WO2019036775A1

WO2019036775A1 - Combination of nonionic triblock copolymers and fillers in sunscreen compositions, composition and uses

Info

Publication number: WO2019036775A1
Application number: PCT/BR2017/050247
Authority: WO
Inventors: Tassia HANASHIRO; Marina Castello ESPOSITO; Angeles FONOLLA-MORENO
Original assignee: L'oreal
Priority date: 2017-08-25
Filing date: 2017-08-25
Publication date: 2019-02-28
Also published as: BR112019025366B1; BR112019025366A2

Abstract

The present invention relates to a combination of nonionic triblock copolymers and fillers, and to a sunscreen composition comprising nonionic triblock copolymers and uses thereof.

Description

COMBINATION OF NONIONIC TRIBLOCK COPOLYMERS AND FILLERS IN SUNSCREEN COMPOSITIONS, COMPOSITION AND USES

FIELD OF THE INVENTION

The present invention relates to a combination of nonionic triblock copolymers and fillers in sunscreen compositions, a sunscreen composition comprising nonionic triblock copolymers and uses thereof.

BACKGROUND OF THE INVENTION

Conventional sunscreen products generally take the form of sunscreen filter actives that are solubilized, emulsified, or dispersed in a cosmetically or physiologically acceptable carrier, which is topically applied to the skin. The sunscreen filters, typically through the aid of polymers and other ingredients included in the vehicle, form a thin, protective, and often water-resistant layer on the skin.

Sunscreen compositions must provide good protection against the sun, a measure of which is the Sun Protection Factor (SPF) value, yet have satisfactory sensory perception, such as a smooth but not greasy feel upon application. However, this combination of properties has been difficult to achieve, particularly because many active sunscreen compounds themselves have an oily or greasy feel, and increasing their content tends to cause the final product to suffer from that effect.

Also, most organic sunscreen filters are oil-like and/or oil-soluble materials. High levels of sunscreen filters in sunscreen products render the products less appealing for their greasy skin feel, stickiness, long drying time, and leave shiny residue on the skin after application. The filters also have the tendency to whiten the skin after application and after becoming wet with water or perspiration which is an undesirable attribute especially among consumers having darker skin tones.

Therefore, it is desirable to have cosmetic sunscreen formulations that provide both good SPF and desirable sensory effects such as non-greasy texture and good dry touch effect.

One way to improve the sensory properties of sunscreen formulations over the disadvantages caused by the high concentration of filters and oil phase, is by the use of fillers in. However, the high levels of fillers can cause agglomeration issues in the formulation and it can result in unsatisfactory appearance of the formulation and texture for the consumer, making it difficult to apply on the skin.

The present inventors have recognized that undesirable aesthetic and performance issues still exist in most sunscreen products. Accordingly, the applicants now reveal a combination comprising nonionic triblock copolymers and high amounts of fillers in a high SPF sunscreen, which avoids agglomeration of fillers in sunscreen composition and produces a less white film than traditional sunscreen compositions, making it aesthetically appealing to consumers.

SUMMARY OF THE INVENTION

The present invention is directed to a combination of nonionic triblock copolymers at a concentration of 0.3-7% by weight and fillers at a concentration of 5- 25% by weight in sunscreen compositions.

The addition of nonionic triblock copolymers avoids agglomeration of fillers, thereby providing less opaque compositions and minimizing a white film effect as compared to traditional sunscreen compositions, making a composition with improved texture, dry touch and aesthetical appeal to consumers.

BRIEF DESCRIPTION OF THE FIGURES FIG. 1 - Graphic showing the results related to Sensorial Test of the compositions of Example 1 .

FIG. 2 - Compares the results of microscopy of the compositions of

Example 1 .

FIG. 3 - Compares the results of Cycle in oven alternating high and low temperatures using squeezes in each temperature of the compositions of Example 1 .

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to a combination , to be used in sunscreen compositions, that comprises:

(a) About 0.3-7% by weight of Nonionic triblock copolymers; and

(b) About 5-25% by weight of a filler or a mixture of fillers. Another embodiment of the invention is directed to a sunscreen composition comprising:

(a) About 0.3-7% by weight of Nonionic triblock copolymers;

(b) About 5-25% by weight of a filler or a mixture of fillers; and

(c) About 20-40% by weight of at least one filter.

An additional embodiment is the use of the combination of the invention, to avoid or minimize agglomeration in sunscreen composition.

The present disclosure is also directed to a method of protecting a keratinous substrate from ultraviolet radiation, which comprises applying a sunscreen composition of the invention to a keratinous substrate and subjecting the keratinous substrate to ultraviolet radiation.

Terms

As used herein, the expression "at least one" means one or more and thus includes individual components as well as mixtures/combinations.

Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients and/or reaction conditions are to be understood as being modified in all instances by the term "about," meaning within +/- 5% of the indicated number.

As used herein, all ranges provided are meant to include every specific range within, and combination of sub ranges between, the given ranges. Thus, a range from 1 -5, includes specifically 1 , 2, 3, 4 and 5, as well as sub ranges such as 2-5, 3-5, 2-3, 2-4, 1 -4, etc. All ranges and values disclosed herein are inclusive and combinable. For examples, any value or point described herein that falls within a range described herein can serve as a minimum or maximum value to derive a sub-range, etc.

The expression "cosmetically/dermatologically acceptable" means that the item in question is compatible with any keratinous substrate. For example, "cosmetically acceptable carrier" means a carrier that is compatible with any keratinous substrate.

Nonionic triblock copolymers

The nonionic triblock copolymers, also known as poloxamers, of ethylene oxide and propylene oxide, also known as OE/OP/OE triblock polycondensates. Because the lengths of the polymer blocks can be customized, many different poloxamers exist, that have slightly different properties.

The addition of the nonionic triblock copolymers into a wide variety of sunscreen compositions of the invention provides consistent, dry, nongreasy, nontacky and nonwaxy sunscreen composition, formulated into conventional topically applicable, cosmetically/dermatologically acceptable vehicles, diluents or carriers thereof.

Mention may be made especially of a nonionic triblock copolymer corresponding to the following formula:

H-(0-CH2-CH2)a-(0-CH(CH₃)-CH2)b-(0-CH2-CH2)a-OH,

In which a, a' are, independently, integers ranging from 2 to 150, and b is an integer ranging from 1 to 100 The nonionic triblock copolymer(s) advantageously have a molecular weight of greater than or equal to 1500 g/mol, better still greater than 2000 g/mol, and less than 500 000 g/mol.

In an embodiment, the nonionic triblock copolymer(s) have a molecular weight of greater than 2,000 g/mol.

In an embodiment, the nonionic triblock copolymer has a molecular weight ranging from about 2,500 g/mol to about 20,000 g/mol, such as from about 8,000 g/mol to about 18,000 g/mol, or such as from about 10,000 g/mol to about 17,000 g/mol or such as from about 12,000 g/mol to aboutl 6,500 g/mol or such as from about 14,000 g/mol to about 1 6,500 g/mol.

In an embodiment, the nonionic triblock copolymer is composed or at least 60% ethylene oxide, or at least 70% ethylene oxide, or at least 80% ethylene oxide.

In an embodiment, the nonionic triblock copolymer is composed of 80% ethylene oxide.

Polyethylene glycol/polypropylene glycol/polyethylene glycol triblock polycondensates of the Poloxamer type are particularly preferred, for example those sold under the trade name Synperonic by the company Croda.

As hydrophilic polymers of the Poloxamer type, examples that may be mentioned include the following compounds: Poloxamer 1 24 sold under the trade name Synperonic PE/L 44 (1 1 OE/21 OP/1 1 OE) by the company Croda;

Poloxamer 184 sold under the trade name Synperonic PE/L 64 (13 OE/30 OP/13 OE) of MW 2900 by the company Croda;

The nonionic triblock copolymers of the invention have solid physical form with overall molecular weight 16500, with 80% of polyethylene oxide (Poloxamer 338).

As nonionic triblock copolymers have a higher polyethylene oxide content, it increases the water solubility of hydrophobic/oily substances improving the miscibility of two substances with different hydrophobicities.

The nonionic triblock copolymer (Poloxamer) of the invention is advantageously present in a concentration from about 0.3 to about 7% by weight of the total composition, preferably at about 0.4 to about 5% by weight, or most preferably at a concentration of about 0.5 to about 2% by weight, including ranges and sub-ranges therebetween, based on the total weight of the combinations and/or compositions of the present disclosure. In various embodiments, the nonionic triblock copolymer (Poloxamer) of the invention is advantageously present in a concentration of about 0.3%, 0.325%, 0.35%, 0.375%, 0.4%, 0.425%, 0.45%, 0.475%, 0.5%, 0.525%, 0.55%, 0.575%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%. 0/95%, 1 %, 1 .5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, or 7% by weight of the total composition based on the total weight of the combinations and/or compositions of the present disclosure.

Fillers

Non-limitative examples of suitable fillers of the invention are: TiO2 composited Silica or Silica encapsulated T1O2 (Silica (and) Titanium Dioxide, from 42% to 45% or TiO2 Encapsulated Silica Bead, also known by the tradename of SUNSIL Tin50, commercially sold by Sunjin Chemical), silica, Silica Silylate, Aluminium Starch Octenylsuccinate, Nylon-12, Methyl Methacrylate crosspolymer, preferably the filler is TiO2 composited Silica (Silica (and) Titanium Dioxide, from 42% to 45% or TiO2 Encapsulated Silica Bead, also known by the tradename of as SUNSIL Tin50, commercially sold by Sunjin Chemical), and mixtures thereof.

The fillers are advantageously present in a concentration from about 5 to 25% by weight of the total concentration of the combinations and/or compositions of the present disclosure. Preferably at about 10 to about 20% by weight, more preferably at a concentration of about 12 to about 1 9% by weight, most preferably at a concentration of about 14 to about 1 9% by weight, including ranges and sub-ranges therebetween, based on the total weight of the combinations and/or compositions of the present disclosure.

In various embodiments, the filler chosen from Silica encapsulated T1O2 is present in a concentration from about 1 to 25% by weight, or from about 2 to about 20% by weight, preferably from about 3 to about 15% by weight, more preferably from about 5 to 14% by weight, even more preferably from about 6 to about 12% by weight, and most preferably from about 4.5 to about 10% by weight, including ranges and subranges therebetween, based on the total weight of the combinations and/or compositions of the present disclosure.

In various embodiments, the filler chosen from silica silylate is present in a concentration from about 0.1 to 2% by weight, or from about 0.2 to about 1 .5% by weight, preferably from about 0.3 to about 1 % by weight, more preferably from about 0.4 to 0.8% by weight, even more preferably from about 0.45 to about 0.75% by weight, and most preferably from about 0.5 to about 0.7% by weight, including ranges and sub- ranges therebetween, based on the total weight of the combinations and/or compositions of the present disclosure.

In various embodiments, the filler chosen from Aluminium Starch Octenylsuccinate is present in a concentration from about 0.5 to 1 0% by weight, or from about 0.75 to about 8% by weight, preferably from about 1 to about 6% by weight, more preferably from about 1 .5 to 5% by weight, even more preferably from about 1 .6 to about 4.5% by weight, and most preferably from about 1 .7 to about 4% by weight, including ranges and sub-ranges therebetween, based on the total weight of the combinations and/or compositions of the present disclosure.

In various embodiments, the filler chosen from Nylon-12 is present in a concentration from about 0.5 to 10% by weight, or from about 0.6 to about 8% by weight, preferably from about 0.75 to about 6% by weight, more preferably from about 1 to 5% by weight, even more preferably from about 1 to about 4% by weight, and most preferably from about 1 to about 3% by weight, including ranges and sub-ranges therebetween, based on the total weight of the combinations and/or compositions of the present disclosure.

In various embodiments, the filler chosen from Methyl Methacrylate crosspolymer is present in a concentration from about 0.5 to 10% by weight, or from about 0.6 to about 8% by weight, preferably from about 0.75 to about 6% by weight, more preferably from about 1 to 5% by weight, even more preferably from about 1 to about 4% by weight, and most preferably from about 1 to about 3% by weight, including ranges and sub-ranges therebetween, based on the total weight of the combinations and/or compositions of the present disclosure.

Filters

The sunscreen filters ("filters") suitable for the present invention typically comprise chemical absorbers, but may also comprise physical blockers. Exemplary sunscreen actives which may be present into the compositions of the present invention are chemical absorbers such as p-aminobenzoic acid derivatives, anthranilates, benzophenones, camphor derivatives, cinnamic derivatives, dibenzoyl methanes, β,β- diphenylacrylate derivatives, salicylic derivatives, triazine derivatives, triazone derivatives, benzimidazole compounds, bis-benzoazolyl derivatives, benzotriazolyl derivatives, methylene bis-(hydroxyphenylbenzotriazole) compounds, cyano compounds, the sunscreen polymers, benzotriazolyl siloxanes and silicones, or mixtures thereof. These are variously described in U.S. Pat. Nos. 2,463,264, 4,367,390, 5,1 66,355 and 5,237,071 and in EP-0,863,145, EP-0,517,104, EP- 0,570,838, EP-0,796,851 , EP-0,775,698, EP-0,878,469, EP-0,933,376, EP-0,893,1 1 9, EP-0,669,323, GB-2,303,549, DE-1 , 972,1 84 and WO-93/04665, also expressly incorporated by reference.

Also exemplary of the filters which may be present in the compositions of this invention are physical blockers such as cerium oxides, chromium oxides, cobalt oxides, iron oxides, red petrolatum, silicone-treated titanium dioxide, titanium dioxide, titanium dioxide coated with stearic acid and aluminum hydroxide (such as the material known by the tradename of MICRO TITANIUM DIOXIDE MT-100 T V AND SOLD BY Tayca), zinc oxide, and/or zirconium oxide, or mixtures thereof. Other such representative sunscreens include the dimers derived from (alpha) alkyl styrene compounds, as described in DE 1 98 55 649, and the 4,4-diarylbutadienes, as described in EP-0, 967,200 and DE 197 55 649. A review of physical blockers may be found at "Sun Protection Effect of Nonorganic Materials," by S. Nakada & H. Konishi, Fragrance Journal, Volume 15, pages 64-70 (1987), which is incorporated by reference herein.

Preferred filters which may be present in the compositions of the instant invention are those selected from: dibenzoyl methanes, salicylic derivatives, triazine derivatives, triazone derivatives, zinc oxide, titanium dioxide, titanium dioxide coated with stearic acid and aluminum hydroxide, camphor derivatives, cyano compounds, siloxanes, benzotriazolyl derivatives, benzotriazolyl siloxane derivatives, and mixtures thereof.

Most preferred filters according to the present invention are:

Butyl methoxydibenzoylmethane

- Ethylhexyl salicylate

Titanium dioxide

Titanium dioxide coated with stearic acid and aluminum hydroxide Ethylhexyl triazone

Terephthalylidene dicamphor sulfonic acid

- Octocrylene

Drometrizole trisiloxane

Bis-ethylhexylloxyphenol methoxyphenyl triazine

Methylene bis-benzotriazolyl tetramethylbutylphenol (commercially available as a mixture in combination with polyglyceryl-10 laurate). Filters are advantageously present in the compositions of the invention in amounts ranging from about 20 to about 40% by weight, based on the total weight of the combinations and/or compositions of the present disclosure. Preferably from about 20 to about 35% by weight, and most preferably about 20-to about 30% by weight, including ranges and sub-ranges therebetween, based on the total weight of the combinations and/or compositions of the present disclosure. Of course, depending upon the nature of the particular formulation, higher or lower amounts may be suitable.

Furthermore, the sunscreen composition of the present invention may present a high Sun Protection Factor from 50 to 70, preferably from 60 to 80.

Composition

The compositions of the present invention can be formulated into a wide variety of product types, including creams, dispersions, emulsions (oil-in-water, water- in-oil, water-in-oil-in-water, and oil-in-water-in-silicone), gels, ointments, lotions, milks, mousses, sprays, tonics, and the like.

In a most especially preferred embodiment of the present invention, the subject cosmetic/dermatological compositions are provided as emulsion oil-in-water.

The topical sunscreen compositions of the present invention typically comprise cosmetic adjuvants chosen from organic solvents, carriers, fragrances, wetting agents, opacifiers, chelating agents, softeners, antioxidants, stabilizers, moisturizing agents, vitamins, bactericides, preservatives, polymers, thickening agents, alkaline or acidifying agents, or any other conventional agent, normally used in the field of dermatology/cosmetic as adjuvant.

Non limiting examples of polymers are ammonium polyacryloyldimethyl taurate, hydroxypropyl methylcellulose, hydroxyethylcellulose, poly C10-30 alkyl acrylate and mixtures thereof.

Non-limiting examples of preserving agents which can be used in accordance with the invention include salicylic acid, phenoxyethanol and mixtures thereof.

Suitable solvents include, but are not limited to water, glycols and polyols such as glycerin, caprylyl glycol, pentylene glycol, butylene glycol, C12-C15 alkyl benzoate, alcohols, and mixtures thereof.

In various embodiments, the solvent is present in a concentration from about 1 5 to 80% by weight, or from about 20 to about 60% by weight, or from about 25 to about 50% by weight, or from about 25 to 40% by weight, or preferably from about 27 to about 35% by weight, and more preferably from about 30 to about 35% by weight, including ranges and sub-ranges therebetween, based on the total weight of the combinations and/or compositions of the present disclosure.

Non-limiting examples of surfactants (which may also be used as emulsifying agents) suitable for the composition of the present invention are fatty acids, glyceryl esters, alkoxylated fatty alcohols, and alkyl phosphates such as stearic acid, glyceryl stearate (and) PEG-100 stearate, potassium cetyl phosphate and mixtures thereof.

Exemplary fatty or oil materials include, but are not limited to, esters and fatty alcohols such as isopropyl lauroyi sarcosinate, stearyl alcohol and mixtures thereof.

Suitable additional actives include, but are not limited to, disodium EDTA, triethanolamine, tocopherol, dimethicone, synthetic wax, C 12-15 alkyl benzoate and mixtures thereof.

The following examples serve to illustrate the invention without however exhibiting a limiting character. In these examples the amounts of the composition ingredients are given as concentration percentage of the component in the total composition.

EXAMPLES

Example 1 - Suitable composition of the invention is as follow:

Composition Composition

Components 1 2

Invention Prior Art

Water Phase

DISODIUM EDTA 0.1 0.1

TRIETHANOLAMINE 1 .25 1 .25

ISOPROPYL LAUROYL SARCOSINATE 0.5 0.5

STEARYL ALCOHOL 0.4 0.4

TEREPHTHALYLIDENE DICAMPHOR SULFONIC

ACID 3 3

PHENOXYETHANOL 0.6 0.6

ALCOHOL DENAT. 0 3

GLYCERIN 6 6

PENTYLENE GLYCOL 2 2 CAPRYLYL GLYCOL 0.3 0.3

WATER QS 100 QS 100

After Emulsion

HYDROXYPROPYL METHYLCELLULOSE 0.1 0.1

ALUMINUM STARCH OCTENYLSUCCINATE 4 4

NYLON-12 2 2

AMMONIUM POLYACRYLOYLDIMETHYL TAURATE 0.5 0.5

METHYL METHACRYLATE CROSSPOLYMER 1 1

DIMETHICONE 2.5 2.5

Oil Phase

OCTOCRYLENE 2 2

DROMETRIZOLE TRISILOXANE 0.5 0.5

BIS-ETHYLHEXYLOXYPHENOL METHOXYPHENYL

TRIAZINE 3 3

SILICA (and) TITANIUM DIOXIDE 7.5 7.5

METHYLENE BIS-BENZOTRIAZOLYL

TETRAMETHYLBUTYLPHENOL (and)

POLYGLYCERYL-10 LAURATE 2 2

STEARIC ACID 2.5 2.5

GLYCERYL STEARATE (and) PEG-1 00 STEARATE 1 .3 1 .3

POTASSIUM CETYL PHOSPHATE 1 .3 1 .3

POLOXAMER 338 0.5

TOCOPHEROL 0.3 0.3

ETHYLHEXYL SALICYLATE 4.5 4.5

TITANIUM DIOXIDE 5 5

ETHYLHEXYL TRIAZONE 2.5 2.5

SYNTHETIC WAX 1 1

C12-15 ALKYL BENZOATE 7.5 7.5

BUTYL METHOXYDIBENZOYLMETHANE 3.5 3.5

SILICA SILYLATE 0.2 0.2

FRAGRANCE 0.5 0.5

One embodiment, in making the example 1 , the following procedure was used:

1) The oil phase was heated until 75°C; 2) The water phase was mixed at room temperature;

3) Preparing the emulsion: put the water phase into the oil phase and mix well;

4) Add the gelling and neutralizer and homogenize while decreasing the temperature;

5) Put the others raw material, mix well. Ensure that the formula is totally homogeneous.

Example 2 - Comparative Test

The compositions of Example 1 were applied to the skin and studied as discussed below.

Sensorial Test

Objective: To evaluate the perception on cosmetic aspects and application of the two formula (the invention and prior art).

Methodology: Sensorial test made by applying Composition 1 and 2 in face skin of 6 women with oily or combination skin type. After that the results were analyzed by an expert.

Parameters: Perception, application, results.

Evaluation time: Results after 4 hours.

Conclusion: Figure 1 and Table 1 show the results of the applied sensorial test comparing the two formulas of Example 1 .

Table 1 - Sensorial Test Result

Sensorial evaluation Composition 1 Composition 2

Invention Prior Art

Sticky 0.2 0.3

Silicon Touch 0.0 0.8

Greasy 1 .0 1 .2

Soft Skin 3.5 3.0

Velvet Touch 5.0 5.0

Silky Touch 0.0 0.0

White 0.3 0.7

Powder aspect 0.0 0.0

Dry touch 3.5 3.0

Shiny 1 .5 1 .3 The Sensorial Test proved that the composition of the invention (composition 1 ) is less sticky, greasy, has a drier touch and shows a less white appearance, compared to the prior art composition 2, having an increase aesthetic appeal.

Example 3 - Comparative Test

Microscopy

An optical microscopy was used to analyze and compare composition 1 and 2 (invention versus prior art), in microscope lens in size 10x.

The results can be seen in Figure 2. Composition 1 show less agglomerates (dark points) than composition 2, demonstrating the achieved improvements of the present invention.

Example 4 - Comparative Test

Cycle

Test done in tubes with an overall duration of 14 days, alternating different temperatures, 4°C and 55°C, and doing squeezes in the referred tubes.

It is observed that the composition of the present invention is homogeneous and fluid and do not present agglomeration, while the one of the prior art visually presents material agglomeration.

Claims

SET OF CLAIMS

1 . A combination, to be used in sunscreen compositions, comprising:

(a) from 0.3-7% by weight of nonionic triblock copolymers composed of polyethylene oxide and polypropylene oxide, having a molecular weight of 16,500, with 80% of polyethylene oxide;

(b) from 5 to 25% by weight of a filler or a mixture of fillers.

2. A combination, according to claim 1 , wherein the filler or the mixture of fillers are selected from Silica encapsulated T1O2 (Silica (and) Titanium Dioxide), Titianium Dioxide, Silica Silylate, Aluminium Starch OctenylSuccinate, Nylon- 12, Methyl Methacrylate crosspolymer, and mixtures thereof, preferably, the filler is a combination of Silica and Titanium Dioxide.

3. A combination, according to claim 1 and 2, wherein the filler or a mixture of fillers is present preferably at a concentration of 10-20% by weight, more preferably 12-19% by weight, most preferably at a concentration of 14-19% by weight.

4. A combination, according to claim 1 wherein the nonionic triblock copolymers (Poloxamer 338) is preferably at a concentration of 0.4-5% by weight, most preferably 0.5-2% by weight.

5. A sunscreen composition, comprising the combination, as defined in any of claims 1 to 5, and about 20-40% by weight of at least one filter, preferably 20- 35% by weight of at least one filter, most preferably 20-30% by weight of at least one filter.

6. The composition according claim 5, wherein the at least one sunscreen is selected from dibenzoyl methanes, salicylic derivatives, triazine derivatives, triazone derivatives, titanium dioxide, camphor derivatives, cyano compounds, siloxanes, benzotriazolyl derivatives, and mixtures thereof.

7. The composition according to claim 5 and 6, wherein the at least one sunscreen is preferably selected from butyl methoxydibenzoylmethane, ethylhexyl salicylate, titanium dioxide, ethylhexyl triazone, terephthalylidene dicamphor sulfonic acid, octocrylene, drometrizole trisiloxane, bis-ethylhexylloxyphenol methoxyphenyl triazine, methylene bis-benzotriazolyl tetramethylbutylphenol (and) polyglyceryl-10 laurate.

8. Use of the combination as defined in any claims 1 -4, to avoid agglomeration in sunscreen compositions.

9. A method of protecting a keratinous substrate from ultraviolet radiation, wherein it comprises applying a sunscreen composition as defined in any of claims 5-8, to a keratinous substrate and subjecting the keratinous substrate to ultraviolet radiation.