Patent Application
20080247975
Topically applicable, water-resistant cosmetic or dermatological compositions well suited for the UV-photoprotection of human skin and/or hair comprising an effective UV-photoprotecting amount of: (a) at least one UV screening agent; and, (b) at least one select copolymer; and, optionally, (c) other cosmetically acceptable ingredients.
Sunscreen compositions are applied to the skin to protect the skin from the sun's ultraviolet rays that can lead to erythema, a reddening of the skin also known as sunburn. Sunlight or ultraviolet radiation in the UV-B range has a wavelength of 290 nm to 320 nm and is known to be the primary cause of sunburn. Ultraviolet rays at a wavelength of 320 nm to 400 nm, known as UV-A radiation, produces tanning of the skin. However, in the process of doing so, the UV-A rays can damage or harm the skin.
Besides the immediate malady of sunburn, excessive sunlight exposure can lead to skin disorders. For instance, prolonged and constant exposure to the sun may lead to actinic keratoses and carcinomas. Another long-term effect is premature aging of the skin. This condition is characterized by skin that is wrinkled, cracked and has lost its elasticity.
As stated above, sunscreens are typically formulated with the goal of inhibiting skin damage from the sun's rays. The sunscreen composition filters or blocks the harmful UV-A and UV-B rays that can damage and harm the skin. It is believed that sunscreen agents accomplish this by absorbing the UV-A and/or UV-B rays.
Typically, the above-described UV-B filters are combined with the above-described UV-A filters in a solution with other lipophilic or oily ingredients and solvents to form an oil phase. The solvents are used to dissolve the sunscreen actives into the oil phase. Typically, but not necessarily, the oil phase is dispersed with the help of emulsifiers and stabilizers into an aqueous solution composed primarily of water, to make an emulsion, which becomes the final sunscreen composition.
A wide variety of cosmetic compositions intended for the photoprotection (UV-A and/or UV-B) of the skin are also known to this art.
U.S. Pat. No. 5,204,090 discloses waterproof sunscreens comprising a water insoluble film forming polymer, which is incorporated herein by reference.
U.S. Pat. No. 5,653,965 discloses film forming polymers for a sunscreen spray, which is incorporated herein by reference.
U.S. Pat. No. 5,487,886 discloses acrylic polymers for sunscreen formulations, which is incorporated herein by reference.
U.S. Pat. No. 5,145,669 discloses water proof sunscreens containing crosslinked copolymer of maleic anhydride, which is incorporated herein by reference.
U.S. Pat. No. 4,663,157 discloses a copolymer of ethylene and acrylic acid for use in sunscreen compositions, which is incorporated herein by reference.
US 2006/0008427 discloses a photo-protective composition that contains a synergistic combination of a least one sunscreen agent and at least one caroteniod, which is incorporated herein by reference.
U.S. Pat. No. 7,108,860 discloses a cosmetic composition that contains at least two rheology modifying agents, which is incorporated herein by reference.
U.S. Pat. No. 7,014,842 discloses a sunscreen composition comprising one or more photoactive compounds and one or more optimization agents, which is incorporated herein by reference.
U.S. Pat. No. 6,409,998 discloses a UV-photoprotecting emulsion comprising micronized insoluble screening agents and associative polymers, which is incorporated herein by reference.
US 2004/0126339 discloses a sunscreen composition that includes a mixture of a skin bonding polymer and at least one sunscreen active ingredient, which is incorporated herein by reference.
U.S. Pat. No. 6,312,672 discloses waterproof sunscreen compositions which include polymers of isoprene, butadiene, and/or styrene, which is incorporated herein by reference.
US 2004/0091434 discloses a topically applicable photostable sunscreen composition containing at least one dibenzoylmethane UV-sunscreen and an effective amount of at least one amphiphilic block copolymer, which is incorporated herein by reference.
US 2003/0021847 discloses a composition for retaining active ingredients in personal care compositions based on one or more polymers having a network structure in an oil phase, which is incorporated herein by reference.
US 2002/0076390 discloses a composition for nails, skin and hair in the form of an aqueous emulsion or dispersion, which is incorporated herein by reference.
U.S. Pat. No. 5,688,858 discloses a polymer suitable as a dispersant, which is incorporated herein by reference.
US 2006/0104923 discloses a sunscreen composition containing fluorinated alkyl ethers, which is incorporated herein by reference.
These anti-sun or sunscreen compositions are quite often provided in the form of an emulsion, of the oil-in-water (O/W) type (namely, a cosmetically and/or dermatologically acceptable carrier comprising an aqueous dispersing continuous phase and a fatty dispersed discontinuous phase) or of the water-in-oil (W/O) type (dispersed aqueous phase in a continuous fatty phase), which contains, at various concentrations, one or more lipophilic conventional organic UV-screening agents and/or inorganic nanopigments of metal oxides, which are suited for selectively absorbing the harmful UV radiation, these screening agents (and the quantities thereof) being selected according to the desired sun protection factor (the sun protection factor (SPF) being mathematically expressed by the ratio of the irradiation time required to attain the erythematogenic threshold with the UV-screening agent to the time required to attain the erythematogenic threshold in the absence of UV-screening agent). In such emulsions, the hydrophilic screening agents are present in the aqueous phase and the lipophilic screening agents are present in the fatty phase.
The oil-in-water emulsions are, in general, more accepted by the consumer than the water-in-oil emulsions because, in particular, of their pleasant feel (similar to water) and their presentation in the form of a non-oily cream or milk; however, they also more readily lose their UV protection efficacy as soon as they come into contact with water. Indeed, the hydrophilic screening agents tend to disappear in water, upon washing in the sea or in a swimming pool, under the shower or when engaged in water sports; thus, anti-sun or sunscreen compositions containing same, whether alone or combined with lipophilic screening agents, no longer provide the desired initial protection as soon as the substrate (skin or hair) to which they have been applied is contacted with water.
Anti-sun (sunscreen) compositions exhibiting improved resistance to water have been formulated as water-in-oil emulsions. Indeed, a hydrophilic screening agent is more stable to water in a water-in-oil emulsion than in an oil-in-water emulsion. However, as indicated above, such compositions are not yet completely satisfactory since they promote, after application, a fat-like impression which is particularly unpleasant for the user.
Thus, serious need continues to exist for anti-sun or sunscreen compositions which impart to the skin and/or the hair effective solar protection which is stable over time and resistant to water (stability to water) and the cosmetic performance of which presents features that would be comparable to those obtained with conventional oil/water emulsions.
It is now surprisingly and unexpectedly determined that specific sunscreen compositions containing at least one UV-screening agent and at least one select copolymer not only provide anti-sun compositions whose cosmetic performance features are comparable to those generally associated with a conventional sunscreen composition formulated as an oil/water emulsion, but also exhibit good stability as well as enhanced stability to water.
Therefore, a first aspect of the present invention is directed to a sunscreen composition comprising at least one sunscreen agent, at least one select copolymer of formula (I), and other cosmetically acceptable ingredients.
A second aspect of the present invention is directed to a method of preparing a sunscreen composition comprising mixing together at least one sunscreen agent, at least one select copolymer of formula (I) and, optionally, other cosmetically acceptable ingredients.
A third aspect of the present invention is directed to a method of increasing the sun protection factor of a sunscreen composition wherein said method comprises incorporating into said compositions an effective amount of at least one select copolymer according to formula (I).
A fourth aspect of the present invention is directed to a method of improved UV protection of mammalian hair and/or skin from the damaging effects of UV radiation wherein said method comprises applying to said skin and/or said hair an effective amount of a sunscreen composition comprising at least one sunscreen agent, at least one select copolymer of formula (I), and, optionally, other cosmetically acceptable ingredients.
A fifth aspect of the present invention is directed to a cosmetic or dermatological composition comprising a select copolymer of formula (I) and other cosmetically acceptable ingredients.
The present invention provides a sunscreen composition comprising:
(a) at least one UV screening agent;
(b) at least one select copolymer comprising
wherein
x and z represent the percentage by weight that each repeating unit or derived monomer is contained within the copolymer;
x and z refer to repeating units;
x and z add up to total 100 weight percent relative to the total weight of the copolymer;
z is from about 0.001% to about 99.999% by weight of the copolymer;
x is from about 0.001% to about 99.999% by weight of the copolymer;
A is a polymer;
G is covalently bonded to the polymer A through an oxygen linking group;
O is an oxygen atom;
wherein
G1, G2, G3, G4 are independently C1-C6alkyl or G1 and G2 or G3 and G4, or G1 and G2 and G3 and G4 together form a C5-C12cycloalkyl group;
G5, G6 independently are H, C1-C18alkyl, phenyl, naphthyl or a group COOC1-C18alkyl;
*denotes a valence and **denotes point of attachment to said polymer A;
wherein R201, R202, R203 and R204 independently of each other are C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl which are substituted by OH, halogen or a group —O—C(O)—R205, C2-C18alkyl which is interrupted by at least one O atom and/or NR205 group, C3-C12cycloalkyl or C6-C10aryl or R20, and R202 and/or R203 and R204 together with the linking carbon atom form a C3-C12cycloalkyl radical;
R205, R206 and R207 independently are hydrogen, C1-C18alkyl or C6-C10aryl;
R208 is hydrogen, OH, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl which are substituted by one or more OH, halogen or a group —O—C(O)—R205, C2-C18alkyl which is interrupted by at least one O atom and/or NR205 group, C3-C12cycloalkyl or C6-C10aryl, C7-C9phenylalkyl, C5-C10heteroaryl, —C(O)—C1-C18alkyl, —O—C1-C18alkyl or —COOC1-C18alkyl;
R209, R210, R211 and R212 are independently hydrogen, phenyl or C1-C18alkyl; or
G11, G12, G13 and G14 are independently C1-C4alkyl or G11 and G12 together and G13 and G14 together, or G11 and G12 together or G13 and G14 together are pentamethylene;
G15 and G16 are each independently of the other hydrogen or C1-C4alkyl;
X is as defined above;
k is 1, 2, 3, or 4
Y is O or NR302 or when k is 1 and R301 represents alkyl or aryl Y is additionally a direct bond;
R302 is H, C1-C18alkyl or phenyl;
if k is 1
R301 is H, straight or branched C1-C18alkyl, C3-C18alkenyl or C3-C18alkinyl, which may be unsubstituted or substituted, by one or more OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl;
C5-C12cycloalkyl or C5-C12cycloalkenyl;
phenyl, C7-C9phenylalkyl or naphthyl which may be unsubstituted or substituted by one or more C1-C8alkyl, halogen, OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl;
—C(O)—C1-C36alkyl, or an acyl moiety of a □,□-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms;
—SO3−Q+, —PO(O−Q+)2, —P(O)(OC1-C8alkyl2)2, —P(O)(OH2)2, —SO2—OH, —SO2—C1-C8alkyl, —CO—NH—C1-C8alkyl, —CONH2, COO—C1-C8alkyl2, COOH or Si(Me)3, wherein Q+ is H+, ammonium or an alkali metal cation;
if k is 2
R301 is C1-C18alkylene, C3-C18alkenylene or C3-C18alkinylene, which may be unsubstituted or substituted, by one or more OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl; or xylylene; or
R301 is a bisacyl radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms;
if k is 3,
R301 is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid; and
if k is 4, R301 is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid;
and, optionally
(c) other cosmetically acceptable ingredients.
According to the instant invention, the instant copolymers of formula (I) have a structure that is selected from the group consisting of copolymer, terpolymer, block, star, random, linear, branched, crosslinked and not crosslinked.
According to the instant invention, the group “—O-G” can be reacted into the polymer “A” during synthesis of polymer A or the group “—O-G” can be reacted or grafted onto polymer “A” during processing; for example, during coextrusion.
The above compounds and their preparation are described in GB2335190, GB 2342649 and GB2361235.
The 4 imino compounds of formula III can be prepared for example according to E. G. Rozantsev, A. V. Chudinov, V. D. Sholle.:Izv. Akad. Nauk. SSSR, Ser. Khim. (9), 2114 (1980), starting from the corresponding 4-oxonitroxide in a condensation reaction with hydroxylamine and subsequent reaction of the OH group. The compounds are described WO 02/100831.
Another embodiment of the instant invention is for formula (I) G is
wherein
G1, G2, G3, G4 are independently C1-C1alkyl or G1 and G2 or G3 and G4, or G1 and G2 and
G3 and G4 together form a C5-C10cycloalkyl group;
G5, G6 independently are H, C1-C18alkyl, phenyl, or a group COOC1-C18alkyl;
*denotes a valence and **denotes point of attachment to said polymer A;
wherein R201, R202, R203 and R204 independently of each other are C1-C6alkyl, C3-C18alkenyl; C1-C18alkyl, or C3-C18alkenyl, which are substituted by OH, halogen or a group —O—C(O)—R205, C2-C18alkyl which is interrupted by at least one O atom and/or NR205 group, C3-C12cycloalkyl or C6-C10aryl;
R205, R206 and R207 independently are hydrogen, C1-C18alkyl or C6-C10aryl;
R208 is hydrogen, OH, C1-C18alkyl; C1-C18alkyl which are substituted by one or more OH, halogen or a group —O—C(O)—R205, C2-C18alkyl which is interrupted by at least one O atom and/or NR205 group, C3-C12cycloalkyl or C6-C10aryl, C7-C9phenylalkyl, C5-C10heteroaryl, —C(O)—C1-C18alkyl, —O—C1-C18alkyl or —COOC1-C18alkyl;
R209, R210, R211 and R212 are independently hydrogen, phenyl or C1-C18alkyl; or
G11, G12, G13 and G14 are independently C1-C4alkyl or G11 and G12 together and G13 and G14 together, or G11 and G12 together or G13 and G14 together are pentamethylene;
G15 and G16 are each independently of the other hydrogen or C1-C4alkyl;
k is 1
Y is O or NR302 or Y is additionally a direct bond;
R302 is H, C1-C18alkyl or phenyl;
if k is 1
R301 is H, straight or branched C1-C18alkyl, C3-C18alkenyl or C3-C18alkinyl, which may be unsubstituted or substituted, by one or more OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl;
C5-C12cycloalkyl or C5-C12cycloalkenyl; C7-C9phenylalkyl which may be unsubstituted or substituted by one or more C1-C8alkyl, halogen, OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl; —C(O)—C1-C36alkyl;
—SO3−Q+, —PO(O−Q+)2, —P(O)(OC1-C8alkyl2)2, —P(O)(OH2)2, —SO2—OH, —SO2—C1-C8alkyl, —CO—NH—C1-C8alkyl, —CONH2, COO—C1-C8alkyl2, COOH or Si(Me)3, wherein Q+ is H+, ammonium or an alkali metal cation.
Another embodiment of the instant invention is for formula (I) G is
wherein
G1, G2, G3, G4 are independently C1-C1-alkyl or G1 and G2 or G3 and G4, or G1 and G2 and G3 and G4 together form a C5-C10cycloalkyl group;
G5, G6 independently are H, C1-C18alkyl, phenyl, or a group COOC1-C18alkyl;
*denotes a valence and **denotes point of attachment to said polymer A;
wherein R201, R202, R203 and R204 independently of each other are C1-C6alkyl, C3-C18alkenyl; C1-C18alkyl, or C3-C18alkenyl, which are substituted by OH, halogen or a group —O—C(O)—R205, C2-C18alkyl which is interrupted by at least one O atom and/or NR205 group, C3-C12cycloalkyl or C6-C10aryl;
R205, R206 and R207 independently are hydrogen, C1-C18alkyl or C6-C10aryl;
R208 is hydrogen, OH, C1-C18alkyl; C1-C18alkyl which are substituted by one or more OH, halogen or a group —O—C(O)—R205, C2-C18alkyl which is interrupted by at least one O atom and/or NR205 group, C3-C12cycloalkyl or C6-C10aryl, C7-C9-phenylalkyl, C5-C10heteroaryl, —C(O)—C1-C18alkyl, —O—C1-C18alkyl or —COOC1-C18alkyl;
R209, R210, R211 and R212 are independently hydrogen, phenyl or C1-C18alkyl.
The alkyl radicals in the various substituents may be linear or branched. Examples of alkyl containing 1 to 18 carbon atoms are methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.
Alkenyl with 3 to 18 carbon atoms is a linear or branched radical as for example propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. Preferred is alkenyl with 3 to 12, particularly preferred with 3 to 6 carbon atoms.
Alkynyl with 3 to 18 is a linear or branched radical as for example propinyl
2-butinyl, 3-butinyl, n-2-octinyl, or n-2-octadecinyl. Preferred is alkinyl with 3 to 12, particularly preferred with 3 to 6 carbon atoms.
Examples for hydroxy substituted alkyl are hydroxy propyl, hydroxy butyl or hydroxy hexyl.
Examples for halogen substituted alkyl are, for example, dichloropropyl, monobromobutyl or trichlorohexyl.
C2-C18alkyl interrupted by at least one O atom is for example —CH2—CH2—O—CH2—CH3, —CH2—CH2—O—CH3— or —CH2—CH2—O—CH2—CH2—CH2—O—CH2—CH3—. It is preferably derived from polyethlene glycol. A general description is —((CH2)a—O)b—H/CH3, wherein a is a number from 1 to 6 and b is a number from 2 to 10.
C2-C18alkyl interrupted by at least one NR205 group may be generally described as—((CH2)a—NR205)b—H/CH3, wherein a, b and R205 are as defined above.
C3-C12cycloalkyl is typically, cyclopropyl, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl or trimethylcyclohexyl.
C6-C10 aryl is for example phenyl or naphthyl, but also comprised are C1-C4alkyl substituted phenyl, C1-C4alkoxy substituted phenyl, hydroxy, halogen or nitro substituted phenyl. Examples for alkyl substituted phenyl are ethylbenzene, toluene, xylene and its isomers, mesitylene or isopropylbenzene. Halogen substituted phenyl is for example dichlorobenzene or bromotoluene.
Alkoxy substituents are typically methoxy, ethoxy, propoxy or butoxy and their corresponding isomers.
C7-C9-phenylalkyl is benzyl, phenylethyl or phenylpropyl.
C5-C10heteroaryl is for example pyrrol, pyrazol, imidazol, 2, 4, dimethylpyrrol, 1-methylpyrrol, thiophene, furane, furfural, indol, cumarone, oxazol, thiazol, isoxazol, isothiazol, triazol, pyridine, alpha-picoline, pyridazine, pyrazine or pyrimidine.
If R is a monovalent radical of a carboxylic acid, it is, for example, an acetyl, propionyl, butyryl, valeroyl, caproyl, stearoyl, lauroyl, acryloyl, methacryloyl, benzoyl, cinnamoyl or beta-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl radical.
C1-C18alkanoyl is for example, formyl, propionyl, butyryl, octanoyl, dodecanoyl but preferably acetyl and C3-C5alkenoyl is in particular acryloyl.
UV screening agents of component (a) useful in the present invention include organic sunscreens and/or inorganic sunscreens which are preferably active in the UV-A and/or UV-B regions (UV absorbers), and are soluble in water or in fats or insoluble in, e.g., cosmetic solvents commonly used. Typically, the compositions of the present invention contain combinations of one or more sunscreen agents. Additionally, the compositions of the present invention contain combinations of two or more sunscreen agents. The combination of sunscreen agents of component (a) can be, for example: two or more inorganic sunscreen agents; two or more organic soluble sunscreen agents; two or more organic micronized or micronizable sunscreen agents; and/or mixtures thereof.
Representative inorganic sunscreens of component (a) include pigments, or alternatively nanopigments (mean size of the primary particles: generally between 5 nm and 100 nm, preferably between 10 nm and 50 nm) formed from coated or uncoated metal oxides, such as, for example, titanium oxide (amorphous or crystalline in the rutile and/or anatase form), iron oxide, zinc oxide, zirconium oxide or cerium oxide nanopigments, which are all known in the art as UV sunscreens. Conventional coating agents are, furthermore, alumina and/or aluminium stearate. Such nanopigments formed from coated or uncoated metal oxides are disclosed in particular in EP 518 772 and EP 518 773.
The organic sunscreens of component (a) may be soluble (non-micronized) or insoluble (micronized or micronizable) in the sunscreen composition of the instant invention.
Suitable insoluble (micronized or micronizable) organic sunscreens or UV absorbers of component (a) may be, e.g. a triazine, a benzotriazole, a benzophenone, a vinyl group-containing amide, a cinnamic acid amide or a sulfonated benzimidazole UV absorber.
A preferred class of triazine compounds is that having the formula
or the corresponding alkali metal, ammonium, mono-, di- or tri-C1-C4alkylammonium, mono-, di- or tri-C2-C4alkanolammonium salts, or the C1-C3alkyl esters thereof or by a radical of formula
Preferred compounds of formula (1) are those, wherein
wherein, in formula (1f), at least one of the radicals R8, R9
and R10 are a radical of formula (1h);
Most preferred triazine derivatives are compounds of formula
Furthermore, triazine derivatives of formula
are preferred, wherein
Most preferred as component (a) are triazine derivatives of formula
Further preferred triazine derivatives according to component (a) correspond to formula
a radical of the formula
R23 is C1-C5alkyl;
T1 and T2, independently from each other, are hydrogen; or C1-C8alkyl;
m1, m2 and m3, independently of one another, are 1 to 4;
p1 is 0; or a number from 1 to 5;
A1 is a radical of the formula
Further preferred triazine derivatives according to component are compounds of formulae
the formula
in which
or the formula
Uppermost of interest are compounds of the formulae (5e) and (5f), in which
Very particularly preferred in this case are triazine compounds of the formula (5e)-(5h), in which R27 and R28 have the same meaning.
Furthermore, interesting triazines correspond to the formula
in which
Preferred compounds correspond to the formula
C18H37; or —O-2-ethylhexyl; —O—(CH2)3—N(C2H5)2;
Further preferred triazine derivatives according to component (a) are those compounds having one of the formulae
as well as 2,4,6-tris(diisobutyl-4′-aminobenzalmalonate)-s-triazine and 2,4-bis(diisobutyl-4-aminobenzalmalonate)-6-(4′-aminobenzylidenecamphor)-s-triazine.
Particularly preferred compounds of formula (1) are those having the formula:
In relation to the compounds of formula (28), when R37, R38 and R39 is an alkali metal it is preferably potassium or, especially sodium; when R37, R38 and R39 is a group N(R40)4 in which R30 has its previous significance, it is preferably a mono-, di- or tri-C1-C4alkylammonium salt, a mono-, di- or tri-C2-C4alkanolammonium salt or a C1-C3alkyl ester thereof; when R40 is a C1-C3alkyl group, it is preferably a C1-C2alkyl group, more preferably a methyl group; and when R30 is polyoxyethylene group, this preferably contains from 2-6 ethylene oxide units.
One preferred class of benzotriazole micronized organic UV absorbers is that having the formula
A further preferred class of benzotriazole micronized organic UV absorbers corresponds to the formula
A still further preferred class of benzotriazole micronized organic UV absorbers corresponds to the formula
A preferred class of vinyl group-containing amide micronized organic UV absorbers corresponds to the formula:
m is 0; or 1.
Preferred compounds of formula (32) are 4-methyl-3-penten-2-one, ethyl-3-methylamino-2-butenoate, 3-methylamino-1-phenyl-2-buten-1-one and 3-methylamino-1-phenyl-2-buten-1-one.
A preferred class of cinnamic acid amide micronized organic UV absorbers corresponds to the formula:
A preferred class of sulfonated benzimidazole micronized organic UV absorbers corresponds to the formula
Further preferred classes of micronized or micronizable UV absorbers used for the present invention are:
The micronized organic UV absorber, component (a), is preferably produced by the method described in GB-A-2303549, namely by a process which comprises grinding the corresponding organic UV absorber, in coarse particle form, in a grinding apparatus, in the presence of 1 to 50%, preferably 5 to 40% by weight, based on the micronized organic UV absorber, of an alkyl polyglucoside having the formula CnH2n+1(C6H10O5)xH, in which n is an integer ranging from 8 to 16 and x is the mean polymerization level of the glucoside moiety (C6H10O5) and ranges from 1.4 to 1.6, or an ester thereof.
Any known process suitable for the preparation of microparticles can be used for the preparation of the micronised UV absorbers, for example wet-milling, wet-kneading, spray-drying from a suitable solvent, by the expansion according to the RESS process (Rapid Expansion of Supercritical Solutions), by reprecipitation from suitable solvents, including supercritical fluids (GASR process=Gas Anti-Solvent Recrystallization/PCA process=Precipitation with Compressed Anti-solvents).
The micronized UV absorbers of component (a) so obtained usually have an average particle size from 0.02 to 2, preferably from 0.03 to 1.5, and more especially from 0.05 to 1.0 micrometer.
The micronizable UV absorbers according to component (a) can also be used as dry substrates in powder form.
The sunscreen composition according to the present invention may additionally contain one or more than one further non-micronized UV filter or UV absorbers as listed in Tables 1 and 2.
The non-micronized UV absorbers as described in Tables 1 and 2 below may be added to the sunscreen composition according to the present invention in amounts from 0.01 to 25% based on weight. One or more of these UV absorbers can be used, inter alia, to improve the solubility or to increase UV absorption of the instant sunscreen composition.
The UV screening agent of component (a) is present in the sunscreen composition in amounts from about 0.01 weight % to about 50 weight % based on the weight of the total composition. Additionally, the UV screening agent of component (a) is present in the sunscreen composition in amounts from about 0.1 weight % to about 30 weight % based on the weight of the total composition. Typically, UV screening agent of component (a) is present in the sunscreen composition in amounts from about 1 weight % to about 20 weight % based on the weight of the total composition. Typically, UV screening agent of component (a) is present in the sunscreen composition in amounts from about 1 weight % to about 5 weight % based on the weight of the total composition.
Typically, sunscreen formulations contain compositions of several UVA, UVB or broad-spectrum sunscreen actives: organic that are oil or water soluble, inorganic or organic particulates.
The term “effective amount” means for example the amount necessary to achieve the desired effect.
The select copolymers of component (b) formula (I) according to the instant invention maybe derived from at least two different monomers. Another aspect of the instant invention is the select copolymers of component (b) may be derived from at least three different monomers. Another aspect of the instant invention is the select copolymers of component (b) may be derived from at least four different monomers.
Additionally, the select copolymers of component (b) formula (I) according to the instant invention maybe derived from one monomer. For example, A is a homopolymer and the group “—O-G” is grafted or reacted onto A, thus producing the select copolymer of component b) formula (I).
The select copolymers of component (b) formula (I) can be used in conjunction with other polymers or copolymers in a sunscreen formulation or personal care composition; for example, the polymers listed in U.S. Pat. No. 6,409,998 and/or in US 2006/0104923.
The polymer A of formula (I) may be derived from monomers that are selected from the group consisting of anionic water soluble monomers, nonionic water soluble monomers, cationic water soluble monomers and water insoluble monomers.
For example, the anionic water-soluble monomers of polymer A of formula (I) may be chosen from monomers of carboxylic acids comprising ethylenic unsaturation, such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid and maleic acid, 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, vinylsulfonic acid and vinylphosphonic acid.
The nonionic water-soluble monomers of polymer A of formula (I) may, for example, be chosen from acrylamides, N—(C1-6 alkylated)acrylamides and N,N-di(C1-3 alkylated)acrylamides, polyethylene glycol acrylate, polyethylene glycol methacrylate, N-vinylacetamide, N-methyl-N-vinylacetamide, N-vinylformamide, N-methyl-N-vinylformamide, N-vinyllactams comprising at least one cyclic group chosen from cyclic groups comprising from 4 to 9 carbon atoms, vinyl alcohol (copolymerized in the form of vinyl acetate and then hydrolyzed), ethylene oxide, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
The cationic water-soluble monomers of polymer A of formula (I) may, for example, be chosen from dimethyldiallylammonium chloride, methylvinylimidazolium chloride, 2-vinylpyridine, 4-vinylpyridine, vinylimidazole, 2-methyl-N-vinylimidazole, vinylpyrrolidone, vinylcarbazole, 2-methyl-5-vinylpyridine, N—(C1-4 alkyl)-4-vinylpyridinium halides, such as N-methyl-4-vinylpyridinium iodide, vinylamine and monomers of the following formula: H2C═CR1—CO—X2 wherein: R1 is chosen from a hydrogen atom and a methyl group; X2 is chosen from linear and branched C1-6 hydrocarbonaceous groups carrying at least one entity chosen from primary, secondary and tertiary amine functional groups; quaternary nitrogen atoms; groups of formula NHR2; and groups of formula NR2R3, wherein R2 and R3, which may be identical or different, can each be chosen from linear and branched C1-6 hydrocarbonaceous groups carrying at least one entity chosen from primary, secondary and tertiary amine functional groups and quaternary nitrogen atoms.
The cationic water-soluble monomers of polymer A of formula (I) may, for example, be chosen from 1-(2-hydroxyethyl)-pyrrolidine, 2-(1-pyrrolidyl)-ethylamine, 2-(1-piperidyl)-ethylamine, 1-(2-hydroxyethyl)-piperidine, 1-(2-aminopropyl)-piperidine, N-(2-hydroxyethyl)-hexamethylenimine, 4-(2-hydroxyethyl)-morpholine, 2-(4-morpholinyl)-ethylamine, 4-(3-aminopropyl)-morpholine, 1-(2-hydroxyethyl)-piperazine, 1-(2-aminoethyl)-piperazine, 1-(2-hydroxyethyl)-2-alkylimidazoline, 1-(3-aminopropyl)-imidazole, (2-aminoethyl)-pyridine, (2-hydroxyethyl)-pyridine, (3-hydroxypropyl)-pyridine, (hydroxymethyl)-pyridine, N-methyl-2-hydroxy-methyl-piperidine, 1-(2-hydroxyethyl)-imidazole, 2-amino-6-methoxybenzothiazole, 4-aminomethyl-pyridine, 4-amino-2-methoxypyrimidine, 2-mercaptopyrimidine, 2-mercapto-benzimidazole, 3-amino-1,2,4-triazole, 2-isopropyl-imidazole, 2-ethyl-imidazole, 4-methyl-imidazole, 2-methyl-imidazole, 2-ethyl-4-methyl-imidazole, 2-phenyl-imidazole and 4-nitro-imidazole.
The water-insoluble monomers of polymer A of formula (I) may, for example, be chosen from vinylaromatic monomers, such as styrene and its alkylated derivatives, for example, 4-butylstyrene, .alpha.-methylstyrene and vinyltoluene; dienes, such as butadiene and 1,3-hexadiene; alkylated derivatives of dienes, such as isoprene and dimethylbutadiene; chloroprene; C1-10 alkyl, C6-10 aryl and C7-20 aralkyl acrylates; C1-10 alkyl, C6-10 aryl and C7-20 aralkyl methacrylates, for example, methyl, ethyl, n-butyl, 2-ethylhexyl, tert-butyl, isobornyl, phenyl and benzyl(meth)acrylates; vinyl acetate; vinyl ethers of formula CH2=CH—O—R and allyl ethers of formula CH2=CH—CH2—O—R wherein R is chosen from C1-6 alkyl groups; acrylonitrile; vinyl chloride; vinylidene chloride; caprolactone; ethylene, propylene, and fluorinated vinyl monomers; and vinyl monomers comprising at least one perfluorinated chain, such as fluoroalkyl acrylates and methacrylates and alkyl .alpha.-fluoroacrylates.
The water-insoluble monomers of polymer A of formula (I) are selected from the group consisting of styrene, methylacrylate, ethylacrylate, butylacrylate, isobutylacrylate, tert. butylacrylate, hydroxyethylacrylate, hydroxypropylacrylate, dimethylaminoethylacrylate, glycidylacrylates, methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, dimethylaminoethyl(meth)acrylate, glycidyl(meth)acrylates, acrylonitrile, acrylamide, methacrylamide, dimethylaminopropyl-methacrylamide, cyclohexyl methacrylate, isobornyl methacrylate, 2-ethyl hexyl acrylate, cetyl methacrylate, stearyl methacrylate, behenyl methacrylate, polypropylene glycol monomethacrylate, polyethylene glycol monomethacrylate and EO-PO-monomethacrylate.
The select copolymers of component b) formula (I) according to the instant invention maybe be crosslinked by multifunctional monomers. These multifunctional monomers are selected from the group consisting of divinyl benzene, trivinylbenzene, divinyltoluene, divinylpyridine, divinylnaphthalene divinylxylene, ethyleneglycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, diethyleneglycol divinyl ether, trivinylcyclohexane, allyl(meth)acrylate, diethyleneglycol di(meth)acrylate, propyleneglycol di(meth)acrylate, 2,2-dimethylpropane-1,3-di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylates, polyethylene glycol 200 di(meth)acrylate, polyethylene glycol 600 di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, poly(butanediol) di(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane triethoxy tri(meth)acrylate, glyceryl propoxy tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, divinyl silane, trivinyl silane, dimethyl divinyl silane, divinyl methyl silane, methyl trivinyl silane, diphenyl divinyl silane, divinyl phenyl silane, trivinyl phenyl silane, divinyl methyl phenyl silane, tetravinyl silane, dimethyl vinyl disiloxane, poly(methyl vinyl siloxane), poly(vinyl hydro siloxane), poly(phenyl vinyl siloxane), and mixtures thereof. The amount of crosslinking monomer(s) may be from about 0 weight percent to about 20 weight percent based on the total weight of the copolymer. The amount of crosslinking monomer(s) may be from about 0.01 weight percent to about 10 weight percent based on the total weight of the copolymer. The amount of crosslinking monomer(s) may be from about 0.01 weight percent to about 5 weight percent based on the total weight of the copolymer.
Another embodiment of the instant invention is a copolymer of formula (I) wherein z is from about 0.001% to about 80% by weight of the copolymer and x is from about 20% to about 99.999% by weight of the copolymer. Another embodiment of the instant invention is a copolymer of formula (I) wherein z is from about 0.001% to about 40% by weight of the copolymer and x is from about 60% to about 99.999% by weight of the copolymer. Another embodiment of the instant invention is a copolymer of formula (I) wherein z is from about 0.001% to about 20% by weight of the copolymer and x is from about 80% to about 99.999% by weight of the copolymer. Another embodiment of the instant invention is a copolymer of formula (I) wherein z is from about 0.001% to about 10% by weight of the copolymer and x is from about 90% to about 99.999% by weight of the copolymer. Another embodiment of the instant invention is a copolymer of formula (I) wherein z is from about 0.001% to about 5% by weight of the copolymer and x is from about 95% to about 99.999% by weight of the copolymer.
The weight-average molecular weight of the select copolymer of component (b) formula (I) exhibits a weight-average molecular weight of about 500 Daltons to about 1,000,000 Daltons. In another aspect of the instant invention, the weight-average molecular weight of the select copolymer of component (b) formula (I) exhibits a weight-average molecular weight of about 500 Daltons to about 500,000 Daltons. In yet another aspect of the instant invention, the weight-average molecular weight of the select copolymer of component (b) formula (I) exhibits a weight-average molecular weight of about 500 Daltons to about 100,000 Daltons. In still another aspect of the instant invention, the weight-average molecular weight of the select copolymer of component (b) formula (I) exhibits a weight-average molecular weight of about 1000 Daltons to about 75,000 Daltons.
The select copolymer of component (b) formula (I) is present in the sunscreen composition in amounts from about 0.01 weight % to about 50 weight % based on the weight of the total composition. In another aspect of the instant invention, the select copolymer of component (b) formula (I) is present in the sunscreen composition in amounts from about 0.1 weight % to about 25 weight % based on the weight of the total composition. In still another aspect of the instant invention, the select copolymer of component (b) formula (I) is present in the sunscreen composition in amounts from about 0.1 weight % to about 10 weight % based on the weight of the total composition.
Another embodiment of the instant invention are select copolymers of component (b) formula (I) that contain less than 250 ppm of residual monomers. Another embodiment of the instant invention are select copolymers of component (b) formula (I) that contain less than 200 ppm of residual monomers. Another embodiment of the instant invention are select copolymers of component (b) formula (I) that contain less than 100 ppm of residual monomers. Another embodiment of the instant invention are select copolymers of component (b) formula (I) that contain less than 50 ppm of residual monomers. Another embodiment of the instant invention are select copolymers of component (b) formula (I) that contain less than 5 ppm of residual monomers.
The select copolymers of the instant invention are water-dispersible and can be distributed throughout the aqueous phase or the oil phase of the instant compositions.
The select copolymers of component (b) can be prepared in the conventional manner, e.g., by mass or solution polymerization. The polymerization in a solvent is preferred in view of the controllability of the polymerization and the viscosity of the final product. Suitable solvents are DMSO, THF, DMF, ethyl, propyl, butyl, acetate, benzene, toluene, xylene, N-butanol, isobutanol, isopropanol, MEK, MIBK, acetone, etc.
The monomers are preferably polymerized using a radical reaction, by addition of peroxides, optionally in the presence of redox systems.
The polymerization time of the select copolymer of component (b) depends on the temperature and the desired final product properties but is preferably within the range of from 0.5 to 10 hours at temperatures ranging from about 50° C. to about 190° C. The polymerization can be carried out continuously, discontinuously or semicontinuously. If it is preferred to obtain a polymer chain having random distribution of monomers, all of the monomers together will be preferably added to the reaction mixture. This may be done in one portion or in the course of time.
On the basis of the reactivity of the monomers, which is known, a skilled artisan can control the polymerization so as to obtain the desired distribution.
The sunscreen compositions according to the invention may also contain agents for tanning and/or for artificial tanning of the skin (self-tanning agents), such as, for example, dihydroxyacetone (DHA).
The sunscreen compositions according to the invention may also contain agents for lightening or brightening of the skin, such as, for example, kojic acid, arbutin.
The compositions of the invention may further comprise, cosmetically acceptable ingredients and adjuvants selected, in particular, from among fatty substances, organic solvents, thickeners, demulcents, opacifiers, colorants, effect pigments, stabilizers, emollients, antifoaming agents, moisturizing agents, antioxidants, vitamins, peptides, amino acids, botanical extracts, particulates, perfumes, preservatives, polymers, fillers, sequestrants, propellants, alkalinizing or acidifying agents or any other ingredient customarily formulated into cosmetics, in particular for the production of anti-sun/sunscreen compositions.
The fatty substances may be an oil or a wax or mixtures thereof, and they also comprise fatty acids, fatty alcohols and esters of fatty acids. The oils may be selected from among animal, vegetable, mineral or synthetic oils and, in particular, from among liquid paraffin, paraffin oil, silicone oils, volatile or otherwise, isoparaffins, polyolefins, fluorinated or perfluorinated oils. Likewise, the waxes may be animal, fossil, vegetable, mineral or synthetic waxes which are also known per se.
Exemplary organic solvents include the lower alcohols and polyols.
Of course, one skilled in this art will take care to select this or these optional additional compounds and/or their quantities such that the advantageous properties, in particular the resistance to water, the stability, which are intrinsically associated with the sunscreen compositions in accordance with the invention are not, or not substantially, altered by the addition(s) envisaged.
The sunscreen compositions of the invention may be formulated according to techniques well known to this art, in particular those suited for the preparation of emulsions of the oil-in-water or water-in-oil type.
The subject sunscreen compositions may be provided, in particular, in the form of a simple or complex (O/W, W/O, O/W/O or WIO/W) emulsion such as a cream, a milk, a gel or a gel cream, of a powder, a lotion, an ointment, a solid stick and may optionally be packaged as an aerosol and provided in the form of a foam, mousse or spray.
When an emulsion is provided, the aqueous phase thereof may comprise a nonionic vesicular dispersion prepared according to known techniques (Bangham, Standish and Watkins, J. Mol. Biol., 13, 238 (1965), FR-2,315,991 and FR-2,416,008).
The sunscreen compositions according to the invention may be formulated for protecting the human epidermis or the hair against the damaging effects of ultraviolet radiation, as an anti-sun composition or as a makeup product.
When the sunscreen compositions according to the invention are formulated for protecting the human epidermis against UV rays, or as anti-sun/sunscreen compositions, same may be provided in the form of a suspension or a dispersion in solvents or fatty substances, in the form of a nonionic vesicular dispersion or, alternatively, in the form of an emulsion, preferably of the oil-in-water type, such as a cream or a milk, in the form of an ointment, a gel, a gel cream, a solid stick, a powder, a stick, an aerosol foam or a spray.
When the sunscreen compositions according to the invention are formulated for protecting the hair against UV rays, same may be provided in the form of a shampoo, a body wash, a lotion, a gel, an alcohol-based system, an emulsion, a nonionic vesicular dispersion and may constitute, for example, a rinse-off composition to be applied before or after shampooing, before or after dyeing or bleaching, before, during or after permanent-waving or hair straightening, a hair-styling or treatment lotion or gel, a lotion or gel for blow drying or hair setting, a composition for permanent waving or straightening, dyeing or bleaching the hair.
When the subject compositions are formulated as makeup products for the eyelashes, the eyebrows or the skin, such as a treatment cream for the epidermis, foundation, lipstick, eyeshadow, blusher, mascara or eyeliner, same may be provided in a solid or pasty, anhydrous or aqueous form, such as oil-in-water or water-in-oil emulsions, nonionic vesicular dispersions or alternatively suspensions.
For example, for the anti-sun formulations in accordance with the invention which have a carrier, vehicle or diluent of the oil-in-water emulsion type, the aqueous phase (comprising in particular the hydrophilic screening agents), generally constitutes from 50% to 95% by weight, preferably from 70% to 90% by weight, relative to the total weight of the formulation, the oily phase (comprising in particular the lipophilic screening agents), from 5% to 50% by weight, preferably from 10% to 30% by weight, relative to the total weight of the formulation, and the (co)emulsifier(s) from 0.5% to 20% by weight, preferably from 2% to 10% by weight, also relative to the total weight of the formulation.
As indicated above, the present invention thus features formulating the subject emulsions for the production of cosmetic compositions for protecting the skin and/or the hair against ultraviolet radiation, in particular solar radiation.
The sunscreen composition of the instant invention may further comprise a fragrance. The term “perfume” or “fragrance” as used herein refers to odoriferous materials which are able to provide a pleasing fragrance to fabrics, and encompasses conventional materials commonly used in cosmetic compositions to counteract a malodor in such compositions and/or provide a pleasing fragrance thereto. The perfumes are preferably in the liquid state at ambient temperature, although solid perfumes are also useful, particularly cyclodextrin/perfume inclusion complexes for controlled release. Included among the perfumes contemplated for use herein are materials such as aldehydes, ketones, esters and the like which are conventionally employed to impart a pleasing fragrance to liquid and solid personal care or cosmetic compositions. Naturally occurring plant and animal oils are also commonly used as components of perfumes. Accordingly, the perfumes useful for the present invention may have relatively simple compositions or may comprise complex mixtures of natural and synthetic chemical components, all of which are intended to provide a pleasant odor or fragrance when applied to fabrics. The perfumes used in personal care or cosmetic compositions are generally selected to meet the normal requirements of odor, stability, price and commercial availability. The term “fragrance” is often used herein to signify a perfume itself, rather than the aroma imparted by such perfume.
The present invention is directed to a method of increasing the sun protection factor of a sunscreen composition wherein said method comprises incorporating into said composition an effective amount of at least one select copolymer according to formula (I)
(a) at least one UV screening agent;
(b) at least one select copolymer comprising
wherein
x and z represent the percentage by weight that each repeating unit or derived monomer is contained within the copolymer;
x and z add up to total 100 weight percent relative to the total weight of the copolymer;
x and z refer to repeating units;
z is from about 0.001% to about 99.999% by weight of the copolymer;
x is from about 0.001% to about 99.999% by weight of the copolymer;
A is a polymer;
G is covalently bonded to the polymer A through an oxygen linking group;
o is an oxygen atom;
wherein
G1, G2, G3, G4 are independently C1-C6alkyl or G1 and G2 or G3 and G4, or G1 and G2 and
G3 and G4 together form a C5-C12cycloalkyl group;
G5, G6 independently are H, C1-C18alkyl, phenyl, naphthyl or a group COOC1-C18alkyl;
*denotes a valence and **denotes point of attachment to said polymer A;
wherein R201, R202, R203 and R204 independently of each other are C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl which are substituted by OH, halogen or a group —O—C(O)—R205, C2-C18alkyl which is interrupted by at least one O atom and/or NR205 group, C3-C12cycloalkyl or C6-C10aryl or R201 and R202 and/or R203 and R204 together with the linking carbon atom form a C3-C12cycloalkyl radical;
R205, R206 and R207 independently are hydrogen, C1-C18alkyl or C6-C10aryl;
R208 is hydrogen, OH, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl which are substituted by one or more OH, halogen or a group —O—C(O)—R205, C2-C18alkyl which is interrupted by at least one O atom and/or NR205 group, C3-C12cycloalkyl or C6-C10aryl, C7-C9phenylalkyl, C5-C10heteroaryl, —C(O)—C1-C18alkyl, —O—C1-C18alkyl or —COOC1-C18alkyl;
R209, R210, R211 and R212 are independently hydrogen, phenyl or C1-C18alkyl; or
G11, G12, G13 and G14 are independently C1-C4alkyl or G11 and G12 together and G13 and G14 together, or G11 and G12 together or G13 and G14 together are pentamethylene;
G15 and G16 are each independently of the other hydrogen or C1-C4alkyl;
X is as defined above;
k is 1, 2, 3, or 4
Y is O or NR302 or when k is 1 and R301 represents alkyl or aryl Y is additionally a direct bond;
R302 is H, C1-C18alkyl or phenyl;
if k is 1
R301 is H, straight or branched C1-C18alkyl, C3-C18alkenyl or C3-C18alkinyl, which may be unsubstituted or substituted, by one or more OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl;
C5-C12cycloalkyl or C5-C12cycloalkenyl;
phenyl, C7-C9phenylalkyl or naphthyl which may be unsubstituted or substituted by one or more C1-C8alkyl, halogen, OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl; —C(O)—C1-C36alkyl, or an acyl moiety of a □,□-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms;
—SO3−Q+, —PO(O−Q+)2, —P(O)(OC1-C8alkyl2)2, —P(O)(OH2)2, —SO2—OH, —SO2—C1-C8alkyl, —CO—NH—C1-C8alkyl, —CONH2, COO—C1-C8alkyl2, COOH or Si(Me)3, wherein Q+ is H+, ammonium or an alkali metal cation;
if k is 2
R301 is C1-C18alkylene, C3-C18alkenylene or C3-C18alkinylene, which may be unsubstituted or substituted, by one or more OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl; or xylylene; or
R301 is a bisacyl radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms;
if k is 3,
R301 is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid; and
if k is 4, R301 is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid;
and, optionally
(c) other cosmetically acceptable ingredients.
The present invention is directed to a method of improved UV protection of mammalian hair and/or skin from the damaging effects of UV radiation wherein said method comprises applying to said skin and/or said hair an effective amount of a sunscreen composition comprising
(a) at least one UV screening agent;
(b) at least one select copolymer comprising
wherein
x and z represent the percentage by weight that each repeating unit or derived monomer is contained within the copolymer;
x and z add up to total 100 weight percent relative to the total weight of the copolymer;
x and z refer to repeating units;
z is from about 0.001% to about 99.999% by weight of the copolymer;
x is from about 0.001% to about 99.999% by weight of the copolymer;
A is a polymer;
G is covalently bonded to the polymer A through an oxygen linking group;
O is an oxygen atom;
wherein
G1, G2, G3, G4 are independently C1-C6alkyl or G1 and G2 or G3 and G4, or G1 and G2 and G3 and G4 together form a C5-C12cycloalkyl group;
G5, G6 independently are H, C1-C18alkyl, phenyl, naphthyl or a group COOC1-C18alkyl;
*denotes a valence and **denotes point of attachment to said polymer A;
wherein R201, R202, R203 and R204 independently of each other are C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl which are substituted by OH, halogen or a group —O—C(O)—R205, C2-C18alkyl which is interrupted by at least one O atom and/or NR205 group, C3-C12cycloalkyl or C6-C10aryl or R20, and R202 and/or R203 and R204 together with the linking carbon atom form a C3-C12cycloalkyl radical;
R205, R206 and R207 independently are hydrogen, C1-C18alkyl or C6-C10aryl;
R208 is hydrogen, OH, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl which are substituted by one or more OH, halogen or a group —O—C(O)—R205, C2-C18alkyl which is interrupted by at least one O atom and/or NR205 group, C3-C12cycloalkyl or C6-C10aryl, C7-C9phenylalkyl, C5-C10heteroaryl, —C(O)—C1-C18alkyl, —O—C1-C18alkyl or —COOC1-C18alkyl;
R209, R210, R211 and R212 are independently hydrogen, phenyl or C1-C18alkyl; or
G11, G12, G13 and G14 are independently C1-C4alkyl or G11 and G12 together and G13 and G14 together, or G11 and G12 together or G13 and G14 together are pentamethylene;
G15 and G16 are each independently of the other hydrogen or C1-C4alkyl;
X is as defined above;
k is 1, 2, 3, or 4
Y is O or NR302 or when k is 1 and R301 represents alkyl or aryl Y is additionally a direct bond;
R302 is H, C1-C18alkyl or phenyl;
if k is 1
R301 is H, straight or branched C1-C18alkyl, C3-C18alkenyl or C3-C18alkinyl, which may be unsubstituted or substituted, by one or more OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl;
C5-C12cycloalkyl or C5-C12cycloalkenyl;
phenyl, C7-C9phenylalkyl or naphthyl which may be unsubstituted or substituted by one or more C1-C8alkyl, halogen, OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl;
—C(O)—C1-C36alkyl, or an acyl moiety of a □,□-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms;
—SO3−Q+, —PO(O−Q+)2, —P(O)(OC1-C8alkyl2)2, —P(O)(OH2)2, —SO2—OH, —SO2—C1-C8alkyl, —CO—NH—C1-C8alkyl, —CONH2, COO—C1-C8alkyl2, COOH or Si(Me)3, wherein Q+ is H+, ammonium or an alkali metal cation;
if k is 2
R301 is C1-C18alkylene, C3-C18alkenylene or C3-C18alkinylene, which may be unsubstituted or substituted, by one or more OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl; or xylylene; or
R301 is a bisacyl radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms;
if k is 3,
R301 is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid; and
if k is 4, R301 is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid;
and, optionally
(c) other cosmetically acceptable ingredients.
The present invention is directed to a cosmetic or dermatological composition comprising a select copolymer of formula (I)
(b) at least one select copolymer comprising
wherein
x and z represent the percentage by weight that each repeating unit or derived monomer is contained within the copolymer;
x and z add up to total 100 weight percent relative to the total weight of the copolymer;
x and z refer to repeating units;
z is from about 0.001% to about 99.999% by weight of the copolymer;
x is from about 0.001% to about 99.999% by weight of the copolymer;
A is a polymer;
G is covalently bonded to the polymer A through an oxygen linking group;
O is an oxygen atom;
wherein
G1, G2, G3, G4 are independently C1-C6alkyl or G1 and G2 or G3 and G4, or G1 and G2 and G3 and G4 together form a C5-C12cycloalkyl group;
G5, G6 independently are H, C1-C18alkyl, phenyl, naphthyl or a group COOC1-C18alkyl;
*denotes a valence and **denotes point of attachment to said polymer A;
wherein R201, R202, R203 and R204 independently of each other are C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl which are substituted by OH, halogen or a group —O—C(O)—R205, C2-C18alkyl which is interrupted by at least one O atom and/or NR205 group, C3-C12cycloalkyl or C6-C10aryl or R20, and R202 and/or R203 and R204 together with the linking carbon atom form a C3-C12cycloalkyl radical;
R205, R206 and R207 independently are hydrogen, C1-C18alkyl or C6-C10aryl;
R208 is hydrogen, OH, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl which are substituted by one or more OH, halogen or a group —O—C(O)—R205, C2-C18alkyl which is interrupted by at least one O atom and/or NR205 group, C3-C12cycloalkyl or C6-C10aryl, C7-C9-phenylalkyl, C5-C10heteroaryl, —C(O)—C1-C18alkyl, —O—C1-C18alkyl or —COOC1-C18alkyl;
R209, R210, R211 and R212 are independently hydrogen, phenyl or C1-C18alkyl; or
G11, G12, G13 and G14 are independently C1-C4alkyl or G11 and G12 together and G13 and
G14 together, or G11 and G12 together or G13 and G14 together are pentamethylene; G15 and G16 are each independently of the other hydrogen or C1-C4alkyl;
X is as defined above;
k is 1, 2, 3, or 4
Y is O or NR302 or when k is 1 and R301 represents alkyl or aryl Y is additionally a direct bond;
R302 is H, C1-C18alkyl or phenyl;
if k is 1
R301 is H, straight or branched C1-C18alkyl, C3-C18alkenyl or C3-C18alkinyl, which may be unsubstituted or substituted, by one or more OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl;
C5-C12cycloalkyl or C5-C12cycloalkenyl;
phenyl, C7-C9phenylalkyl or naphthyl which may be unsubstituted or substituted by one or more C1-C8alkyl, halogen, OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl;
—C(O)—C1-C36alkyl, or an acyl moiety of a □,□-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms;
—SO3−Q+, —PO(O−Q+)2, —P(O)(OC1-C8alkyl2)2, —P(O)(OH2)2, —SO2—OH, —SO2—C1-C8alkyl, —CO—NH—C1-C8alkyl, —CONH2, COO—C1-C8alkyl2, COOH or Si(Me)3, wherein Q+ is H+, ammonium or an alkali metal cation;
if k is 2
R301 is C1-C18alkylene, C3-C18alkenylene or C3-C18alkinylene, which may be unsubstituted or substituted, by one or more OH, C1-C8alkoxy, carboxy, C1-C8alkoxycarbonyl; or xylylene; or
R301 is a bisacyl radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms;
if k is 3,
R301 is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid; and
if k is 4, R301 is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid;
and,
(c) other cosmetically acceptable ingredients.
The following examples describe certain embodiments of this invention, but the invention is not limited thereto. It should be understood that numerous changes to the disclosed embodiments could be made in accordance with the disclosure herein without departing from the spirit or scope of the invention. These examples are therefore not meant to limit the scope of the invention. Rather, the scope of the invention is to be determined only by the appended claims and their equivalents. In these examples all parts given are by weight unless otherwise indicated.
The following examples illustrate the invention.
Materials use and their abbreviations.
Monomers: butylacrylate (BA), hydroxyethylacrylate (HEA), hydroxypropylacrylate (HPA) 4-vinyl-pyridine (4-VP).
Modification agents: cyclohexylacid anhydride (CHAA), succinic acid anhydride (SAA), methoxy-poly-ethyleneglycole (MPEG 550-OH), HCl, NaOH.
Solvents: methoxypropylacetate (MPA), Xylene, methoxypropanol (MP), polystyrene (PS), tetrahydrofuran (THF), polyethyleneoxide (POE/PEG).
ATRP process: initiator is 2-bromoethylpropionate (MBP), the catalyst is CuBr/CuBr2, the ligand is N,N,N′,N″,N″-pentamethyldiethyltriamine (PMDETA). NOR Initiator/regulator is compound O1
which is prepared according to GB 2335190.
All other materials are commercially available and are used as received.
Some of the solvents used for the synthesis of the instant copolymers may not be suitable for human physiological conditions. Once the synthesis is completed, the solvents can be removed and/or replaced with solvents that are more cosmetically acceptable.
In a 3-necked 1000 ml round bottom flask with magnetic stirring bar, cooler, thermometer, dropping funnel 150.10 g n-Butylacrylate (n-BA, 128.17 g/mol), 8.55 g compound O1 (317.48 g/mol) and 122.13 g of MPA are added, three times degassed with N2/vacuum and polymerized at 135° C. under N2 until a conversion of around 8 mol % is reached. 338.89 g of n-BA is slowly added to the reaction with the dropping funnel and polymerized at 135° C. under N2 until a conversion of around 48 mol %. Residual monomers and solvents are distilled of at 80° C. and 12 mbar.
Yield 47%, GPC (THF, PS-Standard, Mn=7800 g/mol, PD=1.27), liquid.
According to analysis via 1H-NMR, the degree of polymerization is 75.
In a 3-necked 500 ml round bottom flask with magnetic stirring bar, cooler, thermometer 214.18 g poly(n-BA) of example 1, 70.90 g 4-vinylpyridine (4-VP, 105.14 g/mol) and 79.70 g of MPA are added, three times degassed with N2/vacuum and polymerized at 125° C. under N2 for 8 h. Residual monomers and solvents are distilled off at 80° C. and 12 mbar.
Yield 85%, GPC (THF, PS-Standard, Mn=8600 g/mol, PD=1.24), liquid. According to analysis via 1H-NMR, the degree of polymerization is: P(BA-b-4VP)=75-b-14.
In a 500 mL flask equipped with a magnetic stirring bar, distillation column with dry ice acetone cooling 92.8 g of Poly(n-BA-b-4-VP) according to example 2 in 107.2 g of Xylene and 114.7 g of MPEG-OH (Mn=550 g/mol) are added and dried by azeotropic distillation of the xylene. Three portions of 0.36 g of tera(isopropyl)orthotitanate are added during 3 h at 190-205° C. The formed n-Butanol is distilled of at low pressure.
187.7 g of Poly(n-BA-MPEGA-b-4-VP) is obtained. Mn=17500 g/mol, PDI=1.6, OH-value=0.05 meq/g. Anaylsis via GPC as well as 1H_NMR indicate almost quantitative conversion of the MPEG-OH.
The resulting polymer is well soluble in water and shows an LCST-type solution behavior (LCST=lower critical solution temperature), i.e. the solubility of the polymer decreases with increasing temperature). A 35 wt % solution of the end product polymer in water is a clear solution at room temperature, but becomes turbid at elevated temperatures above 70° C.
The resulting polymer also formed clear 10 wt % solutions in following organic solvents: butyl acetate, methoxypropylacetate, methoxypropanol, butylglycol and xylene.
In a 6 liter reactor equipped with stirrer, cooler, thermometer, and monomer feed pumps 1519 g n-Butylacrylate, 209 g compound O1 are added, three times degassed with N2/vacuum and heated to 115° C. under N2, where a continuous feed of n-butylacrylate is started over 4 hours and at the same time the reaction mass slowly heated to 135° C. After the end of the monomer feed, the reaction mass is further reacted for 5 h until a solids content of 55% is reached. Afterwards, the non reacted monomer is removed by vacuum distillation.
2812 g of Poly(n-BA) is obtained as liquid polymer, Mn=4554, PDI=1.18 According to analysis via 1H-NMR, the degree of polymerization is: P(nBA)=35.
In the same reactor as in Example 4, 2674 g of example 4 are loaded together with 1133 g 4-vinylpyridine and heated under N2 to 135° C. and reacted for 3.5 h until a solids content of 91% is reached. This polymer is used for subsequent transesterifications without further removal of non-reacted 4-vinylpyridine.
3732 g of Polymer P(nBA-b-4VP) is isolated from the reactor, Mn=4779, PDI=1.19 According to analysis via 1H-NMR, the degree of polymerization is: P(nBA-b-4VP)=35-b-14.
In the same reactor as in Example 4, 3730 g of the example 5 are loaded together with 3503 g of MPEG-OH (M=550 g/mol) and subjected to vacuum degassing at 130° C. for one hour to remove non-reacted 4-vinylpyridine. 12.0 g of LiOMe-solution (10 wt % lithium methanolate in methanol are added slowly and the transesterification started by distilling off n-butanol at 130° C. and reduced pressure. Additional 5 portions of catalyst are added after every hour: 2×12.0 g and additional 3×14.5 g of LiOMe-solution. After 6 h the reaction is completed by collecting the calculated amount of n-butanol.
6322 g of viscous polymer is obtained; Mn=8829, PDI=1.36
Anaylsis via GPC as well as 1H_NMR indicate almost quantitative conversion of the MPEG-OH.
According to analysis via 1H-NMR, the degree of polymerization is: P[(nBA-MPEGA)/-b-4VP]=(23-12)-b-14.
OH-number titration: 0.20 meq/g
Amine number titration: 69 mg KOH/g
The 50 wt % solids solution in water displays an LCST of 67° C.
Aside from water, the polymer 6 gives clear solutions 10 wt % in following organic solvents: butyl acetate, methoxypropylacetate, methoxypropanol, butylglycol and xylene. For testing the polymer 6 is dissolved in water to give a clear 50 wt % solids solution.
In the same reactor as in example 4 are loaded 500 g of a poly(n-BA) (Mn=8304, PDI=1.21), which is made analogous to example 4 and 500 g of MPEG-OH (M=550 g/mol). The mixture is heated to 128° C., than 21 g of LiOMe catalysts solution (10 wt % in methanol) are added slowly and n-butanol is slowly distilled off under reduced pressure. Catalyst addition is repeated 5 times each after one hour with 21 g catalyst solution. The transesterification is conducted in total for 6 h until the calculated amount of n-butanol had been distilled off.
918 g of polymer is obtained; Mn=13305, PDI=1.31
Anaylsis via GPC as well as 1H_NMR indicate almost quantitative conversion of the MPEG-OH.
According to analysis via 1H-NMR, the degree of polymerization is: P(nBA-MPEGA)=(58-19).
The 50 wt % solids solution in water displays an LCST of 70° C.
For testing the polymer 7 is dissolved in water to give a clear 50 wt % solids solution.
In a 250 mL flask equipped with a magnetic stirring bar and distillation column are loaded 65 g of a P(nBA) (Mn=8386, PD=1.21; made analog to Example 4), 7.5 g of MPEG-OH (M=350), 7.5 g MPEG-OH (M=500) and 20 g MPEG-OH (M=2000). The mixture is heated to 125° C. and 2 g of LiOMe catalyst solution (10 wt % in MeOH) are slowly added. The transesterification is started by slowly distilling off n-butanol under reduced pressure and increasing the temperature to 130° C. Two additional portions each of 2 g catalyst solution are added after 1 h and 2 h later. After 4 h total reaction time, the transesterification is terminated after the calculated amount of n-butanol is distilled off.
84 g of polymer is obtained; Mn=10490, PDI=1.61
Analysis via GPC as well as 1H-NMR indicate almost quantitative conversion of the MPEG-OH-mixture.
According to analysis via 1H-NMR, the degree of polymerization is: P(nBA-MPEGA-mix)=(69-7).
In a 250 mL flask equipped with a magnetic stirring bar and distillation column are loaded 65 g of a P(nBA) (Mn=8386, PD=1.21; made analog to Example 4), 7.5 g of MPEG-OH (M=350), 7.5 g MPEG-OH (M=500) and 20 g MPEG-OH (M=5000). The mixture is heated to 125° C. and 2 g of LiOMe catalyst solution (10 wt % in MeOH) are slowly added. The transesterification is started by slowly distilling off n-butanol under reduced pressure and increasing the temperature to 130° C. Two additional portions each of 2 g catalyst solution are added after 1 h and 2 h later. After 4 h total reaction time, the transesterification is terminated after the calculated amount of n-butanol is distilled off.
83 g of polymer is obtained; Mn=9563, PDI=1.75
Analysis via GPC as well as 1H-NMR indicate almost quantitative conversion of the MPEG-OH-mixture.
According to analysis via 1H-NMR, the degree of polymerization is: P(nBA-MPEGA-mix)=(71-6).
In a 250 mL flask equipped with a magnetic stirring bar and distillation column are loaded 38 g of a P(nBA) (Mn=8386, PD=1.21; made analog to Example 4), 35 g MPEG-OH (M=500) and 27 g oleyl alcohol (techn. grade). The mixture is heated to 125° C. and 2 g of LiOMe catalyst solution (10 wt % in MeOH) are slowly added. The transesterification is started by slowly distilling off n-butanol under reduced pressure and increasing the temperature to 135° C. Two additional portions each of 2 g catalyst solution are added after 1 h and 2 h later. After 4 h total reaction time, the transesterification is terminated after the calculated amount of n-butanol is distilled off.
78 g of liquid polymer is obtained; Mn=13374, PDI=1.87
Analysis via GPC as well as 1H-NMR indicate almost quantitative conversion of the MPEG-OH and the unsaturated oleyl alcohol.
According to analysis via 1H-NMR, the degree of polymerization is: P(nBA-MPEGA-OleA)=(32-18-26).
In a 250 ml flask equipped with a magnetic stirring bar and distillation column are loaded 83.3 g of a 60 wt % MPA-solution of a diblock copolymer P(nBA-b-4VP) (synthesized analogous to example 5; degree of polymerization=76-b-14, Mn=8834, PD=1.27) and 54.1 g of a branched iso-C12-15-alcohol mixture (Lial 125, Condea). After heating the mixture to 125° C., the MPA is distilled under reduced pressure before adding 0.28 g catalyst solution (Ti(AcAc)2(iOPr)2 Titan-bis-acetylacetonato-bis-isopropylate, 75 wt % in isopropanol). The transesterification is started by slowly distilling off n-butanol under reduced pressure and increasing the temperature to 145° C. Two additional portions each of 0.28 g catalyst solution are added after 1 h and 2 h later. After 4 h total reaction time, the transesterification is terminated after no further n-butanol formation is observed.
76 g of liquid block copolymer is obtained; Mn=12216, PDI=1.27
Analysis via GPC as well as 1H-NMR indicated almost quantitative conversion of the MPEG-OH and the branched iC12-C15-alcohol.
According to combined analysis of 1H-NMR and GPC, the degree of polymerization is: P[(nBA-iC12-15A)-b-4VP]=(16-60)-b-14.
In a 500 ml flask equipped with a magnetic stirring bar and distillation column are loaded 210 g of a P(nBA) (synthesized analog polymer 4; degree of polymerization=76, Mn=8547, PDI=1.19) and 90 g of styrene and are heated under N2 to 125° C. After 5 h the reaction is terminated and the non-reacted styrene is distilled off at reduced pressure.
175 g of block copolymer is obtained; Mn=11828, PDI=1.21
According to analysis of 1H-NMR the degree of polymerization is: P(nBA-b-S)=(75-b-40).
The resultant very high viscous block copolymer is diluted with MPA to a clear 60 wt % solution.
In a 250 ml flask equipped with a magnetic stirring bar and distillation column are loaded 50 g of a 60 wt % MPA-solution of the diblock copolymer of example 12P(nBA-b-S)=75-b-40) and 26.3 g of a branched iso-C12-15-alcohol mixture (Lial 125, Condea). After heating the mixture to 125° C., the MPA is distilled off under reduced pressure before adding 0.15 g catalyst solution (Ti(AcAc)2(iOPr)2 Titan-bis-acetylacetonato-bis-isopropylate, 75 wt % in isopropanol). The transesterification is started by slowly distilling off n-butanol under reduced pressure and increasing the temperature to 145° C. Two additional portions each of 0.15 g catalyst solution are added after 2 h and 4 h later. After 6 h total reaction time, the reaction is terminated after no further n-butanol formation is observed.
49 g of liquid block copolymer is obtained; Mn=15072, PDI=1.21
Analysis via GPC as well as 1H-NMR indicated good conversion of the branched iC12-C15-alcohol.
According to combined analysis of 1H-NMR and GPC, the degree of polymerization is: P[(nBA-iC12-15A)-b-S=(15-60)-b-40.
In a 500 ml flask equipped with a magnetic stirring bar and distillation column are loaded 150 g of a P(nBA) (synthesized analog polymer 4; degree of polymerization=76, Mn=8547, PDI=1.19) and 150 g of dimethylaminopropyl methacrylamide (DMAPMA) and are heated under N2 to 145° C. After 4.5 h the reaction is terminated and non-reacted monomer DMAPMA is distilled off at high vacuum.
179 g of block copolymer is isolated; Mn=6874, PDI=1.41 (the apparent molecular weight via GPC appeared lower than the starting precursor)
According to analysis of 1H-NMR the degree of polymerization is: P(nBA-b-DMAPMA)=(75-b-23).
The resultant high viscous block copolymer is diluted with MPA to a clear 60 wt % solution.
In a 250 ml flask equipped with a magnetic stirring bar and distillation column are loaded 41.7 g of a 60 wt % MPA-solution of the diblock copolymer 14 P(nBA-b-DMAPMA)=75-b-23) and 30.0 g of a technical behenyl alcohol (BhOH=linear C16-22-alcohol mixture Nafol 1822 from Condea). After heating the mixture to 125° C., the MPA is distilled off under reduced pressure before adding 0.15 g catalyst solution (Ti(AcAc)2(iOPr)2 Titan-bis-acetylacetonato-bis-isopropylate, 75 wt % in isopropanol). The transesterification is started by slowly distilling off n-butanol under reduced pressure and increasing the temperature to 145° C. Two additional portions each of 0.15 g catalyst solution are added after 2 h and 4 h later. After 6 h total reaction time, the reaction is terminated after no further n-butanol formation is observed.
42 g of block copolymer is obtained which solidify at room temperature; Mn=10652, PDI=1.60
Analysis via GPC as well as 1H-NMR indicated good conversion of the behenyl alcohol.
According to combined analysis of 1H-NMR and GPC, the degree of polymerization is: P[(nBA-BhA)-b-S=(20-55)-b-23.
In a 500 ml flask equipped with a magnetic stirring bar and distillation column are loaded 123.4 g of a P(nBA) (synthesized analog polymer 1; degree of polymerization=57, Mn=5866, PDI=1.18) and 211.0 g of tert.-butylacrylate (tBA) and are heated under N2 to 120° C. at gentle reflux. After 16 hours, the reaction is terminated when solids content is 53% and non-reacted monomer tBA is distilled off under vacuum.
223 g of block copolymer is isolated; Mn=10052, PDI=1.22
According to analysis of 1H-NMR the degree of polymerization is: P(nBA-b-tBA)=(57-b-63).
In a 500 ml flask equipped with a magnetic stirring bar and distillation column are loaded 288.7 g of the diblock copolymer 16 (P(nBA-b-tBA)=57/-b-63) and 186.5 g of a technical behenyl alcohol (BhOH=linear C16-22-alcohol mixture Nafol 1822 from Condea). After heating the mixture to 125° C., 0.15 g catalyst solution (Ti(AcAc)2(iOPr)2 Titan-bis-acetylacetonato-bis-isopropylate, 75 wt % in isopropanol) are slowly added. The transesterification is started by slowly distilling off n-butanol under reduced pressure and increasing the temperature to 145° C. Two additional portions each of 0.15 g catalyst solution are added after 2 h and 4 h later. After 6 h total reaction time, the reaction is terminated after no further n-butanol formation is observed.
430 g of block copolymer is obtained which solidify at room temperature; Mn=18877, PDI=1.23
Analysis via GPC as well as 1H-NMR indicated good conversion of the behenyl alcohol.
In a 250 ml flask equipped with a magnetic stirring bar and distillation column are loaded 85 g of P(nBA) (Mn=8793, PDI=1.20 made analogous to Example 4) and 77 g of a technical behenyl alcohol (BhOH=linear C16-22-alcohol mixture Nafol 1822 from Condea). After heating the mixture to 125° C., 0.43 g catalyst solution (Ti(AcAc)2(iOPr)2 Titan-bis-acetylacetonato-bis-isopropylate, 75 wt % in isopropanol) are slowly added. The transesterification is started by slowly distilling off n-butanol under reduced pressure and increasing the temperature to 145° C. Two additional portions each of 0.43 g catalyst solution were added after 2 h and 4 h later. After 6 h total reaction time, the reaction is terminated after no further n-butanol formation is observed.
132 g of block copolymer is isolated which solidify at room temperature; Mn=14811, PDI=1.25
Analysis via GPC indicated good conversion of the behenyl alcohol.
The following substances are polymerized similar to the manner as described in Example 3: 2.27 g compound (O1), 38.22 g n-butylacrylate, 5.84 g vinyl pyridine, and 53.21 g MPEG-OH (Mn=550 g/mol). After completion of the polymerization reaction, all solvents and volatiles are removed by vacuum distillation. A polymeric melt is obtained with a molecular weight of about 15000-20000 Daltons as judged by Gel Permeation Chromotography (GPC). Additionally, a calibrated gas chromatographic analysis of the polymeric melt found that the level of residual 4-vinylpyridine in the melt is less than 2 ppm.
A 50% by weight aqueous solution of the polymer prepared above is prepared.
Combine the ingredients of part A. Heat up part A to 80° C. with mixing. Mix until uniform, and add Nylon-12 with moderate agitation.
Prepare part B: first, disperse Xanthan Gum into the water and heat up to 80° C. When uniform, add the rest of part B one by one, mix until uniform.
Add part A into part B under stirring, and then homogenize with an Ultra Turrax pos 2 for 40 sec/100 g.
Cool down under stirring, to 40° C. and add the ingredients of part C one by one in the given order. Mix until uniform. If necessary, adjust pH with aqueous solution of Sodium Hydroxide to 5.3-6.1
The test protocol described below is used to mimic the application of the sunscreen composition to human skin and test the initial SPF and the SPF after eighty minutes of water exposure of the instant compositions.
The following laboratory equipment is used:
VITRO-SKIN® N-19, Foam block, Hydration Chamber, Powder Free Rubber Finger Cots and Glassless slide mounts are obtained from IMS, Inc. (70 Robinson Blvd, Orange, Conn., USA);
Water bath (#05-719-7F), Corning Hotplate Stirrer (#11-497-8A), Calfamo Compact Digital Stirrer (#14-500-7), Glycerol Aqueous Solution (#AC277366-0010) are obtained from Fisher Scientific Catalog; and
Optometrics SPF 290 is obtained from Optometrics LLC. (8 Nemco Way, Stony Brook Industrial Park, Ayer, Mass., USA).
An aqueous solution of glycerin (300 g of 14.7% by weight) is prepared and poured on the bottom of the hydration chamber. The shelves are placed in the chamber that is covered with a lid. VITRO-SKIN substrate is cut into 4.1 cm×4.1 cm pieces that are placed on the shelves in a hydration chamber and hydrated for 16-22 hours prior to the tests.
Optometrics SPF 290S is turned on followed by the manufacturer's directions for instrument calibration, blank and sample measurements.
A piece of substrate is placed in a slide mount and used as a reference for the in vitro SPF measurements. Another piece of substrate is placed on a plastic-covered foam block and product application is made to the “topography” side of the substrate (the rough side). The test composition (0.033 g) is applied evenly across a 4 cm×4 cm section of the substrate, which results in an application dose of 2 mg/sq. cm and rubbed into the substrate with a finger covered with finger cot. After this, the substrate is placed on a slide mount.
The in vitro SPF measurements are made both prior to and after sample immersion in water with stirring for 80 minutes at a water temperature of 37+/−0.5° C. All initial measurements are made after the 15 minute dry-down period. After water exposure, the samples are removed, air-dried for about 30 minutes, placed back in the controlled humidity chamber for 120 minutes followed by the 15 minute dry-down period. The reference slides are immersed in the water bath for the same amount of time. An Optometrics SPF 290S is used to determine UV absorbance for each formulation in the 290-400 nm wavelength range. A minimum of three consecutive measurements on three separate areas of the slide are conducted. SPF, UVA/UVB and Critical Wavelength in vitro values for each sample—before and after water immersion are recorded. The % SPF remaining after eighty minute exposure to water is calculated by:
(a/b)×100=%SPF remaining
(a) is SPF value after 80 minutes of water exposure and (b) is initial SPF value.
The base sunscreen composition of Instant Example 20 is formulated with the copolymer of Instant Example 19 and compared with other commercially available polymers and copolymers. The composition of Instant Example 20 is prepared individually with the specified amount of each test polymer or copolymer. Commercially available polymers were added to the oil phase or water phase of the formulation, or post-added according to the recommendations described in the manufacturer's literature.
Each sunscreen formulation is evaluated according to the protocol of Instant Example 21. The experimental results are given below.
Instant Example 19 is added at a 1% weight/weight of component (as active) based on the weight of the total composition.
Cosmedia DC is a hydrogenated dimer Dilinoleyl/Dimethylcarbonate Copolymer and is obtained from Cognis.
Polycrylene is Polyester-8 which is a copolymer of adipic acid (q.v.) and neopentyl glycol (q.v.) end-capped with either octyldodecanol (q.v.) or a cyanodiphenylpropenoyl group and is obtained from RTD Hall Star.
DC FA 4001 CM Silicone Acrylate is a copolymer of polytrimethylsiloxymethacrylate and one or more monomers consisting of acrylic acid, methacrylic acid, or one of their simple esters dissolved in cyclopentasiloxane and is obtained from Dow Corning.
Ganex V-220 is a copolymer of vinylpyrrolidone and eicosene and is obtained from ISP.
DC FA 4002 ID Silicone Acrylate is a copolymer of polytrimethylsiloxymethacrylate and one or more monomers consisting of acrylic acid, methacrylic acid, or one of their simple esters dissolved in isododecane and is obtained from Dow Corning.
Phospholipon 90H is hydrogenated lecithin and is obtained from Phospholipid GmbH.
Dermacryl AQF is a copolymer of acrylates and is obtained from National Starch and Chemical Company.
Ganex WP-660 is a copolymer of vinyl pyrrolidone and 1-triacontane and is obtained from ISP.
Stantiv OMA-2 is a linear copolymer of maleic anhydride and octadecene and is dissolved a mixture of methyl acetyl ricinoleate and dimethylheptyl adipate.
Dermacryl-79 is a copolymer of octylacrylamide and one or more monomers consisting of acrylic acid, methacrylic acid or one of their simple esters and is obtained from National Starch and Chemical Company.
The data demonstrate the instant copolymer provide excellent water proofing properties in sunscreen compositions at one-third of the concentration when compared to other polymers and copolymers of the prior art and commerce.
A commercial sunscreen formulation (Cetaphil SPF 15, Galderma) is obtained and is thoroughly mixed individually with the specified amount of each test polymer or copolymer. Each sunscreen formulation is evaluated according to the protocol of Instant Example 21. The experimental results are given below.
Dermacryl AQF is a copolymer of acrylates and is obtained from National Starch and Chemical Company.
Allianz OPT is a copolymer of: methacrylic acid, methyl methacrylate, butyl acrylate, and cetyl-eicosinyl methacrylate and is obtained from ISP.
Cetaphil SPF 15 is a commercial sunscreen formulation that contains sunscreen actives: Avobenzone 3%; Octocrylene 10%; and
Water (solvent),
Isopropyl adipate (emollient, solvent),
Cyclomethicone (emollient, solvent),
Glyceryl Stearate (and) PEG-100 Stearate (emulsifier, non-ionic),
Glycerin (humectant),
Polymethyl Metacrylate (spherical particulate to improve the skin feel,
Phenoxyethanol (preservative),
Benzyl Alcohol (preservative),
Acrylates/C10-30 Alkyl Acrylate Crosspolymer (polymeric emulsifier, rheology modifier),
Tocopheryl Acetate (antioxidant),
Carbomer (rheology modifier),
Disodium EDTA (chelating agent), and
Triethanolamine (pH adjustor).
The data demonstrate the instant terpolymer provide excellent water proofing properties in sunscreen compositions when compared to other polymers and copolymers of the prior art and commerce.
The water resistant properties of the instant copolymers are studied according to: the FDA Final Monograph “Evaluation of Sunscreen Efficacy—Sun Protection Factor (SPF) Assay and Very Water Resistant Assay” (in vivo). The instant copolymers are studied at 1% w/w based on solids and the data obtained from the in vivo evaluation of the very water resistant properties of the sunscreen formulations containing the instant copolymers is given below.
It is found that, at concentration 1% w/w based on solids, the instant copolymers provide a significant improvement of very water-resistant properties of a sunscreen formulation.
A test methodology that utilizes measurements of the contact angle of water to quantify the effects on the surface properties of a skin-substitute substrate is employed. This methodology is used as an effective tool for optimizing product development, differentiating among skin care products, competitive benchmarking, and screening of the polymers. It is described in the article entitled “Correlating Water Contact Angles and Moisturization/Sensory Claims” by Olga V. Dueva-Koganov, Scott Jaynes, Colleen Rocafort, Shaun Barker and Jianwen Mao—Cosmetics & Toiletries, January 2007, Vol. 122, No. 1, pp. 20-27. The data presented in the graph of this article shows that contact angle measurements can be used to quantify and compare the effects of skin care products on the surface properties of a skin-like substrate and is presented in tabular form below. Products that generate relatively low contact angles tend to make more sensory claims related to light and non-greasy feel, while products that produce relatively high contact angles tend to make more claims related to long-term moisturization.
Contact angles are measured instrumentally according to the static or sessile drop method and using deionized water as a probe solution and VITRO SKIN that mimics the surface properties of human skin as a substrate. A piece of hydrated substrate is mounted in a glassless slide and air-dried in a flat position with application side up for 15 minutes. It is used as a reference for untreated substrate during the contact angle measurements. Exactly 0.032 g of aqueous solutions or dispersions of test polymers are applied evenly across a 4 cm×4 cm section of the substrate (on the “skin topography” side). Immediately after product application, the product is rubbed into the substrate with a finger covered with fingercot. After that the substrate is placed in a slide mount and air-dried for 15 minutes. Before measurements, substrate is removed from the slide mount and cut to several small pieces, which are used for the measurements. The use of small size piece is necessary to assure its flat position on the sample table. Extra care is taken to ensure that the rough side is up and the film is flat. Contact angle measurements are conducted expeditiously—within approximately 1 minute. Controlled humidity conditions are utilized.
Powder Free Rubber Finger Cots (#11-392-9B) are available from the Fisher Scientific Catalog.
Instant terpolymers and competitive water-resistant polymers Allianz OPT (ISP) and Dermacryl AQF (National Starch) are evaluated according to the methodology described above.
The instant copolymers and competitive water-resistant polymers demonstrate strong differences in their effects on the surface properties of VITRO SKIN. The results presented in the table above indicate that the instant copolymers can potentially contribute to light skin feel—a desirable characteristic for water resistant polymers. On the contrary—the competitive benchmarks (Allianz OPT and Dermacryl AQF) generate primarily a hydrophobic modification of the substrate and are less likely to produce light skin feel.
This application claims benefit under 35 USC 119(e) of U.S. Provisional app. No. 60/922,023, filed on Apr. 5, 2007, which is incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| 60922023 | Apr 2007 | US |
