2 and Leopearl ISL2 (both manufactured by Chiba Flour Mills), which are inulin stearate.

The content of component (d) in the present invention is not particularly limited, but is preferably 0.1 to 10%, and more preferably 1 to 5% in the emulsion cosmetic. This range improves the dispersibility of (a) in the oil phase, and when a powder (e.g., component (c)) is blended, it improves the dispersibility of the powder, making it possible to provide a formulation with excellent water resistance, abrasion resistance, and stability.

In the present invention, it is preferable to further include component (e) dimethicodimethyi benzalmalonate. Component (e) dimethicodimethyi benzalmalonate used in the present invention is indicated by the INCI (INTERNATIONAL NOMENCLATURE of COSMETIC INGREDIENTS) name Polysilicone-15, and is a silicone derivative in which about 7.5% of dimethicone with a chain length of about 60 is substituted with two types of substituents. It is known that it has high ultraviolet protection ability by itself, while improving the SPA and PA values by a synergistic effect with other ultraviolet protection agents (booster effect). In the present invention, component (e) is preferably contained in the oil phase, and also functions as a component that improves the water resistance and abrasion resistance of the coating film, contributing to the stability of the cosmetic. An example of a commercially available product is PARSOL SLX (manufactured by DSM Nutritional Products).

The content of component (e) in the present invention is not particularly limited, but is preferably 0.1 to 10% in the emulsion cosmetic, and particularly preferably 1 to 5%. This range is preferable because it not only provides a high UV protection effect, but also improves the formulation stability.

In addition to the above-mentioned components, the emulsion cosmetic of the present invention may contain, as appropriate, components used in ordinary cosmetics, such as oily components other than component (e), ultraviolet absorbers, surfactants such as cationic surfactants, nonionic surfactants, anionic surfactants, and amphoteric surfactants, water, water-soluble polymers other than component (a) and component (b), aqueous components such as polyhydric alcohols and lower alcohols, antibacterial agents, preservatives, pH adjusters, cooling agents, powders other than component (c), beauty ingredients such as vitamins and amino acids, and fragrances, within a range that does not impair the effects of the present invention.

The emulsion cosmetic of the present invention can be implemented in various forms, such as liquid, emulsion, cream, solid, gel, paste, etc. The cosmetic of the present invention can be implemented in various forms, such as water-in-oil emulsion, oil-in-water emulsion, etc., but the formulation is not particularly limited. However, from the viewpoint of fresh usability, it is preferable to use an oil-in-water emulsion, since the water-in-water emulsion is considered to have lower water resistance and is required to have improved water resistance. That is, a preferred embodiment of the present invention is an oil-in-water emulsion cosmetic. It can be implemented in various cosmetics, such as skin care cosmetics such as emulsions, creams, beauty essences, lip balms, and sunscreens, makeup cosmetics such as foundations, makeup bases, blushers, eye shadows, lipsticks, and lip glosses, and cosmetics for the scalp or hair such as hair rinses, hair creams, and hair styling products.

One embodiment of the present invention is an emulsion sunscreen cosmetic. Another embodiment of the present invention further comprises an ultraviolet absorbing agent. By improving the water resistance and abrasion resistance of the cosmetic coating film, the ultraviolet absorbing agent is less likely to be removed by sweat or water, resulting in a sunscreen with high ultraviolet protection. There are no particular restrictions on the ultraviolet absorbing agent, and any ultraviolet absorbing agent that is normally used in sunscreen cosmetics can be used. Examples of ultraviolet absorbers include ethylhexyl methoxycinnamate, 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoic acid hexyl ester, ethyl paraaminobenzoate, benzophenone-1, benzophenone-3, benzophenone-6, benzophenone-9, 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine, dioctylbutamide triazone, 4-tert-butyl-4'-methoxy-dibenzoylmethane, 2,4-bis{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-(1,3,5)-triazine, 2,2'-methylenebis[6-(2H-benzotriazol-2yl)-4-(1,1,3,3-tetramethylbutyl)phenol], and polysilicone-15. One or more of these may be used. Among these, ethylhexyl methoxycinnamate, 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoic acid hexyl ester, 4-tert-butyl-4'-methoxy-dibenzoylmethane, 2,4-bis{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-(1,3,5)-triazine, and polysilicone-15 are preferred, and ethylhexyl methoxycinnamate, 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoic acid hexyl ester, and 2,4-bis{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-(1,3,5)-triazine are more preferred. The content of the ultraviolet absorber in the emulsion cosmetic is, for example, 1 to 10%.

Methods for using the emulsion cosmetic of the present invention include using it on hands, fingers, or cotton, impregnating nonwoven fabric, etc., or using it as a spray or aerosol.

The present invention also provides a method for producing an emulsified cosmetic preparation containing (a) an oil phase containing a water-soluble cationic polymer and (b) an aqueous phase containing a water-soluble anionic polymer. The emulsification method may be appropriately selected from methods well known in the art.

The present invention will be explained in more detail below with reference to examples and test examples, but the present invention is not limited to these examples in any way.

[Example 1 (Products 1 to 14 of the present invention) and Comparative Examples 1 to 4: Emulsion cosmetics]
Emulsion cosmetics were prepared using the compositions shown in Table 1 and the manufacturing method described below. The resulting emulsion cosmetics were evaluated for water resistance, abrasion resistance, and sensory evaluation using the methods described below, and the results are shown in Tables 1 to 3.

(Note 1) SIMULGEL EG (SEPPIC) (37.5% mixture of sodium acrylate and sodium acryloyldimethyltaurate copolymer. The content in the formulation indicates the amount of pure compound.)
(Note 2) PEMULENE TR-1 (manufactured by Lubrizol Advanced Materials Inc.)
(Note 3) ACULYN 22 (manufactured by ROHM GMBH) (30% aqueous solution of alkyl acrylate/alkyl methacrylate/polyoxyethylene stearyl ether methacrylate (20E.O.) copolymer. The content in the formulation indicates the amount of pure compound.)
(Note 4) CARBOPOL 980 (manufactured by Lubrizol Advanced Materials Inc.)
(Note 5) MERQUAT 740 POLYMER (manufactured by Lubrizol Japan. Dimethyldiallylammonium chloride-acrylamide copolymer, 43% aqueous solution. The content in the formulation indicates the amount of pure compound.)
(Note 6) Leopard ISK2 (manufactured by Chiba Flour Mills)
(Note 7) TINOSORB S (manufactured by BASF)
(Note 8) Ubinal A PLUS GRANULAR (manufactured by BASF)
(Note 9) PARSOL SLX (manufactured by DSM NUTRITIONAL PRODUCTS)
(Note 10) NIKKOL HCO-40 (manufactured by Nippon Surfactant Industries Co., Ltd.)
(Note 11) Catinal HC-100 (manufactured by Toho Chemical Industry Co., Ltd.)
(Note 12) JAGUAR C-14S(C) (manufactured by SOLVAY)

(Production method)
A: Components 1 to 3 are uniformly dispersed at 70°C.
B: Dissolve ingredients 10 to 15 uniformly at 70°C.
C: Mix and disperse ingredients 16 to 22.
D: Add C to B and disperse evenly.
E: Add D to A and emulsify at 70°C.
F: Cool E to room temperature.
G: Components 4 to 9 were mixed with F to obtain an oil-in-water emulsion cosmetic.

(Evaluation method: (a) Water resistance evaluation)
Each of the above samples was applied to a PMMA plate (HELIOPLATE HD6, manufactured by Labsphere) at 2 mg/ ^cm2 , and the sample was left to stand for 20 minutes. SPF measurement was performed using an SPF analyzer (UV-2000S, manufactured by Labsphere) to measure the pre-water bath SPF value. Next, a water bath was performed. The water bath conditions were that the sample was attached to the side of a container containing 2 L of water at 35°C, and the water in the container was stirred at 300 rpm for 5 minutes using a paddle mixer. After completion of the water bath, the sample was left to stand and dry for 20 minutes, and the post-water bath SPF value was measured using the SPF analyzer. Based on the obtained SPF values before and after the water bath, the water resistance was evaluated and judged in four stages according to the following (a) evaluation criteria.
(a) 4-level evaluation criteria (evaluation): (Judgment)
(SPF measured value after bathing)/(SPF measured value before bathing)=0.7 or more: ◎
(SPF measured value after bathing)/(SPF measured value before bathing)=0.5 or more: ○
(SPF measured value after bathing)/(SPF measured value before bathing)=0.3 or more: △
(SPF measured value after bathing)/(SPF measured value before bathing)=less than 0.3: ×.

(Evaluation method: (b) Abrasion resistance evaluation)
Each of the above samples was applied to a PMMA plate at 2 mg/ ^cm2 , and the sample was left to stand for 20 minutes. SPF measurement was performed using an SPF analyzer (UV-2000S, manufactured by Labsphere) to measure the SPF value before rubbing. Next, rubbing was performed. The friction conditions were as follows: a texture analyzer TA.XT PLUS (manufactured by Eiko Seiki Co., Ltd.) was used to fix the towel fabric to the tip of the jig, and a certain load was applied and moved back and forth five times. After rubbing was completed, the SPF value after rubbing was measured using the SPF analyzer. Based on the obtained SPF values before and after rubbing, the friction resistance was evaluated and judged in four stages according to the following (b) evaluation criteria.
(b) 4-level evaluation criteria (evaluation): (Judgment)
(SPF measured value after rubbing)/(SPF measured value before rubbing)=0.7 or more: ◎
(SPF measured value after rubbing)/(SPF measured value before rubbing)=0.5 or more: ○
(SPF measured value after rubbing)/(SPF measured value before rubbing)=0.3 or more: △
(SPF measured value after rubbing)/(SPF measured value before rubbing)=less than 0.3: ×.

(Evaluation method: (c) Non-stickiness)
A panel of 20 expert assessors applied each of the samples to the forearm and assessed the stickiness during use on a four-level scale according to the following (c) evaluation criteria.
(c) 4-level evaluation criteria (evaluation): (judgment)
No stickiness at all: 4 points Almost no stickiness: 3 points Stickiness: 2 points Very sticky: 1 point According to the above evaluation criteria, the average score was calculated and judged based on the following criteria.
<Evaluation Criteria>:
[Average score]: [Judgment]
3.25 or higher: ◎
2.5 or more and less than 3.25: ○
1.75 or more and less than 2.5: △
Less than 1.75: ×.

(Evaluation method: (d) Non-stickiness)
A panel of 20 expert assessors applied each of the samples to the forearm and assessed the stickiness during use on a four-level scale according to the following evaluation criteria (d).
(d) 4-level evaluation criteria (evaluation): (judgment)
No stickiness at all: 4 points Almost no stickiness: 3 points Stickiness: 2 points Extremely sticky: 1 point According to the above evaluation criteria, the average score was calculated and judged based on the following criteria.
<Evaluation Criteria>:
[Average score]: [Judgment]
3.25 or higher: ◎
2.5 or more and less than 3.25: ○
1.75 or more and less than 2.5: △
Less than 1.75: ×.

(Evaluation method: (e) Freshness)
A panel of 20 expert assessors applied each of the above samples to the forearm and assessed the freshness felt upon application on a four-level scale according to the following evaluation criteria (e).
(e) 4-level evaluation criteria (evaluation): (judgment)
Very moist: 4 points Slightly moist: 3 points Slightly not moist: 2 points Not moist at all: 1 point Using the above evaluation criteria, the average score was calculated and judged based on the following criteria.
<Evaluation Criteria>:
[Average score]: [Judgment]
3.25 or higher: ◎
2.5 or more and less than 3.25: ○
1.75 or more and less than 2.5: △
Less than 1.75: ×.

(Evaluation method: (f) Formulation stability)
Each of the samples was placed in a standard glass bottle and stored in a thermostatic chamber at 50° C. for one month. After one month, the condition was observed and rated using the following four-level rating criteria (f).
(f) 4-level evaluation criteria (evaluation): (Judgment)
No change in appearance observed: ◎
Almost no change in appearance: ○
Slight separation or lumps observed: △
Separation or bumps are visible: ×.

As is clear from the results in Tables 1 to 3, the emulsion cosmetics of the present invention, Products 1 to 14, have high water resistance and abrasion resistance by blending a water-soluble anionic polymer and a water-soluble cationic polymer in separate phases, and are excellent in terms of freshness at the start and lack of stickiness and sliminess on the skin after application. Furthermore, the emulsion cosmetics of the present invention, Products 1 to 14, also have excellent formulation stability. Note that Products 7 to 10 of the present invention are invention Product 1 in which the mass ratio (a)/(b) of components (a) and (b) is changed, and Product 11 of the present invention is a formulation in which the blending amounts of components (a) and (b) are changed from Product 1 of the present invention. On the other hand, Comparative Examples 1, 2, and 3, which do not blend components (a) and (b), did not have water resistance or abrasion resistance, and resulted in a sticky or slimy feel. In Comparative Example 4, in which a water-soluble anionic polymer was blended in the oil phase and a water-soluble cationic polymer was blended in the aqueous phase, the water-soluble cationic polymer formed aggregates with the water-soluble anionic polymer in the formulation, resulting in poor formulation stability.

Example 2: Cream (oil-in-water type)
(Component) (%)
1. Sodium N-stearoyl-N-methyl taurate 0.1
2. Phospholipid/cholesterol mixture 2.2
3. Glycerin 6.5
4. Mica (plate-shaped powder, average particle size 5 to 12 μm) 3.0
5. Polyhydroxystearic acid 0.5
6. Dimethyldiallylammonium chloride-acrylamide copolymer (Note 13) 0.045
7. Propylene glycol dicaprylate 5.0
8. 1,3-butylene glycol 5.0
9. Diglycerin 1.0
10. Inulin stearate (Note 6) 2.0
11. Cetyl ethylhexanoate 3.0
12. Ethylhexyl methoxycinnamate 5.0
13. Dimethicone diethyl benzalmalonate (Note 9) 2.0
14. 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoic acid hexyl ester (Note 8)
1.0
15. Rice germ oil 0.02
16. Tocopherol 0.01
17. Distilled water (remaining amount) 18. Xanthan gum 0.1
19. Carbomer (Note 4) 0.3
20. Sodium hydroxide (appropriate amount) 21. Ethanol (6.5
22. Preservatives: appropriate amount 23. Trehalose: 0.05
24. Seaweed extract 0.01
25. Citric acid 0.02
26. Sodium monohydrogen phosphate 0.15
27. Hydroxyproline 0.05
28. Artemisia capillaris extract 0.05
(Note 13) MERQUAT 550PR (manufactured by Lubrizol Japan. Dimethyldiallylammonium chloride-acrylamide copolymer, 9% aqueous solution. The content in the formulation indicates the amount of pure compound.)
(Production method)
A: Components (1) to (3) and (17) are heated to 70°C and mixed uniformly.
B: Components (4) to (16) are heated to 80°C and mixed uniformly.
C: Add B to A and stir.
D: Add ingredients (18) to (28) heated to 70°C to C and emulsify.
E: D was cooled to room temperature with stirring to obtain a cream.

The cream of Example 2 was a cosmetic product that had excellent water resistance and abrasion resistance, was comfortable to use, was capable of fully exerting the UV protection functions of the UV absorbers and UV scattering agents, and had excellent emulsion stability.

Example 3: Shaking type sunscreen (water-in-oil type)
(Component) (%)
1. 2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine (Note 7)
1.5
2. Ethyl paramethoxycinnamate (ethylhexyl paramethoxycinnamate)
7.5
3. Inulin stearate (Note 6) 1.5
4. 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoic acid hexyl ester (Note 8)
3.0
5. Diethylhexyl succinate 3.5
6. Dimethicone diethyl benzalmalonate (Note 9) 3.0
7. Methylpolysiloxane (Note 14) 0.5
8. Safflower oil 0.1
9. Silylated anhydrous silicic acid 4.0
10. Zinc oxide 7.0
11. Mica (plate-shaped powder, average particle size 5 to 12 μm) 2.0
12. Polyhydroxystearic acid 1.0
13. Dimethyldiallylammonium chloride-acrylamide copolymer (Note 5)
0.1
14. Cyclomethicone 4.0
15. Light isoparaffin 4.0
16. Ethanol 7.0
17. Preservative Appropriate amount 18. Fragrance Appropriate amount 19. Purified water Remaining amount 20. Acrylic acid / alkyl methacrylate copolymer (Note 2) 0.05
21. Hydrolyzed hyaluronic acid 0.01
22. Hydrolyzed collagen 0.01
(Note 14) KF-96-10CS (manufactured by Shin-Etsu Chemical Co., Ltd.)
A sunscreen (shaking) was prepared according to the following method.
(Production method)
A: Heat ingredients (1) to (8) to 80°C and mix uniformly.
B: Components (9) to (15) are mixed uniformly using a roller.
C: Add B to A and mix evenly.
D: Add ingredients (16) to (18) in C and mix evenly.
E: Add (19) to (22) to D and emulsify.
F: E was cooled to room temperature to obtain a shaking type sunscreen (water-in-oil type).

The sunscreen agent (shaking) of Example 3 was a cosmetic product that had excellent water resistance and abrasion resistance, was comfortable to use, was capable of fully exerting the UV protection functions of the UV absorbers and UV scattering agents, and had excellent emulsion stability.

Example 4: Sunscreen (cream) (water-in-oil type)
(Component) (%)
1. Zinc oxide 15
2. Titanium oxide 2
3. PEG-9 Polydimethylsiloxyethyl Dimethicone (Note 15)
0.5
4. O-[2-hydroxy-3(trimethylammonio)propyl]guar gum chloride (Note 12)
0.1
5. Cyclomethicone 6.0
6. Disteardimonium hectorite 1.0
7. Ethylhexyl paramethoxycinnamate 5.0
8. Inulin stearate (Note 6) 1.0
9. 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoic acid hexyl ester (Note 8)
2.0
10. Light paraffin 4.0
11. Isotridecyl isononanoate 2.0
12. Cetyl ethylhexanoate 1.0
13. Tocopherol 0.05
14. Apricot kernel oil 0.01
15. Cyclomethicone remaining 16. PEG-9 Polydimethylsiloxyethyl Dimethicone (Note 15)
0.5
17. Dimethicone diethyl benzalmalonate (Note 9) 3.0
18. Methylsiloxane network polymer (Note 16) 3.0
19. Fragrance (as needed) 20. Disodium edetate (as needed) 21. Purified water 14
22. Alkyl acrylate, alkyl methacrylate, polyoxyethylene stearyl ether methacrylate (20E.O.) copolymer (Note 3)
0.5
23. Hawthorn Extract 0.01
24. Grape Leaf Extract 0.01
25. Concentrated glycerin 1.0
26. Ethanol 15
(Note 15) KF-6028P (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 16) TOSPEARL 3000A (manufactured by Momentive Performance Materials Japan, Inc.)
A sunscreen (cream) was prepared according to the following method.
(Production method)
A: Components (1) to (6) are mixed uniformly with a roller.
B: Components (7) to (19) are heated to 80°C and mixed uniformly.
C: Add B to A and mix evenly.
D: Add ingredients (20) to (26) and mix uniformly.
E: Add D to C and emulsify.
F: E was returned to room temperature to obtain a sunscreen (cream).

The sunscreen (cream) of Example 4 was a cosmetic product that had excellent water resistance and abrasion resistance, was comfortable to use, was capable of fully exerting the UV protection functions of the UV absorbers and UV scattering agents, and had excellent emulsion stability.

Example 5: Cosmetic base (water-in-oil type)
(Component) (%)
1. Zinc oxide 15
2. Silicone-treated ultramarine 0.04
3. Silicone, talc, yellow iron oxide mixture 0.03
4. Nylon 1.0
5. (Acrylates/Ethylhexyl Acrylate/Dimethicone Methacrylate) Copolymer (Note 17)
0.3
6. O-[2-hydroxy-3-(trimethylammonio)propyl]hydroxyethylcellulose chloride (Note 18)
0.3
7. Cyclomethicone 6.0
8. Ethylhexyl paramethoxycinnamate 3.0
9. 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoic acid hexyl ester (Note 8)
2.0
10. Light paraffin 4.0
11. Inulin stearate (Note 6) 1.0
12. Diethylhexyl succinate 3.0
13. Cyclomethicone remaining 14. PEG-9 Polydimethylsiloxyethyl Dimethicone (Note 15)
0.5
15. Dimethicone diethyl benzalmalonate (Note 9) 3.0
16. Methylsiloxane network polymer (Note 16) 3.0
17. Fragrance (appropriate amount) 18. Methylphenylpolysiloxane 0.5
19. Disodium edetate (appropriate amount) 20. Purified water 14
21. Sodium acrylate-sodium acryloyldimethyltaurate copolymer (Note 1)
0.8
22. Methylgluceth-10 0.5
23. Sodium dilauroyl glutamate lysine 0.2
24. Humus soil extract 1.0
25. Concentrated glycerin 1.0
26. Ethanol 15
(Note 17) KP-578P (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 18) Catinal HC-200 (manufactured by Toho Chemical Industry Co., Ltd.)
A cosmetic base was prepared according to the following method.
(Production method)
A: Components (1) to (7) are mixed uniformly with a roller.
B: Components (8) to (18) are heated to 80°C and mixed uniformly.
C: Add B to A and mix evenly.
D: Add ingredients (18) to (26) and mix uniformly.
E: Add D to C and emulsify.
F: E was returned to room temperature to obtain a cosmetic base.

The cosmetic base of Example 5 was a cosmetic preparation that had excellent water resistance and abrasion resistance, was comfortable to use, was capable of fully exerting the UV protection functions of the UV absorbers and UV scattering agents, and had excellent emulsion stability.

Example 6: Aerosol type sunscreen (oil-in-water type)
(Component) (%)
1. Propylene glycol dicaprylate 12
2. Inulin stearate (Note 6) 1.0
3. Dextrin isostearate (Note 19) 0.5
4. Zinc oxide 6.0
5. Polyhydroxystearic acid 0.3
6. O-[2-hydroxy-3-(trimethylammonio)propyl]hydroxyethylcellulose chloride (Note 11)
0.2
7. Ethyl paramethoxycinnamate (ethylhexyl paramethoxycinnamate)
7.0
8. 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoic acid hexyl ester (Note 8)
3.0
9. 2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine (Note 7)
1.0
10. Dimethicone diethyl benzalmalonate (Note 9) 1.0
11. Propylene glycol dicaprylate 8.0
12. Alkyl benzoate (C12-C15) 1.0
13. Methylsiloxane network polymer (Note 16) 8.5
14. PEG-9 Polydimethylsiloxyethyl Dimethicone (Note 15)
0.5
15. O-[2-hydroxy-3-(trimethylammonio)propyl]hydroxyethylcellulose chloride (Note 20)
0.3
16. Dimethyldiallylammonium chloride-acrylamide copolymer (Note 5)
0.3
17. Mica (plate-shaped powder, average particle size 5 to 12 μm) 4.0
18. Natural Vitamin E 0.05
19. Dipropylene glycol 1.0
20. Ethanol 25
21. Purified water remaining amount 22. Sodium acrylate/sodium acryloyldimethyltaurate copolymer
0.8
23. Fragrance (Note 19) Unifilma HVY (manufactured by Chiba Flour Mills)
(Note 29) Catinal LC-100 (manufactured by Toho Chemical Industry Co., Ltd.)
An aerosol type sunscreen was prepared according to the following method.
(Production method)
A: Components (1) to (6) are dispersed using three rollers.
B: Components (7) to (17) are dissolved homogeneously at 70°C.
C: Add B to A and mix evenly.
D: Add (18) to (23) to C and emulsify.
E: 6 g of the concentrate obtained in D was filled into an aluminum pressure container, a valve was then attached, and a propellant (LPG 0.15:14 g) was filled into the pressure container through the valve, thereby obtaining an aerosol-type sunscreen.

The aerosol sunscreen formulation of Example 6 was a cosmetic product that had excellent water resistance and abrasion resistance, was comfortable to use, was capable of fully exerting the UV protection functions of the UV absorbers and UV scattering agents, and had excellent emulsion stability.

Example 7: Hair cosmetic (oil-in-water type)
(Component) (%)
1. Purified water remaining 2. PG 2.0
3. Glycerin 1.0
4. Sodium edetate 0.01
5. Sodium acrylate-sodium acryloyldimethyltaurate copolymer (Note 1)
0.5
6. Methylpolysiloxane (Note 21) 10.0
7. Light liquid paraffin 5.0
8. Dextrin isostearate (Note 19) 1.0
9. Ethyl oleate 1.0
10. Polyoxyethylene hydrogenated castor oil (Note 10) 1.0
11. Fragrance 0.5
12. Mica (plate-shaped powder, average particle size 5 to 12 μm) 4.0
13. O-[2-hydroxy-3-(trimethylammonio)propyl]hydroxyethylcellulose chloride (Note 11)
0.2
14. Sodium hydroxide 0.05
15. Purified water 2.0
16. Ethanol 10
17. Purified water 5.0
18. Acrylic acid/alkyl methacrylate copolymer (Note 2) 0.3
19. L-serine 0.05
20. Glycylglycine 0.05
(Note 21) KF-96-6CS (manufactured by Shin-Etsu Chemical Co., Ltd.)
A hair cosmetic was prepared according to the following method.
(Production method)
A: Mix ingredients (1) to (5) uniformly.
B: Dissolve components (6) to (13) uniformly.
C: Add B to A and emulsify.
D: Add (14) to (15) and mix.
E: Add (16) to (20) to D and mix.
F: E was filled into a dispenser container to obtain a hair cosmetic preparation.

The hair cosmetic of Example 7 was a cosmetic that had excellent water resistance and abrasion resistance, a pleasant feel, and excellent emulsion stability.

As described above in detail, by incorporating a water-soluble cationic polymer in the oil phase and a water-soluble anionic polymer in different phases, that is, in the aqueous phase, it is possible to provide an emulsion cosmetic which improves the water resistance and abrasion resistance of the coating film and has a good feel when used.

This application is based on Japanese Patent Application No. 2018-206251, filed on November 1, 2018, the disclosure of which is hereby incorporated by reference in its entirety.

Claims (9)

An emulsion cosmetic comprising (a) an oil phase containing a water-soluble cationic polymer and (b) an aqueous phase containing a water-soluble anionic polymer,
(a) the water-soluble cationic polymer is one or more selected from the group consisting of dimethyldiallylammonium chloride-acrylamide copolymer, O-[2-hydroxy-3-(trimethylammonio)propyl]hydroxyethylcellulose chloride, and O-[2-hydroxy-3-(trimethylammonio)propyl]guar gum chloride;
(b) An emulsion cosmetic, wherein the water-soluble anionic polymer is one or more selected from the group consisting of carboxyvinyl polymers, acrylic acid/alkyl methacrylate copolymers, sodium acrylate/sodium acryloyldimethyltaurate copolymers, and alkyl acrylate/alkyl methacrylate/polyoxyethylene stearyl ether methacrylate (20 E.O.) copolymers. The emulsion cosmetic according to claim 1, which contains at least one of (c) a metal oxide or a plate-like powder. The emulsion cosmetic according to claim 1 or 2, which contains (d) an inulin fatty acid ester. The emulsion cosmetic according to any one of claims 1 to 3, in which the mass ratio (a)/(b) is 0.05 to 20. The emulsion cosmetic according to any one of claims 1 to 4, wherein the content of (a) is 0.001 to 3 mass% based on the emulsion cosmetic . The emulsion cosmetic according to any one of claims 1 to 5, wherein the content of (b) is 0.001 to 2% by mass based on the emulsion cosmetic . The emulsion cosmetic according to any one of claims 1 to 6, which is an oil-in-water emulsion cosmetic. (e) The emulsion cosmetic according to any one of claims 1 to 7, which contains dimethicodiethyl benzalmalonate. A method for producing an emulsion cosmetic comprising (a) an oil phase containing a water-soluble cationic polymer and (b) an aqueous phase containing a water-soluble anionic polymer, the method comprising the steps of:
(a) the water-soluble cationic polymer is one or more selected from the group consisting of dimethyldiallylammonium chloride-acrylamide copolymer, O-[2-hydroxy-3-(trimethylammonio)propyl]hydroxyethylcellulose chloride, and O-[2-hydroxy-3-(trimethylammonio)propyl]guar gum chloride;
(b) A method for producing an emulsion cosmetic, wherein the water-soluble anionic polymer is one or more selected from the group consisting of carboxyvinyl polymers, acrylic acid/alkyl methacrylate copolymers, sodium acrylate/sodium acryloyldimethyltaurate copolymers, and alkyl acrylate/alkyl methacrylate/polyoxyethylene stearyl ether methacrylate (20 E.O.) copolymers.