WO2005082325A1 - PHOTOSTABILIZATION OF A SUNSCREEN COMPOSITION WITH A COMBINATION OF AN α-CYANO-β,β-DIPHENYLACRYLATE COMPOUND AND A DIALKYL NAPHTHANATE - Google Patents
PHOTOSTABILIZATION OF A SUNSCREEN COMPOSITION WITH A COMBINATION OF AN α-CYANO-β,β-DIPHENYLACRYLATE COMPOUND AND A DIALKYL NAPHTHANATE Download PDFInfo
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- WO2005082325A1 WO2005082325A1 PCT/US2004/040103 US2004040103W WO2005082325A1 WO 2005082325 A1 WO2005082325 A1 WO 2005082325A1 US 2004040103 W US2004040103 W US 2004040103W WO 2005082325 A1 WO2005082325 A1 WO 2005082325A1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/35—Ketones, e.g. benzophenone
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/85—Polyesters
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/86—Polyethers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/52—Stabilizers
Definitions
- the invention relates to sunscreen compositions including a dibenzoylmethane derivative, such as avobenzone, that are made more stable by the addition of (a) an ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate compound, e.g., octocrylene, and (b) a diester or polyester of naphthalene dicarboxylic acid (e.g., diethylhexyl 2,6-naphthalate), having a weight ratio of (a)/(b) of at least 0.95, preferably at least about 1.0.
- a dibenzoylmethane derivative such as avobenzone
- the invention relates to sunscreen compositions which utilize a combination of octocrylene and diethylhexyl 2,6- naphthalate to stabilize other photoactive compounds present in a sunscreen composition and, in particular, to stabilize dibenzoylmethane derivatives, without, or with levels less than 0.5% by weight of, a methoxy-substituted benzophenone derivative, such as benzophenone-3.
- UV radiation having a wavelength from about 280 nm or 290 nm to about 320 nm (UV-B) is harmful to human skin, causing burns that are detrimental to the development of a good sun tan.
- UV-A radiation about 320 nm to about 400 nm
- a sunscreen composition for use on human skin preferably includes both a UN-A and a UN-B filter to prevent most of the sunlight within the full range of about 280 nm or 290 nm to about 400 nm from damaging human skin.
- Ultraviolet radiation from the sun or artificial sources can also cause harm to coatings containing photoactive substances, such as photoactive pigments and dyes, by breaking down chemical bonds in the structure of a component such as a polymer, a pigment, or a dye.
- This photodegradation can lead to color fading, loss of gloss, and loss of physical and protective properties of a coating.
- Photodegradation can take place in several steps which include one or more components of a coating absorbing UN radiation.
- the absorbed radiation can excite the absorbing molecules and raise them to a higher energy level, which can be very reactive. If the molecule cannot be relaxed, bond cleavage and the formation of free radicals will occur. These free radicals can attack one or more color molecules and/or a polymer backbone and form more free radicals.
- UN-A and UN-B filters can also be used to accept UN radiation to protect a pigmented coating.
- the UN-B filters that are most widely used in the U.S. in commercial sunscreen compositions are paramethoxycinnamic acid esters, such as 2-ethylhexyl paramethoxycinnamate, commonly referred to as octyl methoxycinnamate or PARSOL ® MCX, octyl salicylate, and oxybenzone.
- the organic UN-A filters most commonly used in commercial sunscreen compositions are the dibenzoylmethane derivatives, particularly
- a bimolecular pathway leads to the rapid photodegradation of both the dibenzoylmethane derivative and the octyl methoxycinnamate.
- 6,033,649 describe the use of an -cyano- ⁇ , ⁇ -diphenylacrylate compound, such as octocrylene, to stabilize a sunscreen composition including a dibenzoylmethane derivative.
- octocrylene an -cyano- ⁇ , ⁇ -diphenylacrylate compound
- Deflandre et al. teach a minimum 1% by weight of octocrylene
- Gonzenbach et al. teach a minimum of 0.5% by weight of octocrylene to stabilize a dibenzoylmethane derivative, such as avobenzone, in a sunscreen composition.
- 6,491,901 discloses sunscreen compositions containing a dibenzoylmethane derivative with a stabilizing combination of octocrylene and diesters or polyesters of naphthalene dicarboxylic acid wherein the examples have a weight ratio of octocrylene to the diester or polyester of naphthalene dicarboxylic acid in the range of 0.16 to 0.725, and the claims call for a weight ratio between about 0.03 and about 0.9.
- the combination of octocrylene with one or more dialkyl naphthalates acts synergistically to prevent decomposition of avobenzone (see col.4, lines 21-35).
- the combination of octocrylene and dialkyl naphthalates of the '901 patent in the example formulations, disclose 1% to 2.9% octocrylene and 4% to 8% dialkyl naphthalate combinations.
- weight ratios of an ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, e.g., octocrylene, to diakyl naphthalate of at least 0.95, preferably at least about 1.0 provide surprisingly better results for photostabilizing a dibenzoylmethane derivative, such as avobenzone, than lower weight ratios, contrary to the teachings of the '901 patent.
- the formulations contain 0% to about 10%, by weight, to less than .05% by weight benzophenone-3, more preferably about 0.1 to about 0.49% by weight benzophenone-3.
- benzophenone-3 in the formulation, a PA+++ rating UNA protection grade, as defined by the Technical Committee of the Japan Cosmetic Association (JCIA) in the Japanese Persistent Pigment Darkening Protocol, hereby incorporated by reference, and attached as an appendix to this application.
- benzophenone-3 in the formulations represents a separate, preferred embodiment, and is not necessary to provide excellent and surprising photostabilization of one or more dibenzoylmethane derivatives so long as the octocrylene/dialkyl naphthalate weight ratio is at least 0.95, preferably at least about 1.0, as shown in the examples.
- compositions and methods described herein is a composition including a mixture of a dibenzoylmethane derivative, and a combination of (a) an ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate compound, such as octocrylene, and (b) a diester or polyester of naphthalene dicarboxylic acid, wherein the weight ration of (a)/(b) is at least 0.95, preferably at least about 1.0.
- compositions and methods described herein is a composition including a mixture of a dibenzoylmethane derivative, such as avobenzone, together with a combination of (a) an -cyano- ⁇ , ⁇ -diphenylacrylate compound, such as octocrylene, (b) a diester or polyester of naphthalene dicarboxylic acid, wherein the weight ratio of (a) to (b) is at least 0.95, preferably at least about 1.0; and (c) 0 to about 3.0% by weight of benzophenone-3, preferably less than about 0.5% by weight benzophonone-3, more preferably about 0.1% by weight to about 0.49% by weight benzophenone-3.
- a dibenzoylmethane derivative such as avobenzone
- compositions and method described herein is a composition including a mixture of a dibenzoylmethane derivative, such as avobenzone, together with a combination of (a) an ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate compound, such as octocrylene, (b) a diester or polyester of naphthalene dicarboxylic acid, wherein the weight ratio of (a) to (b) is at least 0.95, preferably at least about 1.0 and (c) a compound capable of raising the dielectric constant of an oil phase of the composition to a level of at least about 7.0 preferably at least about 8.0, such as dimethyl capramide and/or diethylhexyl malate.
- a dibenzoylmethane derivative such as avobenzone
- compositions and methods described herein is a composition including a mixture of (a) a dibenzoylmethane derivative, such as avobenzone, (b) an - cyano- ⁇ , ⁇ -diphenylacrylate compound, such as oxybenzone, (c) a diester or polyester of naphthalene dicarboxylic acid, wherein the weight ratio of (b) to (c) is at least 0.95, preferably at least about 1.0; (d) 0 to bout 3.0% by weight of benzophenone-3, preferably less than about 0.5% by weight benzophonone-3, more preferably about 0.1% by weight to about 0.49% by weight benzophenone-3; and (e) a compound capable of raising the dielectric constant of an oil phase of the composition to a level of at least about 7.0 preferably at least about 8.0, such as dimethyl capramide and/or diethylhexyl malate.
- a dibenzoylmethane derivative such as avobenzone
- Yet another aspect of the invention is a composition including a mixture of a dibenzoylmethane derivative, such as avobenzone, an ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate compound, such as octocrylene, a diester or polyester of naphthalene dicarboxylic acid, and less than 0.5% benzophenone-3 capable of receiving a UVA protection grade of PA+++ (has a PFA -Protection Factor of UVA- of at least 8.0) when tested in accordance with the present Japanese Persistent Darkening Protocol.
- a dibenzoylmethane derivative such as avobenzone
- an ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate compound such as octocrylene
- diester or polyester of naphthalene dicarboxylic acid and less than 0.5% benzophenone-3 capable of receiving a UVA protection grade of PA+++ (has a PFA -Protection Factor
- Sunscreen compositions containing a dibenzoylmethane derivative UN-A filter compound such as 4-(l,l-dimethylethyl)-4'-methoxydibenzoylmethane (PARSOL ® 1789) are photostabilized by containing (a) an ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate compound, such as octocrylene; and (b) a diester or polyester of naphthalene dicarboxylic acid, wherein the weight ratio of (a)/(b) is at least 0.95, preferably at least about 1.0.
- a dibenzoylmethane derivative UN-A filter compound such as 4-(l,l-dimethylethyl)-4'-methoxydibenzoylmethane (PARSOL ® 1789) are photostabilized by containing (a) an ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate compound, such as octocrylene; and (b)
- One aspect of the sunscreen compositions and methods described herein is to photostabilize a sunscreen composition containing a dibenzoylmethane derivative, such as avobenzone, by including in the composition a combination of (a) an ⁇ -cyano- ⁇ , ⁇ - diphenylacrylate compound, such as octocrylene, in an amount in the range of about 0.5% to about 8.0% by weight, preferably about 2% to about 7% by weight, more preferably about 1.5% to about 5% by weight, and (b) a diester or polyester of naphthalene dicarboxylic acid (DEH ⁇ ), in an amount in the range of about 0.5% to about 8.0% by weight, preferably about 2% to about 7% by weight, more preferably about 1.5% to about 5% by weight, wherein the weight ratio of (a) to (b) is at lest 0.95, preferably at least about 1.0 to achieve a stable sunscreen composition.
- a dibenzoylmethane derivative such as avobenzone
- an ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate compound is combined with a highly polar solvent or blend of solvents with a high polarity to enhance the photostabilizing effect of the ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate compound, and thereby enhance the stability of the sunscreen composition.
- the photostabilizing effect of the diester or polyester of naphthalene dicarboxylic acid on the dibenzoylmethane derivative is enhanced by adding benzophenone-3, preferably at a level less than about 0.5% by weight.
- a photoactive compound can be considered stable when, for example, after 30 MED irradiation the photoactive compound has retained at least 90% of its original absorbance at a wavelength or a range of wavelengths of interest (e.g., the wavelength at which or near a photoactive compound has a peak absorbance, such as 350-360 nm for avobenzone).
- a sunscreen composition can include a plurality of photoactive compounds and a sunscreen composition, as a whole, can be considered stable when, for example, after 30 MED irradiation the sunscreen composition has retained at least 90% of its original absorbance at one or more wavelengths of interest (e.g., at or near the peak absorbance wavelength of the primary photoactive compounds).
- a dibenzoylmethane derivative is excited, it is prone to degrade according to a number of pathways, however, the degradation of the dibenzoylmethane derivative can be substantially reduced or prevented by the use of a diester or polyester of naphthalene dicarboxylic acid to quench (accept) the triplet excited state energy present in an excited dibenzoylmethane molecule.
- a dibenzoylmethane derivative is excited to its triplet state and the excited state triplet energy is released in a bond breaking step, thereby preventing the dibenzoylmethane derivative from further accepting ultra-violet radiation.
- a diester or polyester of naphthalene dicarboxylic acid may stabilize a dibenzoylmethane derivative by accepting the triplet state (excited state) energy of the excited dibenzoylmethane derivative in such a way as to convert the excited dibenzoylmethane derivative back to a non-excited state that is capable of reaccepting ultraviolet radiation (energy transfer).
- the diester or polyester of naphthalene dicarboxylic acid must transfer or convert the energy that was accepted from the excited dibenzoylmethane derivative. Without intending to be limited to a particular mechanism, it is believed that when a diester or polyester of naphthalene dicarboxylic acid is excited to its triplet state, the triplet excited state energy is dissipated through vibrations (t ' .e., heat), which in this group of molecules is a slow mode of dissipating energy.
- the efficiency of the dissipation of the excited state energy in an excited diester or polyester of naphthalene dicarboxylic acid is greatly improved by a transfer of energy from an excited diester or polyester of naphthalene dicarboxylic acid to an ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate compound.
- a A wherein the ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate compound (octocrylene shown above as A), accepts the triplet excited state energy and forms a diradical (shown above as A ) at the and ⁇ positions of the acrylate, which converts the double bond into a single bond and allows for the free rotation of the phenyl groups. This rotation occurs rapidly and efficiently to dissipate any excited state energy accepted by the -cyano- ⁇ , ⁇ -diphenylacrylate compound.
- a key limitation on one compound's ability to stabilize another is the ability of the two compounds to come into contact with one another.
- ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate compound it is preferred to have at least as much of the ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate compound as the diester and/or polyester of naphthalene dicarboxylic acid so that the ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate compound is abundant enough to quickly come into contact with an excited diester or polyester of naphthalene dicarboxylic acid.
- the dielectric constant of a solvent system is a preferred measure of polarity of a solvent system, for example because the dielectric constant is a measure of both inherent and inducible dipole moments.
- Other measures of polarity include, but are not limited to, the induced and/or inherent (permanent) dipole moment (e.g., in Debye units), the Dimroth- Reichardt E parameter, and ionizing power. See generally, C. Reichardt, "Solvents and
- Q(a) Ae "kr (i) wherein A is the original (pre-exposure) absorbance, e is the natural logarithm base, k is the rate constant of the photodecay, and r is the cumulative dose (e.g., in MED units). Because the absorbance decreases as the cumulative dose increases (photodecay), the overall term -k will be negative, and the greater the value f-k (i.e., closer to zero) and, thus, the lower the rate constant of photodecay, the lower is the rate of photodecay. For example, when (a) is plotted on a log scale versus r on a linear scale, the function forms a straight line with a slope equal to -k.
- the rate constant of photodecay of the set of photoactive compounds can be described as a second-order function of the polarity, preferably the dielectric constant (i.e., relative permittivity) of the filter set dissolved in the solvent system.
- a photoactive compound is one that responds to light photoelectrically.
- a photoactive compound is one that responds to UN radiation photoelectrically.
- photoactive compounds that respond to UN radiation photoelectrically by rapid photo degradation can benefit highly from the compositions disclosed herein, even though the benefits of the compositions disclosed herein are not limited to such compounds.
- Photostability is a potential problem with all UN filters because they are deliberately selected as UN-absorbing molecules.
- a photoactive compound may be a pigment or a dye (e.g., a hydrophobic dye).
- UN filters include compounds selected from the following categories (with specific examples) including: p-aminobenzoic acid, its salts and its derivatives (ethyl, isobutyl, glyceryl esters; p-dimethylaminobenzoic acid); anthranilates (o-aminobenzoates; methyl, menthyl, phenyl, benzyl, phenylethyl, linalyl, terpinyl, and cyclohexenyl esters); salicylates (octyl, amyl, phenyl, benzyl, menthyl (homosalate), glyceryl, and dipropyleneglycol esters); cinnamic acid derivatives (menthyl and benzyl esters, alpha-phenyl cinnamonitrile; butyl cinnamoyl pyruvate); dihydroxycinnamic acid derivatives (umbelliferone, methyl
- 2-ethylhexyl p-methoxycinnamate 4,4'-t-butyl methoxydibenzoylmethane, 2-hydroxy-4-methoxybenzophenone, octyldimethyl p- aminobenzoic acid, digalloyltrioleate, 2,2-dihydroxy-4-methoxybenzophenone, ethyl 4- [bis(hydroxypropyl)]aminobenzoate, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, 2- ethylhexylsalicylate, glycerol p-aminobenzoate, 3,3,5-trimethylcyclohexylsalicylate, methylanthranilate, p-dimethylaminobenzoic acid or aminobenzoate, 2-ethylhexyl p- dimethylaminobenzoate, 2-phenylbenzimidazo
- a sunscreen composition disclosed herein includes a dibenzoylmethane derivative.
- Preferred dibenzoylmethane derivatives include 2-methyldibenzoylmethane; 4- methyldibenzoylmethane; 4-isopropyldibenzoylmethane; 4-tert-butyldibenzoylmethane; 2,4- dimethyldibenzoylmethane; 2,5-dimethyldibenzoylmethane; 4,4'- diisopropyldibenzoylmethane; 4,4'-dimethoxydibenzoylmethane; 4-tert-butyl-4'- methoxydibenzoylmethane; 2-methyl-5-isopropyl-4'-methoxydibenzoylmethane; 2-methyl-5- tert-butyl-4'-methoxydibenzoylmethane; 2,4-dimethyl-4'-methoxydibenzoyl
- a photoactive compound can be added to the composition.
- Additional photoactive compounds can be selected from any of the UV-A filters, UN-B filters, and combinations thereof.
- a photoactive compound preferably is selected from approved (if regulated), cosmetically-acceptable UN-A filters, UN-B filters, and combinations thereof.
- preferred cosmetically-acceptable photoactive compounds and concentrations include: aminobenzoic acid (also called para-aminobenzoic acid and PABA; 15% or less), avobenzone (also called butyl methoxy dibenzoylmethane; 3% or less), cinoxate (also called 2-ethoxyethyl
- ⁇ -methoxycinnamate 3% or less
- dioxybenzone also called benzophenone-8; 3% or less
- homosalate (15% or less)
- menthyl anthranilate also called menthyl 2-aminobenzoate; 5% or less
- octocrylene also called 2-ethylhexyl-2-cyano-3,3 diphenylacrylate; lO'
- octyl methoxycinnamate 7.5% or less
- octyl salicylate also called 2-ethylhexyl salicylate; 5% or less
- oxybenzone also called benzophenone-3; 6% or less
- padimate O also called octyl dimethyl PABA; 8% or less
- phenylbenzimidazole sulfonic acid water soluble; 4% or less
- sulisobenzone also called benzophenone-4; 10% or less
- titanium dioxide 25% or less
- Other preferred cosmetically-acceptable photoactive compounds and concentrations include dieth_anolamine methoxycinnamate (10% or less), ethyl- [bis(hydroxypropyl)] aminobenzoate (5% or less), glyceryl aminobenzoate (3% or less), 4-isopropyl dibenzoylmethane (5% or less), 4-methylbenzylidene camphor (6% or less), terephthalylidene dicamphor sulfonic acid (10% or less), and sulisobenzone (also called benzophenone-4, 10% or less).
- preferred cosmeticaLly-acceptable photoactive compounds and concentrations include: PABA (5% or less), camphor benzalkonium methosulfate (6% or less), homosalate (10% or less), benzophenone-3 (10% or less), phenylbenzimidazole sulfonic acid (8% or less, expressed as acid), terephthalidene dicamphor sulfonic acid (10% or less, expressed as acid), butyl methoxydibenzoylmethane (5% or less), benzylidene camphor sulfonic acid (6% or less, expressed as aci ⁇ i), octocrylene (10% or less, expressed as acid), polyacrylamidomethyl benzylidene camphor- (6% or less), ethylhexyl methoxycinnamate (10% or less), PEG-25 PABA (10% or less), is
- alkyl includes straight chained and branched hydrocarbon groups containing the indicated number of carbon atoms, typically methyl, ethyl, propyl, and butyl groups.
- the term “alkyl” also includes "bridged alkyl,” e.g., a C 4 -C 16 bicyclic or polycyclic hydrocarbon group, for example, norbornyl, adamantyl, bicyclo[2.2.2]octyl, bicyclo[2.2.1]heptyl, bicyclo[3.2.1]octyl, or decahydronaphthyl.
- cycloalkyl is defined as a cyclic hydrocarbon group, e.g., cyclopropyl, cyclobutyl, cyclohexyl, and cyclopentyl.
- alkenyl is defined identically as “alkyl,” except for containing a carbon-carbon double bond.
- cycloalkenyl is identical to “cycloalkyl” except containing a carbon-carbon double bond, e.g., cyclopropyl, cyclobutyl, cyclohexyl, and cyclopentyl.
- aryl alone or in combination, is defined herein as a monocyclic or polycyclic aromatic group, preferably a monocyclic or bicyclic aromatic group, e.g., phenyl or naphthyl.
- a sunscreen composition disclosed herein may include a variety of photoactive compounds, including one or more UN-A photoactive compounds and one or more UN-B photoactive compounds.
- a sunscreen composition includes a photoactive compound selected from the group consisting of p-aminobenzoic acid and salts and derivatives thereof; anthranilate and derivatives thereof; dibenzoylmethane and derivatives thereof; salicylate and derivatives thereof; cinnamic acid and derivatives thereof; dihydroxycinnamic acid and derivatives thereof; camphor and salts and derivatives thereof; trihydroxycinnamic acid and derivatives thereof; dibenzalacetone naphtholsulfonate and salts and derivatives thereof; benzalacetophenone naphtholsulfonate and salts and derivatives thereof; dihydroxy-naphthoic acid and salts thereof; o-hydroxydiphenyldisulfonate and salts and derivatives thereof; p-hydroxydiphenyldisulf
- a preferred combination of photoactive compounds in a sunscreen composition includes a UN-A and a UN-B photoactive compound.
- 2-ethylhexyl-p- methoxycinnamate is included in a mixture with a dibenzoylmethane derivative, the dibenzoylmethane derivative becomes particularly unstable. Without intending to be limited to any particular mechanism, it is believed that the cinnamate ester reacts with an excited- state dibenzoylmethane derivative in a bimolecular pathway that renders both the dibenzoylmethane derivative and the cinnamate ester incapable of absorbing UN radiation.
- a sunscreen composition includes the photoactive compound 2-ethylhexyl-j-»-methoxycinnamate, a dibenzoylmethane derivative, and a combination of (a) and (b) in weight ratios previously defined.
- a methoxy-substituted benzophenone derivative to a sunscreen composition including a dibenzoylmethane derivative and a diester or polyester of naphthalene dicarboxylic acid results in an increase in the stability of the dibenzoylmethane derivative present in the composition.
- a methoxy- substituted benzophenone derivative has dual purposes in the sunscreen composition, both to act as a photoactive compound, and to increase the photostability (lower the rate constant of photodecay) of one or more photoactive compounds present in the sunscreen composition.
- a methoxy- substituted benzophenone derivative quenches (accepts) the singlet excited state of the diester or polyester of naphthalene dicarboxylic acid, and thereby prevents the excited diester or polyester from reaching the triplet excited state.
- a sunscreen composition disclosed herein includes a methoxy-substituted benzophenone derivative such as benzophenone-3.
- the methoxy-substituted benzophenone derivative preferably is present in a sunscreen composition in an amount of 0.5% or less by weight of the total weight of the composition.
- One embodiment of a sunscreen composition disclosed herein includes a mixture of a dibenzoylmethane derivative, and a weight ratio of (a)/(b) of at least 0.95, preferably at least about 1.0, wherein (a) is an ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate compound, and (b) is a diester or polyester of naphthalene dicarboxylic acid selected from the group consisting of formula (I), formula (II), and combinations thereof: 1
- R and R are the same or different and selected from the group consisting of C ⁇ -C 22 alkyl groups, diols having the structure HO — R — OH, and polyglycols having the structure HO — R 4 — ( — O — R 3 — ) n — OH; wherein each R 3 and R 4 is the same or different and selected from the group consisting of C ⁇ -C 6 straight or branched chain alkyl groups; and wherein m and n are each in a range of 1 to 100 and p is in a range of 0 to 100.
- ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate compound any ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate compound may be used in this embodiment, preferably, the ⁇ - cyano- ⁇ , ⁇ -diphenylacrylate compound is 2-ethylhexyl-2-cyano-3,3-diphenylacrylate (also known as octocrylene).
- a composition of this embodiment includes a diester of formula (II) wherein R and R are 2- ethylhexane and p is 0.
- the compositions disclosed herein include a diester or polyester of naphthalene dicarboxylic acid in a range of about 0.1% to about 15% by weight of the total weight of the composition.
- the stability of photoactive compounds present in a sunscreen composition can be increased by controlling the polarity of the oil phase of the composition.
- a sunscreen composition includes an oil phase comprising a dibenzoylmethane derivative, (a) an -cyano- ⁇ , ⁇ - diphenylacrylate compound, (b) a diester or polyester of naphthalene dicarboxylic acid, in a weight ratio of (a)/(b) of at least 0.95, preferably at least about 1.0, and a solvent system, wherein the solvent system includes an effective amount of a polar solvent, or a blend solvents with a high polarity, to increase the photostability of the dibenzoylmethane derivative or other photoactive compounds present in the sunscreen composition.
- Suitable polar solvents for use in a sunscreen composition are disclosed in commonly assigned U.S. Patent Application Serial Nos. 10/097,131 and 10/092,132, the disclosures of which are hereby incorporated herein by reference.
- a composition of this embodiment preferably has a dielectric constant of at least 7, preferably at least about 8.
- sunscreen compositions disclosed herein includes a mixture of a dibenzoylmethane derivative, (a) an ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate compound, (b) a diester or polyester of naphthalene dicarboxylic acid, in a weight ratio of (a)/(b) of at least 0.95, preferably at least about 1.0, and (c) benzophenone-3 in an amount of about 0.1 to 10% by weight, preferably less than about 0.5 % by weight.
- the ⁇ -cyano- ⁇ , ⁇ - diphenylacrylate compound may be used according to this embodiment, preferably, the ⁇ - cyano- ⁇ , ⁇ -diphenylacrylate compound is 2-ethylhexyl-2-cyano-3,3-diphenylacrylate (also known as octocrylene).
- Another embodiment of a sunscreen composition disclosed herein includes a mixture of a dibenzoylmethane derivative, (a) an -cyano- ⁇ , ⁇ -diphenylacrylate compound, and (b) a diester or polyester of naphthalene dicarboxylic acid, in a weight ratio of (a)/(b) of at least 0.95, preferably at least about 1.0, wherein said sunscreen composition has a dielectric constant of at least about 8.
- Octisalate (USP, RTD*HALL STAR) 5.00 Homosalate (NeoHeliopan HMS, Symrise) 7.50 Avobenzone (Parsol 1789, Roche) 3.00 Octocrylene (NeoHeliopan 303, Symrise) 2.50 Diethylhexyl 2,6-naphthalate (Symrise) 2.50 Dimethyl capramide (Spectrasolv DMDA, RTD*HALLSTAR 1.00 Diethylhexyl malate (Spectrasolv 16, RTD*HALLSTAR) 2.01 Benzophenone-3 (NeoHeliopan BB, Symrise) 0.49 B.
- DMDA Diethylhexyl malate
- Benzophenone-3 (NeoHeliopan BB, Symrise) 0.49 B.
- Polyglyceryl-3 distearate (Cremorphor GS-32, BASF) 3.00 Sorbitan isosterate (Crill 6, Croda) 4.00 Stearic acid (V-1655, RTD*HALLSTAR) 3.05 PVP/Eicosene copolymer (Ganex V-220, ISP) 2.00 Dimethicone (100 cSt) (Mirasil DM100, RTD*HALLSTAR) 0.40 Silica 01972, Degussa) 0.25 Deionized water Water Q.S. Disodium EDTA Disodium EDTA 0.05 Carbomer (Carbopol Ultrez 10, B.F. Goodrich) 0.05 D.
- Methylpropanediol (MPDiol, Lyondell) 2.00 Glycerin Glycerin 3.00 Phenoxyethanol()methyl- (CoSept PEP, RTD*HALLSTAR) 0.60 paraben()ethylparaben()propyl- paraben()butylparaben Triethanolamine (TEA) Triethanolamine 1.74
- Oil Phase Blend "A” liquid additives. Heat to 80°C, stirring to dissolve Oxybenzone, Avobenzone. Add “B” additives with stirring until clear and homogeneous. NOTE: Addition of Dimethicone will turn oil phase turbid. Add silica and stir to wet and disperse thoroughly.
- Water Phase Dissolve EDTA salt in water. Sprinkle carbomer on water and allow to wet completely. With stirring, heat to 75°C. Preblend preservative, Methylpropanediol, Glycerin, and TEA, and add to water.
- Stearyl alcohol (Alfol 18, Sasol) 1.00 Polyglyceryl-3 methyl glucose (TegoCare 450, Goldschmidt) 3.00 distearate Steareth-21 (Brij 721, Uniqema) 0.31 Steareth-2 (Brij 721, Uniqema) 0.19 C30-38 Olefin/Isopropyl (Performa V 1608, New Phase) 2.00 maleate/MA copolymer
- Oil Phase In secondary vessel, blend "A” liquid additives. Heat to 80°C, stirring to dissolve Oxybenzone, Avobenzone. Increase heat to 90°C. Add “B” additives with stirring until clear and homogeneous.
- UV rays The damaging effects of UV rays on the skin have become widely recognized by consumers, and there have been reports in the media warning of increases in the level of UV rays due to environmental pollution. This has resulted in the appearance of many "Cosmetics with UV Protection" on the market. These products protect the skin by reducing or blocking the effects of UV rays.
- Cosmetics with UV Protection can be roughly divided into two groups.
- One is “Suntan Cosmetics” which are used for the purpose of obtaining a beautifully suntanned complexion while limiting the affects of UV rays on the skin to a minimum, the other is “Sunscreen Cosmetic” which are used for the purpose of preventing Sunburn and Suntan.
- UV rays that reach the surface of the earth can be divided into the A region of UV light (UVA: 320-400 nm) and the B region of UV light (UVB: 280-320 nm), and these two types of UN rays have different effects on the skin.
- UVB causes erythema of the skin several hours after exposure, and several days after exposure to UVB may lead to increased pigmentation, dryness and scale.
- UVA causes darkening of the skin immediately after exposure (immediate pigment darkening) and in the event of exposure to large amounts of UVA, this darkening appears to be transformed to delayed pigment darkening.
- UVA increases sensitivity of the skin to UVB.
- UV rays contribute to skin cancer and to aging of the skin typified by blotches and 'wrinkles.
- the relative contributions of UVB and UVA to these various reactions are not known, but the effects of the deep penetration of UVA rays cannot be ignored.
- UV Protection in product claims is not always adequate, so there is a need to clarify whether a product protects against UVA or UVB, and to what extent it protects against each.
- SPF is an index of the protection against sunburn provided by cosmetics with UV protection.
- the 5FF value is determined in accordance with the Japan Cosmetic Industry Association SPF Measurement Standards (Effective from January 1992) in Japan, in accordance 'with COLIPA regulations (October 1994) in Europe, and in accordance with FDA regulations (Tentative Final Monograph, May 1993) in the US. Because these methods are quite similar, their SIT values are roughly comparable even though a uniform method is not employed worldwide. Throughout the world the SOF value acts as an index that consumers use in product selection.
- the standard is intended to provide uniform measurement method of WA (Protection Factor of WA) values and labeling method for the grade of UVA protection on stmscreen and suntan cosmetics enable consumers to select products which meet consumers desired UV light protection efficacy.
- WA Treatment Factor of WA
- the standard consist of "I. Measurement Method of UVA Protection efficacy,” listing itemized measurement conditions and “U. Annotation” providing practical points catty out tests using this method.
- Subjects must be asked of their physical conditions and must be excluded if they have photodermatitis or take medicine (such as anti-inflammative agent, anti-hypertensive agent etc.) relating to skin's photosensitivity.
- medicine such as anti-inflammative agent, anti-hypertensive agent etc.
- the skin types are classified based on the typical skin reactions to 30 to 45 minutes sun bathing after a winter season of no sun exposure.
- Test site is the back, and the skin must have almost uniform color without pigmentation, nevus and so
- the standard sample shall be prepared according to the formula described below. Measurement of the standard sample shall be performed concurrently with the measurement of the test sample.
- Formula and Preparation method of the Standard sample a cream containing 5% 4-tert-Butyl-4"- methoxydibenzoylmethane and 3% 2-Ethylhexyl p-methoxycinnamate).
- the amount of the samples to be applied shall be 2 mg/cm2 or 2 ul/cm2 each.
- the area (for applying samples) shall be at least 20 cm2.
- Radiation exposure shall begin at lest 15 minutes after the samples are applied.
- An artificial light shall be used as a source of light, which must satisfy following conditions...
- UV light emission is UVA range shall have a continuous spectrum similar to sun light. Moreover, the ratio of UVA I (340-400 nm) and UVA II (320-340 nm) shall be close to that of sunlight (UVA II/UVA-8-20%).
- UV ray shorter than 320 nm shall be excluded through the use of an appropriate fitter. Monitoring and maintenance shall be performed to insure That the above conditions are always maintained.
- a single radiation field shall be at least 0.5 cm 2 .
- the radiation fields of the untreated area shall be equivalent to the radiation field of the treated area.
- a UV dose progresses geometrically and the increment shall be 25% maximum.
- the MPPD is defined as the minimum dose of UV rays that produces slight darkening over essentially the whole radiation field within 2 to 4 hours after exposure. Determination of MPPD shall be conducted in a room with sufficient lighting at a fixed time within 2 to 4 hours after the end of exposure. At least two trained evaluators are desired to read MPPD).
- PFA value shall be obtained from the following equation by using MPPDs at sites untreated and treated by a test sample.
- PFA value MPPD in protected skin/MPPD in unprotected skin
- PFA value of a test sample is defined as the arithmetic mean of each subject's PFA values obtained from the above equation.
- the figures to the right of the decimal point shall be discarded from the PFA value of the sample that has been calculated according to the above method to make it an integer. Then, when the value is not less than 2, it shall be classified according to the following PA (Protection grade of UVA), and this classification shall be expressed on the label. PA shall be placed together with the SPF value.
- PA Protection grade of UVA
- the subjects shall be selected from applicants who understand the objective of the test by interview questions in the "Questionnaire for subject Selection".
- drugs that contribute to photosensitivity include the following: Hypotensive agents, psychotropic agents, tranquilizers, antihistamines, oral hypoglycemic agents, and tetracycline antibiotics,
- test subjects Because it is necessary for the test subjects to evaluate their own skin types and agree to being a test subject, the minimum age for test subjects was set at 10 and above. It is also recommended that subjects not be older than 60 years old.
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04812586A EP1720512B1 (en) | 2004-02-24 | 2004-12-01 | PHOTOSTABILIZATION OF A SUNSCREEN COMPOSITION WITH A COMBINATION OF AN ALPHA-CYANO-ß,ß-DIPHENYLACRYLATE COMPOUND AND A DIALKYL NAPHTHANATE |
DE602004025290T DE602004025290D1 (en) | 2004-02-24 | 2004-12-01 | LIGHT-TABILIZATION OF A SUN PROTECTION COMPOSITION COMPRISING AN ALPHA-CYANO-β, β-DIPHENYL ACRYLATE COMPOUND AND DIALKYL NAPHTHANATE COMBINATION |
NZ551813A NZ551813A (en) | 2004-02-24 | 2004-12-01 | Photostabilization of a sunscreen composition with a combination of an alpha-cyano-beta,beta-diphenylacrylate compound and a dialkyl naphthanate |
AT04812586T ATE455532T1 (en) | 2004-02-24 | 2004-12-01 | LIGHT STABILIZATION OF A SUN PROTECTION COMPOSITION WITH A COMBINATION OF AN ALPHA-CYANO-ß,ß-DIPHENYL ACRYLATE COMPOUND AND A DIALKYL NAPHTHANATE |
AU2004316397A AU2004316397B9 (en) | 2004-02-24 | 2004-12-01 | Photostabilization of a sunscreen composition with a combination of an alpha-cyano-beta,beta-diphenylacrylate compound and a dialkyl naphthanate |
CA2569324A CA2569324C (en) | 2004-02-24 | 2004-12-01 | Photostabilization of a sunscreen composition with a combination of an .alpha.-cyano-.beta.,.beta.-diphenylacrylate compound and a dialkyl naphthalate |
JP2007500751A JP5060942B2 (en) | 2004-02-24 | 2004-12-01 | Photostabilization of sunscreen compositions combining α-cyano-β, β-diphenylacrylate compounds and dialkyl naphthanates |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US10/785,271 US6899866B2 (en) | 2002-09-06 | 2004-02-24 | Photostabilization of a sunscreen composition with a combination of an α-cyano-β, β-diphenylacrylate compound and a dialkyl naphithalate |
US10/785,271 | 2004-02-24 |
Publications (1)
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WO2005082325A1 true WO2005082325A1 (en) | 2005-09-09 |
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US (1) | US6899866B2 (en) |
EP (1) | EP1720512B1 (en) |
JP (1) | JP5060942B2 (en) |
AT (1) | ATE455532T1 (en) |
AU (1) | AU2004316397B9 (en) |
CA (1) | CA2569324C (en) |
DE (1) | DE602004025290D1 (en) |
ES (1) | ES2336117T3 (en) |
NZ (1) | NZ551813A (en) |
WO (1) | WO2005082325A1 (en) |
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- 2004-12-01 CA CA2569324A patent/CA2569324C/en not_active Expired - Fee Related
- 2004-12-01 WO PCT/US2004/040103 patent/WO2005082325A1/en active Application Filing
- 2004-12-01 ES ES04812586T patent/ES2336117T3/en active Active
- 2004-12-01 DE DE602004025290T patent/DE602004025290D1/en active Active
- 2004-12-01 EP EP04812586A patent/EP1720512B1/en not_active Not-in-force
- 2004-12-01 NZ NZ551813A patent/NZ551813A/en not_active IP Right Cessation
- 2004-12-01 AU AU2004316397A patent/AU2004316397B9/en not_active Ceased
- 2004-12-01 JP JP2007500751A patent/JP5060942B2/en not_active Expired - Fee Related
- 2004-12-01 AT AT04812586T patent/ATE455532T1/en not_active IP Right Cessation
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Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2010050465A1 (en) * | 2008-10-31 | 2010-05-06 | 株式会社 資生堂 | O/w emulsion composition |
WO2010050464A1 (en) * | 2008-10-31 | 2010-05-06 | 株式会社 資生堂 | O/w emulsion composition |
JP2010132648A (en) * | 2008-10-31 | 2010-06-17 | Shiseido Co Ltd | O/w emulsion composition |
JP2010132647A (en) * | 2008-10-31 | 2010-06-17 | Shiseido Co Ltd | O/w emulsion composition |
JP4612103B2 (en) * | 2008-10-31 | 2011-01-12 | 株式会社資生堂 | O / W emulsion composition |
JP4612102B2 (en) * | 2008-10-31 | 2011-01-12 | 株式会社資生堂 | O / W emulsion composition |
US8425884B2 (en) | 2008-10-31 | 2013-04-23 | Shiseido Company, Ltd. | O/W emulsified composition |
CN102202637B (en) * | 2008-10-31 | 2013-05-22 | 株式会社资生堂 | O/w emulsion composition |
US8691191B2 (en) | 2008-10-31 | 2014-04-08 | Shiseido Company, Ltd. | O/W emulsified composition |
US9724544B2 (en) | 2009-01-05 | 2017-08-08 | Ernest T. Armstrong | Vitamin D promoting sunscreen |
WO2011141110A2 (en) | 2010-05-12 | 2011-11-17 | Merck Patent Gmbh | Photo-stabilizing agents |
Also Published As
Publication number | Publication date |
---|---|
CA2569324C (en) | 2011-07-19 |
US6899866B2 (en) | 2005-05-31 |
US20040166072A1 (en) | 2004-08-26 |
JP2007523212A (en) | 2007-08-16 |
AU2004316397B9 (en) | 2009-06-04 |
AU2004316397A1 (en) | 2005-09-09 |
ES2336117T3 (en) | 2010-04-08 |
NZ551813A (en) | 2009-11-27 |
ATE455532T1 (en) | 2010-02-15 |
DE602004025290D1 (en) | 2010-03-11 |
CA2569324A1 (en) | 2005-09-09 |
EP1720512A1 (en) | 2006-11-15 |
JP5060942B2 (en) | 2012-10-31 |
AU2004316397B2 (en) | 2008-10-09 |
EP1720512B1 (en) | 2010-01-20 |
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