JP7362641B2 - sunscreen composition - Google Patents

Description

The present invention relates to sunscreen compositions. In particular, the present invention relates to sunscreen compositions that provide improved ultraviolet (UV) A protection factor (UVAPF).

Desiring to enjoy a healthy lifestyle, people seek to take care of themselves and their external surfaces, such as the skin, scalp, including hair. Specific skin-related issues that people are concerned about include healthy, infection-free skin, good skin tone, adequate hydration, and protection from UV radiation contained in sunlight.

Sunlight includes the infrared region (700 nm to 1 mm), visible region (380 to 780 nm) and UV region (100 to 400 nm). The UV range consists of UVC (100-280 nm), UVB (280-315 nm), and UVA (315-400 nm). Although the human body requires some UV radiation to synthesize/maintain adequate amounts of vitamin D, the harmful effects of UV typically outweigh the benefits. Excessive exposure to UVB is said to cause direct damage to DNA and also cause sunburn, while overexposure to UVA is said to cause immediate pigment darkening and subsequent tanning effects. It is said. Furthermore, UVA is also said to cause DNA damage through oxidative reactions involving reactive oxygen species (Zhang et al., 1997, Free Radical Biology & Medicine, 23, 980-985).

For this reason, people tend to avoid exposure to sunlight as much as possible. However, in many cases it is very difficult, and sometimes impossible, to avoid exposure to sunlight. For such unavoidable reasons, people are using various topical compositions that provide at least some protective effect against the undesirable effects caused by excessive exposure to ultraviolet radiation contained in sunlight, for example: There is a tendency to use sunscreen compositions. These compositions contain sunscreens that absorb ultraviolet light and prevent it from reaching the user's surface, such as the skin, to which the composition is applied.

Organic sunscreens, such as 4-tert-butyl-4'-methoxydibenzoylmethane (BMDM), absorb UVA radiation. The ability of sunscreens to provide a protective effect by absorbing UVA radiation is expressed by the UVA protection factor (UVAPF). On the other hand, organic sunscreens such as 2-ethylhexyl 2-cyano-3,3-diphenylacrylate (OCR) and octylmethoxycinnamate (MCX) absorb UVB radiation. The ability of a sunscreen to provide a protective effect by absorbing UVB radiation is expressed by the sun protection factor (SPF).

European Patent Application No. 2431021 (Unilever) describes dibenzoylmethane or its derivatives, oil-soluble UV-B organic sunscreens, fatty alcohol ethoxylates with saturated carbon chains and HLB higher than 15.5. or selected from the class of fatty alcohol ethoxylates having an unsaturated carbon chain with an HLB higher than 12, polymers of the class of acrylate/R-methacrylate copolymers; or High SPF sunscreen compositions containing less than 8% all-organic sunscreen are disclosed, including an acrylate/R-alkyl acrylate crosspolymer, and a cosmetically acceptable base. The compositions disclosed therein aim to provide an SPF higher than 15 without compromising the desired skin sensation properties.

WO 03/080009 (Unilever) discloses cosmetic compositions comprising organic sunscreen agents together with 4-substituted resorcinol derivatives in a cosmetically acceptable base. This composition exhibits improved storage and oxidative stability. WO 03/080009 discloses, inter alia, a combination of butylmethoxydibenzoylmethane, octylmethoxycinnamate, stearic acid, and 4-substituted resorcinols.

WO 11/147738 (Unilever) relates to sunscreen compositions that provide SPF (15 or higher) and high UV APF (4 or higher). WO 11/147738 describes solid sunscreen compositions comprising butyl methoxydibenzoylmethane, a selected class of nonionic surfactants, and a selected class of polymers in a cosmetically acceptable base. is disclosed. WO 11/147738 further discloses non-solid sunscreen compositions comprising dibenzoylmethane or a derivative thereof, a selected class of nonionic surfactants, a fatty acid, and a cosmetically acceptable base. are doing.

WO 16/142129 (Unilever) discloses the combination of a C12-C20 fatty acid and a C12-C20 fatty acid soap, such as a white pigment such as titanium dioxide in a cosmetically acceptable carrier, wherein the soap The molar ratio of fatty acid to fatty acid is 0.23 to 0.5. WO 16/142129 solves the problem of providing photoprotection while maintaining the sensory properties of the composition when a pigment such as titanium dioxide is added to a fatty acid-containing composition.

Despite past efforts, compositions that provide improved UVAPF remain an interesting topic.

Therefore, there remains a need to develop sunscreen compositions that provide improved UV APF.

A composition comprising a compound selected from resorcinol, phenylethylresorcinol, 4-alkyl substituted resorcinol, and mixtures thereof, together with a UVA organic sunscreen, a selected class of UVB organic sunscreen, a fatty acid, and a soap. It has been found to provide improved UV APF.

In a first aspect, the invention relates to a sunscreen composition comprising:
a. 0.1-5wt% UVA organic sunscreen;
b. 0.1 to 10 wt% 2-ethylhexyl-2-cyano-3,3-diphenylacrylate,
c. 0.1 to 2.5 wt% of a compound selected from resorcinol, phenylethyl resorcinol, 4-alkyl substituted resorcinol, and mixtures thereof;
d. 4-25 wt% fatty acids, and
e. 0.1-10 wt% soap.

In a second aspect, the invention relates to a method of providing improved UV APF, the method comprising applying the sunscreen composition of the first aspect onto the skin and optionally rinsing with water.

In a third aspect, the invention relates to the use of the composition of the first aspect to provide improved UVAPF.

Features according to one aspect of the invention may be utilized in other aspects of the invention. The word "comprising" means "including" but does not necessarily mean "consisting of" or "composed of." In other words, the steps or options listed are not exhaustive. Except for operational and comparative examples or unless otherwise expressly indicated, all numbers disclosed in this disclosure with respect to amounts or reaction conditions of materials, physical properties of materials and/or uses, It should be understood as modified by the word "about". Numerical ranges expressed in the form "x to y" are understood to include x and y. It is understood that when multiple preferred ranges are expressed in the form "x to y" for a particular feature, all ranges combining different endpoints are also contemplated.

Unless otherwise specified, amounts used herein are expressed as weight percentages based on the total weight of the composition, abbreviated as "wt%."

The use of any and all examples or exemplary language such as "for example" provided herein is merely intended to better explain the invention and in no way limits the scope of the invention. It's not something you do.

In a first aspect, the invention relates to a sunscreen composition comprising:
a. 0.1-5wt% UVA organic sunscreen;
b. 0.1 to 10 wt% 2-ethylhexyl-2-cyano-3,3-diphenylacrylate,
c. 0.1 to 2.5 wt% of a compound selected from resorcinol, phenylethyl resorcinol, 4-alkyl substituted resorcinol, and mixtures thereof.
d. 4-25 wt% fatty acids, and
e. 0.1-10 wt% soap.

UVA organic sunscreen The composition according to the invention comprises a UVA organic sunscreen that absorbs UVA radiation and prevents it from reaching surfaces, such as the user's skin.

Sunscreen agents that may be used as UVA organic sunscreens in the composition include dibenzoylmethane compounds, disodium bisdisururisole (sold as Neo Heliopan® AP), diethylaminohydroxybenzoylhexylbenzoin. Examples include the acid salts (commercially available as Uvinul® A Plus), ecamsul (commercially available as Mexoryl SX), and methylanthranilate.

Preferably, the sunscreen agent that can be used as a UVA organic sunscreen is selected from dibenzoylmethane compounds, diethylaminohydroxybenzoylhexylbenzoate, and mixtures thereof.

More preferably, sunscreens that can be used as UVA organic sunscreens include BMDM (commercially available as Parsol® 1789 or Avobenzone), 2-methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane, 2,4-dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane, 4,4'-diisopropyl-dibenzoylmethane, 2-methyl-5-isopropyl-4'-methoxy Dibenzoylmethane, 2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane, 2,4-dimethyl-4'-methoxydibenzoylmethane, 2,6-dimethyl-4-tert-butyl-4' -methoxydibenzoylmethane, and mixtures thereof.

Most preferably, the sunscreen that can be used as a UVA organic sunscreen is BMDM.

The composition contains 0.1 to 5% by weight, preferably 0.5 to 4.5% by weight, more preferably 1 to 4% by weight, even more preferably 1 to 3.5% by weight, even more preferably 1 ~3% by weight, even more preferably 1-2.5% by weight of one or more UVA organic sunscreens.

2-Ethylhexyl 2-cyano-3,3-diphenyl acrylate (OCR)
The composition includes OCR (commercially available as Octocrylene®), which absorbs UVB radiation and prevents it from reaching surfaces such as the skin.

The composition may contain 0.1 to 10% by weight, preferably 0.5 to 9% by weight, more preferably 1 to 8% by weight, even more preferably 1.5 to 7% by weight, even more preferably 2 to 6% by weight. % OCR by weight, even more preferably from 2.5 to 5%, most preferably from 3 to 4%.

Resorcinol, phenylethylresorcinol (PER), 4-alkyl substituted resorcinol The composition includes a compound selected from resorcinol, PER, 4-alkyl substituted resorcinol, and mixtures thereof. Such compounds are known to provide skin brightening effects.

Preferably, the selected compound is a 4-alkyl substituted resorcinol. The alkyl group in the 4-alkyl substituted resorcinol can be a straight chain alkyl or a branched chain alkyl. For example, the alkyl group may be a straight chain alkyl, as in 4-propylresorcinol, or a branched alkyl, as in 4-isopropylresorcinol (IPR).

Examples of 4-alkyl-substituted resorcinols include 4-methylresorcinol, 4-ethylresorcinol (ER), 4-propylresorcinol, IPR, 4-butylresorcinol (BR), 4-pentylresorcinol, 4-hexylresorcinol (HR). , 4-heptylresorcinol, 4-octylresorcinol, and mixtures thereof.

Preferred 4-alkyl substituted resorcinols are ER, BR, HR, and mixtures thereof. More preferred 4-alkyl substituted resorcinols are ER, HR, and mixtures thereof.

It is understood that the composition may include a combination of one or more compounds selected from resorcinol, PER and 4-alkyl substituted resorcinol. For example, the composition can include one or more 4-alkyl substituted resorcinols in the presence or absence of resorcinol. Preferably, the composition comprises one compound selected from resorcinol, PER, 4-alkyl substituted resorcinol.

The composition contains 0.1-2.5% by weight, preferably 0.1-2.25%, more preferably 0.25-2%, even more preferably 0.25-1.5% by weight. , even more preferably from 0.25 to 1% by weight, even more preferably from 0.25 to 0.75% by weight, most preferably from 0.25 to 0.5% by weight of resorcinol, PER, 4-alkyl substituted resorcinol, and mixtures thereof.

Fatty Acids The composition includes fatty acids. When present in the composition together with soap, the fatty acids provide a so-called disappearing cream effect, ie, when the composition is applied to human skin, it disappears on the skin, leaving no obvious streaks of the composition.

The composition preferably comprises fatty acids having in the range 10 to 22, more preferably 12 to 22, even more preferably 14 to 22, even more preferably 16 to 22, even more preferably 18 to 22 carbon atoms. include. It has been found that fatty acids with increasing chain length result in increased UVAPF and/or increased SPF.

Examples of fatty acids that may be used in the composition include lauric, myristic, palmitic, stearic, isostearic, oleic, linoleic, arachidic, behenic, erucic acid, and mixtures thereof.

Alternatively, fatty acids which may be preferably used are stearic acid, palmitic acid or mixtures thereof. The fatty acid in the present invention is historic acid (generally about 90-95%), which is a mixture of stearic acid and palmitic acid, preferably in a ratio of 55:45 to 45:55.

The composition comprises 4-25%, preferably 6-22%, more preferably 8-20%, even more preferably 10-19%, even more preferably 12-18% fatty acids by weight. .

Soap The composition includes a soap. Soaps, when present in combination with fatty acids in the composition, provide a so-called vanishing effect.

The soaps of the present invention are generally prepared by in-situ neutralization of fatty acids present in the composition. Therefore, it is preferred that the soap has a carbon chain length that corresponds to the chain length of the fatty acids in the composition. Soaps are formed from fatty acids by the use of alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide. Among these, potassium hydroxide is more preferred. The soap is therefore preferably a potassium soap (potassium salts of fatty acids).

The composition may contain from 0.1 to 10% by weight, preferably from 1 to 8%, more preferably from 2 to 7%, even more preferably from 2 to 6%, even more preferably from 2 to 5%, most preferably from 2 to 5% by weight. Preferably it contains 2-4% by weight of soap.

Preferably, the composition has a non-ionic interface having an HLB value in the range 9-20, preferably 10-19, more preferably 12-18, even more preferably 13-17, even more preferably 15-17. Further comprising an active agent.

HLB is calculated using the Griffin method, where HLB = 20 × Mh/M, where Mh is the molecular weight of the hydrophilic part of the molecule and M is the molecular weight of the entire molecule, ranging from 0 to 20. give results at any scale). Typical values for various surfactants are shown below:
Value less than 10: fat-soluble (water-insoluble)
Values greater than 10: Water-soluble Values in the range of 4 to 8 indicate antifoaming agents; Values in the range of 7 to 11 indicate W/O (water-in-oil) emulsifiers; Values in the range of 12 to 16 indicate water-soluble emulsifiers. Values in the range 11-14 indicate oil-in-water emulsifiers, values in the range 12-15 indicate wetting agents, typical detergents, values in the range 16-20 indicate solubilizers or hydrotropes. shows.

Preferably, nonionic surfactants with HLB values in the range 9 to 20 are selected from fatty alcohol ethoxylates, alkylphenol ethoxylates, polyoxyethylene sorbitan alkyl esters, and mixtures thereof. Preferably, the nonionic surfactant has at least 9 alkylene oxide groups, preferably at least 9 ethylene oxide groups.

Examples of fatty alcohol ethoxylates that can be used as nonionic surfactants in the composition include polyoxyethylene lauryl ether (HLB = 16.9; commercially available as Brij® 35); polyoxyethylene (20) cetyl ether (HLB=16; commercially available as Brij® 58), polyethylene glycol octadecyl ether (HLB=18.8; commercially available as Brij® 700), and laureth-9 (C12EO9; HLB=14.3; commercially available as Brij® L9).

Examples of alkylphenol ethoxylates that can be used as nonionic surfactants in the composition include octylphenol ethoxylate (HLB=15.5; commercially available as Triton® X165), octylphenol ethoxylate (HLB=17.6; commercially available as Triton® X405), and octylphenol ethoxylate (HLB=18.4; commercially available as Triton® X705).

An example of a polyoxyethylene sorbitan alkyl ester that can be used as a nonionic surfactant in the composition is polyoxyethylene sorbitan monolaurate (HLB=13.3; commercially available as Tween® 21). ), polyoxyethylene sorbitan monolaurate (HLB=16.7; commercially available as Tween® 20), polyoxyethylene sorbitan monopalmitate (HLB=15.6; commercially available as Tween® 20) 40), and polyoxyethylene sorbitan monostearate (HLB = 14.9; commercially available as Tween® 60).

More preferably, the nonionic surfactant with an HLB value in the range of 9 to 20 that may be present in the composition is a fatty alcohol ethoxylate with a saturated carbon chain having an HLB higher than 15.5.

Preferably, the composition comprises 0.5 to 5% by weight, more preferably 1 to 4%, even more preferably 2 to 3% by weight of a nonionic surfactant with an HLB in the range of 9 to 20. include.

Preferably, the composition further comprises a polymer. The polymer acts as a thickening agent in the composition and improves the sensory properties of the composition.

The polymer is preferably selected from the following classes:
- Acrylate/R-methacrylate copolymers, such as acrylate/steareth-20 methacrylate copolymer (commercially available as Aculyn® 22) and acrylate/behene-25 methacrylate copolymer (commercially available as Aculyn® 28) ),
- acrylate/R-methacrylate crosspolymers, such as acrylate/steareth-20 methacrylate crosspolymer (commercially available as Aculyn® 88),
- acrylate copolymer (commercially available as Aculyn 33),
- acrylate/R-alkyl acrylate crosspolymer, such as acrylate/C10-C30 alkyl acrylate crosspolymer (commercially available as Pemulen® TR-2),
- a copolymer of ammonium acryloyldimethyltourate and vinylpyrrolidone (commercially available as Aristoflex® AVC),
- a copolymer of sodium acryloyldimethyltourate and vinylpyrrolidone (commercially available as Aristoflex® AVS), and
- Crosspolymers of acryloyldimethyltouric acid and R-alkyl acrylates and methacrylates. For example, ammonium acryloyldimethyltaurate/behenate-25 methacrylate crosspolymers (commercially available as Aristoflex® HMB and Aristoflex® BLV); and mixtures thereof.

More preferably, the polymer is selected from acrylate/R-methacrylate copolymers, acrylate copolymers, and mixtures thereof.

Preferably, the composition contains 0.1 to 5% by weight, more preferably 0.5 to 4.5%, even more preferably 1 to 4%, even more preferably 1.5 to 3.5% by weight. , even more preferably 2-3% by weight of polymer.

Preferably, the composition comprises water, 5 to 99.9% by weight, preferably 10 to 95% by weight, more preferably 15 to 90% by weight, even more preferably 20 to 80% by weight, in the composition. Even more preferably it comprises a cosmetically acceptable vehicle which may be present in an amount of 25 to 75% by weight, even more preferably 30 to 70% by weight.

Preferably, the composition further comprises one or more skin lightening agents. These one or more skin lightening agents may include niacinamide, vitamin B6, vitamin C, vitamin A, glutathione precursor, galazine, adapalene, aloe extract, ammonium lactate, aributin, azelaic acid, butylated hydroxyanisole, butylated hydroxytoluene. , citric acid ester, deoxyaributin, 1,3-diphenylpropane derivatives, 2,5-dihydroxybenzoic acid and its derivatives, 2-(4-acetoxyphenyl)-1,3-dithiane, 2-(4-hydroxyphenyl) )-1,3-dithiane, ellagic acid, glucopyranosyl-1-ascorbic acid, gluconic acid, glycolic acid, green tea extract, 4-hydroxy-5-methyl-3[2H]-furanone, 4-hydroxyanisole and its derivatives , 4-hydroxybenzoic acid derivatives, hydroxycaprylic acid, inositol ascorbic acid, lactic acid, lemon extract, linoleic acid, magnesium ascorbyl phosphate, 5-octanoylsalicylic acid, salicylic acid, 3,4,5-trihydroxybenzyl derivative, acetyl Glucosamine, Pitera extract, Thinwhite, calcium pantothenate (Melanoblock), Sepiwhite, soybean extract (Bowman Birkin Inhibitor), 12-hydroxystearic acid, and mixtures thereof. When used in the composition, 12-hydroxystearic acid is used as a skin lightening agent and not as a fatty acid.

Preferably, the skin lightening agents that may be used in the composition are niacinamide, vitamin B6, 12-hydroxystearic acid, glutathione precursors, galargin, and mixtures thereof.

When incorporated into the composition, the skin lightening agent comprises 0.001 to 15% by weight, preferably 0.01 to 10%, more preferably 0.1 to 5%, even more preferably It may be added in an amount of 0.5-3% by weight.

Preferably, the composition further comprises an emollient. Examples of emollients that may be used in the compositions include stearyl alcohol, glyceryl monoricinoleic acid, mink oil, cetyl alcohol, isopropyl isostearate, isobutyl palmitate, oleyl alcohol, isopropyl laurate, hexyl laurate, decyl olefin. ate, octadecane-2-ol, isocetyl alcohol, eicosane alcohol, behenyl alcohol, cetyl palmitate, silicone oils such as dimethylpolysiloxane, dibutyl sebacate, isopropyl myristate, isopropyl palmitate, isopropyl stearate, butyl stearate, Polyethylene glycol, triethylene glycol, lanolin, cocoa oil, corn seed oil, olive kernel oil, palm kernel oil, rapeseed oil, safflower seed oil, evening primrose oil, soybean oil, sunflower seed oil, avocado oil, sesame seed oil, Coconut oil, peanut oil, castor oil, acetylated lanolin alcohol, petroleum jelly, mineral oil, butyl myristate, isopropyl linoleate, lauryl lactate, myristyl lactate, decyl oleate, myristyl myristate, and mixtures thereof.

Preferably, the composition further comprises a solvent. Examples of solvents that can be used in the composition include ethyl alcohol, isopropanol, acetone, ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, and mixtures thereof.

Preferably, the composition further comprises a powder. Examples of powders that can be used in the composition include chalk, talc, Fuller's earth, kaolin, starch, gum, colloidal silica sodium polyacrylate, tetraalkyl and/or trialkylaryl ammonium smectites, chemically modified silicic acids. Examples include magnesium aluminum, organically modified montmorillonite clay, hydrated aluminum silicate, fumed silica, carboxyvinyl polymer, sodium carboxymethylcellulose, ethylene glycol monostearate, and mixtures thereof.

Preferably, the composition further includes a preservative to protect against the growth of potentially harmful microorganisms. Examples of ingredients that can be used as preservatives in the composition include alkyl esters of para-hydroxybenzoic acid, hydantoin derivatives, propionate salts, and various quaternary ammonium compounds. More preferably, the ingredients that can be used as preservatives in the composition are sodium benzoate, iodopropynyl butyl carbamate, methylisothiazolinone, iodopropynyl butyl carbamate, phenoxyethanol, methyl paraben, propyl paraben, imidazolidinyl urea, sodium dehydroacetate, Ethylhexylglycerin, benzyl alcohol, alkanediols, and mixtures thereof. Alkanediols suitable for use as preservatives are C ₆ -C ₁₂ alkanes substituted adjacently with hydroxy groups. Illustrative examples include 1,2-octanediol (caprylyl glycol), 2,3-octanediol, 1,2-nonanediol, 1,2-decanediol, 1,2-hexanediol, 3,4 -octanediol, mixtures thereof, and the like, with caprylyl glycol typically being most preferred.

When present in the composition, preservatives are preferably added in an amount of 0.001 to 5%, more preferably 0.01 to 3%, most preferably 0.02 to 2% by weight.

The composition contains antioxidants, binders, biological additives, buffers, colorants, astringents, fragrances, opacifiers, conditioners, exfoliants, pH regulators, skin soothing agents, and skin healing agents. A series of other optional ingredients may further be included.

The composition is preferably formed in the form of a powder, flake, lotion, cream, gel, or mousse. More preferably, the composition is formed in the form of a cream or lotion, most preferably in the form of a cream. The composition may be a leave-on or wash-off type composition. The composition is preferably a leave-on type composition. Packaging for the compositions of the invention can be a patch, bottle, tube, roll ball applicator, propellant-driven aerosol device, squeeze container, or lidded jar.

Resorcinol, phenylethylresorcinol, 4-alkyl substituted resorcinol, and mixtures thereof are found to improve UVAPF when present in the composition of the first aspect. It has also been found that such improved UV APF is obtained only when using OCR in the presence of a UVA organic sunscreen. Improved UV APF was not obtained when other UVB organic sunscreens, such as MCX, were used in place of OCR. OCR is known to stabilize dibenzoylmethane compounds such as BMDM. The improvement in UVAPF obtained in the presence of a compound selected from resorcinol, phenylethylresorcinol, 4-alkyl substituted resorcinol, and mixtures thereof is greater than the UVAPF obtained when OCR is used in place of MCX in the same composition. It is found that the Therefore, surprisingly, replacing one UVB sunscreen, i.e. MCX, with another UVB sunscreen, i.e. OCR, improved UVAPF, which is the function of UVA sunscreens to provide UVAPF.

Preferably, the sunscreen composition is a composition comprising:
a. 0.1 to 5% by weight of a dibenzoylmethane compound,
b. 0.1-10% by weight of 2-ethylhexyl 2-cyano-3,3-diphenylacrylate,
c. 0.1 to 2.5% by weight of a compound selected from BR, ER, HR, and mixtures thereof;
d. 4-25% by weight fatty acids, and
e. 0.1-10% by weight soap.

More preferably a composition comprising a sunscreen composition:
a. 0.1 to 5% by weight of 4-tert-butyl-4'-methoxydibenzoylmethane,
b. 0.1-10% by weight of 2-ethylhexyl 2-cyano-3,3-diphenylacrylate,
c. 0.1 to 2.5% by weight of a compound selected from ER, HR, and mixtures thereof;
d. 4-25% by weight fatty acids, and
e. 0.1-10% by weight soap.

In a second aspect, the invention further relates to a method of providing improved UV APF, wherein the method comprises the steps of:
a. applying the sunscreen composition of the first aspect to the skin;
b. Selectively rinse with water.

The present invention also provides a method of providing improved UVAPF, comprising applying the composition of the first aspect to a surface, such as the skin, in the case of a leave-on composition. The method optionally includes the additional step of at least partially removing the composition from the surface when the composition is in the form of a wash-off composition. Preferably, the method is non-therapeutic or cosmetic. When the composition is applied to the skin, improved UV APF is obtained.

In a third aspect, the invention relates to the use of the composition of the first aspect for improved UV APF.

The invention will now be illustrated by the following non-limiting examples.

protocol
Preparation of the composition
Briefly, the composition of the invention was prepared as follows: demineralized water and potassium hydroxide were placed in a beaker (main beaker) mounted on a magnetic stirrer and heater. The aqueous phase was heated to 75°C and maintained at the same temperature. In a side pot, the fatty acids described in the examples below were heated to 75°C for melting and added to the main beaker maintained at 75°C. The system was stirred for 5 minutes at 75°C. Sunscreen, other oil-soluble ingredients, and non-ionic surfactants as mentioned in the examples were placed in separate beakers and heated to 65-70°C for melting. These were thoroughly mixed and added to the main beaker. Stirring was continued for an additional 5 minutes at 75°C. The stirrer and heater were switched off and mixed manually until the temperature reached ambient temperature (25°C).

In vitro SPF/UVA-PF measurements Thin film transmittance measurements were performed using an SPF-290S SPF meter (Optometrics Corporation). In this test, a 70×70 mm PMMA plate with a roughness of 6 μm from Schoenberg GmbH & Co. was used. Transmittance (%) of various compositions was measured as follows. 2 mg/cm ² of the test sample was applied onto the PMMA plate and distributed evenly using a syringe to ensure uniform dispersion. Drying time for PMMA plates was 30 minutes. After drying, the sample plate was exposed to UV light and a transmittance scan was recorded. This scan gives the transmission as a function of wavelength (290-400 nm) for a given sample. Six to eight different spots were scanned on a single plate. The same was repeated for three plates. Therefore, the data reported is an average over 18 readings. A reference transmittance scan was acquired using a blank plate, with no sample coated with glycerin on the PMMA plate. The transmittance values were used to arrive at the SPF values by using the Win SPF software provided with the instrument. The transmittance values are used to calculate the UVAPF value for each composition.

In-vivo SPF/UVAPF
The compositions described in the examples shown in Table 1 were tested in a random sample of human volunteers performed with appropriate controls. Briefly, the minimum erythema dose (MED) and minimum sustained pigment darkening dose (MPPDD) for each volunteer were estimated prior to sample (compositions in Table 1) application. Test samples were blinded with standard samples of known SPF/UVAPF. The required amount of sample (2 mg/cm ² ) was applied to the dorsal skin of the volunteers. The sample was evenly distributed using a syringe and applied evenly using a finger cot over a period of 20-50 seconds depending on the ease of application of the composition. A new finger cot is used for each sample. After sample application, the subject is exposed to UV and the dose is calculated based on the MED and MPPDD (specific to each volunteer) and the expected or target SPF/UVAPF. Following exposure, volunteers were evaluated for erythema and MPPDD. Evaluation of SPF was performed using ISO Standard 24444:2010. Evaluation of UVAPF was performed using ISO 24442:2011. The data reported here are the average of 5 volunteers.

According to the data in Table 1, compositions according to the invention containing HR together with BMDM, OCR, fatty acids and soap compared to comparative examples (Examples A and B; not according to the invention) containing no HR. (Examples 1 and 2) have been shown to provide improved UVAPF.

Furthermore, the data show that only when the selected UVB sunscreen, namely OCR (Example 1), is used in place of MCX (Example C), the same amount, i.e. 0. It has been shown that improved UV APF is obtained despite containing 5% by weight HR. Thus, HR provides improved UV APF when used in combination with UVA organic sunscreens, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, fatty acids, and soaps. This improved UVAPF was not obtained when MCX was present instead of OCR.

The data in Table 1 also shows that the presence or absence of HR in the compositions of Examples B and C has no effect on UVAPF.

Surprisingly, it was found that the improvement in UVAPF was independent of the dose of HR used. As can be seen from Example 2 (0.25 wt% HR), a UVAPF equal to 17 was obtained, while Example 1 (0.5 wt% HR) showed a UVAPF equal to 14. Such effects are believed to be based on the superoxide quenching potency, which was found to increase as the concentration of HR increased up to a concentration of 2 mM. After that, the superoxide quenching efficiency decreased despite the increase in HR concentration under uniform exposure conditions.

Effect of the amount of soap in the composition on UVAPF and SPF The compositions outlined in Table 2 demonstrate the effect of the presence of soap in the composition compared to the control (no soap).

The data in Table 2 shows that soap enhances SPF as well as UV APF when present in the compositions of the invention.

Additionally, additional compositions shown in Table 3 below were prepared as described above and UVAPF and SPF were measured as described above. The results obtained were as shown in Table 3 below.

The data in Table 3 shows that improved UV APF is obtained when palmitic acid, as shown in Example 6, or stearic acid, as shown in Example 7, is used in the composition.

The data in Table 3 also shows that improved UV APF is obtained when BR, as shown in Example 8, or ER, as shown in Example 9, is used in the composition.

In conclusion, the sunscreen compositions of the present invention provide improved UV APF.

Claims (15)

Sunscreen composition containing:
a. 0.1-5wt% UVA organic sunscreen;
b. 0.1 to 10 wt% 2-ethylhexyl-2-cyano-3,3-diphenylacrylate,
c. 0.1 to 2.5 wt% of a compound selected from resorcinol, phenylethyl resorcinol, 4-alkyl substituted resorcinol, and mixtures thereof;
d. 4-25 wt% fatty acids, and
e. 0.1-10wt% soap. The sunscreen composition according to claim 1, further comprising a nonionic surfactant having an HLB value in the range of 9-20. Sunscreen composition according to claim 1 or 2, wherein the nonionic surfactant is a fatty alcohol ethoxylate with a saturated carbon chain having an HLB in the range of 15.5 to 20. Sunscreen composition according to any one of claims 1 to 3, further comprising 0.1 to 5% by weight of polymer. A sunscreen composition according to any one of claims 1 to 4, comprising 0.1 to 3% by weight of soap. Sunscreen composition according to any one of claims 1 to 5, comprising 8 to 20% by weight of fatty acids. The 4-alkyl-substituted resorcinol is 4-methylresorcinol, 4-ethylresorcinol, 4-propylresorcinol, 4-isopropylresorcinol, 4-butylresorcinol, 4-pentylresorcinol, 4-hexylresorcinol, 4-heptylresorcinol, 4-octyl Sunscreen composition according to any one of claims 1 to 6, selected from resorcinol, and mixtures thereof. A sunscreen composition according to any one of claims 1 to 7, wherein the 4-alkyl-substituted resorcinol is selected from 4-ethylresorcinol, 4-hexylresorcinol, and mixtures thereof. Sunscreen composition according to any one of claims 1 to 8, further comprising 0.001 to 15% by weight of a skin lightening agent. The UVA sunscreen agent includes 4-tert-butyl-4'-methoxydibenzoylmethane, 2-methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane, 2,4-dimethyldibenzoylmethane, Benzoylmethane, 2,5-dimethyldibenzoylmethane, 4,4'-diisopropyldibenzoylmethane, 2-methyl-5-isopropyl-4'-methoxydibenzoylmethane, 2-methyl-5-tert-butyl-4' -methoxydibenzoylmethane, 2,4-dimethyl-4'-methoxydibenzoylmethane, or 2,6-dimethyl-4-tert-butyl-4'-methoxydibenzoylmethane, claims 1 to 9. The sunscreen composition according to any one of the above. A sunscreen composition according to any one of claims 1 to 10, wherein the UVA sunscreen agent is 4-tert-butyl-4'-methoxydibenzoylmethane. A sunscreen composition according to any one of claims 1 to 11, wherein the composition is a leave-on composition. A sunscreen composition according to any one of claims 1 to 11, wherein the composition is a wash-off composition. A non-therapeutic method of providing improved UVAPF, the method comprising the following steps:
f. Applying the sunscreen composition according to any one of claims 1 to 11 and 13 to the skin,
g. selectively, rinse with water ,
method . 14. A non-therapeutic use of a composition according to any one of claims 1 to 13, said non-therapeutic use being for improved ultraviolet A protection of the skin.
Use .