CLIAMS:1. A sunscreen product for extended UV protection comprising Tinosorb M, Octocrylene and at least one sunscreen agent selected from Octisalate and Octyl methoxycinnamate.

2. The sunscreen product as claimed in claim 1, wherein Tinosorb M is present in 0.1-10% by wt, preferably 0.5-5% by wt.

3. The sunscreen product as claimed in claim 1, wherein Octocrylene is present in 0.1-10% by wt, preferably 5-10% by wt.

4. The sunscreen product as claimed in claim 1, wherein Octisalate is present in 0.1-5% by wt, preferably 1-5% by wt.

5. The sunscreen product as claimed in claim 1, wherein Octyl methoxycinnamate is present in 0.1-10% by wt, preferably 3-10% by wt.

6. A cosmetic composition for topical application comprising
a. Tinosorb M, Octocrylene and at least one sunscreen agent selected from Octisalate and Octyl methoxycinnamate; and
b. cosmetically acceptable ingredients.

7. The cosmetic composition as claimed in claim 6, wherein Tinosorb M is present in 0.1-10% by wt.

8. The cosmetic composition as claimed in claim 6, wherein Octocrylene is present in 0.1-10% by wt.

9. The cosmetic composition as claimed in claim 6, wherein Octyl methoxycinnamate is present in 0.1-10% by wt.

10. The cosmetic composition as claimed in claim 6, wherein Octisalate is present in 0.1-5% by wt.

11. The cosmetic composition as claimed in claim 6, wherein said cosmetically acceptable ingredients are selected from silicones, vitamin and/or derivatives thereof, polyols, vehicles, structurants, emollient/s, gelling agent/s, a thickening agent/s, hydrophilic or hydrophobic polymer, emulsifying agent/s, alcohol/s, binders, emollients, preservatives, colorants, perfumes, skin-lightening agents, anti-wrinkle agents and antimicrobials.

12. The cosmetic composition as claimed in claim 6 having an SPF of atleast 18, preferably SPF of atleast 12.

13. The cosmetic composition as claimed in claim 6, wherein the composition is selected from sunscreen lotions, serums, oils, sprays, creams, fairness creams, anti-aging creams, moisturizing creams and hair serums, hair conditioners, mousse, face wash, cleansing compositions, masks and wipes.

14. The cosmetic composition as claimed in claim 6, wherein the composition is adapted to remain photo stable even after 2 hours post application of sunscreen product.

15. The cosmetic composition as claimed in claim 6, wherein said composition provides protection from harmful UV radiations falling in the lower wavelengths of UVB region in the range of 280 – 290 nm. ,TagSPECI:Field of invention

The present invention relates to a cosmetic composition. More particularly the invention provides a sunscreen composition comprising combination of UV filters Tinosorb M, Octocrylene along with at least one sunscreen agents selected from Octisalate and Octyl methoxycinnamte (OMC). The composition of the present invention provides an extension in absorption range of sunscreens.

Background and prior art
The use of sunscreens has increased dramatically after the implication of ultraviolet irradiation in the pathogenesis of skin ageing and more importantly, skin cancer and DNA damage (Figure 1A). Also, radiation below the wavelength of 300 nm is assumed to be most effective in causing erythema as seen in Figure 1B. It is well known that radiation at 290 nm is nearly 4 orders of magnitude more effective than radiation at 320 nm (M.C. Sharma et al, “Ultraviolet radiation received in Antarctica in comparison with the Indian region”, Atmospheric Environment. Part A. General Topics, 26(4), Pages 731–734, 1992) as shown in Figure 1A.
Furthermore, with the rapid depletion of stratospheric ozone nowadays, a higher magnitude of UVB radiation reaches the earth’s surface and this phenomenon is seen to directly correlate with the recent increase in skin cancer cases (L. Narayana et al, “Review: Ultraviolet radiation and skin cancer”, International Journal of Dermatology, 49(9), Pages 978-986, 2010). The most apparent effect of UVB irradiation on the skin is perceived as skin burns and erythema. Sunscreens have been proven to be very effective in preventing erythema which is a standard end point in determining sun protection factor (SPF) protection (Antoniou et al, “Sunscreens – what’s important to know”, Journal of the European Academy of Dermatology and Venereology, 1468-3083, Pages 1110-1119, 2008). SPF is the minimum irradiation dosage required to produce skin erythema. Thus, simply put, SPF effectively quantifies the maximum time of sun exposure to prevent erythema on sunscreen-protected skin.

According to the mechanism by which sunscreens protect from ultraviolet irradiation, i.e. absorption and excitation of organic sunscreens and reflection and scattering by inorganic ones, the photo stability of organic sunscreens thereafter is a question of major concern as this determines their ability to efficiently and effectively absorb radiation throughout the intended duration for which they are expected to provide protection (Antoniou et al, “Sunscreens – what’s important to know”, Journal of the European Academy of Dermatology and Venereology, 1468-3083, Pages 1110-1119, 2008). The excitation caused due to the irradiation absorption in organic sunscreens results in the generation of photo products and this is seen as a lack in photo stability. The consequences of this photo degradation are seen as a reduced ability for these sunscreens to absorb UV irradiation. Hence it is often recommended to reapply sunscreens every 2 hours to circumvent these photo instability issues (L. Narayana et al, “Review: Ultraviolet radiation and skin cancer”, International Journal of Dermatology, 49(9), Pages 978-986, 2010) as shown in Figure 1B.

Each organic sunscreen has unique absorption spectra which peak at specific wavelengths according to the absorbing nature of the molecule. Most formulations providing sunscreen protection (i.e. only UVB protection as a measure of SPF or both UVB and UVA broad spectrum protection) target primarily the ≥300 nm region and are mainly effective only above this wavelength. It may also be noted that well known UVB sunscreens such as Octocrylene, Octisalate and OMC have their respective maximum absorbance wavelength at 305 nm, 305 nm and 310 nm (Figure 1C). While OMC is considered to be an effective UVB sunscreen, it would be desirable to have a higher absorption in the lower wavelength UVB region from 280 – 300 nm given that radiation in this range is more damaging by several magnitudes. Furthermore, OMC and several other sunscreens are associated with numerous problems concerning post radiation efficacy and lower extinction coefficients etc.

EP 2025324 A1 relates to a photo stabilized photoactive composition comprising a mixture of a photoactive compounds that act to absorb UV radiation and thereby protect the substrate (e.g., human skin, resins, films, and the like) from the harmful effects of UV radiation. According to this invention the said photoactive compounds in the composition may include methylene bis-benzotriazolyl tetramethylbutylphenol (Tinosorb M) and salts and their derivatives with other bioactives in combination and further includes 0.1 to 10 wt.% of a triplet quencher such as octocrylene. It is further emphasized that the absorption process causes a photoactive compound to reach an excited state, wherein the excited state is characterized by the presence of excited electronic energy (e.g., singlet state energy or triplet state energy), as compared to the ground state of the photoactive compound. Once a photoactive compound reaches an excited state there exists a number of pathways by which the excited photoactive compound can dissipate its excess energy (e.g., singlet and/or triplet energy), however, many of those pathways adversely affect the ability of the photoactive compound to further absorb UV radiation.

The alkoxy crylene molecules described in this invention accept electronic singlet excited state energy from UV-absorbers, particularly Avobenzone, octyl methoxycinnamate (Octinoxate), and octyl salicylate (Octisalate). Examples 4-6 of the invention describes the combination of avobenzone (UVA) with octylmethoxycinnamate (UVB) and mentions that octocrylene stabilizes octyl methoxycinnamate (OMC), a UVB filter, but does not photostabilize avobenzone, a UVA filter. The invention also reports photostabilization of sunscreen compositions containing the alkoxy crylene molecules when combined with octyl methoxycinnamate and Avobenzone.

US 6800274B2 relates to compounds and methods to increase the photo stability of a sunscreen composition. The invention more particularly relates to photo stable sunscreen compositions and a new class of photoactive compounds and to the use of derivatives of diphenylmethylenemalonic acid and derivatives of fluorine, including derivatives of cyano (9H-fluoren-9-ylidene) acetic acid and diesters and polyesters of 9H-fluoren-9-ylidenemalonic acid to photostabilize a sunscreen composition. The inventors of US’274 have surprisingly found that even at low levels of flourene derivative, the combination of sunscreens can acts synergistically to provide even greater stabilization of dibenzoylmethane derivative.

Uli Osterwalder et.al.UV-A Protection with a New Class of UV Absorber article available online at www.fda.gov/ohrms/dockets/dailys/00/.../cp00001_attachment_03.pdf‎ relates to a study on UVA protection offered by a new class of UV absorber, Tinosorb M. This prior art discloses the drawbacks of UVA filters for lacking inherent photostability and ascertains that the formulators can overcome this problem by combining with Octocrylene or 4-Methylbenzylidene Camphor to their formulations. The study further introduces a new class of UV absorber TINOSRB M, with inherent extraordinary photostability and provides highly efficient sunscreen properties by a triple action involving absorption, light scattering and light reflection. It is also disclosed that the synergistic combination of Tinosorb M and UVB absorber, Octyl Methoxy Cinnamate (OMC) can boost the SPF either by the absorption of UV-B and short UV-A range or by the dispersion of Tinosorb M in the water phase, and thus acting complementary to oil-soluble filters. The study also establishes the compatibility with OMC and its stabilization by Tinosorb M experimentally, where in after irradiation with 10 MED, 27% of OMC alone is lost while in combination with Tinosorb M the loss was only 8%.

WO2008042326 teaches topically applicable sunscreen composition for the photoprotection of human skin and/or hair, comprising photoprotecting synergistically effective amounts of octinoxate, octocrylene, and amiloxate. Description of WO’326 discloses the range/limit of the sunscreen agents as per EU standard that can be used.

WO2013078197 relates to sunscreen compositions comprising a synergistic combination of ultra violet ("UV") filters, and to methods of using the combination of UV filters to protect keratinous substrates such as skin and hair from UV radiation. Compositions according to the disclosure of WO’197 have high SPF values without requiring high overall amounts of UV filtering agents. Methods of using the compositions protect keratinous substances such as skin and hair from UV radiation. A sunscreen composition having the following combination of UV filters: octocrylene, avobenzone, oxybenzone, octisalate, and homosalate.

US 20130129650 relates to sunscreen compositions having a synergistic combination of ultraviolet light (UV) filtering agents that provide a high sun protection factor (SPF). A sunscreen composition is provided comprising the following combination of UV filters: octocrylene, avobenzone, octisalate, and homosalate, and optionally oxybenzone; wherein the ratio of each filter relative to avobenzone. The inventors of US’650 have discovered that when octocrylene, avobenzone, octisalate, and homosalate (UV filters) are combined in particular ratios; they interact synergistically to exhibit a surprisingly effective SPF. This allows for the elimination of most or all oxybenzone and a low overall amount of other UV filters.

Most formulations of prior art providing sunscreen protection (i.e. only UVB protection as a measure of SPF or both UVB and UVA broad spectrum protection) target primarily the ≥300 nm region and are mainly effective only above this wavelength. Thus there is a need to provide a unique composition comprising the combination of sunscreens which provides protection from the harmful UV radiations falling in the lower wavelengths of UVB region in the range of 280 – 300 nm.

The present invention thus provides a novel combination of UV filters that delivers additional protection against the regions of the spectrum affecting DNA and is also effective in contributing to skin erythema. The composition provides additional protection to skin within fifteen minutes of irradiation exposure.

Unlike protection offered by organic sunscreens of prior art which is usually seen to decrease with time on exposure to light, the additional protection in the region <300 nm offered by the herein identified unique combinations is seen to increase with time on exposure to light. More essentially, it is important to note that the combinations specifically described herewith ensure protection within fifteen minutes of exposure to light.

Objects of invention

An object of present invention is to provide a sunscreen composition comprising a synergistic combination of sunscreen agents.
Another object of the invention is to provide a unique combination of sunscreen comprising a combination of sunscreens which provides protection from the harmful UV radiations falling in the lower wavelengths of UVB region in the range of 280 – 300 nm, more specifically 280-290nm.
Yet another object of present invention is to provide a unique combination of sunscreens that delivers additional protection against the regions of the spectrum affecting DNA and is also effective in contributing to skin erythema.

It is a further object of present invention to provide a cosmetic composition comprising the selective combination of the sunscreen agents that provides extended protection from harmful UV radiations.
Summary of the Invention

According to one aspect of the present invention, there is provided a sunscreen product for extended UV protection comprising Tinosorb M, Octocrylene and at least one sunscreen agent selected from Octisalate and Octyl methoxycinnamate.

According to one aspect of the present invention, there is provided a cosmetic composition for topical application comprising
a. Tinosorb M, Octocrylene and at least one sunscreen agent selected from Octisalate and Octyl methoxycinnamate; and
b. cosmetically acceptable ingredients.

Brief Description of Accompanying Drawings
Figure 1A: Average action spectrum for affecting DNA described by the dotted curve and incident sun light (Ref. R. B. Setlow, “The wavelengths in sunlight effective in producing skin cancer: A theoretical analysis, Proceedings of the National Academy of Sciences, 71(9), Pages 3363-3366, 1974).
Figure 1B: Erythemal action spectra and incident sun light (Ref. G. G. Palancar & B. M. Toselli, “Erythemal ultraviolet irradiance in Córdoba, Argentina”, Atmospheric Environment, 36(2), Pages 287–292, 2002).
Figure 1C: Absorbance spectrum of OMC. Y-axis scale = 0 – 1 A.U.

Figure 2A: Absorbance spectrum kinetics of Tinosorb M, Octocrylene and Octisalate. Y-axis scale = 0 – 2.5 A.U.

Figure 2B: Absorbance spectrum kinetics of Tinosorb M, Octocrylene and Octisalate.
Y-axis scale = 0 – 2.5 A.U.
Figure 2C: Absorbance spectrum kinetics of Octocrylene and Octisalate. Y-axis scale = 0 – 2.5 A.U.

Figure 2D: Absorbance spectrum kinetics of Tinosorb M and Octisalate. Y-axis scale = 0 – 2.5 A.U.

Figure 2E: Absorbance spectrum kinetics of Tinosorb M and Octocrylene. Y-axis scale = 0 – 2.5 A.U.
Figure 2F: Absorbance spectrum kinetics of Tinosorb M and OMC. Y-axis scale = 0 – 2.5 A.U.

Figure 2G: Absorbance spectrum kinetics of Octocrylene and OMC. Y-axis scale = 0 – 2.5 A.U.

Figure 3A: Absorbance spectrum kinetics of Tinosorb M at the lower range, with Octocrylene and Octisalate. Y-axis scale = 0 – 2.5 A.U.

Figure 3B: Absorbance spectrum kinetics of Tinosorb M at the higher range, with Octocrylene and Octisalate. Y-axis scale = 0 – 2.5 A.U.

Figure 3C: Absorbance spectrum kinetics of Tinosorb M with Octocrylene at the lower range, and Octisalate. Y-axis scale = 0 – 2.5 A.U.

Figure 3D: Absorbance spectrum kinetics of Tinosorb M, with Octocrylene at the higher range, and Octisalate. Y-axis scale = 0 – 2.5 A.U.

Figure 3E: Absorbance spectrum kinetics of Tinosorb M with Octocrylene and with Octisalate at the lower range. Y-axis scale = 0 – 2.5 A.U.

Figure 3F: Absorbance spectrum kinetics of Tinosorb M, with Octocrylene and with Octisalate at the higher range. Y-axis scale = 0 – 2.5 A.U.

Figure 3G: Absorbance spectrum kinetics of Tinosorb M with Octocrylene and with OMC at the lower range. Y-axis scale = 0 – 2.5 A.U.

Figure 3H: Absorbance spectrum kinetics of Tinosorb M, with Octocrylene and with OMC at the higher range. Y-axis scale = 0 – 2.5 A.U.

Figure 4A: Absorbance spectrum kinetics of Tinosorb M. Y-axis scale = 0 – 1 A.U.

Figure 4B: Absorbance spectrum kinetics of Octocrylene. Y-axis scale = 0 – 1 A.U.

Figure 4C: Absorbance spectrum kinetics of Octisalate. Y-axis scale = 0 – 1 A.U.

Figure 4D: Absorbance spectrum kinetics of OMC. Y-axis scale = 0 – 1 A.U.

Figure 5A: Absorbance spectrum kinetics of Tinosorb M, Octocrylene and Octisalate over 2 hours. Y-axis scale = 0 – 2.5 A.U.
Figure 5B: Absorbance spectrum kinetics of Tinosorb M, Octocrylene and OMC over 2 hours.

Figure 4 B shows degradation of Octocrylene over 30 minutes. It may be noted that the change in absorbance value is significant i.e. from 0.18 to 0.16.

Figure 4 C shows degradation of Octisalate over 30 minutes. It may be noted that the change in absorbance value is very significant i.e. from 0.13 to 0.09.

Figure 4 D shows degradation of OMC over 30 minutes. It may be noted that the change in absorbance value is very significant i.e. from 0.4 to 0.23.

Figure 5A and 5B illustrates combination of select sunscreens remains photo stable even after 2 hours post application of sunscreen.

Figure 6A and 6B illustrates the comparative effect of sunscreen combination of present invention with that of conventional composition.

Detailed Description of Invention

Most sunscreen formulations target primarily the ≥300 nm region and are effective only within this range. Further, their effectiveness reduces with increase in exposure over time (Ref: C. Antoniou et al, “Sunscreens – what’s important to know”, Journal of the European Academy of Dermatology and Venereology, 1468-3083, Pages 1110-1119, 2008). Also, even with the help of sunscreen stabilizers, this reduction in efficacy of these formulations over time is still not yet completely overcome. The invention detailed herewith provides extended photo protection in the lower UVB wavelength region, even below the 300 nm in addition to the primary protection provided in the ≥300 nm region, more specifically 280-290nm.

This novel feature in sun protection is delivered by the cosmetic composition comprising the sunscreen product of present invention. The sunscreen product as provided herein comprises the selective UV filters. The sunscreen product of present invention retains its efficacy over time and in fact even delivers additional protection on exposure to light. Also, this protection is provided within 15 minutes and the combinations are observed to be highly photo stable and do not decrease in efficacy over time. In light of the increasing green house gases and reduction in ozone cover, these benefits are exponential especially in providing protection against the anti aging, DNA damaging and cancer related concerns with UV irradiation.

Where the following terms are used in the specification, they are used as defined below.

The terms “comprising”, “having” and “including” are used in their open and non limiting sense.
The terms “a”, “an”, “the” are understood to encompass the plural as well as the singular.

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

In accordance with the present invention a sunscreen product for extended UV protection is provided consisting of Tinosorb M, Octocrylene and at least one sunscreen agent selected from Octisalate and Octyl methoxycinnamate.

In another embodiment the present invention provides cosmetic composition for extended UV protection comprising
a. Tinosorb M, Octocrylene and at least one sunscreen agent selected from Octisalate and Octyl methoxycinnamate; and
b. cosmetically acceptable ingredients.

Tinosorb M is also known as Bisoctrizole (methylene bis-benzotriazolyl tetramethylbutylphenol) for use as a sunscreen agent. Octocrylene, whose chemical name is 2-ethylhexyl 2-cyano-3,3-diphenyl-2-propenoate. Octisalate (2-ethylhexyl salicylate) is an organic compound used as an ingredient in sunscreens and cosmetics to absorb UVB rays from the sun. Octyl methoxycinnamate (OMC) (2-Ethylhexyl (2E)-3-(4-methoxyphenyl)prop-2-enoate) is an organic compound used as an ingredient in sunscreens and cosmetics to absorb UVB rays from the sun. OMC is an ester formed from methoxycinnamic acid and 2-ethylhexanol.

“Cosmetically acceptable ingredients” means suitable ingredients or constituents that may be added to the combination of the sunscreens of the present invention to provide a cosmetic composition.

The sunscreen product of present invention delivers additional protection against the regions of the spectrum affecting DNA and is also effective in contributing to skin erythema. The composition provides additional protection to skin within fifteen minutes of irradiation exposure. It is essential to note that this protection is numerically equivalent or in excess of that provided at the combination’s initial maximum absorbance wavelength (λm) and continuously increases over time. It is further essential to specify that these combinations are highly photo stable and negligible degradation is observed.

The inventors have also surprisingly found that the extension in absorption range of sunscreens is not limited by the concentration of the individual sunscreens added. Hence, the upper limit of the range for each of the sunscreen in both the stated combinations is determined based on the EU standards determined for the safe use of sunscreens in over-the-counter products.

EU standards limit the amount of sunscreens that may be added to any given cosmetic product that may be sold over-the-counter. Therefore whereas there may not be any upper limit to the concentration of sunscreens used in the combination of the present invention, these have been essentially limited to 10% by wt.- Tinosorb M, OMC and Octocrylene; 5% by wt. - Octisalate.

Accordingly in the present cosmetic composition, Tinosorb M may be present in the composition in an amount from about 0.1 to 10 percent by weight, preferably in an amount from about 0.5 to about 5 percent by weight.

In a further embodiment of the invention, Octocrylene may be present in the composition in an amount from about 0.1 to 10 percent by weight, preferably in an amount from about 5 to about 10 percent by weight.

In a further embodiment of the invention, Octisalate may be present in the composition in an amount from about 0.1 to about 5.0 percent by weight, preferably in an amount from about 1 to about 5 percent by weight.

In a further embodiment of the invention, Octyl methoxycinnamte may be present in the composition in an amount from about 0.1 to about 10.0 percent by weight, preferably in an amount from about 3 to about 10 percent by weight.

The compositions of the invention containing the synergistic combination of sunscreen actives can comprise any form readily known by those of ordinary skill in the art of preparing cosmetic compositions, in particular compositions containing sunscreen active agents. Examples include, but are not limited to, gels, serum or sprays.

In certainly preferred embodiments, the composition can comprise an emulsion, suspension, or dispersion, solutions, colloids etc. Preferable forms of the compositions include solutions, nanoemulsion, microemulsions, encapsulates, liposomes, micelles, gels and other conventional formulation kinds as are commonly used to deliver cosmetic benefits.

The subject invention contemplates the incorporation of the synergistic combination of sunscreen actives in sunscreen and sunblock products and any other topically applied composition where the addition of sunscreen active agents would not detract from the efficacy of the product nor affect the sunscreening ability of the sunscreen active agents. Thus the subject invention also provides a cosmetic composition for topical application to human skin comprising photoprotecting synergistically effective amounts of Tinosorb M, Octocrylene, Octisalate and Octyl methoxy cinnamate

In another embodiment of present invention, a cosmetic composition for topical application to human skin and/or hair is provided comprising the combination of Tinosorb M, Octocrylene, Octisalate and Octyl methoxy cinnamate.

Non-limiting examples of such cosmetic compositions may include sunscreen lotions/serums/oils/sprays/creams, fairness creams, anti-aging creams, moisturizing creams and hair serums/conditioners, mousse, face wash, cleansing compositions, masks, wipes and the like.

Various cosmetic compositions may be made by adding the sunscreen combinations of the present invention. Specialized formulations may be prepared by addition of specific moisturizing, anti ageing, fairness, conditioning, agents to the given cream / lotion / gel / serum / spray formulations.

The compositions of the present invention may contain a wide range of additional, optional components which are referred to herein as "cosmetically acceptable ingredients".

The cosmetically acceptable ingredients includes the cosmetically acceptable additives as may be added to the composition of the present invention include but are not limited to silicones, vitamin and/or derivatives thereof, polyols, vehicles, structurants, emollient/s, gelling agent/s, a thickening agent/s, a hydrophilic or hydrophobic polymer, an emulsifying agent/s, alcohol/s etc. Examples of these ingredients include but are not limited to such substances as binders, emollients, preservatives (such as methyl paraben), colorants, perfumes, skin-lightening agents, anti-wrinkle agents, antimicrobials and the like.

The polyols used are selected from glycerol, ethylene glycol, propylene glycol, pentaerythritol, diglycerol, polyglycerol, their derivatives and combinations thereof. In a preferred embodiment the invention relates to compositions wherein the concentrations of polyol compounds varies from about 0.1 to 10.0 percent by wt; preferably between 0.5 and 5.0 percent by wt, most preferably between 1.0 and 4.0 percent by wt.

The silicone used in the invention is selected from linear, branched, cross linked, silicone oils, volatile and non volatile silicones such as dimethicone copolyol, dimethylpolysiloxane, diethylpolysiloxane, high molecular weight dimethicone, mixed C1-C30 alkyl polysiloxane, phenyl dimethicone, dimethiconol, cyclopentasiloxane, dimethicone, dimethiconol, mixed C1-C30 alkyl polysiloxane, and mixtures thereof. The concentration of silicones is about 0.01 to 5.0 percent; preferably about 0.1 to 3.0 percent, more preferably about 0.5 to 2.0 percent by wt.

The vitamin used in the composition is selected from a group comprising vitamin A, vitamin B (1-12), vitamin C, vitamin D (2-4), vitamin E, vitamin K, their derivatives, such as acetates, propionates, palmitates, phosphates, alone on in combinations thereof. The concentrations of the vitamin and/or its derivative(s) may be about 0.01 to 5.0 percent; preferably about 0.05 and 3.0 percent, and more preferably between 0.5 and 2.0 percent by wt.

Emulsifying agents which may be optionally added to the compositions of the present invention include but are not restricted to oxyalkylenated fatty acid esters of polyols, for example polyethylene glycol stearates, for instance PEG-100 stearate, PEG-50 stearate and PEG-40 stearate; and mixtures thereof, mixture of glyceryl monostearate and of polyethylene glycol stearate (100 EO) (Simulsol 165), oxyalkylenated fatty acid esters of sorbitan comprising, for example, from 20 to 100 EO such as Tween 20 or Tween 60, oxyalkylenated (oxyethylenated and/or oxypropylenated) fatty alcohol ethers; alkoxylated or non-alkoxylated sugar esters, such as sucrose stearate and PEG-20 methylglucose sesquistearate; sorbitan esters such as the sorbitan palmitate (Span 40), esters of diacid and of fatty alcohol, such as dimyristyl tartrate; mixtures of these emulsifiers, for instance the mixture of glyceryl stearate and of PEG-100 stearate (Arlacel 165), and mixtures comprising these emulsifiers, such as the mixture of dimyristyl tartrate, cetearyl alcohol, Pareth-7 and PEG-25 laureth-25, (Cosmacol PSE) , steareth – 2, steareth 21, PPG-15 stearyl ether. The concentrations of the emulsifying agents may be about 0.1% by wt. to about 8.0% by wt.; preferably about 0.4% by wt.to about 4.0% by wt.

Thickeners which may be used in the instant invention include but are not restricted to alkyloamides, carbomer 934,940,941,960,961, cetearyl alcohol, cetyl alcohol, gelatin, gums, and magnesium aluminium silicates, ozocarite, paraffin, tragacanth, sodium alginate, Tinovis ADM, Acrylates/C10-30 Alkyl Acrylate Crosspolymer and ammonium Acryloyl - dimethyltaurate / Vinyl pyridine Copolymer/Carbomer, Hydroxyethyl Acrylate / Sodium Acryloyldimethyl Taurate Copolymer (and) Isohexadecane (and) Polysorbate 60, Simugel INS 100 , Carbopol Ultrez 10 and the like. The concentrations of the thickeners may be about 0.1% by wt to about 2% by wt.; preferably about 0.5% by wt. to about 1% by wt.

Structurants which may be used in compositions of the present invention include those materials which are well known in the art and include fatty acids, fatty alcohols, fatty acid esters, and fatty acid amides, having fatty chains of from 8 to 30 carbons atoms. Preferably the structurant used is stearic acid. The concentrations of the structurants may be about 0.1% by wt. to about 8.0% by wt.; preferably about 0.4% by wt. to about 4.0% by wt.

Various emollients as are known to a person skilled in the art and as are available in the market can be employed as an optional constituent in the instant invention. These include but are not restricted to the group consisting of lanolin, octyl dodecanol, hexyl decanol, oleyl alcohol, decyl oleate, isopropyl stearate, isopropyl palmitate, isopropyl myristate, hexyl laureate, dioctyl cyclohexane, PPG-15 stearyl ether, isohexadecane, stearic acid, cetyl alcohol, mineral oil etc. The concentrations of the emollients may be about 0.1 to 10 percent by wt; preferably about 1 and 5 percent by wt.

Various chelating agents may be used as optional constituents of the instant invention. These may be selected from a group consisting of but not limited to Dimercaptosuccinic acid (DMSA), Dimercapto-propane sulfonate (DMPS), Alpha lipoic acid (ALA), Calcium disodium versante (CaNa2-EDTA), Disodium EDTA, Dimercaprol (BAL). The concentrations of the various chelating agents may be about 0.1 to 1 percent by wt.; preferably about 0.2 to about 0.5 percent by wt.

Various cosmetically and dermatologically suitable preservatives may be added to the instant composition. These may be selected from the group consisting of but not restricted to 2-phenoxyethanol, para-hydroxybenzoic acid esters, also known as parabens, for instance methyl para-hydroxybenzoate (methyl paraben), ethyl para-hydroxybenzoate (ethyl paraben) and propyl para-hydroxybenzoate (propyl paraben) and mixtures thereof; formaldehyde-releasing agents, for instance imidazolidinylurea or diazolidinylurea; haloalkynyl carbamates, for instance 3-iodo-2-propynyl butyl carbamate (IPBC); caprylyl glycol, also known as 1,2-octanediol; sodium benzoate; N-(3-chloroallyl)-hexaminium chloride (or Quaternium-15); polyhexamethylene biguanide hydrochloride (CTFA name: polyaminopropyl biguanide); alkyltrimethylammonium bromides, for instance dodecyltrimethylammonium bromide, myristyltrimethylammonium bromide and hexadecyltrimethylammonium bromide, and mixtures thereof. The concentrations of the various cosmetically and dermatologically suitable preservatives may be about 0.05 by wt. to 1.5 percent by wt.; preferably about 0.1 by wt. and 1 percent by wt..

Anti-ageing active agents which may optionally added to the compositions of the instant invention may be chosen from free-radical scavengers, keratolytic agents, vitamins, anti-elastase and anti-collagenase agents, proteins, fatty acid derivatives, steroids, trace elements, bleaching agents, algal and plankton extracts, enzymes and coenzymes, flavonoids, ceramides, tensioning agents and muscle relaxants, and mixtures thereof. The concentrations of the Anti-ageing active agents may be about 0.001 to about 10 wt %, preferably from about 0.01 to about 5 wt %.

Free-radical scavengers and antioxidants which may be optionally added to the compositions of the instant invention include but are not restricted to phosphonic acid derivatives such as (methylenephosphonic acid), methylene phosphonic acid, methylenephosphonic acid and salts thereof, in particular the sodium salts thereof; ethylenediaminetetraacetic acid and its salts, such as the sodium salt; guanosine; superoxide dismutase; tocopherol (vitamin E) and its derivatives (acetate); ethoxyquine; lactoferrin; lactoperoxidase, and nitroxide derivatives; superoxide dismutases; glutathione peroxidase; plant extracts with free-radical-scavenging activity, such as the aqueous extract of wheatgerm (Detoxiline), green tea, and mixtures thereof. The concentrations of the Free-radical scavengers and antioxidants may be about 0.001 to about 2 wt %, preferably from about 0.01 to about 1 wt %.

The composition of the present invention may further include one or more neutralizers, such as, for example, strong and weak bases. Any suitable neutralizer can be selected, as will be appreciated by one of ordinary skill in the art. Exemplary neutralizers suitable for use in the compositions of the present invention included sodium hydroxide, potassium hydroxide, ammonium hydroxide, diethanolamine, triethanolamine, 2-dimethylamino-2-methyl-1-propanol (DAMP), 2-aminomethyl-1propanol (aminomethyl propanol) (AMP), and the like, or combinations thereof. The neutralizer, if present, may be provided in any amount, e.g., an amount sufficient to achieve a desired pH for the composition. In this respect, the composition preferably has a pH of from about 4-9, more preferably, from about 5-8, and still more preferably from about 5.5-7. Typically, the neutralizer may be present in an amount of from about 0.01% -10% by weight of the composition.

Essential oils and extracts that may be used in the present invention include but are not limited to mentha, jasmine, camphor, white cedar, bitter orange peel, ryu, turpentine, cinnamon, bergamot, citrus unshiu, calamus, pine, lavender, bay, clove, hiba, eucalyptus, lemon, starflower, thyme, peppermint, rose, sage, sesame, ginger, basil, juniper, lemon grass, rosemary, rosewood, avocado, grape, grapeseed, myrrh, cucumber, watercress, calendula, elder flower, geranium, linden blossom, amaranth, seaweed, gingko, ginseng, carrot, guarana, tea tree, jojoba, comfrey, oatmeal, cocoa, neroli, vanilla, green tea, penny royal, aloe vera, menthol, cineole, eugenol, citral, citronelle, borneol, linalool, geraniol, evening primrose, camphor, thymol, spirantol, penene, limonene, rose, lemon grass, peach, honey, almond oil, olive oil, shea butter, olive butter, bearberry, black currant, rosemary, blue lotus, white lily, and terpenoid oils.

The composition of the invention may utilize a fragrance composition comprising a blend of essential oils and synthetic aroma compounds. The blend is often diluted with a carrier like propylene glycol, vegetable oil, or mineral oil. Some examples of synthetic aroma compound that are suitable for soap bar compositions of the present invention include, but are not limited to benzaldehyde, citral, vanillin, ethyl acetate, fructone, octyl acetate, pentyl butanoate, pentyl pentanoate, methyl salicylate, isoamyl acetate, limonene, citronellol, and mixtures thereof. Preferably, the fragrance containing the essential oil is present in the composition of the invention in an amount between approximately 0.1% to approximately 2% by weight.

Various cosmetically acceptable vehicles may be used for the preparation of compositions as per the instant invention. These may be selected from the group consisting of but not restricted to water, alcohols, oils and combinations thereof.

Accordingly, when the surface contemplated is skin, the composition of this invention may contain ingredients, which are added to known creams, lotions, ointments, gels or medicaments, which are physiologically acceptable to skin and which do not contain ingredients, which will reverse or retard the action of sunscreen agent(s).

It has been surprisingly found that a sunscreen composition comprising a combination of Tinosorb M, Octocrylene and Octisalate provides an extension in absorption range of sunscreens (Figures 2A). It has very surprisingly been found that a sunscreen composition comprising a combination of Tinosorb M, Octocrylene and OMC provides an extension in absorption range of sunscreens (Figures 2B).

The present invention provides a unique composition comprising a combination of well-known and cost effective sunscreens which provides protection from the harmful UV radiations falling in the lower wavelengths of UVB region in the range of 280 – 300 nm, more specifically 280-290nm. This combination thus, delivers additional protection against the regions of the spectrum affecting DNA and is also effective in contributing to skin erythema. Moreover this additional protection is provided within fifteen minutes of irradiation exposure. It is essential to note that this protection is numerically equivalent or in excess of that provided at the combination’s initial maximum absorbance wavelength (λm) and continuously increases over time. It is further essential to specify that these combinations are highly photo stable and negligible degradation is observed.

The inventors have observed that if either of the combinations is lacking in even one sunscreen the extension in absorption range is not observed. Figure 2C describes a combination of Octocrylene and Octisalate without the addition of Tinosorb M, wherein the desired extension in absorption range is not observed at 280 nm within fifteen minutes. Figure 2D describes a combination of Tinosorb M and Octisalate without the addition of Octocrylene, wherein the desired extension in absorption range is not observed at 280 nm within fifteen minutes.

Figure 2E describes a combination of Tinosorb M and Octocrylene without the addition of Octisalate or OMC, wherein the desired extension in absorption range is not observed at 280 nm. Figure 2F, describes a combination of Tinosorb M and OMC without the addition of Octocrylene, wherein the desired extension in absorption range is not observed at 280 nm and degradation (photo instability) is observed as well. Figure 2G describes a combination of Octocrylene and OMC without the addition of Tinosorb M, wherein the desired extension in absorption range is not observed at 280 nm within fifteen minutes.

It is also found very surprisingly that the extension in absorption range of sunscreens is not limited by the concentration of the individual sunscreens added. Hence, the upper limit of the range for each of the sunscreen in both the stated combinations is determined based on the EU standards determined for the safe use of sunscreens in over-the-counter products. Therefore
Tinosorb M may be added at a concentration of from about 0.1% w/w to about 10% w/w of the total formulation (Figure 3A, 3B).

It is generally observed that sunscreens degrade post exposure to light (Figure 4A – 4D). This effect is observed for most sunscreens within 15 minutes of exposure to light and degradation (photo instability) is seen. Also it is noted in some sunscreens that there is a shift in the maximum absorbance wavelength (λm) towards the higher end of the spectrum which directly relates to lesser or/minimal protection being provided in the desired UVB region (i.e. 280 – 320 nm). The purpose of the present invention is therefore to provide maximum/enhanced protection in the desired 280 – 300 nm without compromising on the protection provided by the given sunscreen in the region from 300 – 320 nm.

Figure 4 A shows degradation of Tinosorb M over 30 minutes. It may be noted that the change in absorbance value is from 0.037 to 0.029 and the maximum absorbance wavelength (λm) shifts from UVB to UVA region.

The composition of the present invention comprising a combination of sunscreens remains photo stable even after 2 hours post application of sunscreen (Figure 5A, 5B).

This invention can be used in skin and hair care formulations that are meant to protect from the harmful effects of UV radiation. The given combinations, by virtue of their additional protection in the lower UVB wavelengths help against the effects of sun induced skin aging, DNA damage and other melanoma and non-melanoma related concerns.

The compositions of the invention are intended to provide a sun protection factor (SPF) rating of at least 18, with additional preferable embodiments having a sun protection factor of at least 12.

The invention is now illustrated by non limiting examples.

Example 1
Tinosorb M is added at a concentration of from about 0.1% w/w to about 10% w/w of the total formulation (Figure 3A, 3B).

In this example Octocrylene and Octisalate is kept constant and within the desired working range to show working of Tinosorb M.

Table 1: Tinosorb M is added at lower acceptable limit
Sr. No. Ingredient Concentration (µL*/10 mL)*of a 500 ppm stock solution
1 Tinosorb M 4
2 Octocrylene 200
3 Octisalate 100

As evident at all these concentration ranges, the desired extension in absorption range is observed.

Table 2- Tinosorb M is added at higher acceptable limit
Sr. No. Ingredient Concentration (µL*/10 mL)*of a 500 ppm stock solution
1 Tinosorb M 400
2 Octocrylene 200
3 Octisalate 100

As evident at all these concentration ranges, the desired extension in absorption range is observed.

Example 2

Octocrylene is added at a concentration of from about 0.1% w/w to about 10% w/w of the total formulation (Figure 3C, 3D).

In this example Tinosorb M and Octisalate is kept constant within the desired working range to show working of Octocrylene.

Table 3- Octocrylene is added at lower acceptable limit
Sr. No. Ingredient Concentration (µL*/10 mL)*of a 500 ppm stock solution
1 Tinosorb M 54
2 Octocrylene 2
3 Octisalate 100

As evident at all these concentration ranges, the desired extension in absorption range is observed.

Table 4- Octocrylene is added at higher acceptable limit
Sr. No. Ingredient Concentration (µL*/10 mL)*of a 500 ppm stock solution
1 Tinosorb M 54
2 Octocrylene 200
3 Octisalate 100

As evident at all these concentration ranges, the desired extension in absorption range is observed.

Example 3

Octisalate is added at a concentration of from about 0.1% w/w to about 5% w/w of the total formulation (Figure 3E, 3F). In this example Tinosorb M and Octocrylene is kept constant within the desired working range to show working of Octisalate.

Table 5 - Octisalate is added at lower acceptable limit
Sr. No. Ingredient Concentration (µL*/10 mL)*of a 500 ppm stock solution
1 Tinosorb M 54
2 Octocrylene 200
3 Octisalate 2

As evident at all these concentration ranges, the desired extension in absorption range is observed.

Table 6- Octisalate is added at higher acceptable limit
Sr. No. Ingredient Concentration (µL*/10 mL)*of a 500 ppm stock solution
1 Tinosorb M 54
2 Octocrylene 200
3 Octisalate 100
As evident at all these concentration ranges, the desired extension in absorption range is observed.

Example 4
OMC may be added at a concentration of from about 0.1% w/w to about 10% w/w of the total formulation (Figure 3G, 3H). In this example Tinosorb M and Octocrylene is kept constant within the desired working range to show working of OMC.

Table 7- OMC is added at lower acceptable limit
Sr. No. Ingredient Concentration (µL*/10 mL)*of a 500 ppm stock solution
1 Tinosorb M 54
2 Octocrylene 200
3 OMC 2

As evident at all these concentration ranges, the desired extension in absorption range is observed.

Table 8- OMC is added at higher acceptable limit
Sr. No. Ingredient Concentration (µL*/10 mL)*of a 500 ppm stock solution
1 Tinosorb M 54
2 Octocrylene 200
3 OMC 200

As evident at all these concentration ranges, the desired extension in absorption range is observed.

It is thus evident from the above that the present invention relates to a unique combination of 4 sunscreens within the prescribed limit which provides enhanced protection from UV.

Example 5
Comparison of sunscreen combination of present invention with the composition of other combination of sunscreens

The present sunscreen composition was also compared with composition having other combination of sunscreen agents.
a. Replacing one or more sunscreens of the given combination, e.g. Tinosorb M with Tinosorb S; and
b. adding one or more sunscreens to the given combination of the present invention
Observation: It is observed that that such replacement / addition leads to a loss of extended UV protection as provided by the combination of the present invention as depicted in Figure 6a. It was observed that when Tinosorb M was replaced with Tinosorb S no shift in maximum absorption wavelength was observed. Therefore no extended protection at 280 nm was obtained.

Another combination of Tinosorb M + Octocrylene + OMC along with additional sunscreen agents of prior art was prepared.

It was observed that there is no shift in maximum absorption wavelength. It was also noted that the addition of sunscreens made the combination (of Tinosorb M + octocrylene + OMC) less photostable over time as depicted by way of figure 6b.

Example 6
SPF 12 Lotion/cream formulation
Table 9
SPF 12Lotion/Cream # Ingredients % w/w
Water Phase 1 Distilled Water QS
2 Chelating agent(E.g. EDTA) 0.1
3 Thickening agent(E.g. Carbopol Ultrez 10) 1.5
4 Emulsifier A – Water Phase(E.g. Brij 721) 2
Oil Phase 5 Emulsifier B – Oil Phase(E.g. Brij 72) 1
6 Octocrylene 5
7 Octisalate 5
Post emulsion 8 Tinosorb M slurry + water 1 + 1

Example 7
SPF 18 Lotion/cream formulation

Table 10
SPF 18Lotion/Cream # Ingredients % w/w
Water Phase 1 Distilled Water QS
2 Chelating agent(E.g. EDTA) 0.1
3 Thickening Agent(E.g. Carbopol Ultrez 10) 1.5
4 Emulsifier A – Water Phase(E.g. Brij 721) 2
Oil Phase 5 Emulsifier B – Oil Phase(E.g. Brij 72) 1
6 Octocrylene 5
7 OMC 5
Post emulsion 8 Tinosorb M slurry + water 1 + 1

Example 8

Process for preparation of lotion/cream:

Step 1: Prepare a Water Phase by adding and mixing ingredients 1 through 4 at predetermined temperature ranges of from about 45 degrees C to 85 degrees C
Step 2: Prepare Oil Phase by separately adding and mixing ingredients 5 through 7 and maintain temperature up to 85 degrees C as well.
Step 3: Emulsify the Water Phase of Step 1 with the Oil Phase of Step 2. Add ingredient 8 to the emulsion to obtain cosmetic compositions of the present invention.

Example 9
SPF 12 Serum formulation
Table 11
SPF 12 Serum # Ingredients % w/w
Single Phase 1 Distilled Water QS
2 Chelating agent(E.g. EDTA) 0.1
3 Thickening Agent(E.g. Simugel INS 100) 3
4 Octocrylene 5
5 Octisalate 5
6 Tinosorb M slurry + water 1 + 1

Example 10
SPF 18 Serum formulation

Table 12
SPF 18 Serum # Ingredients % w/w
Single Phase 1 Distilled Water QS
2 Chelating agent(E.g. EDTA) 0.1
3 Thickening Agent(E.g. Simugel INS 100) 3
4 Octocrylene 5
5 OMC 5
6 Tinosorb M slurry + water 1 + 1

Example 11
SPF 12 Gel formulation
Table 13

SPF 12 Gel # Ingredients % w/w
Single Phase 1 Distilled Water QS
2 Chelating agent(E.g. EDTA) 0.1
3 Thickening Agent(E.g. Simugel INS 100) 2
4 Octocrylene 5
5 Octisalate 5
6 Tinosorb M slurry + water 1 + 1

Example 12
SPF 18 Gel formulation
Table 14
SPF 18 Gel # Ingredients % w/w
Single Phase 1 Distilled Water QS
2 Chelating agent(E.g. EDTA) 0.1
3 Thickening Agent(E.g. Simugel INS 100) 2
4 Octocrylene 5
5 OMC 5
6 Tinosorb M slurry + water 1 + 1

Example 13
SPF 12 Spray formulation
Table 15

SPF 12 Spray # Ingredients % w/w
Single Phase 1 Distilled Water QS
2 Chelating agent(E.g. EDTA) 0.1
3 Thickening Agent(E.g. Simugel INS 100) 1.2
4 Octocrylene 5
5 Octisalate 5
6 Tinosorb M slurry + water 1 + 1

Example 14

SPF 18 Spray formulation
Table 16
SPF 18 Spray # Ingredients % w/w
Single Phase 1 Distilled Water QS
2 Chelating agent(E.g. EDTA) 0.1
3 Thickening agent(E.g. Simugel INS 100) 1.2
4 Octocrylene 5
5 OMC 5
6 Tinosorb M slurry + water 1 + 1

In the above compositions the concentration of the thickening agents is varied to obtain distinct form of serum, spray, and gel composition. The concentration of thickening agent is directly related to viscosity of a product.

Example 15

Process for preparation of serum/gel/spray

Step 1: Prepare a prototype by adding and mixing sequentially all ingredients from 1 through 6 at room temperature to obtain cosmetic compositions of the present invention. Ensure thorough mixing/dispersion of each ingredient in the formulation.