Compound and cosmetic composition containing same

Abstract

A complex having a pH of 6.0 or higher, preferably a pH of 6.8 to 9.0, more preferably a pH of 6.8 to 7.5, comprising a) at least one phenylbenzimidazole sulfonic acid of formula I or a salt thereof, and b) at least one hydrophilic clay, # imgabs0 # wherein Ar is substituted or unsubstituted phenyl, R is C1-8 alkyl or C1-8 alkoxy, n is 1, 2, 3 or 4, q is 1, 2 or 3, and p is 0, 1 or 2.

Description

Technical Field

[0001] The present invention relates generally to the field of cosmetics, and more particularly to a complex comprising phenylbenzimidazole sulfonic acid and a hydrophilic clay, and a cosmetic composition comprising the complex. The present invention also relates to a method for preparing the complex. The present invention further relates to a cosmetic method for caring for and / or making up keratin materials. Background Art

[0002] UV filters widely used in the cosmetics field can be generally divided into UVA filters and UVB filters. As UVB filters for preventing various skin damages caused by UVB (such as sunburn, redness, wrinkle formation, collagen decomposition and pigmentation), phenylbenzimidazole sulfonic acid derivatives such as " 232"," HS" or "Neo Phenylbenzimidazole sulfonic acid is commercially available as "Hydro"; AP" and other commercially available disodium phenylbenzimidazole tetrasulfonate. However, phenylbenzimidazole sulfonic acid is extremely insoluble in water and therefore needs to be neutralized with an alkaline agent to a pH greater than 7.0 to form a water-soluble phenylbenzimidazole sulfonate. Otherwise, if not fully neutralized, phenylbenzimidazole sulfonic acid will form crystals, which will make its protection against UVB less effective and have a sandy or grainy feel when applied to the skin.

[0003] US 6153176 teaches that low pH formulations containing phenylbenzimidazole sulfonic acid can be prepared in which 75% to 95% of the acid remains in its unneutralized form.

[0004] EP 2178493 notes that the low-pH formulation in US 6153176 is unstable and that phenylbenzimidazole sulfonic acid does, in fact, recrystallize within the formulation. In this regard, EP 2178493 proposes using a basic amino acid to neutralize phenylbenzimidazole sulfonic acid, thereby improving stability and preventing recrystallization of phenylbenzimidazole sulfonic acid in low-pH formulations. However, when this formulation example was repeated and applied to the skin, crystallization of phenylbenzimidazole sulfonic acid was observed.

[0005] In addition, hydrophilic clays are widely used in the cosmetic field as thickeners for water-based cosmetics. US20030152531 discloses a formulation comprising montmorillonite clay as a thickener, with phenylbenzimidazole sulfonic acid listed as a possible sunscreen active substance in the formulation.

[0006] WO 2016000145 discloses a composition in which distearyldimonium hectorite is used as a lipophilic thickener in the oil phase.

[0007] However, the documents published in the prior art do not mention the problem of recrystallization of phenylbenzimidazolesulfonic acid contained in cosmetic formulations when applied on the skin (even if the phenylbenzimidazolesulfonic acid is in the form of a soluble salt), which leads to a loss of UV protection efficiency.

[0008] Summary of the Invention

[0009] There remains a strong need for a more effective method for stably maintaining soluble salts of phenylbenzimidazole sulfonic acid during storage and use of cosmetic formulations, particularly when applied to human skin.

[0010] The inventors of the present invention have conducted in-depth research to solve the above problems and found that the soluble salt of phenylbenzimidazole sulfonic acid can be maintained in a wide pH range from low to alkaline.

[0011] Therefore, according to a first aspect, the present invention provides a complex having a pH of 6.0 or higher, preferably a pH of 6.8 to 9.0, more preferably a pH of 6.8 to 7.5, comprising:

[0012] a) at least one phenylbenzimidazolesulfonic acid of formula I or a salt thereof, and

[0013] b) at least one hydrophilic clay,

[0014]

[0015] in

[0016] Ar is a substituted or unsubstituted phenyl group,

[0017] R is C 1-8 Alkyl or C 1-8 Alkoxy,

[0018] n is 1, 2, 3 or 4,

[0019] q is 1, 2, or 3, and

[0020] p is 0, 1 or 2.

[0021] In some embodiments, for the phenylbenzimidazole sulfonic acid of Formula I, Ar is preferably unsubstituted phenyl, n is 1 or 2, q is 1 or 2, and p is 0.

[0022] In some embodiments, the phenylbenzimidazole sulfonic acid is selected from 2-phenylbenzimidazole-4-sulfonic acid, 2-phenylbenzimidazole-5-sulfonic acid, 2-phenylbenzimidazole-6-sulfonic acid, 2-phenylbenzimidazole-7-sulfonic acid, 2,2'-(1,4-phenylene)bis(1H-benzo[d]imidazole-5,7-disulfonic acid), 2,2'-(1,4-phenylene)bis(1H-benzo[d]imidazole-4,6-disulfonic acid) and combinations thereof; preferably, the phenylbenzimidazole sulfonic acid is selected from 2-phenylbenzimidazole-5-sulfonic acid, 2,2'-(1,4-phenylene)bis(1H-benzo[d]imidazole-5,7-disulfonic acid) and combinations thereof.

[0023] In some embodiments, the phenylbenzimidazole sulfonic acid is neutralized with a basic agent.

[0024] In some embodiments, the alkaline agent is selected from an inorganic base and an organic base; preferably, the alkaline agent is an organic base.

[0025] In some embodiments, the organic base is selected from monoethanolamine, diethanolamine, triethanolamine, aminomethylpropylene glycol, 2-amino-2-methylpropanol (AMP), triisopropanolamine (TIPA), tris[(2-hydroxy)-1-propyl]amine, 2-amino-2-methyl-1,3-propanediol (AMPD), 2-amino-2-hydroxymethyl-1,3-propanediol, N-methylglucamine, basic amino acids, and combinations thereof.

[0026] In some embodiments, the isoelectric point of the basic amino acid is greater than 7; preferably, the basic amino acid is selected from arginine, lysine, histidine and combinations thereof, more preferably, the basic amino acid is arginine.

[0027] In some embodiments, phenylbenzimidazole sulfonic acid is present in an amount of 0.1 wt % to 10 wt %, preferably 1 wt % to 5 wt %, relative to the total weight of the composite.

[0028] In some embodiments, the hydrophilic clay is a synthetic hydrophilic clay; preferably, the hydrophilic clay is hectorite; more preferably, the hydrophilic clay is sodium lithium magnesium silicate.

[0029] In some embodiments, the hydrophilic clay is present in an amount of 0.01 wt% to 20 wt%, preferably 0.05 wt% to 10 wt%, relative to the total weight of the composite.

[0030] In some embodiments, the ratio of phenylbenzimidazole sulfonic acid to hydrophilic clay is from 0.01 to 20, preferably from 0.02 to 10, and more preferably from 0.1 to 5.

[0031] In some embodiments, the complex is an aqueous dispersion.

[0032] According to a second aspect, the present invention provides a cosmetic composition comprising a complex as defined above and optionally a cosmetically acceptable excipient.

[0033] According to a third aspect, the present invention provides a method for preparing the composite of the present invention, comprising the following steps:

[0034] 1) forming a homogeneous system by mixing at least one phenylbenzimidazole sulfonic acid of formula I or a salt thereof with at least one hydrophilic clay; and

[0035] 2) Using an alkaline agent, the pH of the homogeneous system is adjusted to 6.0 or higher, preferably 6.8 to 9.0, more preferably 6.8 to 7.5.

[0036]

[0037] in

[0038] Ar is a substituted or unsubstituted phenyl group,

[0039] R is C 1-8 Alkyl or C 1-8 Alkoxy,

[0040] n is 1, 2, 3 or 4,

[0041] q is 1, 2, or 3, and

[0042] p is 0, 1 or 2.

[0043] In some embodiments, the alkaline agent is a basic amino acid selected from arginine, lysine, histidine, and combinations thereof; preferably, the basic amino acid is arginine.

[0044] In some embodiments, the ratio of phenylbenzimidazole sulfonic acid to hydrophilic clay is from 0.01 to 20, preferably from 0.02 to 10, and more preferably from 0.1 to 5.

[0045] According to a fourth aspect, the present invention provides a cosmetic method for caring for and / or making up keratin materials, comprising applying a complex or a cosmetic composition as defined above.

[0046] Other subjects and features, aspects and advantages of the present invention will appear more clearly after reading the ensuing description and examples. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] These drawings are used to provide a further understanding of the embodiments of the present invention and constitute a part of the specification. In conjunction with the following detailed description of the present invention, they are used to illustrate the embodiments of the present invention, but do not limit the embodiments of the present invention. In the drawings:

[0048] Figure 1 The XRD patterns of sample A-1 and the material Laponite are shown.

[0049] Figure 2 The XRD patterns of sample A-1 and material phenylbenzimidazole sulfonic acid are shown.

[0050] Figure 3 The microscope comparison of sample A-1 and sample A-2 is shown. Specifically, Figure 1 Microscopic comparison of sample A-1 and sample A-2 with and without polarized light is shown.

[0051] Figure 4 The SPF test of sample A-1 and sample A-2 on a PMMA plate and their UV absorption graphs are shown. Detailed Description of the Invention

[0053] I. Definition

[0054] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the invention belongs. When the definition of a term in this specification conflicts with the meaning commonly understood by those skilled in the art to which the invention belongs, the definition set forth herein shall apply.

[0055] In the following, and unless otherwise indicated, the boundaries of the numerical ranges are included in the range, particularly in the expressions "between . . . and . . . " and " to . . . . ".

[0056] Throughout this application, the term "comprising" should be interpreted as encompassing all specifically mentioned features as well as optional, additional, unspecified features. As used herein, the use of the term "comprising" also discloses embodiments in which no features other than those specifically mentioned are present (i.e., "consisting of ...").

[0057] As used herein, the singular forms "a", "an", and "the" include plural references unless the context clearly dictates otherwise. For example, a reference to a Cn alcohol equivalent is intended to include multiple types of Cn alcohol equivalents. Thus, even if language such as "at least one" is used in one place, it is not intended that the use of "a", "an", and "the" elsewhere excludes plural references unless the context clearly dictates otherwise.

[0058] As used herein, the term "and / or," when used in the context of a list of two or more items, means that any one of the listed items may be used alone, or any combination of two or more of the listed items may be used. For example, if a composition is described as containing components A, B, and / or C, the composition may contain only A; only B; only C; a combination of A and B; a combination of A and C; a combination of B and C; or a combination of A, B, and C.

[0059] As used herein, the term "UV filter" refers to a substance that absorbs ultraviolet (UV) light, i.e., electromagnetic radiation with a wavelength between 280 and 400 nanometers. UVA filters are UV filters that absorb UVA light (i.e., electromagnetic radiation with a wavelength between 315 and 400 nanometers). UVB filters are UV filters that absorb UVB light (i.e., electromagnetic radiation with a wavelength between 280 and 315 nanometers).

[0060] In addition, the expression "at least one" used in this specification is equivalent to the expression "one or more".

[0061] Unless otherwise specified, all numerical values used in the specification and claims to indicate the amount of ingredients, etc., should be understood to be modified by the term "about" and have the meaning generally known in the art, for example, within 10% of the indicated number (for example, "about 10%" refers to 9% to 11%, and "about 2%" refers to 1.8% to 2.2%). Therefore, unless otherwise indicated, the numerical values and parameters described herein are approximate and can be adjusted as needed according to the desired purpose. At least, each numerical parameter should be interpreted at least in accordance with the number of reported significant figures and by applying conventional rounding techniques. In addition, the ranges described in the present disclosure and claims are intended to specifically include the entire range, not just (one or more) endpoints. For example, the range of 0 to 10 is intended to disclose all integers between 0 and 10, such as 1, 2, 3, 4, and any subranges formed by any two values therein, etc., all fractions between 0 and 10, such as 1.5, 2.3, 4.57, 6.1113, and any subranges formed by any two values therein, etc., as well as endpoints 0 and 10.

[0062] As used herein, the term "complex" refers to a multi-component structure in which the components are connected by specific intermolecular interactions. Preferably, the complex of the present invention has a spatial network structure.

[0063] Unless otherwise indicated, all percentages mentioned herein are by weight, and all documents mentioned herein are incorporated by reference in their entirety.

[0064] II. Complex

[0065] A complex refers to a multicomponent structure formed by at least two components, wherein the components are connected by various types of intermolecular interactions. In one embodiment, the complex of the present invention has a spatial network structure, wherein the components are connected by intermolecular interactions.

[0066] The complex of the present invention is formed from at least one phenylbenzimidazole sulfonic acid, at least one hydrophilic clay, and an alkaline agent.

[0067] In a preferred embodiment, the complex of the present invention is formed from at least one phenylbenzimidazole sulfonate and at least one hydrophilic clay.

[0068] Preferably, phenylbenzimidazole sulfonate is formed from phenylbenzimidazole sulfonic acid and an alkaline agent at an appropriate pH, such as pH 6.8 to 9.0, more preferably pH 6.8 to 7.5, for example, 6.8, 6.9, 7.0, 7.1, 7.5, 8.0, 8.5, 9.0.

[0069] While not wishing to be bound by theory, it is believed that the phenylbenzimidazole sulfonate forms a complex according to the present invention with the hydrophilic clay through intermolecular interactions, such as hydrogen bonding therebetween, resulting in improved stability of the phenylbenzimidazole sulfonate, which does not recrystallize even when applied to the skin.

[0070] In a preferred embodiment, the complex has a spatial network structure.

[0071] The formation of the complex helps to improve the efficiency of UV protection. Specifically, these components (e.g., phenylbenzimidazole sulfonic acid and hydrophilic clay) can form a complex of the present invention, and the complex can have a spatial network structure. Due to the network structure and the strong intermolecular interactions between these components, these components can be stably present in the structure even if the complex system undergoes environmental changes, such as changes in environmental pH, changes in application scenarios (e.g., applying the complex to skin with a weakly acidic pH), etc. The stable network structure of the complex can prevent these components (e.g., phenylbenzimidazole sulfonic acid as a UV filter) from recrystallizing or agglomerating, thereby resulting in uniform dispersion of these components and achieving efficient and stable UV protection.

[0072] In one embodiment, the complex of the present invention is an aqueous dispersion.

[0073] In another embodiment, the aqueous dispersion can be a hydrogel.

[0074] Phenylbenzimidazole sulfonic acid

[0075] The complex according to the invention comprises at least one phenylbenzimidazolesulfonic acid of the formula I or a salt thereof.

[0076]

[0077] in

[0078] Ar is a substituted or unsubstituted phenyl group,

[0079] R is C 1-8 Alkyl or C 1-8 Alkoxy,

[0080] n is 1, 2, 3 or 4,

[0081] q is 1, 2, or 3, and

[0082] p is 0, 1 or 2.

[0083] The phenylbenzimidazolesulfonic acids of the present invention have an absorption maximum in the UV region and are therefore suitable as UV filters.

[0084] For the purposes of the present invention, it is preferred that Ar is unsubstituted phenyl, n is 1 or 2, q is 1 or 2, and p is 0.

[0085] As representative examples, the phenylbenzimidazole sulfonic acid of the present invention includes, but is not limited to, 2-phenylbenzimidazole-4-sulfonic acid, 2-phenylbenzimidazole-5-sulfonic acid, 2-phenylbenzimidazole-6-sulfonic acid, 2-phenylbenzimidazole-7-sulfonic acid, 2,2'-(1,4-phenylene)bis(1H-benzo[d]imidazole-5,7-disulfonic acid), and 2,2'-(1,4-phenylene)bis(1H-benzo[d]imidazole-4,6-disulfonic acid).

[0086] These compounds may also exist in the form of their alkali metal salts. Alkali metal salts include lithium salts, sodium salts and potassium salts, with sodium salts being particularly preferred.

[0087] Examples of commercially available products include, for example, those from Merck KgaA called 2-Phenylbenzimidazole-5-sulfonic acid, 232, from DSM Nutritional Products Ltd HS or Symrise Neo Hydro; and Symrise's Neo In a preferred embodiment, the phenylbenzimidazole sulfonic acid used in the present invention can be disodium phenyldibenzimidazole tetrasulfonate from DSM Nutritional Products Ltd. HS.

[0088] The appropriate type of phenylbenzimidazole sulfonic acid helps in the formation of the present composition, thereby helping to improve the efficiency of UV protection.

[0089] The phenylbenzimidazole sulfonic acid of formula I according to the present invention has low solubility in water and is therefore preferably neutralized with a basic agent as described below.

[0090] For the purposes of the present invention, the neutralized phenylbenzimidazole sulfonic acid or salt thereof is present in an amount of 0.1% to 10% by weight, preferably 1% to 5% by weight, relative to the total weight of the composite, for example, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.3%, 2.5%, 2.7%, 2.9%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%.

[0091] An appropriate amount of phenylbenzimidazole sulfonic acid or its salt facilitates the formation of the present complex, thereby helping to improve UV protection efficiency. Excessively low amounts of phenylbenzimidazole sulfonic acid can result in insufficient phenylbenzimidazole sulfonic acid in the present composition, making it difficult to form a complex with a uniform spatial network structure, thereby affecting the UV protection efficiency of the resulting composition.

[0092] hydrophilic clay

[0093] The composite according to the present invention comprises at least one hydrophilic clay. A single type of hydrophilic clay can be used, or a combination of two or more different types of hydrophilic clays can be used. As used herein, a hydrophilic clay refers to a clay that swells in water and forms a composite having a spatial network structure through intermolecular interactions with phenylbenzimidazole sulfonic acid. The hydrophilic clay is preferably one that swells in water to form a colloidal dispersion, particularly an aqueous dispersion. The viscosity of the aqueous dispersion will vary depending on the amount of hydrophilic clay added. In general, the viscosity will increase as the amount added increases. Preferably, the hydrophilic clay can be of synthetic origin. The hydrophilic clay used in the present invention is hectorite.

[0094] In one embodiment, hectorite is generally defined as:

[0095] [(Mg 6-x Li x )Si8O 20 (OH)4] -x R +

[0096] wherein 0.57≤x≤1.15, f≤4, and R is selected from the group consisting of Na, Li, K, NH4, and mixtures thereof.

[0097] Preferably, the hydrophilic clay used in the present invention comprises synthetic hectorite (also known as laponite), such as that produced by Laporte under the trade name XLG, RD and Products sold under the name RDS (these products are sodium magnesium silicates, in particular sodium lithium magnesium silicate).

[0098] In a preferred embodiment, the hydrophilic clay used in the present invention is sodium lithium magnesium silicate.

[0099] The presence of a suitable type of hydrophilic clay facilitates the formation of the present complex, thereby helping to improve UV protection efficiency. Without being limited by theory, sodium lithium magnesium silicate is more likely to form a complex with a spatial network structure with phenylbenzimidazole sulfonic acid than other types of hydrophilic clay, and therefore is preferably used.

[0100] For purposes of the present invention, the hydrophilic clay is present in an amount of 0.01% to 20% by weight relative to the total weight of the composite, for example, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.2%, 1.5%, 2%, 2.5%, 3%, 2.5%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%.

[0101] An appropriate amount of hydrophilic clay facilitates the formation of the complex, thereby improving UV protection. Excessive amounts of hydrophilic clay will make it difficult to form a uniform system of hydrophilic clay and phenylbenzimidazole sulfonic acid, resulting in the inability to form a uniform spatial network structure. Excessive amounts of hydrophilic clay will also prevent the formation of a spatial network structure and may lead to recrystallization of phenylbenzimidazole sulfonic acid upon application to the skin.

[0102] The ratio between phenylbenzimidazole sulfonic acid and hydrophilic clay ranges from 0.01 to 20, preferably from 0.05 to 10, and more preferably from 0.1 to 5. For example, the ratio between phenylbenzimidazole sulfonic acid and hydrophilic clay can be 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.75, 0.9, 1, 1.3, 1.5, 1.7, 1.75, 1.8, 2, 2.2, 2.25, 2.5, 2.75, 2.8, 2.9, 3, 3.25, 3.5, 3.75, 4, 5, 7, 10, 15, 20.

[0103] An appropriate ratio of phenylbenzimidazole sulfonic acid to hydrophilic clay facilitates the formation of the complex, thereby improving UV protection efficiency. A high ratio of phenylbenzimidazole sulfonic acid to hydrophilic clay prevents the formation of a spatial network structure and causes recrystallization of the phenylbenzimidazole sulfonic acid upon application to the skin. A low ratio of phenylbenzimidazole sulfonic acid to hydrophilic clay makes it difficult to form a uniform system of hydrophilic clay and phenylbenzimidazole sulfonic acid, resulting in the inability to form a uniform spatial network structure.

[0104] Alkaline reagents

[0105] For the purposes of the present invention, the phenylbenzimidazolesulfonic acid of formula I or its salt is preferably neutralized using an alkaline agent. Preferably, the complex according to the invention has a pH of 6.0 or higher, preferably a pH of 6.8 to 9.0, more preferably a pH of 6.8 to 7.5.

[0106] The alkaline reagent used in the present invention includes inorganic bases and organic bases. The inorganic base can be selected from sodium hydroxide, potassium hydroxide, carbonate, carbamate, bicarbonate, ammonium chloride and combinations thereof. The organic base can be selected from monoethanolamine, diethanolamine, triethanolamine, aminomethyl propylene glycol, 2-amino-2-methyl propanol (AMP), triisopropanolamine (TIPA), tris[(2-hydroxy)-1-propyl]amine, 2-amino-2-methyl-1,3-propanediol (AMPD), 2-amino-2-hydroxymethyl-1,3-propanediol, N-methylglucamine, amino acids and combinations thereof.

[0107] By using an alkaline agent, the pH of the complex according to the present invention can be adjusted to an appropriate range, and the phenylbenzimidazole sulfonic acid of formula I can be dissociated in water.

[0108] Preferably, the alkaline agent used in the complex according to the present invention is a basic amino acid. The basic amino acid in the present invention is not particularly limited, as long as it has an isoelectric point greater than 7. For example, the basic amino acid of the present invention is preferably selected from arginine, lysine, histidine, and combinations thereof. More preferably, arginine can be used as the alkaline agent.

[0109] The appropriate type of alkaline agent aids in the formation of the present complex, thereby helping to improve the efficiency of UV protection.

[0110] While not wishing to be bound by theory, it is believed that by using a basic amino acid as the alkaline agent, the complex of the present invention can be used to prepare cosmetic compositions having a pH of 7 or less, particularly a pH of 6.0 to 7.0, without crystallization of phenylbenzimidazole sulfonic acid.

[0111] III. Preparation Method

[0112] The preparation method of the composite defined above may include, but is not limited to, the steps of mixing at least one phenylbenzimidazole sulfonic acid or salt thereof of Formula I with at least one hydrophilic clay as defined above to form a homogeneous system, and adjusting the pH of the homogeneous system to 6.0 or higher, preferably 6.8 to 9.0, more preferably 6.8 to 7.5. Preferably, the pH is adjusted using an alkaline agent as defined above.

[0113] In a preferred embodiment, the complex of the present invention is prepared by a method comprising the following steps:

[0114] 1) dispersing at least one hydrophilic clay in water to form a dispersion;

[0115] II) forming a homogeneous system by adding at least one phenylbenzimidazole sulfonic acid of formula I or a salt thereof to the dispersion; and

[0116] III) The pH of the homogeneous system is adjusted to 6.0 or higher, preferably 6.8 to 9.0, more preferably 6.8 to 7.5, with an alkaline agent.

[0117]

[0118] in

[0119] Ar is a substituted or unsubstituted phenyl group,

[0120] R is C 1-8 Alkyl or C 1-8 Alkoxy,

[0121] n is 1, 2, 3 or 4,

[0122] q is 1, 2, or 3, and

[0123] p is 0, 1 or 2.

[0124] In step I), the hydrophilic clay is dispersed in water, and the water used can be tap water, mineral water, purified water, etc., as long as it does not affect the formation of the composite of the present invention.

[0125] The hydrophilic clay can be dispersed in water by stirring. Stirring can be performed in various ways. For example, mechanical stirring (such as paddle stirring and turbine stirring), gas stirring (such as bubbling stirring and compressed air stirring), ultrasonic stirring, magnetic stirring, etc. can be used for stirring.

[0126] In step II), phenylbenzimidazole sulfonic acid is added to the dispersion obtained in step I) to form a homogeneous system. The phenylbenzimidazole sulfonic acid can be added to the dispersion all at once or, preferably, added in portions with stirring. The homogeneous system can be obtained by stirring in the same manner as in step I) defined above. While not wishing to be bound by theory, it is believed that the formation of a homogeneous system facilitates the formation of a complex between the phenylbenzimidazole sulfonic acid salt and the hydrophilic clay.

[0127] In a preferred embodiment, the phenylbenzimidazolesulfonic acid is neutralized by a basic agent as defined above.

[0128] In step III), the alkaline agent may be added according to conventional methods.

[0129] In one embodiment, the alkaline agent may be prepared as a premix with water, and then added dropwise to the homogeneous system obtained in step II).

[0130] In another embodiment, an excess amount of a basic agent may be added to the homogeneous system obtained in step II), and then neutralized with an acidic agent to a pH of 6.0 or higher, preferably 6.8 to 9.0, more preferably 6.8 to 7.5.

[0131] As used herein, the term "acidic agent" refers to those agents that can be used to adjust the pH in cosmetics, including but not limited to hyaluronic acid, citric acid, lactic acid, and the like.

[0132] While not wishing to be bound by theory, it is believed that maintaining the pH of the homogeneous system at 6.0 or higher, preferably at a pH of 6.8 to 9.0, more preferably at a pH of 6.8 to 7.5, aids in the formation of a complex of phenylbenzimidazole sulfonate with the hydrophilic clay.

[0133] In another embodiment, step I), step II) and step III) can be performed simultaneously, separately, sequentially or in a different order.

[0134] For example, in one embodiment, the complex of the present invention is prepared by a method comprising the steps of:

[0135] a) forming an aqueous dispersion by adding at least one phenylbenzimidazole sulfonic acid of formula I or a salt thereof to water;

[0136] b) forming a homogeneous system by adding at least one hydrophilic clay to the aqueous dispersion; and

[0137] c) adjusting the pH of the homogeneous system to 6.0 or higher, preferably 6.8 to 9.0, more preferably 6.8 to 7.5, with an alkaline agent.

[0138]

[0139] in

[0140] Ar is a substituted or unsubstituted phenyl group,

[0141] R is C 1-8 Alkyl or C 1-8 Alkoxy,

[0142] n is 1, 2, 3 or 4,

[0143] q is 1, 2, or 3, and

[0144] p is 0, 1 or 2.

[0145] In step a), the phenylbenzimidazole sulfonic acid can be added to the water all at once, or preferably added in batches under stirring. The water used can be tap water, mineral water, purified water, etc., as long as it does not affect the formation of the complex of the present invention.

[0146] In a preferred embodiment, the phenylbenzimidazolesulfonic acid is neutralized with a basic agent as defined above.

[0147] In step b), the hydrophilic clay may be added to the aqueous dispersion obtained in step a) to form a homogeneous system.

[0148] The hydrophilic clay can be added to the aqueous dispersion all at once or preferably added in portions under stirring. A homogeneous system can be obtained by stirring in the same manner as in step I) defined above.

[0149] Step c) is the same as step III) defined above.

[0150] In a further embodiment, the complex of the invention is prepared by a method comprising the steps of:

[0151] a1) forming a homogeneous system by adding at least one hydrophilic clay and at least one phenylbenzimidazole sulfonic acid of formula I or a salt thereof to water; and

[0152] b1) adjusting the pH of the homogeneous system to 6.0 or higher, preferably 6.8 to 9.0, more preferably 6.8 to 7.5, with an alkaline agent.

[0153]

[0154] in

[0155] Ar is a substituted or unsubstituted phenyl group,

[0156] R is C 1-8 Alkyl or C 1-8 Alkoxy,

[0157] n is 1, 2, 3 or 4,

[0158] q is 1, 2, or 3, and

[0159] p is 0, 1 or 2.

[0160] In step a1), the hydrophilic clay and phenylbenzimidazole sulfonic acid are added to water all at once, or preferably added in batches with stirring. A homogeneous system can be obtained by stirring in the same manner as in step I) defined above.

[0161] Step c) is the same as step III) defined above.

[0162] Although the preparation method has been described in conjunction with several preferred embodiments, various modifications can be applied to the preparation method defined above, as long as a uniform system containing phenylbenzimidazole sulfonate and hydrophilic clay can be formed and the pH of the uniform system is maintained at 6.0 or higher, preferably at a pH of 6.8 to 9.0, more preferably at a pH of 6.8 to 7.5. These modified methods are also encompassed within the scope of the present invention.

[0163] IV. Cosmetic Compositions

[0164] The cosmetic composition according to the invention comprises a complex as defined above and further ingredients.

[0165] The cosmetic composition may be in solid, semi-solid, or liquid form, and may be in solution, emulsion, suspension, or anhydrous form. If in solution or suspension form, the composition may contain from about 1% to 99.9%, preferably from about 5% to 95%, and more preferably from about 10% to 90% water. If in emulsion form, the composition may contain from about 1% to 99%, preferably from about 5% to 90%, and more preferably from about 10% to 85% water, and from about 1% to 99%, preferably from about 5% to 90%, and more preferably from about 5% to 75% oil. If in anhydrous form, the composition may contain from about 10% to 99% oil and from 10% to 99% solidifying agent.

[0166] The cosmetic composition can be a skin care product, such as face, hand and foot care products; acne treatment products, shaving products, cleansing products; powders, antiperspirants; hair removal products, makeup products (such as primer, foundation, eye shadow, eyeliner, blush); sunscreen products, etc.

[0167] In one embodiment, the complex is present in the cosmetic composition in an amount of 0.01% to 50%, more preferably 0.05% to 20%, more preferably 0.1% to 10% by weight of phenylbenzimidazole sulfonic acid relative to the total weight of the composition.

[0168] The cosmetic composition may contain other ingredients, such as additives, excipients, diluents and / or other active ingredients, including but not limited to those described herein, as long as the stability of the phenylbenzimidazole salt is not affected and the beneficial effect of not recrystallizing even when applied to the skin is not achieved.

[0169] A. Moisturizer

[0170] The compositions of the present invention may contain one or more humectants. If present, the range may be from about 0.1% to 75%, preferably from about 0.5% to 70%, more preferably from about 0.5% to 40%. Examples of suitable humectants include glycols, sugars, and the like. Suitable glycols are in monomeric or polymeric form and include polyethylene glycol and polypropylene glycol, such as PEG4-10, which is a polyethylene glycol having 4 to 10 repeating ethylene oxide units; and C 1-6 Alkylene glycols, such as propylene glycol, butylene glycol, pentylene glycol, etc. Suitable sugars (some of which are also polyols) are also suitable humectants. Examples of such sugars include glucose, fructose, honey, hydrogenated honey, inositol, maltose, mannitol, maltitol, sorbitol, sucrose, xylitol, xylose, etc. Urea is also suitable. Preferably, the humectant used in the composition of the present invention is C 1-6 Alkylene glycol, preferably C 2-4 Alkylene glycol, most particularly butanediol.

[0171] B. Plant extracts

[0172] The composition of the present invention may contain one or more plant extracts. If present, the recommended range is about 0.0001% to 20%, preferably about 0.0005% to 15%, and more preferably about 0.001% to 10%. Suitable plant extracts include extracts from plants (herbs, rhizomes, flowers, fruits, seeds), such as flowers, fruits, vegetables, etc., including yeast fermentation extract, Padina pavonica extract, Thermus thermophilis fermentation extract, Camelina sativa seed oil, Boswellia serrata extract, olive extract, Acacia dealbata extract, Acersaccharinum (sugar maple) extract, Acidopholus, Acorus, Aesculus, Agaricus, Agave, Agrimonia, algae, aloe, citrus, Brassica, cinnamon, orange, apple, blueberry, cranberry, peach, pear, lemon, lime, pea, seaweed, caffeine, green tea, chamomile, willow bark, mulberry, and those described in the CTFA Cosmetic Ingredient Handbook, 8th edition, volume 2, pages 1646 to 1660.More specific examples include, but are not limited to, licorice (Glycyrrhiza glabra), black willow (Salix nigra), giant kelp (Macrocycstis pyrifera), apple (Pyrus malus), strawberry saxifrage (Saxifraga sarmentosa), grape (Vitis vinifera), black mulberry (Morus nigra), skullcap (Scutellaria baicalensis), Roman chamomile (Anthemis nobilis), clary sage (Salvia sclarea), rosemary (Rosmarinus officinalis), lemon (Citrus limonum), ginseng (Panax ginseng), Siegesbeckia orientalis, black plum (Fructus mume), ascophyllum (Ascophyllum nodosum), wild soybean (Glycinesoja) extract, beet (Beta vulgaris), Balkan lettuce (Haberlea rhodopensis), Japanese knotweed (Polygonum cuspidatum) Cuspidatum), sweet orange (Citrus aurantium dulcis), grape (Vitis vinifera), Selaginella (Selaginella tamariscina), hops (Humulus lupulus), citrus peel (Citrus reticulata Peel), pomegranate (Punica granatum), key-shaped hair algae (Asparagopsis), turmeric (Curcumalonga), waterweed (Menyanthes trifoliata), sunflower (Helianthus annuus), barley (Hordeum vulgare), cucumber (Cucumissa tivus), oak moss (Evernia prunastri), tree moss (Evernia furfuracea), kola nut (Kola acuminata), and mixtures thereof.

[0173] C. Surfactants

[0174] The compositions of the present invention may contain one or more surfactants, especially if in emulsion form. However, such surfactants may also be used if the composition is a solution, suspension, or anhydrous. If present, the surfactant may comprise from about 0.01% to 30%, preferably from about 0.05% to 25%, and more preferably from about 0.1% to 20%, by weight of the total composition. Suitable surfactants may be silicone or organic, nonionic, anionic, amphoteric, or zwitterionic.

[0175] 1. Organic nonionic surfactants

[0176] The composition of the present invention may contain one or more nonionic organic surfactants. Suitable nonionic surfactants include alkoxylated alcohols or ethers formed by the reaction of an alcohol with an alkylene oxide (usually ethylene oxide or propylene oxide). Suitable alcohols include mono-, di- or polybasic short chain (C 1-6 ) alcohol; aromatic or aliphatic saturated or unsaturated fat (C 12-40 ) alcohol, or cholesterol; etc.

[0177] Cholesterol is suitable, as are aromatic or aliphatic saturated or unsaturated fatty alcohols having from 6 to 40, preferably from about 10 to 30, and more preferably from about 12 to 22 carbon atoms. Examples include oleyl alcohol, cetearyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, and the like. Examples of such ingredients include oleth 2-100; steareth 2-100; beheneth 5-30; ceteareth 2-100; ceteth 2-100; cholesterol 2-100, where the numerical range refers to the number of repeating ethylene oxide units, for example, ceteth 2-100 refers to ceteth having a number of repeating ethylene oxide units ranging from 2 to 100. Derivatives of alkoxylated alcohols are also suitable, such as phosphate esters thereof.

[0178] Some preferred organic nonionic surfactants include oleth-3, oleth-5, oleth-3 phosphate, cholesterol-24, ceteth-24, and the like.

[0179] Alkoxylated alcohols formed with monohydric, dihydric, or polyhydric short-chain alcohols (e.g., those having about 1 to 6 carbon atoms) are also suitable. Examples include glucose, glycerol, or alkylated derivatives thereof. Examples include glycereth 2-100, glycoceth 2-100, methyl glycoceth 2-100, and the like. More preferred are methyl glycoceth-20, glycereth-26, and the like.

[0180] Other types of alkoxylated alcohols are suitable surfactants including ethylene oxide polymers with varying numbers of repeating EO groups, commonly known as PEG 12 to 200. More preferred is PEG-75, which is commercially available from Dow Chemical under the tradename Carbowax PEG-3350.

[0181] Other suitable nonionic surfactants include alkoxylated sorbitan and alkoxylated sorbitan derivatives. For example, alkoxylation of sorbitan, particularly ethoxylation, provides polyalkoxylated sorbitan derivatives. Esterification of polyalkoxylated sorbitan provides sorbitan esters, such as polysorbates. For example, the polyalkoxylated sorbitan can be prepared using C 6-30 Fatty acids, preferably C 12-22 Fatty acid esterification. Examples of such ingredients include polysorbate 20-85, sorbitan oleate, sorbitan sesquioleate, sorbitan palmitate, sorbitan sesquiisostearate, sorbitan stearate, and the like.

[0182] 2. Silicone or silane surfactants

[0183] Various types of silicone or silane based surfactants are also suitable. Examples include organosiloxanes substituted with ethylene oxide or propylene oxide groups, such as PEG dimethicone, which is a dimethicone substituted with polyethylene glycol, including those having the INCI names PEG-1 Dimethicone; PEG-4 Dimethicone; PEG-8 Dimethicone; PEG-12 Dimethicone; PEG-20 Dimethicone; and the like.

[0184] Silanes substituted with ethoxy groups or propoxy groups, or both, are also suitable, such as the various types of PEG methyl ether silanes, such as bis-PEG-18 methyl ether dimethyl silane and the like.

[0185] Further examples of silicone-based surfactants include those having the common names dimethicone copolyol; cetyl dimethicone copolyol, and the like.

[0186] D. Biomaterials

[0187] The compositions of the present invention may contain various types of biological materials, such as those derived from cells, fermented materials, and the like. If present, such materials may range from about 0.001% to 30%, preferably from about 0.005% to 25%, and more preferably from about 0.01% to 20%. Examples include fragments of cellular RNA or DNA, or probiotic microorganisms. RNA fragments are particularly preferred.

[0188] E.Thickener

[0189] Unlike the hydrophilic clays that form a complex with a spatial network structure with phenylbenzimidazole sulfonic acid as described above, hydrophilic clays are also widely used as thickeners in the cosmetics field. However, in addition to the hydrophilic clays of the present invention, thickeners may be incorporated into the compositions of the present invention. Any thickener may be added as long as it does not interfere with the formation of a complex with a spatial network structure between the hydrophilic clay and phenylbenzimidazole sulfonic acid. Suitable thickeners may be incorporated into the compositions of the present invention. If present, the recommended range is from about 0.01% to 30%, preferably from about 0.1% to 20%, and more preferably from about 0.5% to 15%, by weight of the total composition.

[0190] Examples of thickeners include animal, vegetable, mineral, silicone, or synthetic waxes, which may have a melting point between about 30°C and 150°C. Examples of such waxes include, but are not limited to, waxes made by Fischer-Tropsch synthesis, such as polyethylene or synthetic waxes; or various plant waxes, such as bayberry, candelilla, ozokerite, gum arabic, beeswax, ceresin, cetyl esters, flower waxes, citrus waxes, carnauba wax, jojoba wax, Japan wax, polyethylene, microcrystalline, rice bran, lanolin wax, mink wax, montan wax, bayberry, ouricury, ozokerite, palm kernel wax, paraffin wax, avocado wax, apple wax, shellac wax, clary wax, spent grain wax, grape wax, and polyalkylene glycol derivatives thereof (e.g., PEG 6-20 beeswax or PEG-12 carnauba wax); or fatty acids or fatty alcohols (including esters thereof), such as hydroxystearic acid (e.g., 12-hydroxystearic acid), glyceryl tristearate, glyceryl tribehenate, and the like.

[0191] Also suitable as thickeners are silicon dioxide, silicates, silicon silylate, and alkali metal or alkaline earth metal derivatives thereof. These silicon dioxides and silicates are typically found in particulate form and include silicon dioxide, silicon silylate, magnesium aluminum silicate, and the like.

[0192] Silicone elastomers can also be used as thickeners. Such elastomers include those formed by addition reaction-curing, by reacting a SiH-containing diorganosiloxane and an organopolysiloxane having terminal ethylenic unsaturation or an α-ω diene in the presence of a platinum metal catalyst. Such elastomers can also be formed by other reaction methods, such as condensation-curing organopolysiloxane compositions via a dehydrogenation reaction between a hydroxyl-terminated diorganopolysiloxane and a SiH-containing diorganopolysiloxane or an α-ω diene in the presence of an organotin compound; or condensation-curing organopolysiloxane compositions using a condensation reaction between a hydroxyl-terminated diorganopolysiloxane and a hydrolyzable organosiloxane in the presence of an organotin compound or a titanate; or peroxide-curing organopolysiloxane compositions that are thermally cured in the presence of an organic peroxide catalyst.

[0193] One type of elastomer that may be suitable is prepared by addition reaction-curing an organopolysiloxane or α-ω diene having at least two lower alkenyl groups in each molecule; and an organopolysiloxane having at least two silicon-bonded hydrogen atoms in each molecule; and a platinum-based catalyst. Although the lower alkenyl groups (e.g., vinyl) may be present anywhere in the molecule, terminal ethylenic unsaturation is preferred at one or both molecular ends. The molecular structure of this component may be linear, branched linear, cyclic, or network. These organopolysiloxanes are exemplified by methylvinylsiloxane, methylvinylsiloxane-dimethylsiloxane copolymer, dimethylvinylsiloxy-terminated dimethylpolysiloxane, dimethylvinylsiloxy-terminated dimethylsiloxane-methylphenylsiloxane copolymer, dimethylvinylsiloxy-terminated dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymer, trimethylsiloxy-terminated dimethylsiloxane-methylvinylsiloxane copolymer, and trimethylsiloxy-terminated dimethylsiloxane-methylphenylsiloxane-methylvinylsiloxane copolymer, dimethylvinylsiloxy-terminated methyl (3,3,3-trifluoropropyl) polysiloxane and dimethylvinylsiloxy-terminated dimethylsiloxane-methyl (3,3,-trifluoropropyl) siloxane copolymer, decadiene, octadiene, heptadiene, hexadiene, pentadiene, or butadiene (tetradiene) or propadiene (tridiene).

[0194] Curing occurs through an addition reaction of the silicon-bonded hydrogen atoms in dimethylmethylhydrogensiloxane with siloxane or α-ω diene, catalyzed by the catalysts mentioned herein. To form a highly crosslinked structure, the methylhydrogensiloxane must contain at least two silicon-bonded hydrogen atoms per molecule to optimize its function as a crosslinker.

[0195] Catalysts for the addition reaction of silicon-bonded hydrogen atoms with alkenyl groups are specifically exemplified by chloroplatinic acid (possibly dissolved in an alcohol or ketone and this solution optionally aged), chloroplatinic acid-olefin complexes, chloroplatinic acid-alkenylsiloxane complexes, chloroplatinic acid-diketone complexes, platinum black, and supported platinum.

[0196] Examples of suitable silicone elastomers for use in the compositions of the present invention may be in powder form, or dispersed or dissolved in a solvent, such as a volatile or non-volatile silicone, or a silicone-compatible medium, such as an alkane or ester. Examples of silicone elastomer powders include vinyl dimethicone / methicone silsesquioxane crosspolymers, such as Shin-Etsu's KSP-100, KSP-101, KSP-102, KSP-103, KSP-104, KSP-105; hybrid silicone powders containing fluoroalkyl groups, such as Shin-Etsu's KSP-200, which is a fluorosilicone elastomer; and hybrid silicone powders containing phenyl groups, such as Shin-Etsu's KSP-300, which is a phenyl-substituted silicone elastomer; and Dow Corning's DC 9506. Examples of silicone elastomer powders dispersed in a silicone-compatible medium include dimethicone / vinyl dimethicone crosspolymers available from various suppliers, including Dow Corning Corporation under the trade names 9040 or 9041, GE Silicones under the trade name SFE 839, or Shin-Etsu Silicones under the trade names KSG-15, KSG-16, and KSG-18. KSG-15 has the CTFA name Cyclopentasiloxane / Dimethicone / Vinyl Dimethicone Crosspolymer. KSG-18 has the INCI name Phenyl Trimethicone / Dimethicone / Phenyl Vinyl Dimethicone Crosspolymer. Silicone elastomers can also be purchased from Grant Industries under the Gransil trademark. Silicone elastomers having long chain alkyl substitutions are also suitable, such as lauryl dimethicone / vinyl dimethicone crosspolymer, which is supplied by Shin Etsu under the trade names KSG-31, KSG-32, KSG-41, KSG-42, KSG-43, and KSG-44. The crosslinked organopolysiloxane elastomers used in the present invention and methods for preparing the same are further described in U.S. Patent No. 4,970,252, issued to Sakuta et al. on November 13, 1990, U.S. Patent No. 5,760,116, issued to Kilgour et al. on June 2, 1998, U.S. Patent No. 5,654,362, issued to Schulz, Jr. et al. on August 5, 1997, and Japanese Patent Application No. 61-18708, assigned to Pola Kasei Kogyo KK, each of which is incorporated herein by reference in its entirety.

[0197] Polysaccharides can be suitable aqueous phase thickening agents. Examples of such polysaccharides include naturally derived materials such as agar, agarose, Alcaligenes polysaccharide, algin, alginic acid, gum arabic, pullulan, chitin, dextran, cassia gum, cellulose gum, gelatin, gellan gum, hyaluronic acid, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, pectin, sclerotium gum, xanthan gum, pectin, trehalose, gelatin, and the like.

[0198] Different types of synthetic polymer thickeners are also suitable. One type includes acrylic polymer thickeners composed of monomers A and B, wherein A is selected from acrylic acid, methacrylic acid and mixtures thereof; and B is selected from acrylic acid, C 1-22 Alkyl ester, methacrylate C 1-22 Alkyl esters and mixtures thereof are suitable. Acrylic polymer solutions include those sold by Seppic, Inc. under the trade name Those sold or under the trade name Those that are sold.

[0199] Also suitable are acrylic polymer thickeners that are copolymers of A, B, and C monomers, wherein A and B are as defined above, and C has the general formula:

[0200]

[0201] Where Z is -(CH2) m ; wherein m is 1 to 10, n is 2 to 3, o is 2 to 200, and R is C 10 - 30 Straight or branched chain alkyl groups. Examples of the above secondary thickeners are copolymers wherein A and B are as defined above, and C is CO, and wherein n, o, and R are as defined above. Examples of such secondary thickeners include acrylates / steareth-20 methacrylate copolymer, which is sold under the trade name Acrysol ICS-1 by Rohm & Haas.

[0202] Also suitable are anionic amphiphilic polymers based on acrylates containing at least one hydrophilic unit and at least one allyl ether unit containing a fatty chain. Preference is given to those in which the hydrophilic unit contains an ethylenically unsaturated anionic monomer, more particularly a vinyl carboxylic acid (e.g. acrylic acid, methacrylic acid or a mixture thereof), and in which the allyl ether unit containing a fatty chain corresponds to a monomer of the formula:

[0203] CH2=CR'CH2OB n R

[0204] wherein R' represents H or CH3, B represents an ethylenoxy group, n is 0 or an integer ranging from 1 to 100, R represents a hydrocarbon radical chosen from alkyl, arylalkyl, aryl, alkylaryl and cycloalkyl radicals, containing 8 to 30 carbon atoms, preferably 10 to 24 and even more particularly 12 to 18 carbon atoms. More preferred in this case are wherein R' represents H, n is equal to 10 and R represents a stearyl (C 18 ) group. This type of anionic amphiphilic polymer is described and prepared in U.S. Patent Nos. 4,677,152 and 4,702,844. Both of which are hereby incorporated by reference in their entirety. In these anionic amphiphilic polymers, the polymer is formed by 20% to 60% by weight of acrylic acid and / or methacrylic acid, 5% to 60% by weight of lower alkyl methacrylate, 2% to 50% by weight of allyl ether containing a fatty chain as mentioned above, and 0 to 1% by weight of a cross-linking agent, the cross-linking agent being a well-known copolymerizable polyethylenic unsaturated monomer, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate, and methylenebisacrylamide. A commercial example of this type of polymer is a crosslinked terpolymer of methacrylic acid, ethyl acrylate, polyethylene glycol ether of stearyl alcohol (having 10 EO units) or Steareth-10, in particular those sold under the names SALCARE SC80 and SALCARE SC90 by the company Allied Colloids, which are aqueous emulsions containing 30% of a crosslinked terpolymer of methacrylic acid, ethyl acrylate and Steareth-10 allyl ether (40 / 50 / 10).

[0205] Also suitable are acrylate copolymers, such as Polyacrylate-3, which is a copolymer of methacrylic acid, methyl methacrylate, methylstyrene isopropyl isocyanate, and PEG-40 behenate monomers; Polyacrylate-10, which is a copolymer of sodium acryloyldimethyltaurate, sodium acrylate, acrylamide, and vinylpyrrolidone monomers; or Polyacrylate-11, which is a copolymer of sodium acryloyldimethacryloyldimethyltaurate, sodium acrylate, hydroxyethyl acrylate, lauryl acrylate, butyl acrylate, and acrylamide monomers.

[0206] Also suitable are cross-linked acrylate-based polymers in which one or more acrylic groups may have substituted long chain alkyl (e.g., 6 to 40, 10 to 30, etc.) groups, such as acrylate / acrylic acid C 10-30 Alkyl ester crosspolymer of acrylic acid C 10-30Copolymers of alkyl esters and one or more monomers of acrylic acid, methacrylic acid or one of their simple esters crosslinked with an allyl ether of sucrose or an allyl ether of pentaerythritol. Such polymers are commonly sold under the trade names Carbopol or Pemulen and have the CTFA name carbomer.

[0207] One particularly suitable type of aqueous phase thickener is the acrylate-based polymeric thickener sold by Clariant under the trademark Aristoflex, such as Aristoflex AVC, which is ammonium acryloyldimethyltaurate / VP copolymer; Aristoflex AVL, which is the same polymer found in AVC dispersed in a mixture containing caprylic / capric triglyceride, trilaureth-4, and polyglyceryl-2 sesquiisostearate; or Aristoflex HMB, which is ammonium acryloyldimethyltaurate / beheneth-25 methacrylate crosspolymer, and the like.

[0208] Also suitable as thickening agents are various polyethylene glycol (PEG) derivatives with a degree of polymerization ranging from 1,000 to 200,000. Such ingredients are designated by the name "PEG" followed by the degree of polymerization in thousands, for example, PEG-45M, which means PEG having 45,000 repeating ethylene oxide units. Examples of suitable PEG derivatives include PEG 2M, 5M, 7M, 9M, 14M, 20M, 23M, 25M, 45M, 65M, 90M, 115M, 160M, 180M, and the like.

[0209] Also suitable are polyglycerols that are repeating glycerol moieties, wherein the number of repeating moieties ranges from 15 to 200, preferably from about 20 to 100. Examples of suitable polyglycerols include those having the CTFA designations Polyglycerol-20, Polyglycerol-40, and the like.

[0210] F. Oil

[0211] In the case where the composition of the present invention is in the form of an emulsion, the composition will contain an oil phase. Oily ingredients are desirable due to their skin moisturizing and protective properties. Suitable oils include silicones, esters, vegetable oils, synthetic oils, including but not limited to those described herein. The oil can be volatile or non-volatile, and is preferably in the form of a pourable liquid at room temperature. The term "volatile" means that the oil has a measurable vapor pressure or a vapor pressure of at least about 2 mm of mercury at 20°C. The term "non-volatile" means that the oil has a vapor pressure of less than about 2 mm of mercury at 20°C.

[0212] 1. Volatile oils

[0213] Suitable volatile oils generally have a viscosity of about 0.5 to 5 centistokes at 25°C and include linear silicones, cyclic silicones, paraffins, or mixtures thereof.

[0214] (a). Volatile silicone:

[0215] Cyclic silicones are one type of volatile silicone that can be used in the composition. Such silicones have the following general formula:

[0216]

[0217] wherein n=3-6, preferably 4, 5 or 6.

[0218] Also suitable are linear volatile silicones, for example, those having the general formula:

[0219] (CH3)3Si─O─[Si(CH3)2─O] n ─Si(CH3)3

[0220] wherein n=0, 1, 2, 3, 4 or 5, preferably 0, 1, 2, 3 or 4.

[0221] Cyclic and linear volatile silicones are available from a variety of commercial sources, including Dow Corning Corporation and General Electric. Dow Corning linear volatile silicones are sold under the trade names Dow Corning 244, 245, 344, and 200 fluids. These fluids include hexamethyldisiloxane (viscosity 0.65 centistokes (abbreviated cst)), octamethyltrisiloxane (1.0 cst), decamethyltetrasiloxane (1.5 cst), dodecamethylpentasiloxane (2 cst), and mixtures thereof, all viscosities being measured at 25°C.

[0222] Suitable branched chain volatile silicones include alkyl trimethicone, such as methyl trimethicone. Branched chain volatile silicones have the following general formula:

[0223]

[0224] Methyl trimethicone is commercially available from Shin-Etsu Silicones under the tradename TMF-1.5 and has a viscosity of 1.5 centistokes at 25°C.

[0225] (b) Volatile alkanes

[0226] Various straight or branched chain alkanes having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms, more preferably 8 to 16 carbon atoms, are also suitable as volatile oils. Suitable hydrocarbons include pentane, hexane, heptane, decane, dodecane, tetradecane, tridecane and C 8-20 Isoparaffins, as disclosed in US Pat. Nos. 3,439,088 and 3,818,105, both of which are hereby incorporated by reference.

[0227] Preferred volatile paraffins have a molecular weight of 70-225, preferably 160 to 190, and a boiling point range of 30°C to 320°C, preferably 60°C to 260°C, and a viscosity of less than about 10 cSt at 25°C. Such paraffins are available from EXXON under the trademark ISOPARS, and from Permethyl Corporation. Suitable C 12 Isoparaffins are manufactured by Permethyl Corporation under the trade name Permethyl 99A. Various commercially available C 16 Isoparaffins such as isohexadecane (having the trade name Permethyl R) are also suitable.

[0228] 2. Non-volatile oil

[0229] Various non-volatile oils are also suitable for use in the compositions of the present invention. Non-volatile oils generally have a viscosity greater than about 5-10 centipoise at 25°C and may have a viscosity range of up to about 1,000,000 centipoise at 25°C. Examples of non-volatile oils include, but are not limited to:

[0230] (a) Esters

[0231] Suitable esters are monoesters, diesters and triesters. The present composition may comprise one or more esters selected from this group or a mixture thereof.

[0232] (i) Monoester

[0233] Monoesters are defined as esters formed by the reaction of a monocarboxylic acid of the formula R—COOH (wherein R is a linear or branched, saturated or unsaturated alkyl group having from 2 to 45 carbon atoms, or a phenyl group) and an alcohol of the formula R—OH (wherein R is a linear or branched, saturated or unsaturated alkyl group having from 2 to 30 carbon atoms, or a phenyl group). Both the alcohol and the acid may be substituted with one or more hydroxyl groups. One or both of the acid or alcohol may be a "fatty" acid or alcohol and may have from about 6 to 30 carbon atoms, more preferably 12, 14, 16, 18 or 22 carbon atoms, in a linear or branched, saturated or unsaturated form. Examples of monoester oils useful in the compositions of the present invention include hexyl laurate, butyl isostearate, cetyl isostearate, cetyl palmitate, isostearyl neopentanoate, stearyl heptanoate, isostearyl isononanoate, stearyl lactate, stearyl octanoate, stearyl stearate, isononyl isononanoate, and the like.

[0234] (ii) Diesters

[0235] Suitable diesters are reaction products of dicarboxylic acids and aliphatic or aromatic alcohols, or aliphatic or aromatic alcohols having at least two substituted hydroxyl groups and monocarboxylic acids. The dicarboxylic acid may contain 2 to 30 carbon atoms and may be straight or branched, saturated or unsaturated. The dicarboxylic acid may be substituted with one or more hydroxyl groups. The aliphatic or aromatic alcohol may also contain 2 to 30 carbon atoms and may be straight or branched, saturated or unsaturated. Preferably, the one or more acids or alcohols are fatty acids or fatty alcohols, i.e., contain 12-22 carbon atoms. The dicarboxylic acid may also be an alpha hydroxy acid. The ester may also be in the form of a dimer or trimer. Examples of diester oils useful in the compositions of the present invention include diisostearyl malate, neopentyl glycol dioctanoate, dibutyl sebacate, dicetearyl dimer dimer linoleate, dicetyl adipate, diisocetyl adipate, diisononyl adipate, diisostearyl dimer linoleate, diisostearyl fumarate, diisostearyl malate, dioctyl malate, and the like.

[0236] (iii) Triesters

[0237] Suitable triesters include tricarboxylic acids and aliphatic or aromatic alcohols, or alternatively the reaction products of aliphatic or aromatic alcohols with monocarboxylic acids having three or more substituted hydroxyl groups. As with the monoesters and diesters mentioned above, the acid and alcohol contain 2 to 30 carbon atoms and may be saturated or unsaturated, straight or branched and may be substituted with one or more hydroxyl groups. Preferably, one or more of the acids or alcohols are fatty acids or alcohols containing 12 to 22 carbon atoms. Examples of triesters include esters of arachidonic acid, citric acid or behenic acid, such as triarachidin, tributyl citrate, triisostearyl citrate, tri-C citrate, and the like. 12-13Alkyl esters, tricaprylin, trioctyl citrate, tridecyl behenate, tri(octyldodecanol) citrate, tridecyl behenate; or tridecyl cocoate, tridecyl isononanoate, etc.

[0238] Esters suitable for use in the compositions of the present invention are further described in the CTFA Cosmetic Ingredient Dictionary and Handbook, 11th Edition, 2006, under the category "Esters," the text of which is hereby incorporated by reference in its entirety.

[0239] (b) Hydrocarbon oil

[0240] It may be desirable to incorporate one or more non-volatile hydrocarbon oils into the compositions of the present invention. Suitable non-volatile hydrocarbon oils include paraffins and olefins, preferably those having greater than about 20 carbon atoms. Examples of such hydrocarbon oils include C 24-28 Olefins, C 30-45 Olefins, C 20-40 Isoparaffins, hydrogenated polyisobutene, polyisobutene, polydecene, hydrogenated polydecene, mineral oil, pentahydrosqualene, squalene, squalane, and mixtures thereof In a preferred embodiment, such hydrocarbons have a molecular weight ranging from about 300 to 1000 Daltons.

[0241] (c) Glycerides of fatty acids

[0242] Synthetic or naturally occurring glycerides or triglycerides of fatty acids are also suitable for use in the composition. Both plant and animal sources can be used. Examples of such oils include castor oil, lanolin oil, C 10-18 Triglycerides, caprylic / capric / triglycerides, sweet almond oil, apricot kernel oil, sesame oil, camelina sativa oil, tamanu seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, ink oil, olive oil, palm oil, illipe butter, rapeseed oil, soybean oil, grapeseed oil, sunflower seed oil, walnut oil, etc.

[0243] Synthetic or semi-synthetic glycerides are also suitable, such as fatty acid mono-, di-, and triglycerides, which are modified natural fats or oils, such as mono-, di-, or triesters of polyols such as glycerol. 12-22) carboxylic acid reacted with one or more repeating glyceryl groups. Glyceryl stearate, diglyceryl diisostearate, polyglyceryl-3 isostearate, polyglyceryl-4 isostearate, polyglyceryl-6 ricinoleate, glyceryl dioleate, diisostearate, glyceryl tetraisostearate, tricaprylin, distearate, linoleic acid, glyceryl myristate, isostearate, PEG castor oils, PEG glyceryl oleates, PEG glyceryl stearates, PEG glyceryl tallowates, and the like.

[0244] (d) Non-volatile silicone

[0245] Non-volatile silicone oils (both water-soluble and non-water-soluble) are also suitable for use in the composition. Such silicones preferably have a viscosity at 25°C ranging from about greater than 5 to 800,000 cSt, preferably 20 to 200,000 cSt. Suitable non-water-soluble silicones include amine-functional silicones, such as amodimethicone.

[0246] For example, such non-volatile silicones may have the following general formula:

[0247]

[0248] Where R and R 1 Each is independent of C 1-30 linear or branched, saturated or unsaturated alkyl, phenyl or aryl, trialkylsiloxy, and x and y are each independently 1-1,000,000; provided that at least one of x or y is present and A is an alkylsiloxy end-capping unit. Preferred are those wherein A is a methylsiloxy end-capping unit, especially trimethylsiloxy, and R and R 1 Each is independent of C 1-30 Straight or branched alkyl, phenyl or trimethylsilyloxy, more preferably C 1-22 Alkyl, phenyl or trimethylsiloxy, most preferably methyl, phenyl or trimethylsiloxy, and the resulting silicone is polydimethylsiloxane, phenyl polydimethylsiloxane, diphenyl polydimethylsiloxane, phenyl polytrimethylsiloxane or trimethylsiloxyphenyl polydimethylsiloxane. Other examples include alkyl polydimethylsiloxanes, such as cetyl polydimethylsiloxane, etc., in which at least one R is a fatty alkyl group (C 12 、C 14 、C 16 、C 18 、C 20 or C 22), and the other R is methyl, and A is a trimethylsiloxy end-capping unit, provided that such alkyl dimethicone is a pourable liquid at room temperature. Phenyl trimethicone is commercially available from Dow Corning Corporation under the trade name 556 Fluid. Trimethylsiloxyphenyl dimethicone is commercially available from Wacker-Chemie under the trade name PDM-1000. Cetyl dimethicone (also known as liquid silicone wax) is commercially available from Dow Corning as Fluid 2502 or from DeGussa Care & Surface Specialties under the trade name Abil Wax 9801 or 9814.

[0249] G.UV filters

[0250] In the compositions of the present invention, it may be desirable to include one or more UV filters in addition to the phenylbenzimidazole sulfonic acid of Formula I or a salt thereof. Such UV filters include chemical UVA or UVB filters, or physical filters in particulate form. Including filters in compositions containing whitening active ingredients provides additional protection to the skin during daylight hours and enhances the effectiveness of the whitening active ingredient on the skin.

[0251] 1. UVA chemical filters

[0252] If desired, the composition may contain one or more UVA filters. Preferred UVA filters are dibenzoylmethane compounds of the formula:

[0253]

[0254] Where R1 is H, OR and NRR, wherein each R is independently H, C 1-20 Straight or branched alkyl; R2 is H or OH; and R3 is H, C 1-20 Straight-chain or branched-chain alkyl.

[0255] Preferred are those wherein R1 is OR, wherein R is C 1-20 Straight or branched alkyl, preferably methyl; R2 is H; and R3 is C 1-20 A straight-chain or branched alkyl group, more preferably a butyl group.

[0256] Examples of suitable UVA filter compounds of this general formula include 4-methyldibenzoylmethane, 2-methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane, 2,4-dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane, 4,4'-diisopropylbenzoylmethane, 4-tert-butyl-4'-methoxydibenzoylmethane, 4,4'-diisopropylbenzoylmethane, 2-methyl-5-isopropyl-4'-methoxydibenzoylmethane, 2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane, etc. Particularly preferred is 4-tert-butyl-4'-methoxydibenzoylmethane, which is also known as Avobenzone. Avobenzone is available from Givaudan-Roure under the trademark Purchased in 1789 from Merck & Co. under the trade name Purchased at 9020.

[0257] Other types of UVA filters include dicamphorsulfonic acid derivatives such as ecamsule, a The filter agent sold is terephthalylidene dicamphorsulfonic acid, having the formula:

[0258]

[0259] In a preferred embodiment of the present invention, the UVA filter is Avobenzone and is present at no more than about 10% by weight of the total composition.

[0260] 2. UVB chemical filters

[0261] In addition to phenylbenzimidazole sulfonic acid or salts thereof of formula I as defined above, there are various UVB chemical filters including α-cyano-β,β-diphenylacrylates, as described in U.S. Patent No. 3,215,724, which is hereby incorporated by reference in its entirety. A specific example of an α-cyano-β,β-diphenylacrylate is Octocrylene, i.e., 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. In some cases, no more than about 10% of the weight of the total composition of Octocrylene may be included in the composition. A suitable amount ranges from about 0.1% to 10% by weight. Octocrylene is available from BASF under the trade name N-539 purchased.

[0262] Other suitable filters include benzylidene camphor derivatives, such as those described in U.S. Pat. No. 3,781,417, which is hereby incorporated by reference in its entirety. Such benzylidene camphor derivatives have the following general formula:

[0263]

[0264] wherein R is p-tolyl or styryl, preferably styryl. Particularly preferred is 4-methylbenzylidenecamphor, a fat-soluble UVB filter compound sold under the trade name Eusolex 6300 by Merck.

[0265] Also suitable are cinnamate derivatives of the general formula:

[0266]

[0267] Where R and R1 are each independently C 1-20 Straight or branched alkyl. Preferably, R is methyl, R1 is a branched C 1-10 Alkyl, preferably C8 alkyl. The preferred compound is ethylhexyl methoxycinnamate, also known as Octoxinate or octyl methoxycinnamate. This compound is available from Givaudan Corporation under the trade name MCX, or from BASF under the trade name MC 80 purchased.

[0268] Also suitable are the monoethanolamine, diethanolamine and triethanolamine derivatives of such methoxycinnamate, including diethanolamine methoxycinnamate, and cinoxate (an aryl ether derivative of the above compounds) is also acceptable. If present, cinoxate should be found in an amount not exceeding about 3% by weight of the total composition.

[0269] Also suitable as UVB screening agents are various benzophenone derivatives of the general formula:

[0270]

[0271] Wherein R to R9 are each independently H, OH, NaO3S, SO3H, SO3Na, CI, R", OR", wherein R" is C 1-20 Straight-chain or branched alkyl groups. Examples of such compounds include benzophenones 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12. Particularly preferred are benzophenone derivatives such as benzophenone 3 (also known as oxybenzone), benzophenone 4 (also known as sulisophenone), benzophenone 5 (sulisophenone sodium), and the like. Most preferred is benzophenone 3.

[0272] Certain menthyl salicylate derivatives having the following general formula are also suitable:

[0273]

[0274] wherein R1, R2, R3 and R4 are each independently H, OH, NH2 or C 1-20 Straight or branched chain alkyl. Particularly preferred are those wherein R1, R2 and R3 are methyl and R4 is hydroxy or NH2, the compound having the name homomenthylsalicylate (also known as homosalate) or menthyl anthranilate. Homosalate is known under the trade name HMS is commercially available from Merck, and menthyl anthranilate is marketed under the trademark Commercially available from Haarmann & Reimer. If present, homosalate should be found at no more than about 15% by weight of the total composition.

[0275] Various aminobenzoic acid derivatives are suitable UVB filters, including those having the following general formula:

[0276]

[0277] wherein R1, R2 and R3 are each independently H, C which may be substituted with one or more hydroxyl groups 1-20 Straight or branched alkyl. Particularly preferred is where R1 is H or C 1-8 Straight or branched alkyl, and R2 and R3 are H or C 1-8 Straight or branched chain alkyl groups. Particularly preferred are PABA, ethylhexyl dimethyl PABA (Padimate O), ethyl dihydroxypropyl PABA, and the like. If present, Padimate O should be found in an amount not exceeding about 8% by weight of the total composition.

[0278] Salicylate derivatives are also acceptable UVB filters. These compounds have the general formula: wherein R is a linear or branched alkyl group, including derivatives of the above compounds formed from monoethanolamine, diethanolamine, or triethanolamine. Particularly preferred are octyl salicylate, TEA salicylate, DEA salicylate, and mixtures thereof.

[0279] If desired, depending on the type and dosage of UV filters, the compositions of the present invention can be formulated to have a specific SPF (sun protection factor) value of about 1 to 50, or even above 50. The calculation of SPF values is well known in the art.

[0280] H. Vitamins and Antioxidants

[0281] It may be desirable to incorporate one or more vitamins or antioxidants into the compositions of the present invention. If present, a suggested range is from about 0.001% to 20%, preferably from about 0.005% to 15%, more preferably from about 0.010% to 10%. Preferably, such vitamins, vitamin derivatives and / or antioxidants are operable to scavenge free radicals in the form of singlet oxygen. Such vitamins may include tocopherol or a derivative thereof, such as tocopheryl acetate, tocopheryl ferulate; ascorbic acid or a derivative thereof, such as ascorbyl palmitate, magnesium ascorbyl phosphate; vitamin A or a derivative thereof, such as retinyl palmitate; or vitamins D, K, B, or derivatives thereof.

[0282] The preparation of the above-mentioned cosmetic composition and others can be completed with reference to any cosmetic formula guide and industry journal available in the cosmetics industry. These references provide standard formulas, which can be modified by adding or replacing the supramolecular complex of the present disclosure in the formula. Suitable guides include Cosmetics and Toiletries Magazine, Volume 111 (March 1996); Formulary: Ideas for Personal Care; Croda, Inc, Parsippany, NJ (1993), and Cosmeticon: Cosmetic Formulary, BASF, which are hereby incorporated by reference in their entirety. The cosmetic composition can be in any form. Suitable forms include, but are not limited to, solid dosage forms, liquids, gels, emulsions, creams, hard gel sticks, roll-on formulas, mousses, aerosol sprays, pad formulas, and film-forming formulas.

[0283] The cosmetic compositions of the present invention may also find a wide range of applications in fields such as personal care, food, dietary supplements, and pharmaceuticals.

[0284] V.Beauty Methods

[0285] The invention also relates to a cosmetic method for caring for and / or making up keratin materials, comprising the application of a complex or cosmetic composition as defined above.

[0286] While not wishing to be bound by theory, it is believed that by applying the complex or cosmetic composition of the present invention, the stability of phenylbenzimidazole sulfonic acid salt is improved, and even when applied to the skin, recrystallization of phenylbenzimidazole sulfonic acid does not occur, resulting in improved UV protection efficiency and achieving a relatively high SPF.

[0287] The present invention will be further described with reference to the following examples, which are presented for purposes of illustration and not limitation. Example

[0288] All materials and instruments used in this example are commercially available ones.

[0289] 1. Sample Preparation

[0290] Sample A-1 and Sample A-2 were prepared according to the formulations in the following table, which also shows the trade names and INCI names of the raw materials used.

[0291] Table 1

[0292]

[0293] According to the formulation in Table 1, hectorite clay or carbopol was added to water and stirred thoroughly to completely disperse it. Subsequently, phenylbenzimidazole sulfonic acid (PBSA) was added to the resulting dispersion and uniformly mixed to form a homogeneous system. Alternatively, a basic amino acid was mixed with a portion of the water to form a premix, which was then added dropwise to the homogeneous system until the pH reached the specified range to obtain Samples A-1 and A-2 as hydrogels.

[0294] Sample A-1 (i.e., PBSA dispersion containing Laponite) was subjected to XRD analysis (D8 Advance X-ray diffractometer manufactured by Bruker) to obtain a pattern for determining the chemical structure of Sample A-1. In addition, XRD analysis of the materials phenylbenzimidazole sulfonic acid and Laponite was also performed as a reference. The obtained XRD pattern is shown in FIG. Figure 1 and Figure 2 shown.

[0295] Specifically, Figure 1 The XRD patterns of sample A-1 and Laponite are shown. Figure 1 As shown, sample A-1 has a spectrum that is different from that of Laponite.

[0296] also, Figure 2 The XRD patterns of sample A-1 and phenylbenzimidazole sulfonic acid are shown. Figure 2 As shown, sample A-1 also has a spectrum different from that of phenylbenzimidazolesulfonic acid.

[0297] Therefore, according to Figure 1 and Figure 2 The XRD patterns of the prepared compositions show that a novel structure (ie, the composite disclosed herein) comprising Laponite and phenylbenzimidazole sulfonic acid is formed, rather than a simple mixture thereof.

[0298] 2. Test Example 1

[0299] The samples A-1 and A-2 prepared above were placed on a glass slide, dried and microscopically examined by a microscope (Leica DM2500) to confirm the presence of crystals. Figure 3 As shown in the upper part, sample A-1 using sodium lithium magnesium silicate achieved good uniformity and continuous spreadability, while sample A-2 using carbomer as a thickener was observed to have poor spreadability and aggregation. Figure 3 As shown in the lower panel, typical needle-shaped crystals, representing recrystallized phenylbenzimidazole sulfonic acid, were observed in Sample A-2, which used carbomer as a thickener. However, no crystals were found in Sample A-1, which used sodium lithium magnesium silicate. This indicates that, in addition to its thickening effect, the hydrophilic clay of the present invention also improves the stability of phenylbenzimidazole sulfonic acid in cosmetic compositions, resulting in improved spreadability and usability. It is speculated that the complex formed between sodium lithium magnesium silicate and the soluble salt of PBSA prevents the recrystallization of phenylbenzimidazole sulfonic acid.

[0300] 3. Test Example 2

[0301] In order to simulate the situation when applied on the skin, in this test, sample A-1 and sample A-2 were applied on a PMMA plate for in vitro SPF testing.

[0302] Specifically, in vitro SPF testing is performed using the following steps:

[0303] The test sample was applied by syringe and evenly distributed on a PMMA plate (50×50 mm, PMMA plate with a roughness of 6 μm, the amount of sample on the PMMA plate can be 1.3 mg / cm 2 )superior;

[0304] The samples were then dried on a PMMA plate for at least 15 min;

[0305] The center and four quadrants of each PMMA plate with a sample were tested to obtain UV absorption data;

[0306] UV absorption was measured by an Optometrics SPF-290S analyzer to obtain a UV absorption curve for each sample;

[0307] Record the UV absorption curve and calculate the average SPF value using the Win SPF software provided by the instrument.

[0308] In this embodiment, the SPF test results were analyzed by Win SPF software to output UV absorption data and graphs of sample A-1 and sample A-2.

[0309] like Figure 4As shown, the PBSA dispersion containing Laponite (Sample A-1) exhibited a uniform distribution on the PMMA plate, wherein no recrystallization of phenylbenzimidazole sulfonic acid was observed, while the PBSA dispersion containing Carbopol polymer (Sample A-2) exhibited poor spreading of PBSA on the PMMA plate, indicating recrystallization of PBSA. Furthermore, as can be seen from the UV absorption graph, the UV absorbance of the PBSA dispersion containing Laponite (Sample A-1) was significantly higher than that of the PBSA dispersion containing Carbopol polymer (Sample A-2). It can be seen that the hydrophilic clay of the present invention improves the stability of phenylbenzimidazole sulfonic acid in cosmetic compositions by forming a complex with phenylbenzimidazole sulfonic acid (i.e., the complex comprising PBSA and sodium lithium magnesium silicate disclosed herein), and will not recrystallize even when applied to the skin, thereby achieving significantly improved protection (especially UV protection) effects.

[0310] Although the invention has been described in conjunction with the preferred embodiments, it is not intended to limit the scope of the invention to the specific forms set forth, but on the contrary, it is intended to cover such alternatives, modifications and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims.

Claims

1. A complex having a pH of 6.0 or higher, preferably a pH of 6.8 to 9.0, more preferably a pH of 6.8 to 7.5, comprising: a) at least one phenylbenzimidazolesulfonic acid of formula I or a salt thereof, and b) at least one hydrophilic clay, in Ar is a substituted or unsubstituted phenyl group, R is C 1-8 Alkyl or C 1-8 Alkoxy, n is 1, 2, 3 or 4, q is 1, 2, or 3, and p is 0, 1 or 2.

2. The composite according to claim 1, wherein: Ar is an unsubstituted phenyl group, n is 1 or 2, q is 1 or 2, and p is 0.

3. The composite according to claim 1 or 2, wherein: The phenylbenzimidazole sulfonic acid is selected from 2-phenylbenzimidazole-4-sulfonic acid, 2-phenylbenzimidazole-5-sulfonic acid, 2-phenylbenzimidazole-6-sulfonic acid, 2-phenylbenzimidazole-7-sulfonic acid, 2,2'-(1,4-phenylene)bis(1H-benzo[d]imidazole-5,7-disulfonic acid), 2,2'-(1,4-phenylene)bis(1H-benzo[d]imidazole-4,6-disulfonic acid) and combinations thereof; Preferably, the phenylbenzimidazole sulfonic acid is selected from 2-phenylbenzimidazole-5-sulfonic acid, 2,2′-(1,4-phenylene)bis(1H-benzo[d]imidazole-5,7-disulfonic acid) and combinations thereof.

4. The composite according to any one of claims 1 to 3, wherein: The phenylbenzimidazole sulfonic acid is neutralized by an alkaline reagent; The alkaline agent is selected from inorganic bases and organic bases; Preferably, the alkaline agent is an organic base.

5. The composite according to claim 4, wherein: The organic base is selected from monoethanolamine, diethanolamine, triethanolamine, aminomethylpropylene glycol, 2-amino-2-methylpropanol (AMP), triisopropanolamine (TIPA), tris[(2-hydroxy)-1-propyl]amine, 2-amino-2-methyl-1,3-propanediol (AMPD), 2-amino-2-hydroxymethyl-1,3-propanediol, N-methylglucamine, basic amino acids and combinations thereof.

6. The composite according to claim 5, wherein: The basic amino acid has an isoelectric point greater than 7; Preferably, the basic amino acid is selected from arginine, lysine, histidine and combinations thereof; More preferably, the basic amino acid is arginine.

7. The composite according to any one of claims 1 to 6, wherein: The phenylbenzimidazole sulfonic acid is present in an amount of 0.1 to 10 wt %, preferably 1 to 5 wt %, relative to the total weight of the composite.

8. The composite according to any one of claims 1 to 7, wherein: The hydrophilic clay is synthetic hydrophilic clay; Preferably, the hydrophilic clay is hectorite; More preferably, the hydrophilic clay is sodium lithium magnesium silicate.

9. The composite according to any one of claims 1 to 8, wherein: The hydrophilic clay is present in an amount ranging from 0.01% to 20% by weight, preferably from 0.05% to 10% by weight, relative to the total weight of the composite.

10. The composite according to any one of claims 1 to 9, wherein: The ratio between the phenylbenzimidazole sulfonic acid and the hydrophilic clay is 0.01 to 20, preferably 0.02 to 10, and more preferably 0.1 to 5.

11. The composite according to any one of claims 1 to 10, which is an aqueous dispersion.

12. A cosmetic composition comprising the complex according to any one of claims 1 to 11 and optionally a cosmetically acceptable excipient.

13. A method for preparing the composite according to any one of claims 1 to 11, comprising the following steps: 1) forming a homogeneous system by mixing at least one phenylbenzimidazole sulfonic acid of formula I or a salt thereof with at least one hydrophilic clay; as well as 2) adjusting the pH of the homogeneous system to 6.0 or higher, preferably 6.8 to 9.0, more preferably 6.8 to 7.5, with an alkaline agent; in Ar is a substituted or unsubstituted phenyl group, R is C 1-8 Alkyl or C 1-8 Alkoxy, n is 1, 2, 3 or 4, q is 1, 2, or 3, and p is 0, 1 or 2.

14. The preparation method according to claim 13, wherein: The alkaline agent is a basic amino acid selected from arginine, lysine, histidine and combinations thereof; Preferably, the basic amino acid is arginine.

15. The preparation method according to claim 13 or 14, wherein: The ratio between the phenylbenzimidazole sulfonic acid and the hydrophilic clay is 0.01 to 20, preferably 0.02 to 10, and more preferably 0.1 to 5.

16. A cosmetic method for caring for and / or making up keratin materials, comprising applying to keratin materials a complex as claimed in any one of claims 1 to 11 or a cosmetic composition as claimed in claim 12.

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