WO2002039974A1

WO2002039974A1 - Personal care compositions

Info

Publication number: WO2002039974A1
Application number: PCT/GB2001/005123
Authority: WO
Inventors: Carole Llewellyn; Edward Galley
Original assignee: Natural Environment Research Council
Priority date: 2000-11-17
Filing date: 2001-11-16
Publication date: 2002-05-23
Also published as: GB0028161D0; AU2002223081A1; EP1341514A1

Abstract

Personal care compositions comprise sunscreening compounds which are mycosprorine-like amino acids (MAAs) of formula (I) in which R1 is:(a) H; or (b) a group of formula (II) -CH(R2 )CH2OH (II)in which R2 is H or Me; or(c) a group of formula III -CH(R3)COOH (III)in which R3 is H or an alkyl group containing 1 to 3 carbon atoms optionally substituted by hydroxy or an ester thereof; or(d) a group of formula IV -CR4 = CHMe (IV)in which R4 is H or -COOH; and R5 is methyl or a group of formula III as defined above or an ester thereof;and an additional organic or inorganic sunscreening agent.

Description

PERSONAL CARE COMPOSITIONS

The present invention relates to personal care compositions containing sunscreening compounds to counteract the deleterious effects of UV radiation. In one aspect of the present invention the personal care compositions are sunscreen compositions in which a sunscreening compound is used to protect the user's skin or hair from UV radiation. The term "sunscreen composition" is used herein to encompass sunscreening compositions such as moisturisers, day creams, tanning lotions and sunblockers which are intended for topical application to provide protection for the skin or hair against the sun's rays or other sources of ultraviolet (UV) radiation. Such sunscreen compositions may contain additional inorganic or organic sunscreening agents. In a further aspect of the present invention the personal care compositions are cosmetic/toiletries compositions containing a sunscreening compound to protect the compositions from the deleterious effects of exposure of the compositions to UV radiation. The term "cosmetic/toiletries composition" is used herein to encompass compositions intended for application to the skin or hair in which the sunscreen compounds are present to protect the compositions from the deleterious effects of exposure of the composition to UV radiation. Examples of cosmetic/toiletries composition include gels such as bath gels or shower gels, shampoos optionally containing conditioning agents and/or antidandruff agents, hair conditioners, liquid soaps, creams and lotions. Such compositions may be emulsions (oil-in-water emulsions or water-in-oil emulsions).

Most UV absorbing molecules that are permitted for use in the cosmetics, toiletries or healthcare field are oil soluble. There are very few water soluble UV absorbing molecules and there are no high efficiency (Extinction coefficient > 15000) water soluble molecules that absorb in the UVA region between 320 nm and 400 nm. Protection of the skin from these wavelengths is essential as these wavelengths are implicated in both direct UV mediated damage and indirect free radical damage. The deleterious effects of this on the skin include premature ageing, polymorphic light eruptions, skin cancer etc. The deleterious effects of UV radiation on cosmetic/toiletries compositions include colour fading, polymer breakdown leading to product structural instability, actives (eg vitamins) being destroyed etc.

One class of water soluble UV absorbing molecules has been disclosed, which are Mycosporine-like amino acids (MAAs). These compounds, which are derived from marine organisms, have been suggested for use as sunscreens.

However, the present inventors have discovered that MAAs are not suitable to be the sole suncreening agent in sunscreen compositions, but do offer benefits when used in conjunction with a conventional sunscreening agent, for example those listed in Council Directive 76/768/EEC of 27 July 1976 on the approximation of the laws of the Member States relating to cosmetic products, as last amended by Commission Directive 200/41/EC of 19 June 2000. In particular, the MAA and conventional sunscreen protect each other from degradation, whilst offering improved UV protection over that achieved with a conventional sunscreening agent alone.

The present invention provides personal care compositions comprising sunscreening compounds which are mycosprorine-like amino acids (MAAs) of formula I

in which Ri is: (a) H; or

(b) a group of formula II

-CH(R₂ )CH₂OH (II) in which R₂ is H or Me; or (c) a group of formula III

-CH(R₃)COOH (III) in which R₃ is H or a straight or branched alkyl group containing 1 to 3 carbon atoms optionally substituted by hydroxy or an ester thereof; or (d) a group of formula IV -C(R₄)=CHMe (IV) in which R₄ is H or -COOH; and R₅ is -CH₃ or a group of formula III as defined above or an ester thereof; and an additional inorganic or organic sunscreening agent.

The compounds of formula I can exist as different tautomers. The present invention embraces all such tautomers and mixtures thereof. The compounds of formula I have an asymmetric carbon atom and can therefore exist as different enantiomers. The present invention embraces all such enantiomers and mixtures thereof. Compounds of formula I in which the group of formula II or III contains a chiral centre can exist as different stereoisomers. The present invention embraces all such stereoisomers and mixtures thereof.

In preferred compounds of formula I in which Ri is a group of formula III, R₃ is H, -CH₂OH, -CH(OH)Me or -CHMe₂. In preferred compounds of formula I in which R₅ is a group of formula III, R₃ is H or -CH₂OH.

Examples of particularly preferred compounds of formula I are=given in Table 1 below. Table 1

The mycosporine-like amino acids can be chemically synthesised or can be extracted from marine micro algae.

For chemical synthesis:

Compounds of formula I may be prepared by dihydroxylating a compound of formula V

with osmium tetraoxide catalysis or by epoxidation with sodium hypochlorite followed by hydrolysis.

Compounds of formula V may be prepared by the condensation of an amine of formula H₂NR₁ with a carbonylcyclohexenyl compound of formula VIA

or by the condensation of an amine of formula H₂NR₅ with a carbonylcyclohexenyl compound of formula VIB

Compounds of formula V may alternatively be prepared from carbonylcyclohexenyl compounds of formula VIA or VIB by reacting the compound of formula VIA or VIB with a chlorinating agent such as Vilsmeier's Reagent to give a compound of formula VILA or VIIB respectively

CL

which is then reacted with an amine of formula H₂NR₁ or H₂NR₅ respectively.

Compounds of formula VIA or VIB may be prepared by reacting a compound of formula VIII

Vn\

with an amine of formula NH2R₅ or NH₂Rι respectively. The compound of formula VIII may be prepared by the methylation of a compound of formula IX

^

The compound of formula IX may be prepared from a compound of formula X

X

by reaction with aqueous cupric chloride.

The compound of formula X may be prepared from 4-methoxybenzylchloride by a process involving the steps of silylation, Birch reduction and protodesilylation.

Compounds of formula I may be prepared by similar reactions to those described above in which the 1 ,2-diol substituent is introduced at an earlier stage. It may then be necessary to protect this diol substituent during subsequent stages of the synthesis by methods which are well known to those skilled in the art.

For extraction from marine micro-algae:

Axenic (bacteria free) micro-algae known to be rich in compounds of formula I (e.g. the dinoflagellate Gymnodinium catenatum) are grown using aseptic techniques in sterilised medium with appropriate trace metal, metal chelating compound and vitamin addition (e.g. f/2 medium or Plymouth Erdschreiber Medium). Photosynthetically active radiation is provided by Philip's daylight fluorescent tubes at a light intensity of 80 or 100μm^"2 s^"1 with supplementary UVR on 12:12 or a 18:6 h light: dark cycle. Temperature is kept at 15-20°C depending on species and optimum conditions of pH and turbulence are chosen. Cells are harvested during logarithmic growth phase using centrifugation or filtration.

The compounds of formula I can then be solvent extracted (e.g. cold tetrahydrofuran.methanol 20:80, v/v), concentrated and chromatographically purified from the cells to produce defined pure compounds. Alternatively cells can be digested and filtered to remove cell debris thus producing an extract containing the compound(s)

The personal care compositions of the present invention may contain 0.05 to 10% of the mycosporine-like amino acid by weight of the total composition. In compositions intended to be applied to the skin or hair to protect the skin or hair from the deleterious effects of exposure to UV radiation, the amount of mycosporine-like amino acid that may be present is preferably in the range 0.5 to 10%, more preferably 1 to 6%. ln compositions in which the mycosporine-like amino acid is present to protect the compositions from the deleterious effects of exposure to UV radiation, the amount of mycosporine-like amino acid present that may be present is preferably less than 1% by weight of the total composition, more preferably 0.05 to 0.6%, most preferably 0.3 to 0.5%.

The additional organic or inorganic sunscreening agent are preferably selected from those listed in Council Directive 76/768/EEC of 27 July 1976 on the approximation of the laws of the Member States relating to cosmetic products, as last amended by Commission Directive 200/41/EC of 19 June 2000, which is herein incorporated by reference. Suitable additional inorganic sunscreening agents include: a) Microfine titanium dioxide; b) Microfine zinc oxide; c) Boron nitride; d) Iron oxides; and e) Talcs

Examples of suitable additional organic sunscreening agents include:

a) para-aminobenzoic acids, esters and derivatives thereof, for example, 2- ethylhexyl para-dimethylaminobenzoate and the octyl ester of para- aminobenzoic acid; b) methoxycinnamate esters such as 2-ethylhexyl para-methoxycinnamate, 2- ethoxyethyl para-methoxycinnamate or α,β-di-(para-methoxycinnamoyl)-α'- (2-ethylhexanoyl)-glycerin; c) benzophenones such as oxybenzone; d) dibenzoylmethanes such as 4-(tert-butyl-4'-methoxydibenzoylmethane; e) 2-phenylbenzimidazole-5 sulfonic acid and its salts and disodium phenyl dibenzimidazole tetrasulfonate; f) alkyl-β,β-diphenylacrylates for example alkyl α-cyano-β,β-diphenylacrylates such as octocrylene; g) triazines such as 2,4,6-trianilino-(p-carbo-2-ethyl-hexyl-1-oxi)-1 ,3,5 triazine; h) camphor derivatives such as methylbenzylidene camphor and terphthalylidene dicamphor sulfonic acid; i) organic pigments sunscreening agents such as methylene bis-benzotriazole tetramethyl butylphenol; j) silicone based sunscreening agents such as drometrizole trisiloxane benzylidene malonate polysiloxane and dimethicodiethyl benzal malonate; and k) salicylates such as octyl salicylates. The additional sunscreening agent may be present in an amount of 0.1 to 25% by weight of the composition.

The sunscreening agents of the present invention may be incorporated into sunscreen products such as aqueous solutions or emulsions in a conventional manner. The emulsion may be an oil-in-water emulsion or a water-in-oil emulsion.

The oil phase of the water-in-oil or oil-in-water emulsions of the present invention may comprise for example:

a) hydrocarbon oils such as paraffin or mineral oils; b) waxes such as beeswax or paraffin wax; c) natural oils such as sunflower oil, apricot kernel oil, shea butter or jojoba oil; d) silicone oils such as dimethicone, cyclomethicone or cetyldimethicone; e) fatty acid esters such as isopropyl palmitate, isopropyl myristate or dioctylmaleate; I) fatty alcohols such as cetyl alcohol or stearyl alcohol; or g) mixtures thereof, for example, the blend of waxes available commercially under the trade name Cutina (Henkel).

In preferred water-in-oil compositions of the present invention the oil phase comprises 5 to 40%, more preferably 10 to 30% by weight of the composition. In preferred oil-in-water compositions of the present invention the oil phase comprises 5 to 30%, more preferably 10 to 20% by weight of the composition.

The emulsifiers used may be any emulsifiers known in the art for use in water-in-oil or oil-in-water emulsions. It has been found that particularly effective water-in-oil and oil-in-water sunscreen compositions can be prepared by using an emulsifier or mixture of emulsifiers selected from known cosmetically acceptable emulsifiers which include: a) sesquioleates such as sorbitan sesquioleate, available commercially for example under the trade name Arlacel 83 (ICI), or polyglyceryl-2- sesquioleate; b) ethoxylated esters of derivatives of natural oils such as the polyethoxylated ester of hydrogenated castor oil available commercially for example under the trade name Arlacel 989 (ICI); c) silicone emulsifiers such as silicone polyols available commercially for example under the trade name ABIL WS08 (Th. Goldschmidt AG); d) anionic emulsifiers such as fatty acid soaps e.g. potassium stearate and fatty acid sulphates e.g. sodium cetostearyl sulphate available commercially under the trade name Dehydag (Henkel); e) ethoxylated fatty alcohols, for example the emulsifiers available commercially under the trade name Brij (ICI); f) sorbitan esters, for example the emulsifiers available commercially under the trade name Span (ICI); g) ethoxylated sorbitan esters, for example the emulsifiers available commercially under the trade name Tween (ICI); h) ethoxylated fatty acid esters such as ethoxylated stearates, for example the emulsifiers available commercially under the trade name Myrj (ICI); i) ethoxylated mono-, di-, and tri-glycerides, for example the emulsifiers available commercially under the trade name Labrafil (Alfa Chem.); j) non-ionic self-emulsifying waxes, for example the wax available commercially under the trade name Polawax(Croda); k) ethoxylated fatty acids, for example, the emulsifiers available commercially under the trade name Tefose (Alfa Chem.); or

I) mixtures thereof.

The amount of emulsifier present in the emulsion compositions of the present invention is preferably in the range 1 to 10%.

The compositions of the present invention may additionally comprise other components which will be well known to those skilled in the art. These include, for example, emolients such as isopropyl myristate or triglycerides of fatty acids e.g. lauric triglyceride or capric/caprylic triglyceride, such as the triglyceride available commercially under the trade name Migliol 810 (Huls UK); moisturisers such as D- panthenol; humectants such as glycerin or 1 ,3-butylene glycol; antioxidants such as DL-α-tocopherylacetate or butylated hydroxytoluene; emulsion stabilising salts such as sodium chloride, sodium citrate or magnesium sulphate; film formers to assist spreading on the surface of the skin such as alkylated polyvinylpyrrolidone e.g. available commercially under the trade name Antaron (GAF); thickeners such as acrylic acid polymers e.g. available commercially under the trade name Carbopol (B.F. Goodrich) or modified celluloses e.g. hydroxyethylcellulose available commercially under the trade name Natrosol (Hercules) or alkylgalactomanans available under the trade name N-Hance; preservatives such as bronopol, sodium dehydroacetate, polyhexamethylenebiguanide hydrochloride, isothiazolone or diazolidinylurea; sequestering agents such as EDTA salts; perfumes and colourings.

The invention will be illustrated by the following examples which are given by way of example only. All percentages are by weight of the final composition. Examples 1 to 19 and 41 to 47 relate to compositions containing sunscreening compounds of formula I and an additional inorganic or organic sunscreening agent intended to protect the user's skin or hair from exposure to UV radiation (sunscreening compositions). Examples 20 to 40 are cosmetic/toiletries compositions containing sunscreening compositions of formula I and an additional organic and inorganic sunscreening agent to protect the compositions from deleterious effects of exposure to UV radiation.

Example 1

The following components are used to make a sunscreen composition of the present invention. No Description %

1 Cetyl Nonanoate 8.73

2 Light Liquid Paraffin WOM 14 7.82 3 Diglyceryl esters 5.3

4 Silicone Fluid 1000 4.8

5 Microcrystalline Wax 2.0

6 Ceteareth 2 phosphate 1.00

7 Cetyl Alcohol 0.5

8 Almond Oil BP 1973 0.5

9 Butylmethoxy dibenzoyl methane 1.2

10 Octyl methoxy cinnamate 1.0

11 Di octyl Butamido triazone 1.0

12 Butylated Hydroxytoluene 0.048

13 Acrylates cross polymer 0.38

14 Tetrapropoxy ethylenediamine 1.0

15 1 ,3-Butylene Glycol 4.8

16 Preservative qs

17 Sun Filter see table below

18 Water To 100%

Method

A Ingredients 1 to 12 are mixed and heated to 65°C. B Ingredients 13 to 18 are mixed and heated to 70°C to dissolve.

C Part A is added to part B with stirring, then homogenised for 20 minutes to give a water resistant sun lotion having an SPF of 6.

The amount of sunscreening compound of formula I used is as set out below.

Example Sun Filter %

1A Asterina-330 0.5

1 B Mycosporine-2-glycine 0.5

1C N-methyl mycosporine threonine 0.6

1 D Palythenic acid 0.4

1E Palythene 0.3

1 F Palythine 0.5

1G Palythinol 0.5 1 H Porphyra-334 0.5

11 Shinorine 0.5

U Usijirene 0.5

1 K Palythene serine 0.5

1 L N-methyl mycosporine serine 0.5

1M N-methyl mycosporine valine 0.5

Example 2

The following components are used to make a sunscreen composition of the present invention.

No Description %

1 Cetyl Nonanoate 8.73

2 Light Liquid Paraffin WOM 14 7.82

3 Diglyceryl esters 5.3

4 Silicone Fluid 1000 4.8

5 Microcrystalline Wax 1.9

6 Ceteareth 2 phosphate 1.00

7 Cetyl Alcohol 0.5

8 Almond Oil BP 1973 0.5

9 Butylmethoxy dibenzoyl methane 1.2

10 Octyl methoxy cinnamate 1.0

11 3 Benzylidene Camphor 2.0

12 Butylated Hydroxytoluene 0.05

13 Acrylates cross polymer 0.4

14 Tetrapropoxy ethylenediamine 1.2

15 1 ,3-Butylene Glycol 5.0

16 Preservative qs

17 Sun Filter See Table below

18 Water To 100% Method

A Ingredients 1 to 12 are mixed and heated to 65°C. B Ingredients 13 to 18 are mixed and heated to 70°C to dissolve. C Part A is added to part B with stirring, then homogenised for 20 minutes to give sunscreen compositions of the present invention having an SPF of 6.

The amount of sunscreening compound of formula I used is as set out below.

Example Sun Filter %

2A Asterina-330 0.5

2B Mycosporine-2-glycine 0.5

2C N-methyl mycosporine threonine 0.6

2D Palythenic acid 0.4

2E Palythene 0.3

2F Palythine 0.5

2G Palythinol 0.5

2H Porphyra-334 0.5

21 Shinorine 0.5

2J Usijirene 0.5

2K Palythene serine 0.5

2L N-methyl mycosporine serine 0.5

2M N-methyl mycosporine valine 0.5

Example 3

No Description %

1 Dioctyl Maleate 10.0

2 Diglyceryl esters 5.3

3 Silicone Fluid 1000 4.8

4 Microcrystalline Wax 1.9

5 Ceteareth 2 phosphate 1.0

6 Cetyl Alcohol 0.48 7 Almond Oil 0.48

8 Butylmethoxy dibenzoyl methane 2.9

9 Octyl methoxy cinnamate 1.9

10 Octocrylene 8.00 11 Butylated Hydroxytoluene 0.048

12 Acrylates cross polymer 0.4

13 Tetrapropoxy ethylenediamine 1.1

14 1 ,3-Butylene Glycol 4.8

15 Preservative qs 16 Sun Filter See Table below

17 Water To 100%

Method

A Ingredients 1 to 11 are mixed and heated to 65°C to melt together. B Ingredients 12 to 17 are mixed and heated to 70°C.

C Part A is added to part B slowly with stirring.

D Homogenise for 20 minutes to give sunscreen compositions of the present invention having an SPF of 25.

The amount of sunscreening compound of formula I used is as set out below.

Example Filter %

3A Asterina-330 5

3B Mycosporine-2-g lyci ne 5

3C N-methyl mycosporine threonine 5

3D Palythenic acid 5

3E Palythene 5

3F Palythine 5

3G Palythinol 5

3H Porphyra-334 5

31 Shinorine 5

3J Usijirene 5

3K Palythene serine 5 3L N-methyl mycosporine serine 5 3M N-methyl mycosporine valine 5

Example 4 The following components are used to make a sunscreen composition of the present invention.

No Description %

1 Dioctyl Maleate 9.9

2 Diglyceryl esters 5.3

3 Silicone Fluid 1000 5

4 Microcrystalline Wax 2

5 Ceteareth 2 phosphate 1

6 Cetyl Alcohol 0.5

7 Almond Oil 0.5

8 Butylmethoxy dibenzoyl methane 3

9 Methylene bis-benzotriazole tetramethyl butylphenol 0.2

10 Octyl methoxy cinnamate 2

11 Butylated Hydroxytoluene 0.05

12 Acrylates cross polymer 0.4

13 Tetrapropoxy ethylenediamine 1.2

14 1 ,3-Butylene Glycol 5

15 Preservative qs

16 Sun Filter See Table below

17 Water To 100%

Method

A Ingredients 1 to 11 are mixed and heated to 65°C to melt together.

B Ingredients 12 to 17 are mixed and heated to 70°C.

C Part A is added to part B slowly with stirring.

D Homogenise for 20 minutes to give sunscreen compositions of the present invention having an SPF of 25. The amount of sunscreening compound of formula I used is as set out below.

Example Sun Filter %

4A Asterina-330 5

4B Mycosporine-2-glycine 5

4C N-methyl mycosporine threonine 5

4D Palythenic acid 5

4E Palythene 5

4F Palythine 5

4G Palythinol 5

4H Porphyra-334 5

41 Shinorine 5

4J Usijirene 5

4K Palythene serine 5

4L N-methyl mycosporine serine 5

4M N-methyl mycosporine valine 5

Example 5

Example Description %

1 Dioctyl Maleate 9.93

2 Diglyceryl esters 5.33

3 Silicone Fluid 1000 4.84

4 Microcrystalline Wax 1.94

5 Ceteareth 2 phosphate 0.97

6 Cetyl Alcohol 0.48

7 Almond Oil 0.48

8 Butylmethoxy dibenzoyl methane 2.91 9 2 Phenylbenzylimidazole 5-Sulphonic Acid

Sodium Salt 3

10 Octyl methoxy cinnamate 1.94 11 Butylated Hydroxytoluene 0.04

12 Acrylates cross polymer 0.38

13 Tetrapropoxy ethylenediamine 1.16

14 1 ,3-Butylene Glycol 4.84 15 Preservative qs

16 Sun Filter See Table below

17 Water To 100

Method A Ingredients 1 to 11 are mixed and heated to 65°C to melt together.

B Ingredients 12 to 17 are mixed and heated to 70°C.

C Part A is added to part B slowly with stirring.

The amount of sunscreening compound of formula I used is as set out below.

Example Sun Filter %

5A Asterina-330 5

5B Mycosporine-2-glycine 5

5C N-methyl mycosporine threonine 5

5D Palythenic acid 5

5E Palythene 5

5F Palythine 5

5G Palythinol 5

5H Porphyra-334 5

51 Shinorine 5

5J Usijirene 5

5K Palythene serine 5

5L N-methyl mycosporine serine 5

5M N-methyl mycosporine valine 5 Example 6

No Description %

1 Octyl Stearate 13.5

2 Isopropyl Myristate 5.0

3 Isohexadecane 3.0

4 Lecithin 0.1

5 Zinc Oxide Microfine 9.0

6 Titanium Dioxide MT100T 2.15

7 Polyglyceryl-3-Oleate 1.75

8 Cetyl Dimethicone Copolyol 1.35

9 1 ,3-Butylene Glycol 3.0

10 Magnesium Sulphate BP 0.75

11 Salt Pure Vacuum Dried 0.75

12 Preservative qs

13 Sun Filter See table below

14 Purified Water To 100

Method

A Ingredients 5 and 6 are dispersed into 1 , 2, 3, 4, 7 and 8 at 70°C with a rotor/stator homogeniser. B Ingredients 9 to 13 are dissolved in 14. C Part B is slowly added to part A with stirring. D The resulting emulsion is homogenised to achieve the required viscosity to give sunscreen compositions of the present invention having an SPF of 8.

The amount of sunscreening compound of formula I used is as set out below. Example Sun Filter % 6A Asterina-330 1.5

6B Mycosporine-2-glycine 1.5

6C N-methyl mycosporine threonine 1.5 6D Palythenic acid 1.5

6E Palythene 1.5

6F Palythine 1.5

6G Palythinol 1.5

6H Porphyra-334 1.5

61 Shinorine 1.5

6J Usijirene 1.5

6K Palythene serine 1.5

6L N-methyl mycosporine serine 1.5

6M N-methyl mycosporine valine 1.5

Example 7

No Description %

1 Cetyl Nonanoate 8.7

2 Light Liquid Paraffin WOM 7.8

3 Diglyceryl esters 5.3

4 Silicone Fluid 1000 4.8

5 Microcrystalline Wax 1.9

6 Ceteareth 2 phosphate 1.0

7 Cetyl Alcohol 0.5

8 Almond Oil BP 1973 0.5

9 Butylmethoxy dibenzoyl methane 1.2

10 Octyl Triazone 1.0

11 3 Benzylidene Camphor 2.0

12 Butylated Hydroxytoluene 0.05

13 Acrylates cross polymer 0.4

14 Tetrapropoxy ethylenediamine 1.2

15 1 ,3-Butylene Glycol 5.0

16 Preservative qs

17 Sun Filter See Table below 18 Water To 100%

Method

A Ingredients 1 and 12 are mixed and heated to 65°C. B Ingredients 13 to 18 are mixed and heated to 70°C to dissolve.

C Part A is added to part B with stirring, then homogenised for 20 minutes to give sunscreen compositions of the present invention having an SPF of 6.

The amount of sunscreening compound of formula I used is as set out below.

Example Sun Filter %

7A Asterina-330 0.5

7B Mycosporine-2-glycine 0.5

7C N-methyl mycosporine threonine 0.6

7D Palythenic acid 0.4

7E Palythene 0.3

7F Palythine 0.5

7G Palythinol 0.5

7H Porphyra-334 0.5

71 Shinorine 0.5

7J Usijirene 0.5

7K Palythene serine 0.5

7L N-methyl mycosporine serine 0.5

7M N-methyl mycosporine valine 0.5

Example 8

No Description %

1 Octyl Stearate 13.5 2 Isopropyl Myristate 5.0

3 Isohexadecane 3.0

4 Methylene bis benzotriazole tetramethyl butylphenol 2.0

5 Zinc Oxide Microfine 9.0

6 Titanium Dioxide MT100T 2.15

7 Polyglyceryl-3-Oleate 1.75 8 Cetyl Dimethicone Copolyol 1.35

9 1 ,3-Butylene Glycol 3.0

10 Mag Sulphate BP 0.75

11 Salt Pure Vacuum Dried 0.75

12 Preservative qs 13 Sun Filter See Table below

14 Purified Water To 100

Method

A Ingredients 5 and 6 are dispersed into 1 , 2, 3, 4, 7 and 8 with rotor/stator homogeniser B Ingredients 9 to 13 are dissolved into 14. C Part B is slowly added to part A with stirring.

D The resulting emulsion is homogenised to achieve the required viscosity to give sunscreen compositions of the present invention having an SPF of 8.

The amount of sunscreening compound of formula I used is as set out below.

No Sun Filter %

8A Asterina-330 1.5

8B Mycosporine-2-glycine 1.5

8C N-methyl mycosporine threonine 1.5

8D Palythenic acid 1.5

8E Palythene 1.5

8F Palythine 1.5

8G Palythinol 1.5

8H Porphyra-334 1.5

81 Shinorine 1.5

8J Usijirene 1.5

8K Palythine serine 1.5 8L N-methyl mycosporine serine 1.5

8M N-methyl mycosporine valine 1.5

Example 9 The following components are used to make a sunscreen composition of the present invention.

No Description %

I Octyl Stearate 13.5 2 Isopropyl Myristate 5.0

3 Isohexadecane 3.0

4 Di octyl Butamido triazone 2.0

5 Zinc Oxide Microfine 9.0

6 Titanium Dioxide MT100T 2.15 7 Polyglyceryl-3 Oleate 1.75

8 Cetyl Dimethicone Copolyol 1.35

9 1 ,3-Butylene Glycol 3.0

10 Magnesium Sulphate BP 0.75

I I Salt Pure Vacuum Dried 0.75 12 Preservative qs

13 Sun Filter See Table below^'

14 Purified Water To 100

Method A Ingredients 5 and 6 are dispersed into 1 , 2, 3, 4, 7 and 8 with a rotor/stator homogeniser.

B Ingredients 9 to 13 are dissolved in 14.

C Part B is slowly added to part A with stirring.

The amount of sunscreening compound of formula I used is as set out below. Example Sun Filter %

9A Asterina-330 1.5

9B Mycosporine-2-glycine 1.5

9C N-methyl mycosporine threonine 1.5

9D Palythenic acid 1.5

9E Palythene 1.5

9F Palythine 1.5

9G Palythinol 1.5

9H Porphyra-334 1.5

91 Shinorine 1.5

9J Usijirene 1.5

9K Palythine serine 1.5

9L N-methyl mycosporine serine 1.5

9M N-methyl mycosporine valine 1.5

Example 10

No Description %

1 Octyl Stearate 13.4

2 Isopropyl Myristate 4.9

3 Isohexadecane 3.0

4 Methyl Benzylidene Camphor 2.00

5 Titanium Dioxide MT100T 4.6

6 Zinc Oxide Microfine 14.0

7 Polyglyceryl-3 Oleate 175

8 Cetyl Dimethicone Copolyol 1.35

9 1 ,3-Butylene Glycol 3.0

10 Magnesium Sulphate BP 0J4

11 Salt Pure Vacuum Dried 0J4

12 Preservative qs 13 Sun Filter See Table below

14 Purified Water To 100

B Ingredients 9, 10, 11 , 12 and 13 are dissolved in 14.

C Part B is slowly added to part A with stirring.

D The emulsion is homogenised to viscosity to give sunscreen compositions of the present invention having an SPF of 30.

The amount of sunscreening compound of formula I used is as set out below.

Example Sun Filter %

10A Asterina-330 7

10B Mycosporine-2-glycine 7

10C N-methyl mycosporine threonine 10

10D Palythenic acid 10

10E Palythene 8

10F Palythine 7

10G Palythinol 7

10H Porphyra-334 7

101 Shinorine 7

10J Usijirene 7

10K Palythine serine 7

10L N-methyl mycosporine serine 7

10M N-methyl mycosporine valine 7

Example 11 The following components are used to make a sunscreen composition of the present invention.

No Description %

1 Octyl Stearate 13.4 2 Isopropyl Myristate 4.9

3 Isohexadecane 3.0

4 Lecithin 0.1

5 Titanium Dioxide MT100T 4.5 6 Zinc Oxide Microfine 14.0

7 Polyglyceryl-3 Oleate 175

8 Cetyl Dimethicone Copolyol 1.35

9 1 ,3-Butylene Glycol 3.0

10 Magnesium Sulphate BP 074 11 Salt Pure Vacuum Dried 074

12 Preservative qs

13 Sun Filter See Table below

14 Purified Water To 100

Method

A Ingredients 5 and 6 are dispersed into 1 , 2, 3, 4, 7 and 8 at 70°C with a rotor/stator homogeniser. B Ingredients 9, 10, 11 , 12 and 13 are dissolved in 14. C Part B is slowly added to part A with stirring. D The emulsion is homogenised to viscosity to give sunscreen compositions of the present invention having an SPF of 30.

The amount of sunscreening compound of formula I used is as set out below.

Example Sun Filter %

11A Asterina-330 7

11 B Mycosporine-2-glycine 7

11 C N-methyl mycosporine threonine 10

11D Palythenic acid 10

11 E Palythene 8

11 F Palythine 7

11 G Palythinol 7

11 H Porphyra-334 7 111 Shinorine 7

11J Usijirene 7

11 K Palythine serine 7

11L N-methyl mycosporine serine 7

11M N-methyl mycosporine valine 7

Example 12

No Description %

1 C12-C15 Alcohols Benzoate 12.0

2 Octyl methoxy cinnamate 3.8

3 Butylmethoxy dibenzoyl methane 3.0

4 Silicone Fluid 1000 2.0

5 Microcrystalline Wax 1.5

6 DL-A-Tocopheryl Acetate 0.2

7 PVP/Hexadecene Copolymer 175

8 Triclosan 0.20

9 Butylated Hydroxytoluene BP 0.05

10 Glyceryl-3 Glucose Distearate 2.00

11 Acr lates/Vinyl Ester Copolymer 0.14

12 Titanium Dioxide T 805 0.30

13 Sequestrene NA4 0.02

14 1 ,3-Butylene Glycol 5.00

15 Sorbithom TEP 0.50

16 Caustic Potash Soln 45% w/w 0.07

17 Preservative qs

18 Sun Filter See Table below

19 Water To 100

Method A Ingredients 1 to 10 are mixed and melted together at 60°C. B Ingredients 11 to 18 are mixed and dissolved together and heated to 65°C. C Part A is added to part B with stirring and homogenised for 20 minutes to give sunscreen compositions of the present invention having an SPF of

15.

The amount of sunscreening compound of formula I used is as set out below.

Example Sun Filter %

12A Asterina-330 2.5

12B Mycosporine-2-glycine 2.5

12C N-methyl mycosporine threonine 2.5

12D Palythenic acid 2.5

12E Palythene 2.5

12F Palythine 2.5

12G Palythinol 2.5

12H Porphyra-334 2.5

121 Shinorine 2.5

12J Usijirene 2.5

12K Palythine 2.5

12L N-methyl mycosporine serine 2.5

12M N-methyl mycosporine valine 2.5

Example 13

1 C12-C15 Alcohols Benzoate 8.08

2 Octyl methoxy cinnamate 1.41

3 Butylmethoxy dibenzoyl methane 0.80

4 4-Methylbenzylidene Camphor 0.50 5 Silicone Fluid 1000 2.02

6 Microcrystalline Wax 1.01

7 DL-A-Tocopheryl Acetate 0.20 8 Triclosan 0.20

9 Glyceryl-3 Glucose Distearate 2.02

10 Acrylates/Vinyl Ester Copolymer 0.10

11 1 ,3-Buytlene Glycol 5.05 12 Sequestrene NA4 0.02

13 Caustic Potash Soln 45% w/w 0.06

14 PVP/Hexadecene Copolymer 176

15 Preservative qs

16 Sun Filter See Table below 17 Water To 100

Method

A Ingredients 1 to 9 are melted together at 65°C. B Ingredients 10 to 16 are dispersed and dissolved into 17 and heated to 65°C.

C Part A is added to part B with stirring and homogenised for 20 minutes to give sunscreen compositions of the present invention having an SPF of 4.

The amount of sunscreening compound of formula I used is as set out below.

Example Sun Filter %

13A Asterina-330 0.5

13B Mycosporine-2-glycine 0.5

13C N-methyl mycosporine threonine 0.5

13D Palythenic acid 0.5

13E Palythene 0.5

13F Palythine 0.5

13G Palythinol 0.5

13H Porphyra-334 0.5

131 Shinorine 0.5

13J Usijirene 0.5

13K Palythine 0.5

13L N-methyl mycosporine serine 0.5 13M N-methyl mycosporine valine 0.5

Example 14

No Description %

1 C12-C15 Alcohols Benzoate 12.8

2 Octyl methoxy cinnamate 2.97

3 Butylmethoxy dibenzoyl methane 1.98

4 4-Methylbenzylidene Camphor 0.99

5 Silicone Fluid 1000 1.98

6 Microcrystalline Wax 2.22

7 DL-A-Tocopheryl Acetate 0.19

8 PVP/Hexadecene Copolymer 1.73

9 Glyceryl-3 Glucose Distearate 1.98

10 Acrylates/Vinyl Ester Copolymer 0.09

11 Triclosan 0.19

12 1 ,3-Butylene Glycol 4.95

13 Sequestrene NA4 0.01

14 Caustic Potash Soln 45% w/w 0.05

15 Preservative QS

16 Sun Filter See Table below

17 Water To 100

Method

A Ingredients 1 to 9 are mixed and melted together at 65°C. B Ingredients 10, 11 , 12, 13, 14, 15, 16 are dissolved into 17 and heated to 65°C. C Part A is added to part B with stirring and homogenised for 20 minutes to give sunscreen compositions of the present invention having an SPF of 25. The amount of sunscreening compound of formula I used is as set out below.

Example Sun Filter %

14A Asterina-330 3

14B Mycosporine-2-glycine 3

14C N-methyl mycosporine threonine 3

14D Palythenic acid 3

14E Palythene 3

14F Palythine 3

14G Palythinol 3

14H Porphyra-334 3

141 Shinorine 3

14J Usijirene 3

14K Palythine 3

14L N-methyl mycosporine serine 3

14M N-methyl mycosporine valine 3

Example 15

No Description %

1 1 ,3-Butylene Glycol 10.9

2 Sequestrene NA4 0.43 3 Citric Acid Monohydrate BP 0.04

4 Tetrapropoxy ethylenediamine 2.61

5 . Cetyl Nonanoate 19.6

6 Diglyceryl esters 12.0

7 Microcrystalline Wax 4.36 8 Light Liquid Paraffin WOM 14 14.9

9 Cetyl Alcohol 1.09

10 Silicone Fluid 1000 10.9 11 Butylmethoxy dibenzoyl methane 272

12 Octyl methoxy cinnamate 2.18

13 Ceteareth 2 phosphate 2.18

14 Theobroma Oil BP Deodorised 1.09 15 Butylated Hydroxytoluene BP 0.10

16 DL-A-Tocopheryl Acetate 0.43

17 Acrylates/Vinyl Ester Copolymer 0.87

18 Preservative qs

19 Sun Filter See Table below 20 Water To 100

Method A Ingredients 1 , 2, 3, 4, 17, 18 and 19 are dissolved into 20 and heated to 70°C. B Ingredients 5 to 16 are mixed and melted at 70°C.

C Part B is added to part A with stirring and homogenised for 20 minutes to give sunscreen compositions of the present invention having an SPF of 4.

The amount of sunscreening compound of formula I used is as set out below.

Example Sun Filter %

15A Asterina-330 0.5

15B Mycosporine-2-glycine 0.5

15C N-methyl mycosporine threonine 0.5

15D Palythenic acid 0.5

15E Palythene 0.5

15F Palythine 0.5

15G Palythinol 0.5

15H Porphyra-334 0.5

151 Shinorine 0.5

15J Usijirene 0.5

15K Palythine 0.5

15L N-methyl mycosporine serine 0.5 15M N-methyl mycosporine valine 0.5

Example 16

No Description %

1 Tetrapropoxy ethylenediamine 1.16

2 1 ,3-Butylene Glycol 4.85

3 Citric Acid Monohydrate BP PDR 0.01

4 Sequestrene NA4 0.19

5 Dioctyl Maleate 9.94

6 Diglyceryl esters 5.33

7 Microcrystalline Wax 1.94

8 Silicone Fluid 1000 4.85

9 Cetyl Alcohol 0.48

10 Octyl methoxy cinnamate 2.12

11 Butylmethoxy dibenzoyl methane 2.91

12 Butylated Hydroxytoluene BP 0.04

13 DL-A-Tocopheryl Acetate 0.19

14 Theobroma Oil BP 0.48

15 Ceteareth 2 phosphate 0.97

16 Acrylates Vinyl Ester Copolymer 0.38

17 Preservative qs

18 Sun Filter See Table below

19 Water To 100

Method

A Ingredients 1 , 2, 3, 4, 16, 17 and 18 are dissolved in 19 and heated to 70°C. B Ingredients 5 to 15 are mixed and heated to 70°C. C Part B is added to part A with stirring and then homogenised for 20 minutes to give sunscreen compositions of the present invention having an SPF of 20.

The amount of sunscreening compound of formula I used is as set out below.

Example Sun Filter %

16A Asterina-330 2.5

16B Mycosporine-2-glycine 2.5

16C N-methyl mycosporine threonine 2.5

16D Palythenic acid 2.5

16E Palythene 2.5

16F Palythine 2.5

16G Palythinol 2.5

16H Porphyra-334 2.5

161 Shinorine 2.5

16J Usijirene 2.5

16K Palythine 2.5

16L N-methyl mycosporine serine 2.5

16M N-methyl mycosporine valine 2.5

Example 17

No Description %

1 C12-C15 Alcohols Benzoate 14.0

2 Octyl methoxy cinnamate 9.00

3 Butylmethoxy dibenzoyl methane 5.00

4 Silicone Fluid 1000 2.00

5 Microcrystalline Wax 2.50

6 DL-A-Tocopheryl Acetate 0.20

7 PVP/Hexadecene Copolymer 175

8 Propyl Hydroxybenzoate BP 0.10 9 Glyceryl-3 Glucose Distearate 2.50

10 Titanium Dioxide MT100T 3.00

11 TiO2 UV-Titan M212 2.00

12 Sequestrene NA4 0.02 13 Citric Acid Monohydrate BP PDR 0.05

14 1 ,3-Butylene Glycol 5.00

15 Keltrol 0.30

16 Preservatives qs

17 Sun Filter See Table below 18 Water To 100

Method

A Ingredients 1 to 9 are mixed and melted together at 65°C. B Ingredients 10 and 11 are dispersed into A with rotor/stator homogeniser. C Ingredients 12 to 17 are dissolved in 18.

D Part B is added to part C with mixing and homogenised for 20 minutes to give sunscreen compositions of the present invention having an SPF of

50.

The amount of sunscreening compound of formula I used is as set out below.

Example Sun Filter %

17A Asterina-330 10

17B Mycosporine-2-gJycine 10

17C N-methyl mycosporine threonine 10

17D Palythenic acid 10

17E Palythene 10

17F Palythine 10

17G Palythinol 10

17H Porphyra-334 10

171 Shinorine 10

17J Usijirene 10

17K Palythine 10 17L N-methyl mycosporine serine 10 17M N-methyl mycosporine valine 10

Example 18

No Description %

1 Dioctyl Maleate 10.0

2 Diglyceryl esters 5.3

3 Silicone Fluid 1000 4.8

4 Microcrystalline Wax 1.9

5 Ceteareth 2 phosphate 1.0

6 Cetyl Alcohol 0.48

7 Almond Oil 0.48

8 Butylmethoxy dibenzoyl methane 2.9

9 Octyl methoxy cinnamate 1.9

10 Dimethico diethylbenzalmalonate 8.00

11 Butylated Hydroxytoluene 0.048

12 Acrylates cross polymer 0.4

13 Tetrapropoxy ethylenediamine 1.1

14 1 ,3-Butylene Glycol 4.8

15 Preservative qs

16 Sun Filter See Table below

17 Water To 100%

Method

A Ingredients 1 to 11 mix and heat to 65°C to melt together.

B Ingredients 12 to 17 mix and heat to 70°C. C Part A is added to part B slowly with stirring. D Homogenise for 20 minutes to give sunscreen compositions of the present invention having an SPF of 25. The amount of sunscreening compound of formula I used is as set out below.

Example Sun Filter %

18A Asterina-330 5

18B Mycosporine-2-glycine 5

18C N-methyl mycosporine threonine 5

18D Palythenic acid 5

18E Palythene 5

18F Palythine 5

18G Palythinol 5

18H Porphyra-334 5

181 Shinorine 5

18J Usijirene 5

18K Palythine 5

18L N-methyl mycosporine serine 5

18M N-methyl mycosporine valine 5

Example 19

No Description %

1 Dioctyl Maleate 10.0

2 Diglyceryl esters 5.3

3 Silicone Fluid 1000 4.8

4 Microcrystalline Wax 1.9

5 Ceteareth 2 phosphate 1.0

6 Cetyl Alcohol 0.48

7 Almond Oil 0.48

8 Butylmethoxy dibenzoyl methane 2.9

9 Octyl methoxy cinnamate 1.9

10 Benzophenone 4 8.00

11 Butylated Hydroxytoluene 0.048

12 Acrylates cross polymer 0.4 13 Tetrapropoxy ethylenediamine 1.1

14 1 ,3-Butylene Glycol 4.8

15 Preservative qs

16 Sun Filter See Table below

17 Water To 100%

Method

A Ingredients 1 to 9 and 11 mix and heat to 65°C to melt together.

B IngredientslO and 12 to 17 mix and heat to 70°C. C Part A is added to part B slowly with stirring.

The amount of sunscreening compound of formula I used is as set out below.

Example Sun Filter %

19A Asterina-330 5

19B Mycosporine-2-glycine 5

19C N-methyl mycosporine threonine 5

19D Palythenic acid 5

19E Palythene 5

19F Palythine 5

19G Palythinol 5

19H Porphyra-334 5

191 Shinorine 5

19J Usijirene 5

19K Palythine 5

19L N-methyl mycosporine serine 5

19M N-methyl mycosporine valine 5

Examples 20 - 39

In these examples of cosmetic/toiletries compositions, a sunscreening compound of formula I and an additional organic or inorganic sunscreening agent are incorporated to protect the compositions from the deleterious effects of exposure to UV radiation. The amounts of the compounds of formula I to be used are given in Table A below.

Table A

Example UV Protector of Formula I %

A Asterina-330 0.1

B Mycosporine-2-glycine 0.5

C N-methyl mycosporine threonine 0.6

D Palythenic acid 0.4

E Palythene 0.3

F Palythine 0.05

G Palythinol 0.5

H Porphyra-334 0.2

I Shinorine 0.05

J Usijirene 0.5

K Palythine 0.5

L N-methyl mycosporine serine 0.2

M N-methyl mycosporine valine 0.4

Example 20 - Bath Gel

%w/

Sodium laureth sulfate 46

Disodium pareth-3 sulfosuccinate 25

Laurie fatty acids 11.5

Diethanolamine 11.5

Methyl gluceth-10 ethoxylated 2.5

Laneth-16 3

Preservative qs

Parfum qs

Benzophenone 4 0.5 UV protector See Table A

Method

Stage 1

The following materials are added to water in order using stirring:

Sodium laureth sulfate, Disodium pareth sulfosuccinate, lauric fatty acids, diethanolamine, methyl gluceth-10, laneth-16, benzophenone 4 and UV Protector.

Stage 2

Maintaining the stirring, the bulk is heated to 65°C. when uniform, the bulk is cooled with constant stirring to below 35°C.

Stage 3

The preservative and perfume are added and the product is made to weight with purified water. The product is stirred until cool and uniform.

Example 21 - Bath Gel

%w/w

Aqua 75.5

Sodium lauryl sulfate 20 Cocamidopropyl betaine 1.5

Sodium chloride 0.2

PEG-6 Cocamide 1

Dipropylene glycol 0.25

PEG-18 glyceryl oleate/cocoate 0.5 Preservative qs

Parfum qs

Benzophenone 4 0.5

UV protector See Table A Method

Stage 1

The following materials are added to the water in order using stirring:

Sodium lauryl sulfate, sodium chloride, PEG-6 cocamide, dipropylene glycol,

PEG-18, cocamidopropyl betaines, benzophenone 4 and UV protector.

Stage 2

Maintaining stirring, the bulk is heated to 65°C. Once uniform, the bulk is cooled with constant stirring to below 35°C.

Stage 3

Example 22 - Shower Gel

%w/w Aqua 77

Sodium lauryl sulfate 10.5

Cocoamphocarboxypropionate 6

Sodium lauroyl sarcosinate 3

Cocamide MEA 3 Preservative qs

Parfum qs

Benzophenone 4 0.5

UV protector See Table A

Method

Stage 1

The following materials are added to the water in order with stirring: Sodium lauryl sulfate, cocoamphocarboxypropionate, sodium lauroyl sarcosinate, cocamide MEA, benzophenone 4 and UV protector

Stage 2 Maintaining stirring, the bulk is heated to 65°C. Once uniform, the bulk is cooled with constant stirring to below 35°C.

Stage 3

Example 23 - Shower Gel

%w/w Aqua 75

Sodium lauryl sulfate 20

Cocamidopropyl betaine 1.5

Sodium chloride 0.2

PEG-6 Cocamide 1 Dipropylene glycol 0.25

PEG-18 glyceryl oleate/cocoate 0.5

PEG-40 hydrogenated castor oil 0.5

Polyquaternium-7 0.04

PEG-7 glyceryl cocoate 0.5 Tetrasodium EDTA 0.02

Preservative qs

Benzophenone 4 0.5

UV protector see Table A Method

Stage 1

The following materials are added to the water in order with stirring: polyquaternium-7, tetrasodium EDTA, sodium lauryl sulfate, sodium chloride, PEG-6, dipropylene glycol, PEG-18, PEG-40, PEG-7, cocamidopropyl betaines, benzophenone 4 and UV protector.

Stage 3

Example 24 - Shampoo

%w/w

Aqua 84.36 Ammonium lauryl sulfate 5.04

Lauroyl sarcosine 5

Lauramide DEA 5

Tetrasodium EDTA 0.1

Preservative qs Parfum qs

Benzophenone 4 0.5

UV protector see Table A

Method

Stage 1

The following materials are added to the water in order with stirring: tetrasodium EDTA, ammonium lauryl sulfate, lauroyl sarcosinate, lauramide DEA, benzophenone 4 and UV protector

Stage 3

The preservative and perfume are added and the product is made to weight with purified water. The product was stirred until cool and uniform.

Example 25 - Shampoo

%w/w

Aqua 87 Sodium lauryl sulfate 7.8

Sodium chloride 0.8

Cocamidopropyl betaine 0.75

Glycol distearate 0.8

Laureth-3 2 Preservative qs

Parfum qs

Benzophenone 4 0.5

UV protector See Table A

Method

Stage 1

The following materials are added to the water in order with stirring: sodium lauryl sulfate, sodium chloride, laureth-3, cocamidopropyl betaines, benzophenone 4 and UV protector. Stage 2

Maintaining stirring, the bulk is heated to 65°C. Glycol distearate is then added and dispersed. Once uniform, the bulk was cooled with constant stirring to below

35°C.

Stage 3

The preservative and perfume are added and the product is made to weight with purified water. The product is stirred until cool and uniform and the pearl had set up.

Example 26 - Shampoo and Conditioner

%w/w

Aqua 67.4 Alpha olefin sulfonate 25

Cocamide DEA 2

Lauramide DEA 1

Oleamide MIPA 1.5

Cocamidopropyl betaine 2 Oleth-3 phosphate 0.1

Lauric acid 0.25

Sodium chloride 0.25

Preservative qs

Parfum qs Benzophenone 4 0.5

UV protector See Table A

Method

Stage 1

The following materials are added to the water in order with stirring: alpha olefin sulfonate, cocamide DEA, lauramide DEA, oleamide MIPA, cocamidopropyl betaine, lauric acid, oleth-3 phosphate, benzophenone 4 and UV protector.

Stage 2

Stage 3 The preservative and perfume are added and the product is made to weight with purified water. The product is stirred until cool and uniform.

Example 27 - Shampoo and Conditioner

%w/w

Aqua 82.5

Sodium lauryl sulfate 8

Cocamidopropyl betaine 2

Ethylene glycol monostearate 3 Dimethicone 3.5

Hydroxypropyl guar hydroxypropyltrimonium chloride 0.4

Citric acid 0.02

Tetrasodium EDTA 0.05

Preservative qs Parfum qs

Benzophenone 4 0.5

UV protector See Table A

Method

Stage 1

The following materials are added to the water in order with stirring: hydroxypropyl guar hydroxypropyltrimonium chloride, citric acid, tetrasodium EDTA, sodium lauryl sulfate, cocamidopropyl betaine, ethylene glycol monostearate, benzophenone 4 and UV protector.

Stage 2

Maintaining stirring, the bulk is heated to 75°C. Once uniform, dimethicone is added and dispersed. The bulk is then cooled with constant stirring to below 35°C.

Stage 3

Example 28 - Anti-dandruff Shampoo %w/w

Aqua 76.85

Sodium N-methyl-N-myristoyl-taurate 13.65

Laneth-10 acetate 1

Coconut oil diethanolamine condensate 5 Zinc pyrithione (dispersion) 2

Preservative qs

Parfum qs

Benzophenone 4 0.5

UV Protector See Table A

Method

Stage 1

The following materials are added to the water in order with stirring: sodium N-methyl-N-myristoyl-taurate, laneth-10, coconut oil, zinc pyrithione dispersion, benzophenone 4 and UV protector. Stage 2

Stage 3

Example 29 - Antidandruff Shampoo

%w/w

Aqua 82.5

Sodium lauryl sulfate 8

Cocamidopropyl betaine 2 Ethylene glycol monostearate 3

Dimethicone 3.5

Hydroxypropyl guar hydroxypropyltrimonium chloride 0.4

Citric acid 0.02

Tetrasodium EDTA 0.05 Zinc pyrithione (dispersion) 1

Preservative qs

Parfum qs

Benzophenone 4 0.5

UV Protector See Table A

Method

Stage 1

The following materials are added to the water in order with stirring: hydroxypropyl guar hydroxypropyltrimonium chloride, citric acid, tetrasodium EDTA, sodium lauryl sulfate, cocamidopropyl betaine, ethylene glycol monostearate, zinc pyrithione dispersion, benzophenone 4 and UV protector Stage 2

Stage 3

The preservative and perfume are added and the product is made to weight with purified water. The product is stirred until cool and uniform. Example 30 - Liquid Soap

%w/w

Aqua 83.2

Magnesium aluminium silicate 1

Potassium hydroxide 2 Propylene glycol 2.5

Sodium laureth sulfate 1.8

Oleic acid 9

Preservative qs

Parfum qs Benzophenone 4 0.5

UV Protector See Table A

Method

Stage 1

Magnesium aluminium silicate is added to the water and dispersed using stirring then potassium hydroxide is added and dispersed. Propylene glycol, sodium laureth sulfate, oleic acid, benzophenone 4 and the UV protector are then added. Stage 2

Maintaining the stirring, the bulk is heated to 75°C, giving enough time for the oleic acid to saponify. The bulk is then cooled with constant stirring to below 35°C.

Stage 3

Example 31 - Beaded Shower Gel

%w/w

Aqua 76.5

Sodium lauryl sulfate 9.5

Citric acid 0.02 Tetrasodium EDTA 0.05

Mica beads 0.1

Acrylates copolymer 6

PEG-40 hydrogenated castor oil 0.5

PEG-6 Cocamide 1 Dipropylene glycol 0.25

PEG-18 glyceryl oleate/cocoate 0.5

Preservative qs

Parfum qs

Benzophenone 4 0.5 UV Protector See Table A

Method

Stage 1 The following materials are added to the water in order with stirring: citric acid, tetrasodium EDTA, sodium lauryl sulfate, PEG-40, PEG-6, PEG-18, acrylates copolymer, dipropylene glycol, benzophenone 4 and UV Protector Stage 2

Maintaining stirring, the bulk is heated to 70°C. Once uniform, the bulk is then cooled with constant stirring to below 35°C.

Stage 3

The preservative, perfume and mica are added and the product is made to weight with purified water. The product is stirred until cool and uniform.

Example 32 - Oil-in-Water Emulsion

%w/w

Aqua 62.5

Carbomer 940 0.35

1 ,3-Butylene glycol 2 Tetrasodium EDTA 0.05

Potassium Hydroxide 0.06

Polysorbate 80 1

Paraffinum liquidum 18

Preservative qs Octyl Methoxycinnamate 0.5

UV protector See Table A

Method

Stage 1

EDTA is dispersed in the water using stirring. Carbomer is then added and hydrated using homogenisation for 30 minutes. The UV protector is added and dispersed using stirring.

Butylene glycol and polysorbate 80 are then added and mixed until uniform using stirring. This phase is then heated to 70°C. Stage 2

The paraffinum liquidum is weighed into a separate vessel and heated to 70°C.

Stage 3

The oil phase is added to the aqueous phase and an emulsion is formed using high shear homogenisation for 10 minutes. The potassium hydroxide and octyl methoxycinnamate is then added and the shear was maintained for a further 5 minutes.

Stage 4

The emulsion is cooled to below 35°C using stirring. The preservative is then added and the product is made to weight with purified water. The emulsion is stirred until cool and uniform.

Example 33 - Oil-in-Water Emulsion

%w/w

Aqua 76.5

Glycerin 5 Paraffinium liquidum 5

Dicaprylyl maleate 3

Petrolatum 3

Cetyl alcohol 2

Steareth-2 1.5 Glyceryl stearate 1.5

Steareth-21 1

Sodium citrate 0.06

Citric acid 0.02

Hydroxyethyl cellulose 0.3 Tetrasodium EDTA 0.05

Preservative qs

Parfum qs Octyl methoxycinnamte 0.5

UV Protector See Table A

Stage 1 EDTA, citric acid, sodium citrate and glycerin are dispersed in the water using stirring. For sample 1 , the hydroxyethyl cellulose is then added and hydrated using homogenisation for 5 minutes. The UV Protector is added and dispersed with stirring. This phase was then heated to 70°C.

Stage 2

The oils and waxes are mixed in a separate vessel and heated to 70°C until melted.

Stage 3 The oil phase is added to the aqueous phase and an emulsion is formed using high shear homogenisation for 10 minutes and the octyl methoxycinnamate is added.

Stage 4 The emulsion is cooled to below 35°C using stirring. The preservative and perfume are then added and the product is made to weight with purified water.

The emulsion is stirred until cool and uniform.

Example 34 - Water-in-Oil Emulsion %w/w

Aqua 76.43

1 ,3-Butylene glycol 5

Sodium chloride 1

Cetyl dimethicone copolyol 1.5 Sorbitan isostearate 0.5

Stearic acid 0.05

Paraffinum liquidum 15 Butylated hydroxytoluene 0.02

Preservative qs

Octyl methoxycinnamate 0.5

UV Protector See Table A

Method

Stage 1

Sodium chloride, butylene glycol and UV Protector are added to the water using stirring. This phase is heated to 70°C maintaining stirring.

Stage 2

The oil phase is mixed and heated to 70°C until melted and uniform.

Stage 3

Using high speed stirring, the aqueous phase is slowly added to the oil phase and stirred until emulsified and uniform. The emulsion is then transferred to a homogeniser and high shear was applied for 5 minutes and then the octyl methoxycinnamate is added.

Stage 4

The emulsion is cooled to below 35°C with stirring and the preservative is added.

Stirring continued until cool and uniform.

Example 35 - Cold Cream

%w/w

Aqua 68.5

Magnesium aluminium silicate 1

Synthetic beeswax 1.5 Fatty acid ester 1.5

Paraffinum liquidum 20 Sorbitan monopalmitate fatty acid ester 3.5

Polysorbate 60 3.5

Preservative qs

Octyl methoxycinnamate 0.5 UV Protector See Table A

Method

Stage 1 Magnesium aluminium silicate is added to the water and dispersed using stirring, followed by the addition and dispersion of polysorbate 60 and the UV protector. This phase is heated to 70°C maintaining stirring.

Stage 2 The oil phase is mixed in a separate vessel and heated to 70°C until melted and uniform.

Stage 3

Maintaining the temperature of both phases, the oil phase is added to the aqueous phase and an emulsion is formed using high shear homogenisation for 10 minutes and the octyl methoxycinnamate added.

Stage 4

Example 36 - Body Lotion

%w/w Aqua 68.47

Carbomer 940 0.3

Sodium hydroxide 0.028 Glycerine 5

Glyceryl monostearate and polyoxyethylene 4

Stearate fatty acid ester 2

Paraffinum liquidum 15 Cholesterol 5

Oleyl alcohol 2

Tetrasodium EDTA 0.05

Preservative qs

Octyl methoxycinnamate 0.5 UV Protector See Table A

Method

Stage 1 EDTA is dispersed in the water using stirring. The Carbomer is then added and hydrated using homogenisation for 30 minutes. Glycerin and the UV protector are then added and stirred until uniform using stirring. This phase is then heated to 70°C.

Stage 2

The oil phase is mixed in a separate vessel and heated to 70°C until melted and uniform.

Stage 3 The oil phase is added to the aqueous phase and an emulsion is formed using high shear homogenisation for 10 minutes. Sodium hydroxide and octyl methoxycinnamate are then added and the shear is maintained for a further 5 minutes. Stage 4

Example 37 - Hair Conditioner

%w/w

Aqua 89.3

Cetyl trimethyl ammonium chloride 1.5 Alumina 0.5

Petrolatum 1.5

Glyceryl stearate 0.2

Acetylated lanolin alcohol 2

Mineral oil (and) lanolin alcohol 2 Stearyl alcohol 2.5

Preservative qs

Parfum qs

Octyl methoxycinnamate 0.5

UV protector See Table A

Method

Stage 1

The materials are added to the water in the order shown above (excluding the parfum and preservative) with stirring. With constant stirring, the bulk is heated to 70°C until all materials are dispersed, melted and uniform.

Stage 2

The product was cooled to below 35°C using stirring. The preservative and perfume are then added and the product is made to weight with purified water. The product is then stirred until cool and uniform. Example 38 - Hair Conditioner

%w/w

Aqua 89.5

Cetyl alcohol 4 Cocamide MEA 2

Stearamidopropyl dimethylamine 1

Centrimonium chloride 0.5

Citric acid 0.02

Lactic acid 0.4 hydroxyethyl cellulose 0.5

Tetrasodium EDTA 0.05

Preservative qs

Parfum qs

Octyl methoxycinnamate 0.5 UV Protector See Table A

Method

Stage 1 EDTA, citric acid and lactic acid were added to the water and dispersed with stirring. The hydroxyethyl cellulose was added and hydrated using a homogeniser for 5 minutes and the UV protector and octyl methoxycinnamate was then added.

The other materials were added to the water in the order shown above (excluding the parfum and preservative) with stirring. With constant stirring, the bulk was heated to 70°C until all materials were dispersed, melted and uniform.

Stage 2 The product was cooled to below 35°C using stirring. The preservative and perfume were then added and the product was made to weight with purified water. The product was then stirred until cool and uniform. Example 39 - Fluid Foundation

%w/w

Aqua 61

Carbomer 941 0.5

Lanolin oil 5

Paraffinum liquidum 3.5

Stearyl alcohol (and) ceteareth-20 condensate 3

Triethanolamine 0.5

Ethanol 26

Tetrasodium EDTA 0.02

Pigments qs

Preservative qs

Octyl methoxycinnamate 0.5

UV protector See table A

Method

Stage 1

EDTA is added to the water and dispersed with stirring. The carbomer is added and hydrated using a homogeniser for 30 minutes and then the UV protector is added. This phase was then heated to 70°C.

Stage 2

Stage 3

The oil phase is added to the aqueous phase and an emulsion is formed using high shear homogenisation for 10 minutes. Sodium hydroxide and octyl methoxycinnamate is then added and the shear is maintained for a further 5 minutes. Maintaining the shear, the pigments are slowly added and dispersed. The emulsion is sheared until uniform. Stage 4

The emulsion is then cooled to below 35°C with stirring. The preservative is added and the product is made to weight with purified water.

Example 40 - Body Scrub

%w/w

Aqua 65.5

Lauroamphodiacetate 8 sodium lauryl sulfate 6 Hexylene glycol 6

PEG-40 castor oil 4

Polysorbate 80 1.5

Cetyl acetate 1

Acetylated lanolin alcohol 0.5 Methyl gluceth-20 2

Glycerin 4

Polyethylene 1

Parfum qs

Preservative qs Octyl methoxycinnamate 0.5

UV Protector See Table A

Method

Stage 1

The materials (excluding the parfum, preservative and polyethylene) are added to the water in order with stirring. This is heated to 70°C, maintaining the stirring. The bulk is stirred until uniform.

Stage 2

Maintaining the stirring the product is cooled to 35°C. The parfum, preservative and polyethylene are added and the product is made to weight with purified water. The product is stirred until the polyethylene is evenly distributed and the product is uniform.

Examples 41 - 45

In these examples of hair toiletry compositions, a sunscreening compound of formula I and an additional organic or inorganic sunscreening agent are incorporated to protect the hair from the deleterious effects of exposure to UV radiation. This damage is noticed as both natural and artificial hair colour fading, increased brittleness, dullness and tendency to split, loss of shine, feel or control and damage to the natural proteins and lipids in the hair. The amounts of the compounds of formula I to be used are given in Table B below.

Table B

Example UV Protector of Formula I %

A Asterina-330 0.1

B Mycosporine-2-glycine 1.5

C N-methyl mycosporine threonine 1.0

D Palythenic acid 0.4

E Palythene 0.3

F Palythine 2.5

G Palythinol 0.5

H Porphyra-334 1.2

I Shinorine 0.1

J Usijirene 0.5

K Palythine 0.5

L N-methyl mycosporine serine 1.2

M N-methyl mycosporine valine 0.4 Example 41 - Shampoo

%w/w

Aqua to 100

Sodium lauryl sulfate 7.8

Sodium chloride 0.8

Cocamidopropyl betaine 0.75

Glycol distearate 0.8

Laureth-3 2

Preservative qs

Parfum qs

Benzophenone 4 0.5

UV protector See Table B

Method

Stage 1

The following materials are added to the water in order with stirring: sodium lauryl sulfate, sodium chloride, laureth-3, cocamidopropyl betaines, benzophenone 4 and UV protector.

Stage 2

35°C.

Stage 3

The preservative and perfume are added and the product is made to weight with purified water. The product is stirred until cool and uniform and the pearl had set up. Example 42 - Shampoo and Conditioner

%w/w

Aqua to 100

Alpha olefin sulfonate 25 Cocamide DEA 2

Lauramide DEA 1

Oleamide MIPA 1.5

Cocamidopropyl betaine 2

Oleth-3 phosphate 0.1 Lauric acid 0.25

Sodium chloride 0.25

Preservative qs

Parfum qs

Benzophenone 4 0.5 UV protector See Table B

Method

Stage 1 The following materials are added to the water in order with stirring: alpha olefin sulfonate, cocamide DEA, lauramide DEA, oleamide MIPA, cocamidopropyl betaine, lauric acid, oleth-3 phosphate, benzophenone 4 and UV protector.

Stage 2

Stage 3 The preservative and perfume are added and the product is made to weight with purified water. The product is stirred until cool and uniform. Example 43 - Shampoo and Conditioner

%w/w

Aqua to 100

Sodium lauryl sulfate 8

Cocamidopropyl betaine 2

Ethylene glycol monostearate 3

Dimethicone 3.5

Hydroxypropyl guar hydroxypropyltrimonium chloride 0.4

Citric acid 0.02

Tetrasodium EDTA 0.05

Preservative qs

Parfum qs

Benzophenone 4 0.5

UV protector See Table B

Method

Stage 1 The following materials are added to the water in order with stirring: hydroxypropyl guar hydroxypropyltrimonium chloride, citric acid, tetrasodium EDTA, sodium lauryl sulfate, cocamidopropyl betaine, ethylene glycol monostearate, benzophenone 4 and UV protector.

Stage 2

Stage 3

The preservative and perfume are added and the product is made to weight with purified water. The product is stirred until cool and uniform. Example 44 - Hair Conditioner

%w/w

Aqua to 100 Cetyl trimethyl ammonium chloride 1.5

Alumina 0.5

Petrolatum 1.5

Glyceryl stearate 0.2

Acetylated lanolin alcohol 2 Mineral oil (and) lanolin alcohol 2

Stearyl alcohol 2.5

Preservative qs

Parfum qs

Benzophenone 4 0.5 UV protector See Table B

Method

Stage 1 The materials are added to the water in the order shown above (excluding the parfum and preservative) with stirring. With constant stirring, the bulk is heated to 70°C until all materials are dispersed, melted and uniform.

Stage 2 The product was cooled to below 35°C using stirring. The preservative and perfume are then added and the product is made to weight with purified water. The product is then stirred until cool and uniform. Example 45 - Hair Conditioner

%w/w

Aqua to 100

Cetyl alcohol 4 Cocamide MEA 2

Stearamidopropyl dimethylamine 1

Centrimonium chloride 0.5

Citric acid 0.02

Lactic acid 0.4 hydroxyethyl cellulose 0.5

Tetrasodium EDTA 0.05

Preservative qs

Parfum qs

Benzophenone 4 0.5 UV Protector See Table B

Method

Stage 1 EDTA, citric acid and lactic acid were added to the water and dispersed with stirring. The hydroxyethyl cellulose was added and hydrated using a homogeniser for 5 minutes and the UV protector was then added.

Stage 2

The product was cooled to below 35°C using stirring. The preservative and perfume were then added and the product was made to weight with purified water. The product was then stirred until cool and uniform. Example 46 and 47

In these examples of skincare and cosmetic compositions, a sunscreening compound of formula I and an additional organic or inorganic sunscreening agent are incorporated to protect the skin from the deleterious effects of exposure to UV radiation. This damage is noticed as the generation of harmful reactive oxygen species in the skin, damage to cellular structures such as langerhan cells, keratinocytes and melanocytes, damage to collagen and elastin resulting in premature ageing, damage to DNA, mitochondria and other intracellular constituents, and damage to the natural proteins and lipids in the skin. The amounts of the compounds of formula I to be used are given in Table C below. Table C

Example UV Protector of Formula I %

A Asterina-330 0.1

B Mycosporine-2-glycine 1.5

C N-methyl mycosporine threonine 1.0

D Palythenic acid 0.4

E Palythene 5.0

F Palythine 2.5

G Palythinol 0.5

H Porphyra-334 1.2

I Shinorine 0.3

J Usijirene 7.5

K Palythine 0.5

L N-methyl mycosporine serine 10.0

M N-methyl mycosporine valine 0.4

Example 46 - Dav Cream

%w/w

Aqua to 100

Glycerin 5

Paraffinium liquidurr 1 5 Dicaprylyl maleate 3

Petrolatum 3

Cetyl alcohol 2

Steareth-2 1.5 Glyceryl stearate 1.5

Steareth-21 1

Sodium citrate 0.06

Citric acid 0.02

Hydroxyethyl cellulose 0.3 Tetrasodium EDTA 0.05

Preservative qs

Parfum qs

Benzophenone 4 0.5

UV Protector See Table C

Method

Stage 1

EDTA, citric acid, sodium citrate and glycerin are dispersed in the water using stirring. For sample 1 , the hydroxyethyl cellulose is then added and hydrated using homogenisation for 5 minutes. The UV Protector and benzophenone 4 are added and dispersed with stirring. This phase was then heated to 70°C.

Stage 2 The oils and waxes are mixed in a separate vessel and heated to 70°C until melted.

Stage 3

The oil phase is added to the aqueous phase and an emulsion is formed using high shear homogenisation for 10 minutes. Stage 4

The emulsion is cooled to below 35°C using stirring. The preservative and perfume are then added and the product is made to weight with purified water.

The emulsion is stirred until cool and uniform.

Example 47 - Fluid Foundation

%w/w

Aqua to 100

Carbomer 941 0.5

Lanolin oil 5

Paraffinum liquidum 3.5

Stearyl alcohol (and) ceteareth-20 condensate 3

Triethanolamine 0.5

Ethanol 26

Tetrasodium EDTA 0.02

Pigments qs

Preservative qs

Benzophenone 4 0.5

UV protector See table C

Method

Stage 1

Stage 2

The oil phase is mixed in a separate vessel and heated to 70°C until melted and uniform. Stage 3

The oil phase is added to the aqueous phase and an emulsion is formed using high shear homogenisation for 10 minutes. Sodium hydroxide is then added and the shear is maintained for a further 5 minutes. Maintaining the shear, the pigments and benzophenone 4 are slowly added and dispersed. The emulsion is sheared until uniform.

Stage 4

Claims

1. Personal care compositions comprising:

(i) sunscreening compounds which are mycosprorine-like amino acids (MAAs) of formula I:

in which R-i is:

(a) H; or

(b) a group of formula II -CH(R₂ )CH₂OH (II) in which R₂ is H or Me; or

(c) a group of formula III

-CH(R₃)COOH (111) in which R₃ is H or an alkyl group containing 1 to 3 carbon atoms optionally substituted by hydroxy or an ester thereof; or

(d) a group of formula IV

-CR₄ = CHMe (IV) in which R₄ is H or -COOH; and

R₅ is methyl or a group of formula HI as defined above or an ester thereof; and (ii) an additional inorganic or organic sunscreening agent.

2. Personal care compositions as claimed in claim 1 wherein Ri is a group of formula HI and R₃ is selected from H, -CH₂OH, -CH(OH)Me and -CHMe₂.

3. Personal care compositions as claimed in claim 1 or claim 2 wherein R₅ is a group of formula III and R₃ is H or -CH₂OH.

4. Personal care compositions as claimed in any one of claims 1 to 3 wherein the mycosporine-like amino acid is selected from palythine, palythine serine, palythinol, asterina, mycosporine-2-glycine, shinorine, porphyra-334, N-methyl mycosporine serine, N-methyl mycosporine threonine, mycosporine-glycine valine, palythenic acid, usijirene and palythene.

5. Personal care compositions as claimed in any one of claims 1 to 4 wherein compositions contain 0.05 to 10% of the mycosporine-like amino acid by weight of the total composition.

6. Personal care compositions as claimed in any one of claims 1 to 5 wherein the additional inorganic or organic sunscreening agent is selected from: a) Microfine titanium dioxide; b) Microfine zinc oxide; and c) Boron nitride; d) Iron oxides; e) Talcs; f) para-aminobenzoic acids, esters and derivatives thereof; g) methoxycinnamate esters; h) benzophenones; i) dibenzoylmethanes; j) 2-phenylbenzimidazole-5-sulphonic acid and its salts and disodium phenyl dibenzimidazole tetrasulfonate; k) alkyl-β,β-diphenylacrylates;

I) triazines; m) camphor derivatives; n) organic pigments sunscreening agents; o) silicone based sunscreening agents; and p) salicylates.

7. Personal care compositions as claimed in claim 6 wherein the additional organic sunscreening agent is selected from 2-ethylhexyl para-dimethylamino- benzoate, the octyl ester of para-aminobenzoic acid, 2-ethylhexyl para- methoxycinnamate, 2-ethoxyethyl para-methoxycinnamate, α,β-di-(para- methoxycinnamoyl)-α'-(2-ethylhexanoyl)-glycerin, oxybenzone, 4-(tert-butyl-4'- methoxydibenzoylmethane, octocrylene, 2,4,6-trianilino-(p-carbo-2-ethylhexyl-1 '- oxy)-1 ,3,5 triazine, bis-octyloxyphenol methoxyphenyl triazine, methylbenzylidene camphor, terphthalylidene dicamphor sulfonic acid, methylene bis-benzotriazxole tetramethyl butylphenol, drometrizole trisiloxane, benzylidene malonate polysiloxane, dimethicodiethyl benzal malonate or octyl salicylate.

8. Use of a mycosporine-like amino acid of formula I as defined in any one of claims 1 to 3 in combination with an additional inorganic or organic sunscreening agent in the preparation of personal care compositions to provide protection to the user's skin or hair against the deleterious effects of UV radiation.

9. Use of a mycosporine-like amino acid of formula I as defined in any one of claims 1 to 3 in combination with an additional inorganic or organic sunscreening agent in the preparation of personal care compositions to protect the compositions from the deleterious effects of exposure of the composition to UV radiation.

10. Use of a mycosporine-like amino acid of formula I in combination with an additional inorganic or organic sunscreening agent as claimed in either claim 8 or claim 9 wherein the mycosporine-like amino acid is selected from palythine, palythine serine, palythinol, asterina, mycosporine-2-glycine, shinorine, porphyra- 334, N-methyl mycosporine serine, N-methyl mycosporine threonine, mycosporine-glycine valine, palythenic acid, usijirene and palythene.

11. Use of a mycosporine-like amino acid of formula I in combination with an additional inorganic or organic sunscreening agent as claimed in any one of claims 8 to 10 wherein the additional inorganic or organic sunscreening agent is selected from: a) Microfine titanium dioxide; b) Microfine zinc oxide; and c) Boron nitride; d) Iron oxides; e) Talcs; f) para-aminobenzoic acids, esters and derivatives thereof; g) methoxycinnamate esters; h) benzophenones; i) dibenzoylmethanes; j) 2-phenylbenzimidazole-5-sulphonic acid and its salts and disodium phenyl dibenzimidazole tetrasulfonate; k) alkyl-β,β-diphenylacrylates; I) triazines; m) camphor derivatives n) organic pigments sunscreening agents o) silicone based sunscreening agents; and p) salicylates.

12. Use of a mycosporine-like amino acid of formula I in combination with an additional inorganic or organic sunscreening agent as claimed in claim 11 wherein the additional organic sunscreening agent is selected from 2-ethylhexyl para-dimethylaminobenzoate, the octyl ester of para-aminobenzoic acid, 2- ethylhexyl para-methoxycinnamate, 2-ethoxyethyl para-methoxycinnamate, α,β-di- (para-methoxycinnamoyl)-α'-(2-ethylhexanoyl)-glycerin, oxybenzone, 4-(tert-butyl- 4'-methoxydibenzoylmethane, octocrylene, 2,4,6-trianilino-(p-carbo-2-ethylhexyl-1 '- oxy)-1 , 3, 5 triazine, bis-octyloxyphenol methoxyphenyl triazine, methylbenzylidene camphor, terphthalylidene dicamphor sulfonic acid, methylene bis-benzotriazxole tetramethyl butylphenol, drometrizole trisiloxane, benzylidene malonate polysiloxane, dimethicodiethyl benzal malonate or octyl salicylate.

13. Use of a mycosporine-like amino acid of formula I in combination with an additional inorganic or organic sunscreening agent as claimed in any of claims 8 to 12, wherein the personal care composition contains 0.05 to 10% by weight of the mycosporine-like amino acid and 0.1 to 25% by weight of the additional inorganic or organic sunscreening agent.