KÖHLER MANUELA (DE)
JESKE LISA (DE)
| WO2013041515A1 | 2013-03-28 |
| EP2359801A1 | 2011-08-24 | |||
| DE1154901B | 1963-09-26 | |||
| US20160166485A1 | 2016-06-16 | |||
| EP0818450A1 | 1998-01-14 |
"Amphibious superamphiphilic fabrics with self-healing underwater superoleophilicity", MATER. HORIZ., vol. 6, 2019, pages 122
"International Cosmetic Ingredient Dictionary and Handbook", 2010, article "emulsifying agent"
CAS , no. 288254-16-0
| Claims 1 . Method of protection of the human skin from UV radiation, in particular IIV-A and/or UV-B radiation, involving the steps of a) applying a first cosmetic composition A comprising a polymer polymerized from a monomer mixture comprising (i) at least one triglycidylether according to one of the formulas I and II, wherein R1 stands independently for an alkylgroup having 1 to 4 carbon atoms or a hydrogen atom, R2 stands independently for a linear or branched, saturated or nonsaturated hydrocarbon group containing 1 to 18 carbon atoms or a hydrogen atom, and u, v, w, x, y and z stand independently for an integer number in the range from 1 to 100; and (ii) at least one alkylamine comprising 3 to 30 carbon atoms; and b) applying a second cosmetic composition B comprising at least one UV-filter. Method according to claim 1 characterized in that the polymer is polymerized from a monomer mixture comprising (i) 10% to 90% by weight of at least one trig lycidy lether according to one of the formulas I to II, wherein R1, R2, u, v, w, x, y and z are defined as described in claim 1, and (ii) 10% to 90% by weight of at least one alkylamine comprising 3 to 30 carbon atoms. Method according to any of the proceeding claims characterized in that the polymer is polymerized from a monomer mixture comprising (i) 50% to 90% by weight of at least one triglycidylether according to one of the formulas I to II, wherein R1, R2, u, v, w, x, y and z are defined as described in claim 1, and (ii) 10% to 50% by weight of at least one alkylamine comprising 3 to 30 carbon atoms. Method according to any of the proceeding claims characterized in that the polymer is polymerized from a monomer mixture comprising (i) 75% to 88% by weight of at least one triglycidylether according to one of the formulas I to II, wherein R1, R2, u, v, w, x, y and z are defined as described in claim 1, and (ii) 12% to 25% by weight of at least one alkylamine comprising 3 to 30 carbon atoms. Method according to any of the proceeding claims characterized in that the polymer is polymerized from a monomer mixture comprising at least one triglycidylether according to formula I, whereby R1 is a hydrogen atom and the integer values of x, y and z is less than 20, more preferred less than 10, still more preferred less than 6 and most preferred x, y and z are all equal to 1. Method according to any of the proceeding claims characterized in that the polymer is polymerized from a monomer mixture comprising at least one triglycidylether according to formula II, whereby R1 is a hydrogen atom, R2 stands for a methyl group and/or a hydrogen atom, and the integer values of u, v and w is less than 20, more preferred less than 10, still more preferred less than 6 and most preferred u, v and w are all equal to 1. Method according to any of the proceeding claims characterized in that the amine is a primary amine. Method according to any of the proceeding claims characterized in that the amine comprises a linear alkyl chain comprising 10 to 25 carbon atoms, more preferably 14 to 22 and most preferred 18 carbon atoms. Method according to any of the proceeding claims characterized in that the polymer is preferably formed by a) dissolving the triglycidylether in ethanol, b) then adding the amine to the solution, and c) then stirring the obtained mixture to obtain the product. Method according to claim 9 characterized in that the reaction product obtained in step c) is further reacted in a further step d) with a nucleophile in order to open the remaining epoxide groups. Method according to claim 10 characterized in that the nucleophile is selected from the group of water, alcohols, amines, hydrohalic acids, thiols and/or phosphorous acids. Method according to claim 10 characterized in that the nucleophile is selected from the group of water, hydrochloric acid, and alcohols. Method according to any of the proceeding claims characterized in that the cosmetic composition A comprises the polymer according to the invention in a total quantity ranging from 0.5 to 30% by weight, more preferably 1 to 20% by weight and most preferably from 5 to 18% by weight, calculated to the total weight of the composition A. Method according to any of the proceeding claims characterized in that the cosmetic composition A comprises at least one water-soluble UV filter. Method according to any of the proceeding claims characterized in that the composition B contains one or more organic UV filters selected from the group of the compounds 2-phenylbenzimidazole-5-sulphonic acid and/or salts thereof; phenylene- 1 ,4-bis(2-benzimidazyl)-3,3'-5,5'-tetrasulphonic acid salts; 1,4-di(2-oxo-10-sulpho-3- bornylidenemethyl)benzene and salts thereof; 4-(2-oxo-3- bornylidenemethyl)benzenesulphonic acid salts; 2-methyl-5-(2-oxo-3- bornylidenemethyl)sulphonic acid salts; 2,2'-methylenebis(6-(2H-benzotriazol-2-yl)-4- (1 ,1 , 3, 3-tetramethyl butyl) phenol); 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3- [1 ,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]phenol; 3-(4- methylbenzylidene)camphor; 3-benzylidenecamphor; terephthalidenedicamphorsulphonic acid; 2-ethylhexyl 2-cyano-3,3-diphenylacrylate; 2-ethylhexyl 4-(dimethylamino)benzoate; amyl 4-(dimethylamino)benzoate; di(2- ethylhexyl) 4-methoxybenzalmalonate; 2-ethylhexyl 4-methoxycinnamate; isoamyl 4- methoxycinnamate; 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'- methylbenzophenone; 2,2'-dihydroxy-4-methoxybenzophenone; homomenthyl salicylate; 2-ethylhexyl 2-hydroxybenzoate; dimethicodiethylbenzalmalonate; 3-(4- (2,2-bisethoxycarbonylvinyl)phenoxy)propenyl)methoxysiloxane/dimethylsiloxan e copolymer; dioctylbutylamidotriazone; 2,4-bis[5-1 (dimethylpropyl)benzoxazol-2-yl(4- phenyl)imino]-6-(2-ethylhexyl)imino-1 ,3,5-triazine with; tris(2-ethylhexyl) 4,4',4"-(1 ,3,5- triazine-2,4,6-triyltriimino)trisbenzoate (also: 2,4,6-tris[anilino(p-carbo-2'-ethyl-1'- hexyloxy)]-1 ,3,5-triazine; 2,4,6-tribiphenyl-4-yl-1 ,3,5-triazine; and merocyanine. Use of a polymer polymerized from a monomer mixture comprising a) at least one triglycidylether according to one of the formulas I to II, wherein R1, R2, u, v, w, x, y and z are defined as described in claim 1 , and b) at least one alkylamine comprising 3 to 30 carbon atoms; to form a coating on the human skin, which allows the UV light protection to be increased if UV-filters are applied onto the coating. |
The present invention belongs to the cosmetic field and relates to a two component sunscreen composition allowing for an effective protection of the human skin from UV radiation. Furthermore, the invention is directed to a method of protecting the human skin from UV radiation.
A beautiful and attractive appearance is a desire for many people. One typical sign of such an appearance is a healthy and smooth looking skin. Therefore, in order to take care on the skin, it is for many people a daily routine to apply cosmetic products such as body lotions and sunscreen compositions.
For example, compositions containing UV-filters are commonly used to protect the skin from the ultraviolet (UV) radiation of the sunlight. In addition to the acute damage (sunburn), longterm damage such as an increased risk of skin cancer occurs in case of excessive irradiation with light from the UV-B range (wavelength: 280-320 nm). The excessive exposure of UV-B and UV-A radiation (wavelength: 320-400 nm) also leads to a weakening of the elastic and collagen fibers of the connective tissue. This leads to numerous photo-toxic and photo- allergic reactions and results in premature skin ageing.
To protect the skin, a number of light protection filter substances have been developed, which can be used in cosmetic preparations. These UV-A and UV-B filters are grouped in the most developed countries in the form of positive lists such as Annex VI of the Regulation (EC) No 1223/2009 of the European Parliament and of the Council.
However, it is noted that the UV protection of current sunscreen compositions is limited such there is a general need for measures to increase the protection of current sunscreens.
Furthermore, it is often observed that the application of conventional sunscreens comprising UV filters as well as an oil and water phase to the skin may lead to a non-perfect coverage of the skin which then is not fully protected to the UV rays. The reason for the non-perfect coverage of the sunscreen on the skin may be the competitive spreading behavior between the oil and water and the hydrophobic character of the skin. Thus, it remains desirable to improve the full-coverage of the skin with the UV filters contained in the water and/or oil phase.
Another aspect is that it is often observed that after application of the sunscreen to the human skin the sunscreen may be removed with water e.g. by swimming in the sea. Depending on the sunscreen and UV filter the water resistance of the applied sunscreen may vary. However, the water resistance of conventional sunscreen compositions is still limited. Accordingly, there is a general need to provide measures to increase the water resistance on the human skin of sunscreens.
The documents WO 2013041515 A1 , US 20160166485 A1 and EP 0818450 A1 disclose UV filters and the use thereof.
The article “Amphibious superamphiphilic fabrics with self-healing underwater superoleophilicity’, (Mater. Horiz., 2019, 6, 122) discloses compositions comprising a coating solution prepared by mixing glyceryl propoxylate triglycidyl ether with octadecylamine in ethanol. However, the article does not disclose cosmetic compositions at all.
It was now surprisingly found by the applicant that the disadvantages discussed above can be addressed by the present invention.
The present invention is a method of protection of the human skin from UV radiation, in particular IIV-A and/or IIV-B radiation, involving the steps of a) applying a first cosmetic composition A comprising a polymer polymerized from a monomer mixture comprising
(i) at least one triglycidylether according to one of the formulas (I and II), and wherein
R 1 stands independently for an alkylgroup having 1 to 4 carbon atoms or a hydrogen atom,
R 2 stands independently for a linear or branched, saturated or non-saturated hydrocarbon group containing 1 to 18 carbon atoms or a hydrogen atom, and u, v, w, x, y and z stand independently for an integer number in the range from 1 to 100; and
(ii) at least one alkylamine comprising 3 to 30 carbon atoms; and b) applying a second cosmetic composition B comprising at least one UV-filter.
A second aspect of the invention is the use of a polymer polymerized from a monomer mixture comprising
(i) at least one triglycidylether according to one of the formulas I to II, wherein R 1 , R 2 , u, v, w, x, y and z are defined as described above, and
(ii) at least one alkylamine comprising 3 to 30 carbon atoms; to form a coating on the human skin, which allows the UV protection factor or the UV light protection to be increased if UV-filters are applied onto the coating.
In terms of the present invention the term “UV protection factor or the UV light protection to be increased” is understood in a way that fewer UV-A and UV-B radiation reaches the human skin. A third aspect of the invention is a cosmetic composition A comprising at least one polymer polymerized from a monomer mixture comprising
(i) at least one triglycidylether according to one of the formulas I to II, wherein R 1 , R 2 , u, v, w, x, y and z are defined as described above, and
(ii) at least one alkylamine comprising 3 to 30 carbon atoms.
A forth aspect of the invention is a kit comprising the cosmetic composition A and a second cosmetic composition B, wherein the second composition comprises at least one UV filter.
A fifth aspect of the invention is a polymer polymerized from a monomer mixture comprising
(i) at least one triglycidylether according to one of the formulas I to II, wherein R 1 , R 2 , u, v, w, x, y and z are defined as described above, and
(ii) at least one alkylamine comprising 3 to 30 carbon atoms.
It was surprisingly noticed that the invention allows the UV protection factor to be achieved to be significantly increased. Further, a more even coverage of the UV filters is achieved upon application to a skin or a surface. Accordingly, the objectives of the present invention are solved.
All the weight percentages (% by weight) given below relate, unless otherwise stated, to the total weight of the cosmetic composition A.
If ratios of certain components are disclosed in the following description, these ratios refer, unless otherwise stated, to weight ratios of the components.
Unless otherwise stated, all tests and measurements were performed under “normal conditions”. The term "normal conditions" refers to 20°C, 1013 hPa and a relative humidity of 50%. In the following description the terms ..according to the invention”, “preferred according to the invention” and so on are always directed to the use according to the invention, to the method according to the invention and to the cosmetic composition according to the invention.
For the purposes of the present disclosure, the term "free from" means that the proportion of the respective polymer is less than 0.05% by weight. This ensures that entrainments or impurities with these polymers are not included as "free from" according to the invention.
The term “skin” refers solely to the human skin.
Emulsifiers are understood to be all substances which are listed in the International Cosmetic Ingredient Dictionary and Handbook, Thirteenth Edition 2010, (ISBN 1-882621-47-6) under the name "emulsifying agent". Surfactants are understood to be all substances which are listed in the International Cosmetic Ingredient Dictionary and Handbook, Thirteenth Edition 2010, (ISBN 1-882621-47-6) under the name "surfactant".
Without being bound by the theory it is believed that the amine reacts with the epoxide groups of the triglycidylether allowing a structured network to be created. Alternatively, the amine allows for nucleophilic substitution at the carbon atom with the OH group or the Nu group. It should be noted that every amine may react with up to two triglycidylether such that extensive crosslinking occurs, allowing not a clear chemical structure to be defined.
It is preferred according to the invention if the polymer is polymerized from a monomer mixture comprising
(i) 10% to 90% by weight of at least one triglycidylether according to one of the formulas I to II, wherein R 1 , R 2 , u, v, w, x, y and z are defined as described above, and
(ii) 10% to 90% by weight of at least one alkylamine comprising 3 to 30 carbon atoms.
It is further preferred according to the invention if the polymer is polymerized from a monomer mixture comprising
(i) 50% to 90% by weight of at least one triglycidylether according to one of the formulas I to II, wherein R 1 , R 2 , u, v, w, x, y and z are defined as described above, and (ii) 10% to 50% by weight of at least one alkylamine comprising 3 to 30 carbon atoms.
It is more preferred according to the invention if the polymer is polymerized from a monomer mixture comprising
(i) 50% to 90% by weight of at least one triglycidylether according to one of the formulas I to II, wherein R 1 , R 2 , u, v, w, x, y and z are defined as described above, and
(ii) 10% to 50% by weight of at least one alkylamine comprising 3 to 30 carbon atoms.
It is most preferred according to the invention if the polymer is polymerized from a monomer mixture comprising
(i) 75% to 88% by weight of at least one triglycidylether according to one of the formulas I to II, wherein R 1 , R 2 , u, v, w, x, y and z are defined as described above, and
(ii) 12% to 25% by weight of at least one alkylamine comprising 3 to 30 carbon atoms.
For the case that the polymer is polymerized from a monomer mixture comprising at least one triglycidylether according to formula I, it is preferred if R 1 is a hydrogen atom. It is further preferred if the sum of the integer values of x, y and z is less than 20, more preferred less than 10 and most preferred less than 6. It is most preferred if x, y and z are all equal to 1.
For the case that the polymer is polymerized from a monomer mixture comprising at least one triglycidylether according to formula II, it is preferred if R 1 is a hydrogen atom. It is further preferred if R 2 stands for a methyl group and/or a hydrogen atom, whereby it is most preferred if R 2 stands for a methyl group. It is further preferred if the sum of the integer values of u, v and w is less than 20, more preferred less than 10 and most preferred less than 6. It is most preferred if u, v and w are all equal to 1 .
Furthermore, it is preferred if the amine is a primary amine. It is further preferred if the amine comprises a linear alkyl chain comprising 10 to 25 carbon atoms, more preferably 14 to 22 and most preferred 18 carbon atoms. The polymer of the invention is preferably formed by a) dissolving the triglycidylether accoding to the invention in ethanol, b) then adding the amine to the solution, and c) stirring the obtained mixture to obtain the product.
It is preferred if the ratio by weight between the triglycidylether accoding to the invention and ethanol is in the range from 1:1 to 1 :100, more preferably from 1 :2 to 1:50, more preferably from 1 :5 to 1 :20, and most preferred from 1 :9 to 1 :11.
It is further preferred if the mixture is stirred at 50°C for at least 5 minutes. Most preferably for 12 to 20 minutes.
If desired, ethanol may be removed from the reaction product.
In one further aspect of the present invention it is further preferred if the reaction product obtained in step c) is further reacted in a further step d) with another nucleophile in order to ensure that all epoxide groups are opened and no closed epoxide rings remain in the polymeric structure. Preferred nucleophiles may be selected from the group of water, alcohols, amines, hydrohalic acids, thiols and/or phosphorous acids. Most preferred nucleophils are water, hydrochloric acid, and alcohols.
It is particular preferred if the polymers formed according to the invention are characterized in that they have an average molecular weight in the range from 1000 to 1000000 Dalton, more preferably in the range from 3000 to 100000 Dalton and most preferably 4000 to 10000 Dalton.
According to the invention the average molecular weight of the polymers according to the invention is determined by GPC analysis using a reference material, eg. Poly(styrene) standards.
It is further preferred, if the cosmetic composition A, which is according to the invention, comprises the polymer according to the invention in a total quantity ranging from 0.5 to 30% by weight, more preferably 1 to 20% by weight and most preferably from 5 to 18% by weight, calculated to the total weight of the composition A.
Composition A is further preferably characterized in that in comprises ethanol. If ethanol is contained, the total quantity of ethanol is preferably in the range from 15 to 95% by weight, more preferably from 50 to 90% by weight and most preferably from 60 to 80% by weight, calculated to the total weight of the composition A. Moreover, it is further preferred if the composition A comprises water. If water is contained, the total quantity of water is preferably in the range from 5 to 95% by weight, more preferably from 15 to 80% by weight and most preferably from 20 to 70% by weight, calculated to the total weight of the composition A.
Additionally, it is further preferred if the composition A comprises glycerol. If glycerol is contained, the total quantity of glycerol is preferably in the range from 1 to 30% by weight, more preferably from 2 to 20% by weight and most preferably from 2 to 10% by weight, calculated to the total weight of the composition A.
The composition A may further comprise additional ingredients commonly contained in cosmetic compositions.
For example, it is preferred if composition A comprises ethylhexylglycerin, hexandiol, and/or phenoxyethanol.
For the case that ethylhexylglycerin is contained it is preferred if the total quantity of ethylhexylglycerin is in the range from 0.1 to 3% by weight, calculated to the total weight of composition A.
For the case that hexandiol is contained it is preferred if the total quantity of hexandiol is in the range from 0.1 to 3% by weight, calculated to the total weight of composition A.
For the case that phenoxyethanol is contained it is preferred if the total quantity of phenoxyethanol is in the range from 0.1 to 3% by weight, calculated to the total weight of composition A.
Furthermore, it is preferred, if composition A comprises propylene glycol, whereby it is further preferred if the total quantity of propylene glycol is in the range from 1 to 30% by weight, calculated to the total weight of the composition A.
Furthermore, the composition A may comprise panthenol, urea, cera microcristallina, cetyl palmitate, sodium hyaluronate, glycyrrhetinic acid, ascorbic acid, caffeine, menthol, titanium oxide, zinc oxide, iron oxide, talc, perfume and/or emulsifier. In one aspect of the present invention the composition A is characterized in that no UV-filter is contained.
In another aspect of the present invention the composition A comprises at least one water- soluble UV filter. Embodiments of the present invention which are advantageous according to the invention are characterized in that the total amount of water-soluble UV filters in the preparation is from 0.1 to 18% by weight, based on the total weight of the composition A.
It is advantageous according to the invention if sulfonic acid salts are used as water-soluble UV filters. Preferred examples are 1 , 4-di (2-oxo-10-sulfo-3-bomylidenemethyl) benzene and its salts; 4- (2-oxo-3-bornylidenemethyl) benzenesulfonic acid; 2-methyl-5- (2-oxo-3- bornylidenemethyl) sulfonic acid salts; Terephthalidendicamphersulfonsaure; Compounds 2- phenylbenzimidazole-5-sulfonic acid and I or salts thereof and I or phenylene-1,4-bis (2- benzimidazyl) -3,3'-5,5'-tetrasulfonic acid salts.
The counterion of the salts is usually sodium, potassium or ammonium ions, the sodium salts being preferred according to the invention.
According to the invention, the water-soluble UV filters are preferably selected from the group of the compounds 2-phenylbenzimidazole-5-sulfonic acid and I or salts thereof and I or phenylene-1 ,4-bis (2-benzimidazyl) -3,3'-5 , 5'-tetrasulfonsauresalze. The use of 2- phenylbenzimidazole-5-sulfonic acid and I or salts thereof is particularly preferred according to the invention.
The preferred use concentration for 2-phenylbenzimidazole-5-sulfonic acid and I or salts thereof is from 0.1 to 12% by weight, based on the total weight of the composition A.
Furthermore, it is still possible and preferred if composition A comprises at least one additional UV-filter, which may preferably be selected from the group consisting of 2,2'- methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1 , 1 , 3,3-tetramethylbutyl) phenol); 2- (2H- Benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1 ,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl] propyl] phenol ; 3- (4-methylbenzylidene) camphor; 3-benzylidenecamphor; ethylhexyl salicylate; 2-ethylhexyl-2-cyano-3,3-diphenylacrylate; 4- (dimethylamino) benzoic acid (2-ethylhexyl) ester; 4- (dimethylamino) benzoic acid amyl ester; 4- Methoxybenzalmalon-sauredi (2-ethylhexyl) ester; 4-methoxycinnamate (2-ethylhexyl) ester; Isoamyl 4-methoxycinnamate; 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'- methylbenzophenone; 2,2'-dihydroxy-4-methoxybenzophenone; homomenthyl; 2-ethylhexyl 2-hydroxybenzoate; dimethicodiethylbenzalmalonate; 3- (4- (2,2-ethoxycarbonylvinyl) phenoxy) propenyl) methoxysiloxane I dimethylsiloxane copolymer; 4- (tert-butyl) -4'- methoxydibenzoylmethane; Hexyl 2- (4'-diethylamino-2'-hydroxybenzoyl) benzoate; dioctylbutylamidotriazone (INCI: diethylhexyl-butamidotriazone); 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) imino] -6- (2-ethylhexyl) -imino-1,3,5-triazine having the (CAS No 288254-16-0); 2,4-Bis - {[4- (2-ethylhexyl oxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1, 3,5-triazine (INCI: bis-ethylhexyloxyphenol methoxyphenyl triazine) ; 4,4 4 "- (1,3,5-triazine- 2 ,4,6-triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester) (also: 2 ,4,6-tris [anilino] (p-carbo- 2'-ethyl-1'-hexyloxy)] - 1 , 3,5-triazine (INCI: ethylhexyl triazone); 2, 4, 6-tribiphenyl-4-yl-1, 3,5- triazine merocyanines; titanium dioxide and zinc oxide.
Although, for the case that the composition A contains at least one UV filter, it is already possible to enhanced the UV protection by applying composition A, it was surprisingly noticed that the optimum UV protection may be achieved if composition A is applied to the human skin in a first step and in a second step a conventional cosmetic sunscreen, herein named as composition B, is applied.
It is an advantage, if the composition B is an emulsion. Emulsions, here in particular W/O, O/W or W/O/W emulsions, are often used as cosmetic or medical preparations. Emulsions are generally understood as meaning heterogeneous systems which comprise two liquids which are immiscible or only miscible with one another to a limited extent, which liquids are normally referred to as phases. In an emulsion, one of the two liquids is dispersed in the other liquid in the form of very fine droplets.
If the two liquids are water and oil and if oil droplets are finely distributed in water, then this is an oil in water emulsion (O/W emulsion, e.g., milk). The basic character of an O/W emulsion is determined by the water. In the case of a water-in-oil emulsion (W/O emulsion, e.g., butter), the principle is reversed, the basic character here being determined by the oil.
Alternatively, composition B is a single phase alcohol (ethanol) containing formulation. High quantities of ethanol are used in this kind of formulations in order to provide a clear solution of all ingredients. The amount is ethanol is chosen to be sufficient to form a stable and transparent single phase formulation.
In accordance with the present invention the composition B is preferably characterized in that it is an O/W emulsion, a W/O emulsion or a single phase alcoholic solution.
Composition B comprises at least one UV filter.
Composition B according to the invention is advantageously characterized in that the composition comprises one or more organic IIV-A filters selected from the group of the compounds 4- (tert-butyl) -4'-methoxydibenzoylmethane and 2- (4'-diethylamino-2 ' - hydroxybenzoyl) -benzoic acid hexyl ester.
It is inventively preferred if the organic IIV-A filter compound 4- (tert-butyl) -4'- methoxydibenzoylmethane is used in composition B.
The advantageous total use according to the invention for the organic IIV-A filter, in particular 4- (tert-butyl) -4'-methoxydibenzoylmethane and/or 2- (4'-diethylamino-2'- hydroxybenzoyl) - benzoic acid hexyl ester, is/are from 1 to 5 weight -%, preferably 1.5 to 4.5% by weight, particularly preferably 2 to 4% by weight, based on the total weight of the composition B.
Embodiments of the present invention which are advantageous according to the invention are characterized in that the composition B contains one or more organic UV filters selected from the group of the compounds 2-phenylbenzimidazole-5-sulphonic acid and/or salts thereof; phenylene-1,4-bis(2-benzimidazyl)-3,3'-5,5'-tetrasulphonic acid salts; 1,4-di(2-oxo- 10-sulpho-3-bornylidenemethyl)benzene and salts thereof; 4-(2-oxo-3- bornylidenemethyl)benzenesulphonic acid salts; 2-methyl-5-(2-oxo-3- bornylidenemethyl)sulphonic acid salts; 2,2'-methylenebis(6-(2H-benzotriazol-2-yl)-4- (1,1 , 3, 3-tetramethyl butyl) phenol); 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1 ,3,3,3- tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]phenol ; 3-(4-methylbenzylidene)camphor; 3-benzylidenecamphor; terephthalidenedicamphorsulphonic acid; 2-ethylhexyl 2-cyano-3,3- diphenylacrylate; 2-ethylhexyl 4-(dimethylamino)benzoate; amyl 4-(dimethylamino)benzoate; di(2-ethylhexyl) 4-methoxybenzalmalonate; 2-ethylhexyl 4-methoxycinnamate; isoamyl 4- methoxycinnamate; 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'- methylbenzophenone; 2,2'-dihydroxy-4-methoxybenzophenone; homomenthyl salicylate; 2- ethylhexyl 2- hydroxy benzoate; dimethicodiethylbenzalmalonate; 3-(4-(2,2- bisethoxycarbonylvinyl)phenoxy)propenyl)methoxysiloxane/dime thylsiloxan e copolymer; dioctylbutylamidotriazone (INCI: Diethylhexyl Butamido Triazone); 2,4-bis[5-1 (dimethylpropyl)benzoxazol-2-yl(4-phenyl)imino]-6-(2-ethylhe xyl)imino-1,3,5-triazine with (CAS No. 288254-16-0); tris(2-ethylhexyl) 4,4',4"-(1,3,5-triazine-2,4,6- triyltriimino)trisbenzoate (also: 2,4,6-tris[anilino(p-carbo-2'-ethyl-1'-hexyloxy)]-1 ,3,5-triazine (INCI: Ethylhexyl Triazone); 2,4,6-tribiphenyl-4-yl-1 ,3,5-triazine; and merocyanine.
It is inventively preferred if the composition B contains 2-phenylbenzimidazole-5-sulfonic acid and I or salts thereof. For the case that the composition B contains 2-phenylbenzimidazole-5- sulfonic acid and I or salts the total quantity of those substances is preferably in the range from 0.5 to 5% by weight, more preferably 0.6 to 4.5% by weight and most preferably 0.8 to 4% by weight, based on the total weight of the composition B.
It is further advantageous if the composition B comprises 2-ethylhexyl-2-cyano-3,3- diphenylacrylate (octocrylene), whereby it is further preferred if the total quantity of this substance is in the range from 1 to 12% by weight, preferably 1.5 to 6% by weight, particularly preferably 2 to 3.5% by weight based on the total weight of composition B.
It is further preferred if the composition B comprises Homosalate in a total quantity from 1 to 12% by weight, preferably 1.5 to 6% by weight, particularly preferably 2 to 3.5% by weight based on the total weight of composition B.
It is further preferred if the composition B comprises Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine in a total quantity from 0.5 to 12% by weight, preferably 0.6 to 6% by weight, particularly preferably 0.7 to 2.5% by weight based on the total weight of composition B.
It is further preferred if the composition B comprises Ethylhexyl Salicylate in a total quantity from 0.5 to 12% by weight, preferably 2 to 9% by weight, particularly preferably 3 to 7.5% by weight based on the total weight of composition B.
It is further preferred if the composition B comprises Silica Dimethyl Silylate in a total quantity from 0.1 to 2% by weight, preferably 0.4 to 1.5% by weight, particularly preferably 0.6 to 1.3% by weight based on the total weight of composition B.
Moreover, the composition B of the present invention is preferably characterized in that at least one inorganic UV-filter is contained, especially zinc oxide and/or titanium dioxide. It is especially preferred, if the total quantity of zinc oxide and/or titanium dioxide in the composition B of the present invention is in the range from 0.1 to 5% by weight, calculated to the total weight of the composition B.
For the case that composition B is an emulsion, it is preferred if the total quantity of the oil phase in the composition B is in the range from 0.9 to 25% by weight, more preferably 1 to 20% by weight, more preferably 1.1 to 19% by weight and most preferably from 1.2 to 18% by weight, calculated to the total weight of the composition B.
For the case that composition B is an emulsion, it is preferred if the ratio of the total quantity of the emulsifier to the total quantity of the oil phase is in the range from 1:1 to 1 :7, more preferably 1:1.1 to 1 :4, more preferably 1 :1.2 to 1:3 and most preferably 1:1.4 to 1:2.8. It is noted that by definition emulsifier and surfactants are not calculated to the total quantity of the oil phase.
According to the invention, it is further preferred if the composition B contains phenoxyethanol. In the case the composition B contains phenoxyethanol the total quantity of phenoxyethanol is preferably in the range from 0.1 % by weight to 2% by weight and more preferably from 0.4% by weight to 1% by weight, calculated to the total weight of the composition B.
Moreover, preferred composition B of the present invention are therein characterized that they contain ethylhexylglycerin, whereby it is further preferred if the total quantity of ethylhexylglycerin is in the range from 0.05% to 0.5% by weight, calculated to the total weight of the composition B.
Furthermore, it is preferred if the composition B does not contain an alkylparabene such as propyl parabene and/or butyl parabene.
According to the invention it is further preferred if the composition B comprises at least one polymeric rheology modifier. The term “polymeric rheology modifier” is understood as a polymer which increases the viscosity of the composition B if added to it. Preferred are the polymeric rheology modifier selected from the group carbomer, xanthan gum and hydroxyethylcellulose. Most preferred are carbomer and/or xanthan gum. The total quantity of the polymeric rheology modifier is preferably in the range from 0.01 to 0.8% by weight, more preferably 0.05 to 0.5% by weight and most preferably 0.15 to 0.4% by weight, calculated to the total weight of the composition B.
In addition, preferred compositions B are characterized in that they contain ethanol. In the case that ethanol is contained in the emulsions according to the invention, it if further preferred if the total quantity of ethanol is in the range from 2% by weight to 6% by weight, calculated to the total weight of the composition B.
Further, it is preferred if the composition B comprises glycerol, whereby it is further preferred if the total quantity of glycerol is at least 2% by weight, more preferably at least 2.5% by weight, more preferably at least 3% by weight, more preferably at least 5% by weight, more preferably at least 6% by weight, more preferably at least 7% by weight, more preferably at least 8% by weight, more preferably at least 9% by weight, more preferably at least 10% by weight, more preferably at least 11% by weight, more preferably at least 12% by weight; and whereby the total quantity of glycerol should not exceed 14% by weight, calculated to the total weight of the composition B.
Preferred embodiments of the invention are further characterized in that the composition B comprises at least cetyl alcohol, stearyl alcohol and/or cetearyl alcohol. In the case cetyl alcohol, stearyl alcohol and/or cetearyl alcohol are contained, the total quantity of those substance is preferably in the range from 0.5 to 8% by weight, more preferably from 1 to 6% by weight, calculated to the total weight of the composition B.
Additionally, it is preferred according to the invention if the total quantity of water in composition B is in the range from 45% to 95% by weight, more preferably from 48% to 70% by weight and most preferably from 52% to 65% by weight, calculated to the total weight of the composition B.
According to the invention the composition B may preferably contain at least one compound selected from the group of limonene, linalool, citral, alpha-isomethylionone and geraniol.
Embodiments of the present invention which are advantageous according to the invention are characterized in that the composition B contains as further ingredients one or more compounds selected from the group of the compounds alpha-lipoic acid, folic acid, phytoene, D-biotin, coenzyme Q10, alpha-glucosylrutin, carnitine, carnosine, natural and I or synthetic isoflavonoids, flavonoids, creatine, creatinine, taurine, p-alanine, tocopheryl acetate, dihydroxyacetone, glycyrrhetinic acid, 8-hexadecene-1 , 16-dicarboxylic acid, glycerylglycose, (2-hydroxyethyl) urea and I or licochalcone A.
According to the invention it is further preferred if the composition B has a pH value in the range from 4.5 to 8.
Examples:
The following examples should illustrate the compositions of this invention, without intending to limit the invention to these examples. The numerical values in the examples are percentages by weight, based on the total weight of the compositions.
The polymer of the invention was synthesized in the following manner:
5 g of Glycerol propoxylate triglycidyl ether (GPTE) (formula II, wherein R 1 is an hydrogen, R 2 is a methyl group and u, v and w are each equal to 1 , was added to 50 ml ethanol and then stirred for 30 min. 1 g of Octadecylamine (ODA) was added to the as-prepared solution. The solution was then further stirred for 15 min at 50 °C.
The obtained polymer had an average molecular weight of 5220 Da, determined using GPC analysis with Polystyrene as calibration standard. The resulting molecule was further analyzed and the structure was confirmed, as also described in the article “Amphibious superamphiphilic fabrics with self-healing underwater superoleophilicity’ , (Mater. Horiz., 2019, 6, 122).
In the reaction process a nucleophilic substitution occurs, wherein amine group of the alkylamine attacks the electrophilic C of the C-0 bond of the epoxide group causing it to break, resulting in ring opening. This reaction may occur multiple times resulting in a continuous polymerization network.
For the following experiments, the output of the procedure described above was used under the designation polymer blend.
The following composition A was used in the experiments:
The following sunscreen composition B were used in the experiments:
The experiments determining the absorbance of the protective method were carried out in the following manner: The composition A was applied by drip method over a PMMA (Polymethylmethacrylat) plate, all the excess removed and then let it dry between 5 to 30 minutes. Once dried 2 mg/cm 2 of the selected composition B was applied. When PMMA plates where used normal UV abs. analysis have been done. The absorption corresponds directly to the obtained light protection in the UV-A and IIV-B range. The higher the absorption, the higher the protection of the deposited compositions.
The following results were obtained for the UV absorption measurements on the PMMA plates:
Further synthesis were performed:
5 g of Glycerol propoxylate triglycidyl ether (GPTE) according to formula I, wherein R 1 is a hydrogen atom and x,y and z are each equal to 1 , were added to 50 ml ethanol and then stirred for 30 min. 1 g of Octadecylamine (ODA) was added to the as-prepared solution. The solution was then further stirred for 15 min at 50 °C to obtain the final product.
The reaction products obtained in both reactions were one time further reacted in order to open the remaining epoxide groups. In order to do that Water was added to the reaction solution then pH of the reaction mixture was modified step-wise by addition of 1M HCI to reach pH 2. Via 1 H-NMR in CDCI3 at 300 MHz the change in contained number of epoxide groups was monitored. Before adding HCI the ratio of epoxide group (2.7 ppm) and the partial alkane group (4.1 -3.2 ppm) was 1 :44. After addition to reach pH 2 the ratio was 1 : 188.
All blends obtained were individually mixed with ethanol in a ratio of 12:88. Further all obtained mixtures were individually used in combination with the compositions B as disclosed above.
Furthermore, all blends of the prepared polymers and ethanol, were mixed with 2- phenylbenzimidazole-5-sulfonic acid, whereby the total quantity of 2-phenylbenzimidazole-5- sulfonic acid was 5% by weight, calculated to the total weight of all contained ingredients.