WO2025118267A1

WO2025118267A1 - A composite and cosmetic composition comprising the same

Info

Publication number: WO2025118267A1
Application number: PCT/CN2023/137424
Authority: WO
Inventors: Kefeng TONG; Weining Zhou; Lingling LUO; Gang Lin; Bin Zheng; Leyla BOUMGHAR BOURTCHAI
Original assignee: Estee Lauder Cos Innovation R & D China Co Ltd; ELC Management LLC
Current assignee: Estee Lauder Cos Innovation R & D China Co Ltd; ELC Management LLC
Priority date: 2023-12-08
Filing date: 2023-12-08
Publication date: 2025-06-12
Anticipated expiration: 2026-06-08
Also published as: TW202523272A; CN120456892A

Abstract

A composite 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, comprises: a) at least one phenylbenzimidazole sulfonic acid of the Formula I or a salt thereof, and b) at least one hydrophilic clay wherein Ar is a substituted or unsubstituted phenyl, R is a C _1-8-alkyl or a C _1-8-alkoxy, n is 1, 2, 3 or 4, q is 1, 2 or 3, and p is 0, 1 or 2.

Description

A COMPOSITE AND COSMETIC COMPOSITION COMPRISING THE SAME

TECHNICAL FIELD

The present invention generally relates to cosmetic field and specifically relates to a composite comprising a phenylbenzimidazole sulfonic acid and a hydrophilic clay, and a cosmetic composition comprising the same. The present invention also relates to a preparation method of the composite. The present invention further relates to a cosmetic process for caring for and/or making up keratin materials.

BACKGROUND ART

UV filters widely used in the cosmetic field can be generally divided into UVA filters and UVB filters. As UVB filters to prevent various skin damages such as sunburn, redness, wrinkle formation, collagen breakdown and pigmentation caused by UVB, phenylbenzimidazole sulfonic acid derivatives such as phenylbenzimidazole sulfonic acid commercially available as232, HS or NeoHydro; disodium phenyldibenzimidazole tetrasulfonate commercially available as "NeoAP" , etc. are commonly used. However, phenylbenzimidazole sulfonic acid is very insoluble in water and therefore needs to be neutralized with an alkaline agent to a pH greater than 7.0 to form water soluble salts of phenylbenzimidazole sulfonic acid. Otherwise, phenylbenzimidazole sulfonic acid will form crystals if it is not sufficiently neutralized, which renders it less effective on UVB protection and gives a sandy or grainy feel when applied on skin.

US 6153176 indicated that low pH formulations containing phenylbenzimidazole sulfonic acid could be prepared in which 75%to 95 %of the acid remains in its non-neutralised form.

EP 2178493 indicated that the low pH formulations in US 6153176 are unstable and the phenylbenzimidazole sulfonic acid did in fact recrystallize in the formulations. In this regard, EP 2178493 proposed the use of basic amino acids to neutralise the phenylbenzimidazole sulfonic acid, thereby improving the stability to avoid the recrystallization of phenylbenzimidazole sulfonic acid in the low pH formulations. However, crystals of phenylbenzimidazole sulfonic acid were found when we repeated and applied the formulation examples on skin.

Moreover, hydrophilic clays are widely used in the cosmetic field as thickeners for water-based cosmetics. US 20030152531 disclosed a formulation comprising smectite clay as thickener with phenylbenzimidazole sulfonic acid being listed as possible sunscreen active material in the formulation.

WO 2016000145 disclosed a composition, wherein disteardimonium hectorite is used as a lipophilic thickener in oil phase.

However, none of the documents published in the prior art mention the problem of recrystallization of phenylbenzimidazole sulfonic acid contained in cosmetic formulations when applied to the skin, although the phenylbenzimidazole sulfonic acid is in the soluble salt form, resulting in loss in UV protection efficiency.

SUMMARY OF THE INVENTION

A more effective approach that can stably maintain the soluble salts of phenylbenzimidazole sulfonic acid in cosmetic formulations during storage and application (especially application on human skin) is still on demand strongly.

The inventors of the present invention have intensively studied to solve the above problem and found that the soluble salts of phenyl benzimidazole sulfonic acid can be maintained over a wide range from low pH to alkaline.

Thus, according to a first aspect, the present invention provides a composite 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 the Formula I or a salt thereof, and

b) at least one hydrophilic clay

wherein

Ar is a substituted or unsubstituted phenyl,

R is a C_1-8-alkyl or a C_1-8-alkoxy,

n is 1, 2, 3 or 4,

q is 1, 2 or 3, and

p is 0, 1 or 2.

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.

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

In some embodiments, the phenylbenzimidazole sulfonic acid is neutralized by an alkaline agent.

In some embodiments, the alkaline agent is selected from the group consisting of inorganic and organic base; preferably, the alkaline agent is an organic base.

In some embodiments, the organic base is selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, aminomethylpropanediol, 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 acid and the combination thereof.

In some embodiments, the basic amino acid has an isoelectric point greater than 7; preferably, the basic amino acid is selected from the group consisting of arginine, lysine, histidine and the combination thereof, more preferably, the basic amino acid is arginine.

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

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

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

In some embodiments, the ratio between the phenylbenzimidazole sulfonic acid and the hydrophilic clay ranges from 0.01 to 20, preferably from 0.02 to 10, more preferably 0.1 to 5.

In some embodiments, the composite is an aqueous dispersion.

According to a second aspect, the present invention provides a cosmetic composition comprising the composite as defined above and optional cosmetically acceptable excipients.

According to a third aspect, the present invention provides a preparation method of the composite of the present invention, comprising the steps of:

1) forming a homogeneous system by mixing at least one phenylbenzimidazole sulfonic acid of the Formula I or a salt thereof and at least one hydrophilic clay, and

2) adjusting 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,

wherein

Ar is a substituted or unsubstituted phenyl,

R is a C_1-8-alkyl or a C_1-8-alkoxy,

n is 1, 2, 3 or 4,

q is 1, 2 or 3, and

p is 0, 1 or 2.

In some embodiments, the alkaline agent is a basic amino acid selected from the group consisting of arginine, lysine, histidine and the combination thereof; preferably, the basic amino acid is arginine.

According to a fourth aspect, the present invention provides a cosmetic process for caring for and/or making up keratin materials comprising applying the composite or the cosmetic composition as defined above.

Other subjects and characteristics, aspects and advantages of the present invention will emerge even more clearly on reading the description and the examples that follow.

Description of the drawings

The drawings are used to provide a further understanding of the embodiments of the present invention, and constitute a part of the description. Together with the following detailed description of the invention, they are used to illustrate the embodiments of the present invention, but do not constitute a limitation to the embodiments of the present invention. In the drawings:

Figure 1 shows the XRD patterns of Sample A-1 and the material Laponite.

Figure 2 shows the XRD patterns of Sample A-1 and the material phenylbenzimidazole sulfonic acid.

Figure 3 shows microscope comparison of Sample A-1 versus Sample A-2. Specifically, Figure 1 shows microscope comparison of Sample A-1 versus Sample A-2 with or without polarized light.

Figure 4 shows the SPF test of Sample A-1 and Sample A-2 on PMMA plates and their UV absorbance graph.

DETAILED DESCRIPTION OF THE INVENTION

I. Definitions

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art the present invention belongs to. When the definition of a term in the present description conflicts with the meaning as commonly understood by those skilled in the art the present invention belongs to, the definition described herein shall apply.

In that which follows and unless otherwise indicated, the limits of a range of values are included within this range, in particular in the expressions "between... and…" and "from... to... ".

Throughout the instant application, the term “comprising” is to be interpreted as encompassing all specifically mentioned features as well optional, additional, unspecified ones. As used herein, the use of the term “comprising” also discloses the embodiment wherein no features other than the specifically mentioned features are present (i.e. “consisting of” ) .

As used herein, the singular forms "a" , "an" , and "the" include plural referents unless the context clearly dictates otherwise. For example, reference to a Cn alcohol equivalent is intended to include multiple types of Cn alcohol equivalents. Thus, even use of language such as "at least one" in one location is not intended to imply that other uses of "a" , "an" , and "the" excludes plural referents unless the context clearly dictates otherwise.

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

The term "UV filter" used herein represents a substance that absorbs ultraviolet (UV) light, i.e. electromagnetic radiation of the wavelength between 280 and 400 nm. UVA filter is the UV filter that absorb UVA light, i.e. electromagnetic radiation of the wavelength between 315 and 400 nm. UVB filter is the UV filter that absorb UVB light, i.e. electromagnetic radiation of the wavelength between 280 and 315 nm.

Moreover, the expression "at least one" used in the present description is equivalent to the expression "one or more" .

Unless otherwise specified, all numerical values expressing amount of ingredients and the like which are used in the description and claims are to be understood as being modified by the term “about” , with conventionally known meaning in the art, e.g., within 10%of the indicated number (e.g. "about 10%" means 9%-11%and "about 2%" means 1.8%-2.2%) . Accordingly, unless indicated to the contrary, the numerical values and parameters described herein are approximate values which are capable of being changed according to the desired purpose as required. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Further, the ranges stated in this disclosure and the claims are intended to include the entire range specifically and not just the endpoint (s) . For example, a range stated to be 0 to 10 is intended to disclose all whole numbers between 0 and 10 such as, for example 1, 2, 3, 4 and any sub-ranges formed by any two values thereof, etc., all fractional numbers between 0 and 10, for example 1.5, 2.3, 4.57, 6.1113 and any sub-ranges formed by any two values thereof, etc., and the endpoints 0 and 10.

The term “composite” used herein refers to a multi-component structure in which the components are connected by specific intermolecular interactions. Preferably the composite of present invention has a spatial network structure.

Unless otherwise specified, all percentages mentioned herein are percentages by weight, and all documents mentioned herein are incorporated by reference in their entirety.

II. Composite

Composite means a muti-component structure formed by at least two components, wherein the components are connected by various types of intermolecular interactions. In an embodiment, the composite of present invention has a spatial network structure, wherein the components are connected by intermolecular interactions.

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

In a preferred embodiment, the composite of the present invention is formed from at least one salt of phenylbenzimidazole sulfonic acid and at least one hydrophilic clay.

Preferably, the salt of phenylbenzimidazole sulfonic acid is formed from the phenylbenzimidazole sulfonic acid and the alkaline reagent at a suitable pH, such as a pH of 6.8 to 9.0, more preferably a pH of 6.8 to 7.5. For example, 6.8, 6.9, 7.0, 7.1, 7.5, 8.0, 8.5, 9.0.

While not wishing to be bound by theory, it is believed that the salt of phenylbenzimidazole sulfonic acid and hydrophilic clay form the composite according to the present invention through intermolecular interactions, such as hydrogen bonding interaction therebetween, resulting in improved stability of the salt of phenylbenzimidazole sulfonic acid, which does not recrystallize even when applied to the skin.

In a preferred embodiment, the composite has a spatial network structure.

The formation present composite contributes to improved UV protection efficiency. Specifically, the components (e.g., phenylbenzimidazole sulfonic acid and hydrophilic clay) can form a composite of present invention, which can have a spatial network structure. Due to the network structure, also because of the solid intermolecular interactions between the components, these components can be stably present in the structure, even the composite system experiences an atmosphere change, e.g., the atmosphere pH change, the application scenario change (e.g., the composite is applied on skin which has a slight acid pH) and the like. The stable network structure of composite can prevent the components (e.g., phenylbenzimidazole sulfonic acid as an UV filter) from recrystallization or agglomeration, thereby resulting in uniform dispersion of the components, and achieving an efficient and stable UV protection.

In one embodiment, the composite of the present invention is an aqueous dispersion.

In another embodiment, the aqueous dispersion may be a hydrogel.

Phenylbenzimidazole sulfonic acid

The composite according to the present invention comprises at least one phenylbenzimidazole sulfonic acid of the Formula I or a salt thereof.

wherein

Ar is a substituted or unsubstituted phenyl,

R is a C_1-8-alkyl or a C_1-8-alkoxy,

n is 1, 2, 3 or 4,

q is 1, 2 or 3, and

p is 0, 1 or 2.

The phenylbenzimidazole sulfonic acid of the present invention has a maximum absorption in the UV region, and therefore is suitable as a UV filter.

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.

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) .

These compounds may also be present in the form of the alkali metal salts thereof. The alkali metal salt includes lithium salt, sodium salt, and potassium salt, and sodium salt is particularly preferred.

Examples of commercially available products include, for example, 2-phenylbenzimidazole-5-sulfonic acid under the name232 by Merck KgaA, HS by DSM Nutritional Products Ltd, or Neo Hydro by Symrise; and disodium phenyldibenzimidazole tetrasulfonate under the name NeoAP by Symrise. In a preferable embodiment, the phenylbenzimidazole sulfonic acid used in present invention can beHS by DSM Nutritional Products Ltd.

An appropriate type of phenylbenzimidazole sulfonic acid contributes to the formation of present composition, thereby contributes to the improved UV protection efficiency.

The phenylbenzimidazole sulfonic acid of formula I according to the present invention has low solubility in water, therefore it is preferably neutralized with an alkaline reagent as described below.

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

An appropriate amount of phenylbenzimidazole sulfonic acid or the salt thereof contributes to the formation of present composite, thereby contributes to the improved UV protection efficiency. An overly low amount of phenylbenzimidazole sulfonic acid will lead to insufficient phenylbenzimidazole sulfonic acid in present composition, which will cause difficulties in forming a composite with uniform spatial network structure, thereby affecting UV protection efficiency of the obtained composition.

Hydrophilic clay

The composite according to the present invention comprises at least one hydrophilic clay. A single type of hydrophilic clay may be used, or a combination of two or more different types of hydrophilic clay may be used. As used herein, the hydrophilic clay refers to clay that swells in water and forms a composite with a spatial network structure through intermolecular interactions with phenylbenzimidazole sulfonic acid. The hydrophilic clays are preferably those swell in water to form colloidal dispersions, especially aqueous dispersions. The viscosity of the aqueous dispersion varies depending on the amount of the hydrophilic clay added. Generally, as the amount added increases, the viscosity increases. Preferably, the hydrophilic clay can be synthetic origin. The hydrophilic clay used in the present invention is a hectorite.

In one embodiment, the hectorite is typically defined as:
[ (Mg_6-x Li_x) Si₈O₂₀ (OH) ₄] ^-x R⁺

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

Preferably, the hydrophilic clay used in the present invention includes synthetic hectorites (also known as laponites) , such as the products sold by the company Laporte under the namesXLG, RD andRDS (these products are sodium magnesium silicates and in particular sodium lithium magnesium silicates) .

In a preferable embodiment, the hydrophilic clay used in present invention is sodium lithium magnesium silicate.

An appropriate type of hydrophilic clay contributes to the formation of present composite, thereby contributes to the improved UV protection efficiency. Without being limited by theory, compared with other types of hydrophilic clays, lithium magnesium sodium silicate is more likely to form the composite with a spatial network structure with phenylbenzimidazole sulfonic acid, so it is preferably used.

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

An appropriate amount of hydrophilic clay contributes to the formation of present composite, thereby contributes to the improved UV protection efficiency. An overly high amount of hydrophilic clay will cause difficulties in forming a homogeneous system of hydrophilic clay and phenylbenzimidazole sulfonic acid, resulting in a failure to form a uniform spatial network structure. An overly low amount of hydrophilic clay will also result in a failure to form the spatial network structure and cause the recrystallization of phenylbenzimidazole sulfonic acid when applying to skin.

The ratio between the phenylbenzimidazole sulfonic acid and the hydrophilic clay ranges from 0.01 to 20, preferably from 0.05 to 10, more preferably 0.1 to 5. For example, the ratio between the phenylbenzimidazole sulfonic acid and the hydrophilic clay may 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.

An appropriate ratio between the phenylbenzimidazole sulfonic acid and the hydrophilic clay contributes to the formation of present composite, thereby contributes to the improved UV protection efficiency. An overly high ratio between the phenylbenzimidazole sulfonic acid and the hydrophilic clay will result in a failure to form the spatial network structure and cause the recrystallization of phenylbenzimidazole sulfonic acid when applying to skin. An overly low ratio between the phenylbenzimidazole sulfonic acid and the hydrophilic clay will cause difficulties in forming a homogeneous system of hydrophilic clay and phenylbenzimidazole sulfonic acid, resulting in a failure to form a uniform spatial network structure.

Alkaline agent

For the purposes of the present invention, the phenylbenzimidazole sulfonic acid of the Formula I or the salt thereof is preferably neutralized with an alkaline reagent. Preferably, the composite according to the present 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.

The alkaline reagent used in the present invention includes inorganic and organic base. The inorganic base can be selected from the group consisting of sodium hydroxide and potassium hydroxide, carbonates, carbamates, hydrogen carbonates, ammonium chloride and the combination thereof. The organic base can be selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, aminomethylpropanediol, 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, amino acid and the combination thereof.

By using an alkaline reagent, the pH of the composite according to the present invention can be adjusted to a suitable range, the phenylbenzimidazole sulfonic acid of Formula I can be aqueously dissociated.

Preferably, the alkaline reagent used in the composite 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 the group consisting of arginine, lysine, histidine and the combination thereof. More preferably, arginine can be used as the alkaline reagent.

An appropriate type of alkaline agent contributes to the formation of present composite, thereby contributes to the improved UV protection efficiency.

While not wishing to be bound by theory, it is believed that the composite of the present invention can be used to prepare a cosmetic composition with a pH at or below 7, especially a pH from 6.0 to 7.0 without crystallization of phenylbenzimidazole sulfonic acid by using the basic amino acid as alkaline reagent.

III. Preparation Method

The preparation method of the composite defined above may include, but not limited to, forming a homogeneous system by mixing at least one phenylbenzimidazole sulfonic acid of the Formula I or a salt thereof and at least one hydrophilic clay as defined above and adjusting 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 the alkaline reagents as defined above.

In a preferable embodiment, the composite of the present invention is prepared by a method comprising the steps of:

I) forming a dispersion by dispersing at least one hydrophilic clay in water,

II) forming a homogeneous system by adding at least one phenylbenzimidazole sulfonic acid of the Formula I or a salt thereof into the dispersion, and

III) adjusting 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,

wherein

Ar is a substituted or unsubstituted phenyl,

R is a C_1-8-alkyl or a C_1-8-alkoxy,

n is 1, 2, 3 or 4,

q is 1, 2 or 3, and

p is 0, 1 or 2.

In the 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.

The hydrophilic clay can be dispersed in water by stirring. The stirring can be carried out in various ways. For example, mechanical stirring such as paddle stirring and turbine stirring, gas stirring such as bubble stirring and compressed air stirring, ultrasonic stirring, magnetic stirring, and the like can be used in the stirring.

In the step II) , the phenylbenzimidazole sulfonic acid is added into the dispersion obtained in the step I) to form a homogeneous system. The phenylbenzimidazole sulfonic acid can be added into the dispersion all at once or in batches preferably 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 the composite of the salt of phenylbenzimidazole sulfonic acid and the hydrophilic clay.

In a preferable embodiment, the phenylbenzimidazole sulfonic acid is neutralized by the alkaline agent as defined above.

In the step III) , the alkaline agent can be added according to conventional methods.

In one embodiment, the alkaline reagent can be prepared as a premix with water and then added dropwise to the homogeneous system obtained in step II) .

In another embodiment, an excess of alkaline reagent can be added into the homogeneous system obtained in step II) , and then neutralized with an acidic agent to 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.

The term “acidic agent“ used herein refers to those that can be used to adjust pH in cosmetics, including but not limited to hyaluronic acid, citric acid, lactic acid, etc.

While not wishing to be bound by theory, it is believed that maintaining the homogeneous system at 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, facilitates the formation of the composite of the salt of phenylbenzimidazole sulfonic acid and the hydrophilic clay.

In another embodiment, the step I) , step II) and step III) can be performed simultaneously, or separately, or sequentially, or in a changed order.

For example, in one embodiment, the composite of the present invention is prepared by a method comprising the steps of:

a) forming an aqueous dispersion by adding at least one phenylbenzimidazole sulfonic acid of the Formula I or a salt thereof into water,

b) forming a homogeneous system by adding at least one hydrophilic clay into the aqueous dispersion, and

c) adjusting 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,

wherein

Ar is a substituted or unsubstituted phenyl,

R is a C_1-8-alkyl or a C_1-8-alkoxy,

n is 1, 2, 3 or 4,

q is 1, 2 or 3, and

p is 0, 1 or 2.

In the step a) , the phenylbenzimidazole sulfonic acid can be added into water all at once or in batches preferably with stirring. 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.

In a preferable embodiment, the phenylbenzimidazole sulfonic acid is neutralized by the alkaline agent define above.

In the step b) , the hydrophilic clay can be added into the aqueous dispersion obtained in the step a) to form a homogeneous system.

The hydrophilic clay can be added into the aqueous dispersion all at once or in batches preferably with stirring. The homogeneous system can be obtained by stirring in the same manner as in step I) defined above.

The step c) is the same as the step III) defined above,

In a further embodiment, the composite of the present invention is prepared by a method comprising the steps of:

a1) forming a homogeneous system by adding at least one hydrophilic clay and at least one phenylbenzimidazole sulfonic acid of the Formula I or a salt thereof into water, and

b1) adjusting 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,

wherein

Ar is a substituted or unsubstituted phenyl,

R is a C_1-8-alkyl or a C_1-8-alkoxy,

n is 1, 2, 3 or 4,

q is 1, 2 or 3, and

p is 0, 1 or 2.

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

The step c) is the same as the step III) defined above.

While the preparation method has been described in connection with several preferred embodiment, various changes can be applied to the preparation method defined above as long as a homogeneous system containing the salt of phenylbenzimidazole sulfonic acid and hydrophilic clay can be formed, and the pH of the homogeneous system is maintained at 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. These modified methods are also covered by the scope of the present invention.

IV. Cosmetic Composition

The cosmetic composition according to the present invention comprises the composite with the definitions as defined above and other ingredients.

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

The cosmetic composition may be skin care products such as facial, hand and foot care products; acne treatment products, shaving products, cleansing products; powders, antiperspirants; hair remover products, colour makeup products such as makeup base, foundation, eye shadow, eyeliner, blush; sunscreen products; and the like.

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

As long as the beneficial effect that the stability of the phenylbenzimidazole salt is not affected and recrystallization does not occur even when applied to the skin, the cosmetic composition may comprise other ingredients such as additives, excipients, diluents, and/or other active ingredients, including but not limited to those described herein.

A. Humectants

The composition of the present invention may contain one or more humectants. If present, they may range 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 and polypropylene glycols such as PEG 4-10, which are polyethylene glycols having from 4 to 10 repeating ethylene oxide units; as well as C_1-6 alkylene glycols such as propylene glycol, butylene glycol, pentylene glycol, and the like. Suitable sugars, some of which are also polyhydric alcohols, are also suitable humectants. Examples of such sugars include glucose, fructose, honey, hydrogenated honey, inositol, maltose, mannitol, maltitol, sorbitol, sucrose, xylitol, xylose, and so on. Also suitable is urea. Preferably, the humectants used in the composition of the present invention are C_1-6, preferably C_2-4 alkylene glycols, most particularly butylene glycol.

B. Botanical Extracts

The composition of the present invention may contain one or more botanical extracts. If present suggested ranges are from about 0.0001 to 20%, preferably from about 0.0005 to 15%, more preferably from about 0.001 to 10%. Suitable botanical extracts include extracts from plants (herbs, roots, flowers, fruits, seeds) such as flowers, fruits, vegetables, and so on, including yeast ferment extract, Padina pavonica extract, Thermus thermophilis ferment extract, Camelina sativa seed oil, Boswellia serrata extract, olive extract, Acacia dealbata extract, Acer saccharinum (sugar maple) , 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, willowbark, mulberry, poppy, and those set forth on pages 1646 through 1660 of the CTFA Cosmetic Ingredient Handbook, Eighth Edition, Volume 2. Further specific examples include, but are not limited to, Glycyrrhiza glabra, Salix nigra, Macrocycstis pyrifera, Pyrus malus, Saxifraga sarmentosa, Vitis vinifera, Morus nigra, Scutellaria baicalensis, Anthemis nobilis, Salvia sclarea, Rosmarinus officianalis, Citrus limonum, Panax ginseng, Siegesbeckia orientalis, Fructus mume, Ascophyllum nodosum, Glycine soja extract, Beta vulgaris, Haberlea rhodopensis, Polygonum cuspidatum, Citrus aurantium dulcis, Vitis vinifera, Selaginella tamariscina, Humulus lupulus, Citrus reticulata Peel, Punica granatum, Asparagopsis, Curcuma longa, Menyanthes trifoliata, Helianthus annuus, Hordeum vulgare, Cucumis sativus, Evernia prunastri, Everniafurfuracea, Kola acuminata, and mixtures thereof.

C. Surfactants

The composition of the present invention may contain one or more surfactants, especially if in the emulsion form. However, such surfactants may be used if the compositions are solutions, suspensions, or anhydrous also. If present, the surfactant may range from about 0.01 to 30%, preferably from about 0.05 to 25%, 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.

1. Organic Nonionic Surfactants

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 or propylene oxide. Suitable alcohols include mono-, di-, or polyhydric short chain (C_1-6) alcohols; aromatic or aliphatic saturated or unsaturated fatty (C_12-40) alcohols, of cholesterol; and so on.

Cholesterol is suitable, or an aromatic or aliphatic saturated or unsaturated fatty alcohol which may have from 6 to 40, preferably from about 10 to 30, 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; Choleth 2-100 wherein the number range means the number of repeating ethylene oxide units, e.g. Ceteth 2-100 means Ceteth where the number of repeating ethylene oxide units ranges from 2 to 100. Derivatives of alkoxylated alcohols are also suitable, such as phosphoric acid esters thereof.

Some preferred organic nonionic surfactants include Oleth-3, Oleth-5, Oleth-3 phosphate, Choleth-24; Ceteth-24; and so on.

Also suitable are alkoxylated alcohols formed with mono-, di-, or polyhydric short chain alcohols, for example those having from about 1 to 6 carbon atoms. Examples include glucose, glycerin, or alkylated derivatives thereof. Examples include glycereth 2-100; gluceth 2-100; methyl gluceth 2-100 and so on. More preferred are methyl gluceth-20; glycereth-26 and the like.

Other types of alkoxylated alcohols are suitable surfactants, including ethylene oxide polymers having varying numbers of repeating EO groups, generally referred to as PEG 12 to 200. More preferred are PEG-75, which may be purchased from Dow Chemical under the trade name Carbowax PEG-3350.

Other suitable nonionic surfactants include alkoxylated sorbitan and alkoxylated sorbitan derivatives. For example, alkoxylation, in particular ethoxylation of sorbitan provides polyalkoxylated sorbitan derivatives. Esterification of polyalkoxylated sorbitan provides sorbitan esters such as the polysorbates. For example, the polyalkyoxylated sorbitan can be esterified with C_6-30, preferably C_12-22 fatty acids. Examples of such ingredients include Polysorbates 20-85, sorbitan oleate, sorbitan sesquioleate, sorbitan palmitate, sorbitan sesquiisostearate, sorbitan stearate, and so on.

2. Silicone or Silane Surfactants

Also suitable are various types of silicone or silane-based surfactants. Examples include organosiloxanes substituted with ethylene oxide or propylene oxide groups such as PEG dimethicones which are dimethicones substituted with polyethylene glycols including those having the INCI names PEG-1 dimethicone; PEG-4 dimethicone; PEG-8 dimethicone; PEG-12 dimethicone; PEG-20 dimethicone; and so on.

Also suitable are silanes substituted with ethoxy groups or propoxy groups or both, such as various types of PEG methyl ether silanes such as bis-PEG-18 methyl ether dimethyl silane; and so on.

Further examples of silicone-based surfactants include those having the generic names dimethicone copolyol; cetyl dimethicone copolyol; and so on.

D. Biological Materials

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

E. Thickeners

Different from forming a composite with a spatial network structure with phenylbenzimidazole sulfonic acid as described above, the hydrophilic clay is also widely used as a thickener in the cosmetic field. However, the thickeners other than the hydrophilic clay of the present invention may be incorporated into the composition of the present invention. As long as it does not affect the formation of the composite with a spatial network structure between the hydrophilic clay and phenylbenzimidazole sulfonic acid, the thickener can be added appropriately. Suitable thickeners may be incorporated into the composition of the present invention. If present, suggested ranges are from about 0.01 to 30%, preferably from about 0.1 to 20%, more preferably from about 0.5 to 15%by weight of the total composition.

Examples of thickeners include animal, vegetable, mineral, silicone, or synthetic waxes which may have melting points ranging from about 30 to 150℃. including but not limited to Examples of such waxes include waxes made by Fischer-Tropsch synthesis, such as polyethylene or synthetic wax; or various vegetable waxes such as bayberry, candelilla, ozokerite, acacia, beeswax, ceresin, cetyl esters, flower wax, citrus wax, carnauba wax, jojoba wax, japan wax, polyethylene, microcrystalline, rice bran, lanolin wax, mink, montan, bayberry, ouricury, ozokerite, palm kernel wax, paraffin, avocado wax, apple wax, shellac wax, clary wax, spent grain wax, grape wax, and polyalkylene glycol derivatives thereof such as PEG6-20 beeswax, or PEG-12 carnauba wax; or fatty acids or fatty alcohols, including esters thereof, such as hydroxystearic acids (for example 12-hydroxy stearic acid) , tristearin, tribehenin, and so on.

Also suitable as thickening agents are silicas, silicates, silica silylate, and alkali metal or alkaline earth metal derivatives thereof. These silicas and silicates are generally found in the particulate form and include silica, silica silylate, magnesium aluminum silicate, and the like.

Silicone elastomers may also be used as thickening agents. Such elastomers include those that are formed by addition reaction-curing, by reacting an SiH-containing diorganosiloxane and an organopolysiloxane having terminal olefinic unsaturation, or an alpha-omega diene hydrocarbon, in the presence of a platinum metal catalyst. Such elastomers may also be formed by other reaction methods such as condensation-curing organopolysiloxane compositions in the presence of an organotin compound via a dehydrogenation reaction between hydroxyl-terminated diorganopolysiloxane and SiH-containing diorganopolysiloxane or alpha omega diene; or by condensation-curing organopolysiloxane compositions in the presence of an organotin compound or a titanate ester using a condensation reaction between an hydroxyl-terminated diorganopolysiloxane and a hydrolysable organosiloxane; peroxide-curing organopolysiloxane compositions which thermally cure in the presence of an organoperoxide catalyst.

One type of elastomer that may be suitable is prepared by addition reaction-curing an organopolysiloxane having at least 2 lower alkenyl groups in each molecule or an alpha-omega diene; and an organopolysiloxane having at least 2 silicon-bonded hydrogen atoms in each molecule; and a platinum-type catalyst. While the lower alkenyl groups such as vinyl, can be present at any position in the molecule, terminal olefinic unsaturation on one or both molecular terminals is preferred. The molecular structure of this component may be straight chain, branched straight chain, cyclic, or a network. These organopolysiloxanes are exemplified by methylvinylsiloxanes, methylvinylsiloxane-dimethylsiloxane copolymers, dimethylvinylsiloxy-terminated dimethylpolysiloxanes, dimethylvinylsiloxy-terminated dimethylsiloxane-methylphenylsiloxane copolymers, dimethylvinylsiloxy-terminated dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymers, trimethylsiloxy-terminated dimethylsiloxane-methylvinylsiloxane copolymers, trimethylsiloxy-terminated dimethylsiloxane-methylphenylsiloxane-methylvinylsiloxane copolymers, dimethylvinylsiloxy-terminated methyl (3, 3, 3-trifluoropropyl) polysiloxanes, and dimethylvinylsiloxy-terminated dimethylsiloxane-methyl (3, 3, -trifluoropropyl) siloxane copolymers, decadiene, octadiene, heptadiene, hexadiene, pentadiene, or tetradiene, or tridiene.

Curing proceeds by the addition reaction of the silicon-bonded hydrogen atoms in the dimethyl methylhydrogen siloxane, with the siloxane or alpha-omega diene under catalysis using the catalyst mentioned herein. To form a highly crosslinked structure, the methyl hydrogen siloxane must contain at least 2 silicon-bonded hydrogen atoms in each molecule to optimize function as a crosslinker.

The catalyst used in the addition reaction of silicon-bonded hydrogen atoms and alkenyl groups, and is concretely 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 carrier-supported platinum.

Examples of suitable silicone elastomers for use in the compositions of the present invention may be in the powder form, or dispersed or solubilized in solvents such as volatile or non-volatile silicones, or silicone compatible vehicles such as paraffinic hydrocarbons or esters. Examples of silicone elastomer powders include vinyl dimethicone/methicone silesquioxane crosspolymers like Shin-Etsu's KSP-100, KSP-101, KSP-102, KSP-103, KSP-104, KSP-105, hybrid silicone powders that contain a fluoroalkyl group like Shin-Etsu's KSP-200 which is a fluoro-silicone elastomer, and hybrid silicone powders that contain a phenyl group such as Shin-Etsu's KSP-300, which is a phenyl substituted silicone elastomer; and Dow Coming's DC 9506. Examples of silicone elastomer powders dispersed in a silicone compatible vehicle include dimethicone/vinyl dimethicone crosspolymers supplied by a variety of suppliers including Dow Corning Corporation under the tradenames 9040 or 9041, GE Silicones under the tradename SFE 839, or Shin-Etsu Silicones under the tradenames KSG-15, 16, 18. KSG-15 has the CTFA name cyclopentasiloxane/dimethicone/vinyl dimethicone crosspolymer. KSG-18 has the INCI name phenyl trimethicone/dimethicone/phenyl vinyl dimethicone crossoplymer. Silicone elastomers may also be purchased from Grant Industries under the Gransil trademark. Also suitable are silicone elastomers having long chain alkyl substitutions such as lauryl dimethicone/vinyl dimethicone crosspolymers supplied by Shin Etsu under the tradenames KSG-31, KSG-32, KSG-41, KSG-42, KSG-43, and KSG-44. Cross-linked organopolysiloxane elastomers used in the present invention and processes for making them are further described in U.S. Pat. No. 4,970,252 to Sakuta et al., issued Nov. 13, 1990; U.S. Pat. No. 5,760,116 to Kilgour et al., issued Jun. 2, 1998; U.S. Pat. No. 5,654,362 to Schulz, Jr. et al. issued Aug. 5, 1997; and Japanese Patent Application JP 61-18708, assigned to Pola Kasei Kogyo KK, each of which are herein incorporated by reference in its entirety.

Polysaccharides may be suitable aqueous phase thickening agents. Examples of such polysaccharides include naturally derived materials such as agar, agarose, alicaligenes polysaccharides, algin, alginic acid, acacia gum, amylopectin, chitin, dextran, cassia gum, cellulose gum, gelatin, gellan gum, hyaluronic acid, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, pectin, sclerotium gum, xanthan gum, pectin, trehelose, gelatin, and so on.

Also suitable are different types of synthetic polymeric thickeners. One type includes acrylic polymeric thickeners comprised of monomers A and B wherein A is selected from the group consisting of acrylic acid, methacrylic acid, and mixtures thereof; and B is selected from the group consisting of a C1-22 alkyl acrylate, a C1-22 alky methacrylate, and mixtures thereof are suitable. Acrylic polymer solutions include those sold by Seppic, Inc., under the tradenameor those sold under the tradename

Also suitable are acrylic polymeric thickeners that are copolymer of A, B, and C monomers wherein A and B are as defined above, and C has the general formula:

wherein Z is- (CH₂) _m; wherein m is 1-10, n is 2-3, o is 2-200, and R is a C_10-30 straight or branched chain alkyl. Examples of the secondary thickening agent above, are copolymers where A and B are defined as above, and C is CO, and wherein n, o, and R are as above defined. Examples of such secondary thickening agents include acrylates/steareth-20 methacrylate copolymer, which is sold by Rohm&Haas under the tradename Acrysol ICS-1.

Also suitable are acrylate based anionic amphiphilic polymers containing at least one hydrophilic unit and at least one allyl ether unit containing a fatty chain. Preferred are those where the hydrophilic unit contains an ethylenically unsaturated anionic monomer, more specificially a vinyl carboxylic acid such as acrylic acid, methacrylic acid or mixtures thereof, and where the allyl ether unit containing a fatty chain corresponds to the monomer of formula:
CH₂=CR’CH₂OB_nR

wherein R' denotes H or CH₃, B denotes the ethylenoxy radical, n is zero or an integer ranging from 1 to 100, R denotes a hydrocarbon radical selected from alkyl, arylalkyl, aryl, alkylaryl and cycloalkyl radicals which contain from 8 to 30 carbon atoms, preferably from 10 to 24, and even more particularly from 12 to 18 carbon atoms. More preferred in this case is where R' denotes H, n is equal to 10 and R denotes a stearyl (C₁₈) radical. Anionic amphiphilic polymers of this type are 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. Among these anionic amphiphilic polymers, polymers formed of 20 to 60%by weight acrylic acid and/or methacrylic acid, of 5 to 60%by weight lower alkyl methacrylates, of 2 to 50%by weight allyl ether containing a fatty chain as mentioned above, and of 0 to 1%by weight of a crosslinking agent which is a well-known copolymerizable polyethylenic unsaturated monomer, for instance diallyl phthalate, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate and methylenebisacrylamide. One commercial example of such polymers are crosslinked terpolymers of methacrylic acid, of ethyl acrylate, of polyethylene glycol (having 10 EO units) ether of stearyl alcohol or steareth-10, in particular those sold by the company Allied Colloids under the names SALCARE SC80 and SALCARE SC90, which are aqueous emulsions containing 30%of a crosslinked terpolymer of methacrylic acid, of ethyl acrylate and of steareth-10 allyl ether (40/50/10) .

Also suitable are acrylate copolymers such as Polyacrylate-3 which is a copolymer of methacrylic acid, methylmethacrylate, methylstyrene isopropylisocyanate, and PEG-40 behenate monomers; Polyacrylate-10 which is a copolymer of sodium acryloyldimethyltaurate, sodium acrylate, acrylamide and vinyl pyrrolidone monomers; or Polyacrylate-11, which is a copolymer of sodium acryloyldimethylacryloyldimethyl taurate, sodium acrylate, hydroxyethyl acrylate, lauryl acrylate, butyl acrylate, and acrylamide monomers.

Also suitable are crosslinked acrylate based polymers where one or more of the acrylic groups may have substituted long chain alkyl (such as 6-40, 10-30, and the like) groups, for example acrylates/C10-30 alkyl acrylate crosspolymer which is a copolymer of C10-30 alkyl acrylate and one or more monomers of acrylic acid, methacrylic acid, or one of their simple esters crosslinked with the allyl ether of sucrose or the allyl ether of pentaerythritol. Such polymers are commonly sold under the Carbopol or Pemulen tradenames and have the CTFA name carbomer.

One particularly suitable type of aqueous phase thickening agent are acrylate based polymeric thickeners sold by Clariant under the Aristoflex trademark such as Aristoflex AVC, which is ammonium acryloyldimethyltaurate/VP copolymer; Aristoflex AVL which is the same polymer has found in AVC dispersed in 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.

Also suitable as thickening agents are various polyethylene glycols (PEG) derivatives where the degree of polymerization ranges from 1,000 to 200,000. Such ingredients are indicated by the designation “PEG” followed by the degree of polymerization in thousands, such as 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.

Also suitable are polyglycerins which are repeating glycerin moieties where the number of repeating moieties ranges from 15 to 200, preferably from about 20-100. Examples of suitable polyglycerins include those having the CTFA names polyglycerin-20, polyglycerin-40, and the like.

F. Oils

In the case that the compositions of the present invention are in emulsion form, the composition will contain an oil phase. Oily ingredients are desirable for the skin moisturizing and protective properties. Suitable oils include silicones, esters, vegetable oils, synthetic oils, including but not limited to those set forth herein. The oils may be volatile or nonvolatile, and are 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℃. The term "nonvolatile" means that the oil has a vapor pressure of less than about 2 mm. of mercury at 20℃.

1. Volatile Oils

Suitable volatile oils generally have a viscosity ranging from about 0.5 to 5 centistokes 25℃. and include linear silicones, cyclic silicones, paraffinic hydrocarbons, or mixtures thereof.

(a) . Volatile Silicones

Cyclic silicones are one type of volatile silicone that may be used in the composition. Such silicones have the general formula:

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

Also suitable are linear volatile silicones, for example, those having the general formula:
(CH₃) ₃Si-O- [Si (CH₃) ₂-O] _n-Si (CH₃) ₃

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

Cyclic and linear volatile silicones are available from various commercial sources including Dow Corning Corporation and General Electric. The Dow Corning linear volatile silicones are sold under the tradenames 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, with all viscosity measurements being at 25℃.

Suitable branched volatile silicones include alkyl trimethicones such as methyl trimethicone, a branched volatile silicone having the general formula:

Methyl trimethicone may be purchased from Shin-Etsu Silicones under the tradename TMF-1.5, having a viscosity of 1.5 centistokes at 25 ℃.

(b) . Volatile Paraffinic Hydrocarbons

Also suitable as the volatile oils are various straight or branched chain paraffinic hydrocarbons 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. Suitable hydrocarbons include pentane, hexane, heptane, decane, dodecane, tetradecane, tridecane, and C_8-20 isoparaffins as disclosed in U.S. Pat. Nos. 3,439,088 and 3,818,105, both of which are hereby incorporated by reference.

Preferred volatile paraffinic hydrocarbons have a molecular weight of 70-225, preferably 160 to 190 and a boiling point range of 30 to 320, preferably 60℃to 260℃., and a viscosity of less than about 10 cst. at 25 ℃. Such paraffinic hydrocarbons are available from EXXON under the ISOPARS trademark, and from the Permethyl Corporation. Suitable C₁₂ isoparaffins are manufactured by Permethyl Corporation under the tradename Permethyl 99A. Various C₁₆ isoparaffins commercially available, such as isohexadecane (having the tradename Permethyl R) , are also suitable.

2. Non-Volatile Oils

A variety of nonvolatile oils are also suitable for use in the compositions of the present invention. The nonvolatile oils generally have a viscosity of greater than about 5 to 10 centistokes at 25℃, and may range in viscosity up to about 1,000,000 centipoise at 25℃. Examples of nonvolatile oils include, but are not limited to:

(a) . Esters

Suitable esters are mono-, di-, and triesters. The composition may comprise one or more esters selected from the group, or mixtures thereof.

(i) Monoesters

Monoesters are defined as esters formed by the reaction of a monocarboxylic acid having the formula R-COOH, wherein R is a straight or branched chain saturated or unsaturated alkyl having 2 to 45 carbon atoms, or phenyl; and an alcohol having the formula R-OH wherein R is a straight or branched chain saturated or unsaturated alkyl having 2-30 carbon atoms, or phenyl. Both the alcohol and the acid may be substituted with one or more hydroxyl groups. Either 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 straight or branched chain, saturated or unsaturated form. Examples of monoester oils that may be used in the compositions of the present invention include hexyl laurate, butyl isostearate, hexadecyl isostearate, cetyl palmitate, isostearyl neopentanoate, stearyl heptanoate, isostearyl isononanoate, steary lactate, stearyl octanoate, stearyl stearate, isononyl isononanoate, and so on.

(ii) . Diesters

Suitable diesters are the reaction product of a dicarboxylic acid and an aliphatic or aromatic alcohol or an aliphatic or aromatic alcohol having at least two substituted hydroxyl groups and a monocarboxylic acid. The dicarboxylic acid may contain from 2 to 30 carbon atoms, and may be in the straight or branched chain, saturated or unsaturated form. 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 in the straight or branched chain, saturated, or unsaturated form. Preferably, one or more of the acid or alcohol is a fatty acid or alcohol, i.e. contains 12-22 carbon atoms. The dicarboxylic acid may also be an alpha hydroxy acid. The ester may be in the dimer or trimer form. Examples of diester oils that may be used in the compositions of the present invention include diisotearyl malate, neopentyl glycol dioctanoate, dibutyl sebacate, dicetearyl dimer dilinoleate, dicetyl adipate, diisocetyl adipate, diisononyl adipate, diisostearyl dimer dilinoleate, diisostearyl fumarate, diisostearyl malate, dioctyl malate, and so on.

(iii) . Triesters

Suitable triesters comprise the reaction product of a tricarboxylic acid and an aliphatic or aromatic alcohol or alternatively the reaction product of an aliphatic or aromatic alcohol having three or more substituted hydroxyl groups with a monocarboxylic acid. As with the mono-and diesters mentioned above, the acid and alcohol contain 2 to 30 carbon atoms, and may be saturated or unsaturated, straight or branched chain, and may be substituted with one or more hydroxyl groups. Preferably, one or more of the acid or alcohol is a fatty acid or alcohol containing 12 to 22 carbon atoms. Examples of triesters include esters of arachidonic, citric, or behenic acids, such as triarachidin, tributyl citrate, triisostearyl citrate, tri C_12-13 alkyl citrate, tricaprylin, tricaprylyl citrate, tridecyl behenate, trioctyldodecyl citrate, tridecyl behenate; or tridecyl cocoate, tridecyl isononanoate, and so on.

Esters suitable for use in the composition of the present invention are further described in the C.T.F.A. Cosmetic Ingredient Dictionary and Handbook, Eleventh Edition, 2006, under the classification of “Esters” , the text of which is hereby incorporated by reference in its entirety.

(b) . Hydrocarbon Oils

It may be desirable to incorporate one or more nonvolatile hydrocarbon oils into the composition of the present invention. Suitable nonvolatile hydrocarbon oils include paraffinic hydrocarbons 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 one preferred embodiment such hydrocarbons have a molecular weight ranging from about 300 to 1000 Daltons.

(c) . Glyceryl Esters of Fatty Acids

Synthetic or naturally occurring glyceryl esters of fatty acids, or triglycerides, are also suitable for use in the compositions. Both vegetable and animal sources may 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, and the like.

Also suitable are synthetic or semi-synthetic glyceryl esters, such as fatty acid mono-, di-, and triglycerides which are natural fats or oils that have been modified, for example, mono-, di-or triesters of polyols such as glycerin. In an example, a fatty (C_12-22) carboxylic acid is reacted with one or more repeating glyceryl groups. glyceryl stearate, diglyceryl diiosostearate, polyglyceryl-3 isostearate, polyglyceryl-4 isostearate, polyglyceryl-6 ricinoleate, glyceryl dioleate, glyceryl diisotearate, glyceryl tetraisostearate, glyceryl trioctanoate, diglyceryl distearate, glyceryl linoleate, glyceryl myristate, glyceryl isostearate, PEG castor oils, PEG glyceryl oleates, PEG glyceryl stearates, PEG glyceryl tallowates, and so on.

(d) . Nonvolatile Silicones

Nonvolatile silicone oils, both water soluble and water insoluble, are also suitable for use in the composition. Such silicones preferably have a viscosity ranging from about greater than 5 to 800,000 cst, preferably 20 to 200,000 cst at 25℃. Suitable water insoluble silicones include amine functional silicones such as amodimethicone.

For example, such nonvolatile silicones may have the following general formula:

wherein R and R¹ are each independently C_1-30 straight or branched chain, saturated or unsaturated alkyl, phenyl or aryl, trialkylsiloxy, and x and y are each independently 1-1,000,000; with the proviso that there is at least one of either x or y, and A is alkyl siloxy endcap unit. Preferred is where A is a methyl siloxy endcap unit; in particular trimethylsiloxy, and R and R¹ are each independently a C_1-30 straight or branched chain alkyl, phenyl, or trimethylsiloxy, more preferably a C_1-22 alkyl, phenyl, or trimethylsiloxy, most preferably methyl, phenyl, or trimethylsiloxy, and resulting silicone is dimethicone, phenyl dimethicone, diphenyl dimethicone, phenyl trimethicone, or trimethylsiloxyphenyl dimethicone. Other examples include alkyl dimethicones such as cetyl dimethicone, and the like wherein at least one R is a fatty alkyl (C₁₂, C₁₄, C₁₆, C₁₈, C₂₀, or C₂₂) , and the other R is methyl, and A is a trimethylsiloxy endcap unit, provided such alkyl dimethicone is a pourable liquid at room temperature. Phenyl trimethicone can be purchased from Dow Corning Corporation under the tradename 556 Fluid. Trimethylsiloxyphenyl dimethicone can be purchased from Wacker-Chemie under the tradename PDM-1000. Cetyl dimethicone, also referred to as a liquid silicone wax, may be purchased from Dow Corning as Fluid 2502, or from DeGussa Care&Surface Specialties under the trade names Abil Wax 9801, or 9814.

G. UV filters

It may also be desirable to include one or more UV filters other than the phenylbenzimidazole sulfonic acid of the Formula I or a salt thereof in the compositions of the present invention. Such UV filters include chemical UVA or UVB filters or physical filters in the particulate form. Inclusion of filters in the compositions containing the whitening active ingredient will provide additional protection to skin during daylight hours and promote the effectiveness of the whitening active ingredient on the skin.

1. UVA Chemical filters

If desired, the composition may comprise one or more UVA filters. Preferred UVA filters are dibenzoylmethane compounds of the formula:

wherein R₁ is H, OR and NRR wherein each R is independently H, C_1-20 straight or branched chain alkyl; R₂ is H or OH; and R₃ is H, C_1-20 straight or branched chain alkyl.

Preferred is where R₁ is OR where R is a C_1-20 straight or branched alkyl, preferably methyl; R₂ is H; and R₃ is a C_1-20 straight or branched chain alkyl, more preferably, butyl.

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'-methoxydibenzoymethane, 2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane, and so on. Particularly preferred is 4-tert-butyl-4'-methoxydibenzoylmethane, also referred to as Avobenzone. Avobenzone is commercially available from Givaudan-Roure under the trademark1789, and Merck&Co. under the tradename9020.

Other types of UVA filters include dicamphor sulfonic acid derivatives, such as ecamsule, a filter sold under the trade namewhich is terephthalylidene dicamphor sulfonic acid, having the formula:

In the preferred embodiment of the present invention the UVA filter is Avobenzone, and it is present at not greater than about 10%by weight of the total composition.

2. UVB Chemical Filters

In addition to the phenylbenzimidazole sulfonic acid of the Formula I or a salt thereof as defined above, a variety of UVB chemical filters exist including alpha-cyano-beta, beta-diphenyl acrylic acid esters as set forth in U.S. Pat. No. 3,215,724, which is hereby incorporated by reference in its entirety. One particular example of an alpha-cyano-beta, beta-diphenyl acrylic acid ester is Octocrylene, which is 2-ethylhexyl 2-cyano-3, 3-diphenylacrylate. In certain cases the composition may contain no more than about 10%by weight of the total composition of octocrylene. Suitable amounts range from about 0.1-10%by weight. Octocrylene may be purchased from BASF under the tradenameN-539.

Other suitable filters include benzylidene camphor derivatives as set forth in U.S. Pat. No. 3,781,417, which is hereby incorporated by reference in its entirety. Such benzylidene camphor derivatives have the general formula:

wherein R is p-tolyl or styryl, preferably styryl. Particularly preferred is 4-methylbenzylidene camphor, which is a lipid soluble UVB filter compound sold under the tradename Eusolex 6300 by Merck.

Also suitable are cinnamate derivatives having the general formula:

wherein R and R₁ are each independently a C_1-20 straight or branched chain alkyl. Preferred is where R is methyl and R₁ is a branched chain C_1-10, preferably C₈ alkyl. The preferred compound is ethylhexyl methoxycinnamate, also referred to as Octoxinate or octyl methoxycinnamate. The compound may be purchased from Givaudan Corporation under the tradenameMCX, or BASF under the tradenameMC 80.

Also suitable are mono-, di-, and triethanolamine derivatives of such methoxy cinnamates including diethanolamine methoxycinnamate. Cinoxate, the aromatic ether derivative of the above compound is also acceptable. If present, the Cinoxate should be found at no more than about 3%by weight of the total composition.

Also suitable as UVB screening agents are various benzophenone derivatives having the general formula:

wherein R through R₉ are each independently H, OH, NaO₃S, SO₃H, SO₃Na, Cl, R”, OR” where R” is C_1-20 straight or branched chain alkyl Examples of such compounds include Benzophenone 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12. Particularly preferred is where the benzophenone derivative is Benzophenone 3 (also referred to as Oxybenzone) , Benzophenone 4 (also referred to as Sulisobenzone) , Benzophenone 5 (Sulisobenzone Sodium) , and the like. Most preferred is Benzophenone 3.

Also suitable are certain menthyl salicylate derivatives having the general formula:

wherein R₁, R₂, R₃, and R₄ are each independently H, OH, NH₂, or C_1-20 straight or branched chain alkyl. Particularly preferred is where R₁, R₂,and R₃ are methyl and R₄ is hydroxyl or NH₂, the compound having the name homomenthyl salicylate (also known as Homosalate) or menthyl anthranilate. Homosalate is available commercially from Merck under the trademarkHMS and menthyl anthranilate is commercially available from Haarmann&Reimer under the trademarkIf present, the Homosalate should be found at no more than about 15%by weight of the total composition.

Various amino benzoic acid derivatives are suitable UVB filters including those having the general formula:

wherein R₁, R₂, and R₃ are each independently H, C_1-20 straight or branched chain alkyl which may be substituted with one or more hydroxy groups. Particularly preferred is wherein 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. Particularly preferred are PABA, ethyl hexyl dimethyl PABA (Padimate O) , ethyldihydroxypropyl PABA, and the like. If present Padimate O should be found at no more than about 8%by weight of the total composition.

Salicylate derivatives are also acceptable UVB filters. Such compounds have the general formula: wherein R is a straight or branched chain alkyl, including derivatives of the above compound formed from mono-, di-, or triethanolamines. Particularly preferred are octyl salicylate, TEA-salicylate, DEA-salicylate, and mixtures thereof.

If desired, the compositions of the present invention may be formulated to have certain SPF (sun protective factor) values ranging from about 1-50, even 50+, depending on the type and dosage of UV filters. Calculation of SPF values is well known in the art.

H. Vitamins and Antioxidants

It may be desirable to incorporate one or more vitamins or antioxidants in the composition of the present invention. If present, suggested ranges are 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 its derivatives such as tocopherol acetate, tocopherol ferulate; ascorbic acid or its derivatives such as ascorbyl palmitate, magnesium ascorbyl phosphate; Vitamin A or its derivatives such as retinyl palmitate; or vitamins D, K, B, or derivatives thereof.

Preparation of the above-named cosmetic compositions and others may be accomplished with reference to any of the cosmetic formulation guidebooks and Industry journals which are available in the cosmetic industry. These references supply standard formulations which may be modified by the addition or substitution of the supramolecular complexes of the present disclosure into the formulation. Suitable guidebooks include Cosmetics and Toiletries Magazine, Vol. 111 (March, 1996) ; Formulary: Ideas for Personal Care; Croda, Inc, Parsippany, N.J. (1993) ; and Cosmeticon: Cosmetic Formulary, BASF, which are hereby incorporated in their entirety by reference. The cosmetic composition may be in any form. Suitable forms include but are not limited to solid doses, liquids, gels, lotions, creams, hard gel sticks, roll-ons formulations, mousses, aerosol sprays, pad-applied formulations, and film-forming formulations.

The cosmetic composition of the present invention may also find a broad range of applications in fields such as personal care, food, dietary supplements, and pharmaceutics.

V. Cosmetic Process

The present invention is also directed to a cosmetic process for caring for and/or making up keratin materials, comprising applying the composite or the cosmetic composition as defined above.

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

The invention will be further described in connection with the following example which is set forth for purposes of illustration without being limiting in nature.

EXAMPLES

All materials or apparatus used in present examples are those can be commercially purchased.

1. Preparation of Samples.

The Sample A-1 and Sample A-2 were prepared according to the formula in the table below, which also shows the trade names and INCI name of the raw materials used.

Table1

According to the formula in Table 1, hectorite clay or CARBOPOL is added into water and stirred thoroughly to fully disperse. Then, the phenylbenzimidazole sulfonic acid (PBSA) is added into the obtained dispersion and mixed evenly to form a homogeneous system. Separately, the basic amino acid and partial water are mixed to form a pre-mixture, and then the pre-mixture is added dropwise to the homogeneous system until the pH value reaches the specified range to obtain Sample A-1 and Sample A-2 as hydrogels.

Sample A-1 (i.e., the PBSA dispersion comprising Laponite) was subjected to XRD analysis (D8 Advance X-ray diffractometer manufactured by Bruker) to obtain a pattern for determination of Sample A-1’s chemical structure. In addition, the materials phenylbenzimidazole sulfonic acid and Laponite were also subjected to XRD analysis for reference. The obtained XRD patterns are as shown in Figures 1 and 2.

Specifically, Figure 1 shows the XRD patterns of Sample A-1 and the material Laponite. As shown in Figure 1, Sample A-1 has a pattern different from that of Laponite.

In addition, Figure 2 shows the XRD patterns of Sample A-1 and the material phenylbenzimidazole sulfonic acid. As shown in Figure 2, Sample A-1 also has a pattern different from that of phenylbenzimidazole sulfonic acid.

Thus, according to the XRD patterns of Figures 1 and 2, a new structure comprising Laponite and phenylbenzimidazole sulfonic acid (i.e., the composite of present disclosure) rather than a simple mixture thereof was formed.

2. Test Example 1

Sample A-1 and Sample A-2 prepared above were placed on a glass slide, dried and checked microscopically through a microscope (Leica dm 2500) for the presence of crystals. As shown in the upper part of Figure 3, Sample A-1 using lithium magnesium sodium silicate achieved good uniformity and continuous spreading, while poor spreading is observed in Sample A-2 using carbomer as thickener, resulting in agglomeration. Further, as shown in the lower part of Figure 3, typical needle crystals that are recrystallized phenylbenzimidazole sulfonic acid were observed in Sample A-2 using carbomer as thickener, while no crystals were found in Sample A-1 using lithium magnesium sodium silicate. It can be seen that in addition to the role of a thickener, the hydrophilic clay of the present invention also improves the stability of phenylbenzimidazole sulfonic acid in cosmetic compositions, thereby achieving better spreading and usability. It can be speculated that the composite formation of sodium lithium magnesium silicates and soluble salts of PBSA leads to the prevention of the recrystallization of phenylbenzimidazole sulfonic acid.

3. Test Example 2

In order to simulate the scenario when applied to skin, in this test, Sample A-1 and Sample A-2 were applied to PMMA plates for in vitro SPF testing.

Specifically, the in vitro SPF testing was performed by the following procedures:

A test sample was applied and distributed uniformly on a PMMA plate (50×50 mm PMMA plate with 6μm roughness, the amount of sample on PMMA plate can be 1.3 mg/cm²) by a syringe;

The sample was then dried on the PMMA plate for at least 15 minutes;

The plate center and the four quadrants of each PMMA plate with sample were tested to obtain the UV absorption data;

The UV absorption was measured by Optometrics SPF-290S Analyzer to obtain UV absorption curve of each sample;

The UV absorption curves were recorded and the average SPF value is calculated using Win SPF software provided with the instrument.

In present example, the results of SPF testing were analyzed by Win SPF software to output UV absorbance data and graphs of Sample A-1 and Sample A-2.

As shown in Figure 4, the PBSA dispersion containing Laponite (Sample A-1) showed 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) showed poor spreading of PBSA on the PMMA plate, which means recrystallization of PBSA. In addition, as we can see from the UV absorbance graphs that compared with PBSA dispersion containing Carbopol polymer (Sample A-2) , a significantly higher UV absorbance for the PBSA dispersion containing Laponite (Sample A-1) was observed. 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 composite with phenylbenzimidazole sulfonic acid (i.e., the composite comprising PBSA and sodium lithium magnesium silicate of present disclosure) , and will not recrystallize even when applied to the skin, thus achieving a significantly improved protection (especially UV protection) efficiency.

While the invention has been described in connection with the preferred embodiment, it is not intended to limit the scope of the invention to the particular form 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

A composite 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 the Formula I or a salt thereof, and

b) at least one hydrophilic clay

wherein

Ar is a substituted or unsubstituted phenyl,

R is a C_1-8-alkyl or a C_1-8-alkoxy,

n is 1, 2, 3 or 4,

q is 1, 2 or 3, and

p is 0, 1 or 2.
The composite according to claim 1, wherein

Ar is unsubstituted phenyl,

n is 1 or 2,

q is 1 or 2, and

p is 0.
The composite according to claim 1 or 2, wherein

the phenylbenzimidazole sulfonic acid is selected from the group consisting of 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 the combination thereof;

preferably, the phenylbenzimidazole sulfonic acid is selected from the group consisting of 2-phenylbenzimidazole-5-sulfonic acid, 2, 2'- (1, 4-phenylene) bis (1H-benzo [d] imidazole-5, 7-disulfonic acid) and the combination thereof.
The composite according to any one of claims 1-3, wherein

the phenylbenzimidazole sulfonic acid is neutralized by an alkaline agent,

the alkaline agent is selected from the group consisting of inorganic and organic base;

preferably, the alkaline agent is an organic base.
The composite according to claims 4, wherein

the organic base is selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, aminomethylpropanediol, 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 acid and the combination thereof.
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 the group consisting of arginine, lysine, histidine and the combination thereof,

more preferably, the basic amino acid is arginine.
The composite according to any one of claims 1-6, wherein

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

the hydrophilic clay is a synthetic hydrophilic clay;

preferably, the hydrophilic clay is a hectorite;

more preferably, the hydrophilic clay is sodium lithium magnesium silicate.
The composite according to any one of claims 1-8, wherein

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

the ratio between the phenylbenzimidazole sulfonic acid and the hydrophilic clay ranges from 0.01 to 20, preferably from 0.02 to 10, more preferably 0.1 to 5.
The composite according to any one of claims 1-10, which is an aqueous dispersion.
The cosmetic composition comprising the composite according to any one of claims 1-11 and optional cosmetically acceptable excipients.
A preparation method of the composite according to any one of claims 1-11, comprising the steps of:

1) forming a homogeneous system by mixing at least one phenylbenzimidazole sulfonic acid of the Formula I or a salt thereof and at least one hydrophilic clay, and

2) adjusting 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,

wherein

Ar is a substituted or unsubstituted phenyl,

R is a C_1-8-alkyl or a C_1-8-alkoxy,

n is 1, 2, 3 or 4,

q is 1, 2 or 3, and

p is 0, 1 or 2.
The preparation method according to claim 13, wherein

the alkaline agent is a basic amino acid selected from the group consisting of arginine, lysine, histidine and the combination thereof;

preferably, the basic amino acid is arginine.
The preparation method according to claim 13 or 14, wherein

the ratio between the phenylbenzimidazole sulfonic acid and the hydrophilic clay ranges from 0.01 to 20, preferably from 0.02 to 10, more preferably 0.1 to 5.
A cosmetic process for caring for and/or making up keratin materials comprising applying the composite as defined in anyone of claims 1-11 or the cosmetic composition as defined in claim 12 to the keratin materials.