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(en)An ultraviolet-absorbing composite powder comprising a plurality of composite powder particles, wherein the composite powder particle consists of an inorganic or organic core particle having an average particle diameter of 0.5-100 μm, and a compound of formula (1):
which is adsorbed to the surface of the core particle is provided. The composite powder of the invention exhibits an excellent UV ray protecting property as well as smooth and comfortable texture, and is useful for manufacturing cosmetic products.
which is adsorbed to the surface of the core particle is provided. The composite powder of the invention exhibits an excellent UV ray protecting property as well as smooth and comfortable texture, and is useful for manufacturing cosmetic products.
1.ApplicationNumber: US-59349006-A
1.PublishNumber: US-2007104662-A1
2.Date Publish: 20070510
3.Inventor: SATONAKA KENYA
YOSHIOKA TAKATSUGU
MOTOKI TAKASHI
YAMAGATA TOMOHIRO
4.Inventor Harmonized: SATONAKA KENYA(JP)
YOSHIOKA TAKATSUGU(JP)
MOTOKI TAKASHI(JP)
YAMAGATA TOMOHIRO(JP)
5.Country: US
6.Claims:
(en)An ultraviolet-absorbing composite powder comprising a plurality of composite powder particles, wherein the composite powder particle consists of an inorganic or organic core particle having an average particle diameter of 0.5-100 μm, and a compound of formula (1):
which is adsorbed to the surface of the core particle is provided. The composite powder of the invention exhibits an excellent UV ray protecting property as well as smooth and comfortable texture, and is useful for manufacturing cosmetic products.
7.Description:
(en)FIELD OF THE INVENTION
The instant application relates to a composite powder having core particle and benzotriazol UV absorber coating which is coated on the surface of the core particle, and cosmetic composition comprising the same.
ART RELATED
Ultraviolet light is divided into UV-C (200-280 nm wavelength) which is absorbed by the ozone layer, UV-B (280-320 nm) which causes sunburn, and UV-A (320-400 nm) which promotes suntan after exposure. According to recent studies, UV-A and UV-B cause harmful effects including not only sunburn and suntan but also pigment deposition, dry skin, skin roughness and skin aging. In addition, depletion of the ozone layer results in increased UV radiation reaching the Earth's surface, which in turn can lead to a greater chance of overexposure to UV radiation and the related effects to the skin. There are increasing desire for cosmetics with UV-protecting property.
Organic ultraviolet absorbers, which have been used for protecting against UV radiation, have various problems in using the same for manufacturing cosmetic products, for examples, (1) being less soluble to oils, especially silicone oils, which are conventionally used in cosmetics; (2) usually cause sticky feelings to the skin; (3) being less stable against light; (4) discoloration and/or unpleasant odor occurs upon time. On the other hand, conventionally used inorganic UV absorbers have problems such as (1) cause squeaky feeling, (2) result in white appearance when applied to the skin and (3) act as light catalyst. Due to those problems, the amount of the inorganic UV absorbers being added to cosmetic product has been limited. In addition, many conventional cosmetic products with UV protecting property comprises sole UV absorber and there are no products having UV protecting properties against wide range of UV rays including UV-A and UV-B.
A new UV absorber which is excellent in light stability and can protect against wide range UV rays, 2,2′-methylenebis[6-(2H-benzotriazolyl-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] has been developed (see U.S. Pat. No. 5,225,951, the contents of which is herein incorporated by reference). In this specification, the compound is abbreviated as “MBBT”. This organic UV absorber is insoluble to water as well as to oils used in cosmetic products and provides the UV protecting effect by absorbing, scattering and reflecting UV rays. The UV protecting effect based on the UV ray scattering and reflecting may vary depending on the particle size of the compound and particle size range of 150-200 nm is optimal. In addition, combined use of MBBT with another UV absorber will synergistically increase the UV protecting property of the compound.
U.S. Pat. No. 6,235,271, the contents of which is herein incorporated by reference, discloses a product comprising micronized MBBT of the optimal particle size dispersed in water. Said aqueous dispersion of micronized MBBT is used conveniently for manufacturing cosmetic product and has been available on market (TINOSORB® M, Ciba Specialty Chemicals, Basel, Switzerland). However, said product cannot be used for manufacturing non-aqueous formulation. In addition, MBBT particles will aggregate when a salt is added to the dispersion and the UV protecting action of the aggregated MBBT will decrease significantly. For manufacturing water in oil type emulsion, salts such as sodium sulfate and sodium chloride are added to stabilize the emulsion and therefore, it was difficult to manufacture water in oil emulsion with the aqueous dispersion of MBBT. In addition, a large amount of MBBT in a cosmetic composition may cause unpleasant texture of the product.
Japanese Patent Application Laid Open No. 2004-168913 proposes incorporating MBBT particles in a polymer matrix which is soluble in organic solvents. However, the MBBT particles tend to aggregate upon incorporating the same into the polymer matrix and therefore, hardly maintain the optimal particle size. Accordingly, the resulting product could not provide enough UV-protecting effect.
SUMMARY OF THE INVENTION
An object of the application is to provide a transparent composite powder which has excellent ultraviolet-absorbing ability and is comfortable to wear. A further object of the application is to provide a cosmetic composition having a high ultraviolet-protecting property comprising said composite powder.
The instant application provides a composite powder comprising a plurality of composite powder particles, wherein the composite powder particle consists of an inorganic or organic core particle having an average particle diameter of 0.5-100 μm, and a compound of formula (1):
which is coated on the surface of the core particle. The benzotriazol type ultraviolet-absorber of formula (1) is insoluble in water or oils used for manufacturing cosmetic compositions.
Further, the instant application provides a cosmetic composition comprising the above described composite powder. Preferably, the cosmetic composition further comprises a methoxy cinnamate derivative such as octyl methoxy cinnamate and isoamyl methoxy cinnamate or butyl methoxydibenzoylmethane (BMDBM). By the combined use of the composite powder of the invention and a methoxy cinnamate derivative or BMDBM, the photostability of the methoxy cinnamate derivative or BMDBM can be enhanced and the ultraviolet protecting property of the cosmetic composition will be synergistically increased.
Further more, the instant application provides a method for manufacturing the composite powder of the invention, which comprises the step of mixing the core particles and the compound of formula (1) in an aqueous solvent under the presence of an aqueous soluble salt of a metal selected from the group consisting of Al, Mg, Ca, Zn, Zr and Ti whereby the compound of formula (1) adsorbs to the surface of the core particles.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 depicts the graph showing the result of test example 1.
FIG. 2 is an electron micrograph of the composite powder obtained in example 1.
FIG. 3 is an electron micrograph of the composite powder obtained in Example 5.
BEST MODE FOR CARRYING OUT THE INVENTION
The compound of formula (1), a benzotriazole type UV absorber, is preferably in the form of fine particles having an average particle diameter of equal to or less than 200 nm, more preferably, 150-200 nm. Higher UV protecting property of the resulting composite powder can be achieved by employing the particles within said size range. The compound of formula (1) is available on market and TINOSORB® M (Ciba Specialty Chemicals, Basel, Switzerland) can preferably used in this invention. TINOSORB® M is an aqueous dispersion containing 50% of powdery compound of formula (1) having an average particle diameter of 200 nm or less.
The inorganic or organic core particle having an average particle diameter of 0.5-100 μm may be any material used for manufacturing cosmetic products. For example, inorganic particles such as talc, kaolin, sericite, white mica, bronze mica, black mica, synthetic mica, red mica, lithia mica, vermiculite, magnesium carbonate, calcium carbonate, diatomite, magnesium silicate, calcium silicate, aluminum silicate, barium silicate, barium sulfate, strontium silicate, metal tungstate, silica, hydroxyapatite, zeolite, boron nitride and ceramics powder, organic particles such as nylon powder, silicone powder, polyethylene powder, polystyrene powder, benzoguanamine powder, polyethylene tetrafluoride, distyrene benzene polymer powder, epoxy powder, acrylic powder, microcrystalline cellulose and urethane powder, as well as white pigments such as titanium oxide, micro titanium dioxide, zinc oxide and micro zinc oxide. Among them, talc, mica, sericite, kaolin and barium sulfate are preferably used. Lamellar particles are especially useful since the resulting composite particles will have uneven surface which provide less supecular reflection and cause less glossy-finish. When spherical particles such as silica or cellulose are used as core particles, the surface of the resulting composite particle becomes uneven due to the treatment with the compound of formula (1) and therefore, the composite powder having a higher diffuse reflection property can be obtained and the cosmetic composition comprising said composite powder can provide an excellent power to minimize the appearance of skin pores.
The average particle diameter of the core particles is preferably 0.5-100 μm, more preferably, 1-50 μm. When the average particle size is less than 0.5 μm, the composite powder with the good properties cannot be obtained using the benzotriazole UV-absorber having an average particle size of 200 nm or less. In contrast, when the particle diameter of the core particles is 100 μm or more, the texture of the resulting composite powder becomes unpleasant.
The composite powder of the invention may be manufactured by mixing the core particles and the compound of formula (1) in an aqueous solvent under the presence of an aqueous soluble salt of a metal selected from the group consisting of Al, Mg, Ca, Zn, Zr and Ti whereby coating the core particle by the compound of formula (1). According to the method of the invention, the particles of the compound of formula (1) are adsorbed to the surface of the core particles in an oriented manner. Examples of the aqueous soluble salt of a metal selected from the group consisting of Al, Mg, Ca, Zn, Zr and Ti used in the instant method may include aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum calcium sulfate, magnesium chloride, magnesium sulfate, magnesium nitrate, calcium sulfate, calcium chloride, calcium nitrate, calcium acetate, zinc chloride, zinc nitrate, zinc sulfate, zinc acetate, zirconium sulfate, zirconium chloride, titanium oxysulfate and titanium tetrachloride. Among the above, aluminum sulfate is especially useful in view of its availability. The metal salts may be used as aqueous solutions thereof.
Upon manufacturing the composite powder of the present invention, the amount of the benzotriazole type UV-absorber of formula (1) may be 1 wt % or more, and 35 wt % or less, especially, 3-30 wt % based on the total amount of the core particles and the UV absorber. By adjusting the amount of the UV-absorber, the resulting composite powder can exhibit good UV protecting effect as well as good and comfortable texture.
According to the method for manufacturing the composite powder of the invention, the amount of the salt of a metal selected from the group consisting of Al, Mg, Ca, Zn, Zr and Ti per one part by weight of the compound of formula (1) may preferably be ¼ part by weight or more so that the particles of the benzotriazole type UV-absorber are adsorbed well to the surface of the core particles, and 2 parts by weight or less in view of the comfortable texture of the resulting composite powder, and especially, ½-1 part by weight.
The composite powder of the invention consists of plurality of composite powder particles that comprises core particles and compound of formula (1) adsorbed thereto in an oriented manner. The details of the surface treatment is not specifically limited and may be carried out based on known procedures. For example, the core particles are dispersed in water and 1-35 wt % of the compound of formula (1), based on the total amount of the core particles and the compound of formula (1), is added to the dispersion and stirred vigorously. The oriented adsorption of a part of the benzotriazole compound to the surface of the core particles occurs during this stage. Then, an aqueous soluble salt of a metal selected from the group consisting of Al, Mg, Ca, Zn, Zr and Ti in an amount of ¼-2 parts by weight per one part by weight of the compound of formula (1) in the form of aqueous solution is added to the mixture. By adding the aqueous solution of the salt, the oriented adsorption of the particles of the compound of formula (1) to the surface of the core particles is completed. Thus obtained mixture is then dehydrated and washed by centrifugation or the like, and dried at 80-120° C. to give the desired composite powder having UV ray protecting property.
Thus obtained composite powder of the invention has the structure wherein particles of the insoluble benzotriazole UV absorber of formula (1) are adsorbed uniformly to the surface of the core particle and the UV absorber particles are not aggregated each other. Due to the structure, the composite particle behaves as if it is primary particle consisting of single particle. Accordingly, the composite powder of the invention comprising plurality of the composite particles is highly transparent, has smooth and comfortable texture, and provides an excellent UV ray protecting property. The composite powder of the invention is preferably used for manufacturing cosmetic products.
The composite powder of the invention may be used without further processing or the surface of the composite particle may include treated with a hydrophobic agent to give hydrophobic powder. Examples of hydrophobic agents for the hydrophobic treatment may be silicone agent, fatty acid, fatty acid soap and fatty acid ester. Examples of silicone agents may include silicone oils such as methylhydrogenpoly siloxane, dimethylpoly siloxane and methylphenylpoly siloxane, alkyl silanes such as methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane and octyltrimethoxysilane, fluoroalkyl silanes such as trifluoromethylethyltrimethoxysilane and heptadecafluorodecyl trimethoxysilane. Examples of fatty acids may include palmitic acid, isostearic acid, stearic acid, lauric acid, myristic acid, behenic acid, oleic acid, rosin acid and 1,2-hydroxystearic acid. Examples of fatty acid soaps may include aluminum stearate, calcium stearate and aluminum 1,2-hydroxystearate. Examples of fatty acid esters may include dextrin fatty acid ester, cholesterol fatty acid ester, sucrose fatty acid ester and starch fatty acid ester. The hydrophobic treatment of the composite powder of the invention may be carried out with one or more of the hydrophobic agents as above and according to a conventionally known method.
The instant invention further provide a cosmetic composition comprising the composite powder of the invention. The cosmetic composition of the present invention may comprise further ingredients which are added to conventional cosmetic products, if desired. Examples of the ingredients other than the composite powder of the invention may include solid/half solid oil such as vaseline, lanoline, ceresin, microcrystalline wax, carnauba wax, candelilla wax, higher fatty acid and higher alcohol, fluid oil such as squalan, fluid paraffin, ester oil, diglyceride, triglyceride, silicone oil, olive oil, avocado oil and mink oil, fluoride oils such as perfluoro polyether, perfluorodecalin and perfluorooctane, water- and oil-soluble polymer, surface active agent, inorganic and organic pigments, silicone, metal soap, lecithin, amino acid, collagen, polymer, inorganic or organic pigment whose surface is treated by fluoride compound, colorant such as tar color and natural color, ethanol, antiseptic agent, antioxidant, dye, thickener, pH adjustor, flavoring agent, UV absorber, moisturizing agent, blood circulation improver, cool feeling agent, bactericide, skin activating agent and water. Those ingredients may be added to the cosmetic composition of the invention as long as they deteriorate the object of the invention.
The cosmetic composition of the present invention may preferably comprise an additional UV absorbing agent selected from a methoxy cinnamate derivative such as octyl methoxy cinnamate or isoamyl methoxy cinnamate and butyl methoxydibenzoylmethane (BMDBM). By the combined use of the composite powder and a methoxy cinnamate derivative or BMDBM, a synergistic UV-protecting property can be provided to the resulting composition. Preferably, the additional UV absorbing agent is a methoxy cinnamate derivative, especially, octyl methoxy cinnamate.
The octyl methoxy cinnamate used in the instant invention is a transparent pale yellow liquid with weak characteristic odor and is a UV-B absorber widely used for manufacturing cosmetic products. The compound is commercially available, for example PARSOL® MCX (DSM Nutritional Products), Uvinul® MC-80 (BASF), NOMUCORT® TAB (Nisshin Oillio) and Escarole® (ISP). Isoamyl methoxy cinnamate is also available on market as Neo Heliopan® E1000 (H&R).
The cosmetic composition of the invention may further comprise one or more additional UV filter substances and adjuvants shown in the table below:
Suitable UV filter substances and adjuvants which can be additionally used with the UV Ray absorbing composite powder according to the present invention No. Chemical Name CAS No. 1 (+/−)-1,7,7-trimethyl-3-[(4- 36861-47-9 methyiphenyl)methylene]bicyclo- [2.2.1]heptan-2-one; p-methyl benzylidene camphor 2 1,7,7-trimethyl-3- 15087-24-8 (phenylmethylene)bicyclo[2.2.1]heptan-2- one; benzylidene camphor 3 (2-Hydroxy-4-methoxyphenyl)(4- 1641-17-4 methylphenyl)methanone 4 2,4-dihydroxybenzophenone 131-56-6 5 2,2′,4,4′-tetrahydroxybenzophenone 131-55-5 6 2-Hydroxy-4-methoxy benzophenone; 131-57-7 7 2-Hydroxy-4-methoxy benzophenone-5-sulfonic 4065-45-6 acid 8 2,2′-dihydroxy-4,4′-dimethoxybenzophenone 131-54-4 9 2,2′-Dihydroxy-4-methoxybenzophenone 131-53-3 10 Alpha-(2-oxoborn-3-ylidene)toluene-4- 56039-58-8 sulphonic acid and its salts (Mexoryl SL) 11 1-[4-(1,1-dimethylethyl)phenyl]-3-(4- 70356-09-1 methoxyphenyl)propane-1,3-dione (Avobenzone) 12 Methyl N,N,N-trimethyl-4-[(4,7,7-trimethyl- 52793-97-2 3-oxobicyclo[2,2,1]hept-2- ylidene)methyl]anilinium sulphate (Mexoryl SO) 22 3,3,5-Trimethyl cyclohexyl-2-hydroxy 118-56-9 benzoate; homosalate 23 Isopentyl p-methoxycinnamate; isoamyl 71617-10-2 methoxy cinnamate 27 Menthyl-o-aminobenzoate 134-09-8 28 Menthyl salicylate 89-46-3 29 2-Ethylhexyl 2-cyano,3,3-diphenylacrylate; 6197-30-4 octocrylene 30 2-ethylhexyl 4-(dimethylamino)benzoate 21245-02-3 31 2-ethylhexyl 4-methoxycinnamate; octyl 5466-77-3 methoxy cinnamate 32 2-ethylhexyl salicylate 118-60-5 33 Benzoic acid,4,4′,4′′-(1,3,5-triazine- 88122-99-0 2,4,6-triyltriimino)tris-, tris(2- ethylhexyl)ester; 2,4,6-Trianilino-(p- carbo-2′-ethylhexyl-1′-oxl)-1,3,5-triazine (Octyl Triazone) 34 4-aminobenzoic acid 150-13-0 35 Benzoic acid, 4-amino-, ethyl ester, 113010-52-9 polymer with oxirane 38 2-phenyl-1H-benzimidazole-5-sulphonic 27503-81-7 acid; phenylbenzimidazolsulfonic acid 39 2-Propenamide, N-[[4-((4,7,7-trimethyl-3-oxobicyclo[2.2.]hept- 147897-12-9 2-ylidene)methyl]phenyl]methyl)-, homopolymer 40 Triethanolamine salicylate 2174-16-5 41 3,3′-(1,4-phenylenedimethylene)bis[7,7- 90457-82-2 dimethyl-2-oxo-bicyclo[2.2.1]heptane-1 methanesulfonic acid] (Cibafast H) 42 Titanium dioxide 13463-67-7 44 Zinc oxide 1314-13-2 45 2,2′-Methylene-bis-[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3- 103597-45-1 tetramethylbutyl)-phenol](Tinosorb M) 46 2,4-bis{(4-(2-ethylhexyloxy)-2-hydroxy]- 187393-00-6 phenyl)-6-(4-methoxyphenyl)-(1,3,5)- triazine (Tinosorb S) 47 1H-Benzimidazole-4,6-disulfonic acid, 2,2′- 180898-37-7 (1,4-phenylene)bis-, disodium salt 48 Benzoic acid, 4,4′-[[6-[[4-[[(1,1-dimethylethyl)amino]carbonyl]- 154702-15-5 phenyl]amino]1,3,5-triazine-2,4-diyl]diimino]bis-, bis(2-ethylhe- xyl)ester; diethylhexyl butamido triazone (Uvasorb HEB) 49 Phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3- 155633-54-8 [1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]-; drometrizole trisiloxane (Mexoryl XL) 50 Dimethicodiethylbenzalmalonate; Polysilicone 15 (Parsol SLX) 207574-74-1 51 Benzenesulfonic acid, 3-(2H-benzotnazol-2-yl)-4-hydroxy-5-(1- 92484-48-5 methylpropyl)-, monosodium salt (Tinogard HS) 52 Benzoic acid, 2-[4-(diethylamino)-2- 302776-68-7 hydroxybenzoyl]-, hexyl ester (Uvinul A Plus) 53 1-Dodecanaminium, N-[3-[[4-(dimethylamino)benzoyl]amino]- 156679-41-3 propyl]N,N-dimethyl-, salt with 4-methylbenzenesulfonic acid (1:1) (Escalol HP610) 54 1-Propanaminium, N,N,N-trimethyl-3-[(1-oxo-3-phenyl-2- 177190-98-6 propenyl)amino]-, chloride 55 1H-Benzimidazole-4,6-disulfonic acid, 2,2′- 170864-82-1 (1,4-phenylene)bis- 56 1,3,5-Triazine, 2,4,6-tris(4- 7753-12-0 methoxyphenyl)- 57 1,3,5-Triazine, 2,4,6-tris[4-[(2- 208114-14-1 ethylhexyl)oxy]phenyl]- 58 1-Propanaminium, 3-[(3-[3-(2H-benzotriazol- 340964-15-0 2-yl)-5-(1,1-dimethylethyl)-4- hydroxyphenyl]-1-oxopropyl]amino]-N,N- diethyl-N-methyl-, methyl sulfate (salt) 59 2-Propenoic acid, 3-(1H-imidazol-4-yl)- 104-98-3 60 Benzoic acid, 2-hydroxy-, [4-(1- 94134-93-7 methylethyl)phenyl]methyl ester 61 1,2,3-Propanetriol, 1-(4-aminobenzoate) 136-44-7 (Glyceryl PABA) 62 Benzeneacetic acid, 3,4-dimethoxy-a-oxo- 4732-70-1 63 2-Propenoic acid, 2-cyano-3,3-diphenyl-, 5232-99-5 ethyl ester 64 Anthralinic acid, p-menth-3-yl ester 134-09-8 65 2,2′-bis(1,4-phenylene)-1H-benzimidazole- 349580-12-7, 4,6-disulphonic acid mono sodium salt or Disodium phenyl dibenzimidazole tetrasulfonate (Neo Heliopan AP) 66 1,3,5-Triazine-2,4,6-triamine, N,N′-bis[4- 288254-16-0 [5-(1,1-dimethylpropyl)-2- benzoxazolyl]phenyl]-N″-(2-ethylhexyl)- (Uvasorb K2A) 67 68 sterols (cholesterol, lanosterol, phytosterols), as described in WO0341675 69 mycosporines and/or mycosporine-like amino acids as described in WO2002039974, e.g. Helioguard 365 from Milbelle AG, isolated mycosporine like amino acids from the red alga porphyra umbilicalis (INCI: Porphyra Umbilicalis )that are encapsulated into liposomes,) 70 alpha-lipoic-acid as described in DE 10229995 71 synthetic organic polymers as described in EP 1371358, [0033]-[0041] 72 phyllosilicates as described in EP 1371357 [0034]-[0037] 73 silica compounds as described in EP1371356, [0033]-[0041] 74 inorganic particles as described in DE10138496 [0043]-[0055] 75 latex particles as described in DEfl0138496 [0027]-[0040] 76 1H-Benzimidazole-4,6-disulfonic acid, 2,2′- 180898-37-7 (1,4-phenylene)bis-, disodium salt; Bisimidazylate (Neo Heliopan APC) 77 78 79 E or Z isomer or mixture of E/Z isomers 80 81 Di-2-ethylhexyl-3,5-dimethoxy-4-hydroxy- benzalmalonate (Oxynex ST, EMD Chemicals, as described in U.S. Pat. No. 20040247536) 82 2,4,6-Tris-1,1′,4′,1″-terphenyl-4-yl- 1,3,5-triazine
The form or product type of the instant cosmetic composition is not specifically limited and may be in the form of make up products such as powdery foundation, cream foundation, oil base foundation, two-way foundation, stick type foundation, loose powder, eye shadow, cheek blush and lipstick, skin care products such as lotion, emulsion and cream as well as body cosmetics such as body powder and baby powder.
As water- and oil-containing emulsions (e.g. W/O, O/W, O/W/O and W/O/W emulsions or microemulsions) the preparations contain, for example, from 0.1 to 30% by weight, preferably from 0.1 to 15% by weight and especially from 0.5 to 10% by weight, based on the total weight of the composition, of one or more UV absorbers including the composite powder of the invention, from 1 to 60% by weight, especially from 5 to 50% by weight and preferably from 10 to 35% by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30% by weight, especially from 1 to 30% by weight und preferably from 4 to 20% by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90% by weight, especially from 30 to 90% by weight, based on the total weight of the composition, of water, and from 0 to 88.9% by weight, especially from 1 to 50 % by weight, of further cosmetically acceptable adjuvants.
The cosmetic or pharmaceutical compositions/preparations according to the invention may also contain one or one more additional compounds as described below.
Fatty Alcohols
Guerbet alcohols based on fatty alcohols having from 6 to 18, preferably from 8 to 10 carbon atoms including cetyl alcohol, stearyl alcohol, cetearyl alcohol, oleyl alcohol, octyldodecanol, benzoate of C12-C15 alcohols, acetylated lanolin alcohol, etc.
Esters of Fatty Acids
Esters of linear C6-C24 fatty acids with linear C3-C24 alcohols, esters of branched C6 C13carboxylic acids with linear C6-C24 fatty alcohols, esters of linear C6-C24 fatty acids with branched alcohols, especially 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C6-C22 fatty alcohols, especially dioctyl malates, esters of linear and/or branched fatty acids with polyhydric alcohols (for example propylene glycol, dimer diol or trimer triol) and/or Guerbet alcohols, for example caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and technical-grade mixtures thereof (obtained, for example, in the pressure removal of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or in the dimerisation of unsaturated fatty acids) with alcohols, for example, isopropyl alcohol, caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linoyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and technical-grade mixtures thereof (obtained, for example, in the high-pressure hydrogenation of technical-grade methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as monomer fractions in the dimerisation of unsaturated fatty alcohols).
Examples of such ester oils are isopropylmyristate, isopropylpalmitate, isopropylstearate, isopropyl isostearate, isopropyloleate, n-butylstearate, n-hexyllaurate, n-decyloleate, isooctylstearate, iso-nonylstearate, isononyl isononanoate, 2-ethylhexylpalmitate, 2-hexyllaurate, 2-hexyldecylstearate, 2-octyldodecylpalmitate, oleyloleate, oleylerucate, erucyloleate, erucylerucate, cetearyl octanoate, cetyl palmitate, cetyl stearate, cetyl oleate, cetyl behenate, cetyl acetate, myristyl myristate, myristyl behenate, myristyl oleate, myristyl stearate, myristyl palmitate, myristyl lactate, propylene glycol dicaprylate/caprate, stearyl heptanoate, diisostearyl malate, octyl hydroxystearate, etc.
Other Adjuvants
Alpha glucosylrutin (CAS No. 130603-71-3), 2-butyloctyl o-hydroxybenzoate (CAS No. 190085-41-7), vitamin E (CAS No. 1406-18-4), vitamin E acetate (CAS No. 58-95-7), diethylhexyl 2,6- naphthalate, di-n-butyl adipate, di(2-ethylhexyl)-adipate, di(2-ethylhexyl)-succinate and diisotridecyl acelaat, and also diol esters, such as ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di(2-ethylhexanoate), propylene glycol diisostearate, propylene glycol dipelargonate, butanediol diisostearate and neopentyl glycol dicaprylate. Esters of C6-C24 fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, saturated and/or unsaturated, especially benzoic acid, esters of C2-C12dicarboxylic acids with linear or branched alcohols having from 1 to 22 carbon atoms or polyols having from 2 to 10 carbon atoms and from 2 to 6 hydroxy groups, or iminodisuccinic acid and imiondisuccinic acid salts [CAS 7408-20-0] or latex particles, aloe vera, chamomile, ginko biloba, ginseng, coenzyme Q10, laminaria ochroleuca extract, magnolia oborata extract, melalenca alternifolia leaf oil, rubus idaeus seed oil, vaccinium macrocarpon seed oil, pumpkin seed extract, pumpkin seed oil, grape seed extract, carnosine, alpha-arbutin, madecassoside, termino-laside, tetrahydrocurcuminoids (THC), mycosporines, mycosporine like amino acids from the red alga porphyra umbilicalis, mycosporine-like amino acids (as described in WO2002039974), cis-9-octadecenedioic acid, lipoic acid, laurimino dipropiomic acid tocopheryl phosphates (LDTP), microcrystalline cellulose (MCC), polycarbonates as described in WO 0341676, sterols (cholesterol, lanosterol, phytosterols), as described in W00341675 and linear poly-alpha-glucans as described in U.S. Pat. No. 6,616,935, the contents of those references are herein incorporated by reference.
Natural or Synthetic Triglycerides Including Glyceryl Esters and Derivatives
Di- or tri-glycerides, based on C6-C18 fatty acids, modified by reaction with other alcohols (caprylic/capric triglyceride, wheat germ glycerides, etc.). Fatty acid esters of polyglycerin (polyglyceryl-n such as polyglyceryl-4 caprate, polyglyceryl-2 isostearate, etc. or castor oil, hydrogenated vegetable oil, sweet almond oil, wheat germ oil, sesame oil, hydrogenated cottonseed oil, coconut oil, avocado oil, corn oil, hydrogenated castor oil, shea butter, cocoa butter, soybean oil, mink oil, sunflower oil, safflower oil, macadamia nut oil, olive oil, hydrogenated tallow, apricot kernel oil, hazelnut oil, borago oil, etc.
Waxes including esters of long-chain acids and alcohols as well as compounds having wax-like properties, e.g., carnauba wax, beeswax (white or yellow), lanolin wax, candellila wax, ozokerite, japan wax, paraffin wax, microcrystalline wax, ceresin, cetearyl esters wax, synthetic beeswax, etc. Also, hydrophilic waxes as Cetearyl Alcohol or partial glycerides.
Pearlescent Waxes
Alkylene glycol esters, especially ethylene glycol distearate; fatty acid alkanolamides, especially coco fatty acid diethanolamide; partial glycerides, especially stearic acid monoglyceride; esters of polyvalent, unsubstituted or hydroxy-substituted carboxylic acids with fatty alcohols having from 6 to 22 carbon atoms, especially long-chained esters of tartaric acid; fatty substances, for example fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon atoms, especially laurone and distearyl ether; fatty acids, such as stearic acid, hydroxystearic acid or behenic acid, ring-opening products of olefin epoxides having from 12 to 22 carbon atoms with fatty alcohols having from 12 to 22 carbon atoms and/or polyols having from 2 to 15 carbon atoms and from 2 to 10 hydroxy groups, and mixtures thereof.
Hydrocarbon Oils
Mineral oil (light or heavy), petrolatum (yellow or white), microcrystalline wax, paraffinic and isoparaffinic compounds, hydrogenated isoparaffinic molecules as polydecenes and polybutene, hydrogenated polyisobutene, squalane, isohexadecane, isododecane and others from plant and animal kingdom.
Silicones or Siloxanes (Organosubstituted Polysiloxanes)
Dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones, and also amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/or alkyl-modified silicone compounds, which at room temperature may be in either liquid or resinous form. Linear polysiloxanes, dimethicone (Dow Corning 200 fluid, Rhodia Mirasil DM), dimethiconol, cyclic silicone fluids, cyclopentasiloxanes volatiles (Dow Corning 345 fluid), phenyltrimethicone (Dow Corning 556 fluid). Also suitable are simethicones, which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units with hydrogenated silicates. A detailed survey by Todd et al. of suitable volatile silicones may in addition be found in Cosm. Toil. 91, 27 (1976).
Fluorinated or Perfluorinated Oils
Perfluorhexane, dimethylcyclohexane, ethylcyclopentane, polyperfluoromethylisopropyl ether.
Emulsifiers
Any conventionally usable emulsifier can be used for the compositions. Emulsifier systems may comprise for example: carboxylic acids and their salts: alkaline soap of sodium, potassium and ammonium, metallic soap of calcium or magnesium, organic basis soap such as Lauric, palmitic, stearic and oleic acid etc. Alkyl phosphates or phosphoric acid esters, acid phosphate, diethanolamine phosphate, potassium cetyl phosphate. Ethoxylated carboxylic acids or polyethyleneglycol esters, PEG-n acylates. Linear fatty alcohols having from 8 to 22 carbon atoms, branched from 2 to 30 mol of ethylene oxide and/or from 0 to 5 mol propylene oxide with with fatty acids having from 12 to 22 carbon atoms and with alkylphenols having from 8 to 15 carbon atoms in the alkyl group. Fatty alcohol polyglycolether such as laureth-n, ceteareth-n, steareth-n, oleth-n. Fatty acid polyglycolether such as PEG-n stearate, PEG-n oleate, PEG-n cocoate. Monoglycerides and polyol esters. C12-C22 fatty acid mono- and di-esters of addition products of from 1 to 30 mol of ethylene oxide with polyols. Fatty acid and polyglycerol ester such as monostearate glycerol, diisostearoyl polyglyceryl-3-diisostearates, polyglyceryl-3-diisostearates, triglyceryl diisostearates, polyglyceryl-2-sesquiisostearates or polyglyceryl dimerates. Mixtures of compounds from a plurality of those substance classes are also suitable. Fatty acid polyglycolesters such as monostearate diethylene glycol, fatty acid and polyethylene glycol esters, fatty acid and saccharose esters such as sucro esters, glycerol and saccharose esters such as sucro glycerides. Sorbitol and sorbitan, sorbitan mono- and di-esters of saturated and unsaturated fatty acids having from 6 to 22 carbon atoms and ethylene oxide addition products. Polysorbate-n series, sorbitan esters such as sesquiisostearate, sorbitan, PEG-(6)-isostearate sorbitan, PEG-(10)-sorbitan laurate, PEG-17-dioleate sorbitan. Glucose derivatives, C8-C22 alkyl-mono and oligo-glycosides and ethoxylated analogues with glucose being preferred as the sugar component. O/W emulsifiers such as methyl gluceth-20 sesquistearate, sorbitan stearate/sucrose cocoate, methyl glucose sesquistearate, cetearyl alcohol/cetearyl glucoside. W/O emulsifiers such as methyl glucose dioleate/ methyl glucose isostearate. Sulfates and sulfonated derivatives, dialkylsulfosuccinates, dioctyl succinate, alkyl lauryl sulfonate, linear sulfonated parafins, sulfonated tetraproplyne sulfonate, sodium lauryl sulfates, amonium and ethanolamine lauryl sulfates, lauyl ether sulfates, sodium laureth sulfates, sulfosuccinates, aceyl isothionates, alkanolamide sulfates, taurines, methyl taurines, imidazole sulfates. Amine derivatives, amine salts, ethoxylated amines, oxide amine with chains containing an heterocycle such as alkyl imidazolines, pyridine derivatives, isoquinoteines, cetyl pyridinium chlorure, cetyl pyridinium bromide, quaternary ammonium such as cetyltrimethylbroide amonium broide (CTBA), stearylalkonium. Amide derivatives, alkanolamides such as acylamide DEA, ethoxylated amides such as PEG-n acylamide, oxydeamide. Polysiloxane/polyalkyl/polyether copolymers and derivatives, dimethicone, copolyols, silicone polyethylene oxide copolymer, silicone glycol copolymer. Propoxylated or POE-n ethers (Meroxapols), Polaxamers or poly(oxyethylene)m-block-poly(oxypropylene)n-block(oxyethylene). Zwitterionic surfactants that carry at least one quaternary ammonium group and at least one carboxylate and/or sulfonate group in the molecule. Zwitterionic surfactants that are especially suitable are betaines, such as N alkyl-N,N dimethylammonium glycinates, cocoalkyldimethylammonium glycinate, N acylaminopropyl N,N dimethylammonium glycinates, cocoacylaminopropyldimethylammonium glycinate and 2 alkyl-3-carboxymethyl-3-hydroxyethylimidazolines each having from 8 to 18 carbon atoms in the alkyl or acyl group and also cocoacylaminoethylhydroxyethylcarboxymethylglycinate, N-alkylbetaine, N-alkylaminobetaines. Alkylimidazolines, alkylopeptides, lipoaminoacides, self emulsifying bases and the compounds as described in K. F. DePolo, A short textbook of cosmetology, Chapter 8, Table 8-7, p 250-251.
Non ionic emulsifiers such as PEG-6 beeswax (and) PEG-6 stearate (and) polyglyceryl-2 isostearate [Apifac], glyceryl stearate (and) PEG-100 stearate. [Arlacel 165], PEG-5 glyceryl stearate [arlatone 983 S], sorbitan oleate (and) polyglyceryl-3 ricinoleate. [Arlacel 1689], sorbitan stearate and sucrose cocoate [arlatone 2121], glyceryl stearate and laureth-23 [Cerasynth 945], cetearyl alcohol and ceteth-20 [Cetomacrogol Wax], cetearyl alcohol and colysorbate 60 and PEG-150 and stearate-20 [Polawax GP 200, Polawax NF], cetearyl alcohol and cetearyl polyglucoside [Emulgade PL 1618], cetearyl alcohol and ceteareth-20 [Emulgade 1000NI, Cosmowax], cetearyl alcohol and PEG-40 castor oil [Emulgade F Special], cetearyl alcohol and PEG-40 castor oil and sodium cetearyl sulfate [Emulgade F], stearyl alcohol and steareth-7 and steareth-10 [Emulgator E 2155], cetearyl alcohol and steareth-7 and steareth-10 [Emulsifying wax U.S.N.F], glyceryl stearate and PEG-75 stearate [Gelot 64], propylene glycol ceteth-3 acetate [Hetester PCS], propylene glycol isoceth-3 acetate [Hetester PHA], cetearyl alcohol and ceteth-12 and oleth-12 (Lanbritol Wax N 21), PEG-6 stearate and PEG-32 stearate [Tefose 1500], PEG-6 stearate and ceteth-20 and steareth-20 [Tefose 2000], PEG-6 stearate and ceteth-20 and glyceryl stearate and steareth-20 [Tefose 2561], glyceryl stearate and ceteareth-20 [Teginacid H, C, X].
Anionic emulsifiers such as PEG-2 stearate SE, glyceryl stearate SE [Monelgine, Cutina KD], propylene glycol stearate [Tegin P], cetearyl Alcohol and Sodium cetearyl sulfate [Lanette N, Cutina LE, Crodacol GP], cetearyl alcohol and sodium lauryl sulfate [Lanette W], trilaneth-4 phopshate and glycol stearate and PEG-2 stearate [Sedefos 75], glyceryl stearate and sodium lauryl Sulfate [Teginacid Special]. Cationic acid bases such as cetearyl alcohol and cetrimonium bromide.
The emulsifiers may be used in an amount of, for example, from 1 to 30% by weight, especially from 4 to 20% by weight and preferably from 5 to 10% by weight, based on the total weight of the composition.
When formulated in O/W emulsions, the preferably amount of such emulsifier system could represent 5% to 20% of the oil phase.
Adjuvants and Additives
The cosmetic/pharmaceutical preparations, for example creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments, may in addition contain, as further adjuvants and additives, mild surfactants, super-fatting agents, consistency regulators, thickeners, polymers, stabilisers, biogenic active ingredients, deodorising active ingredients, anti-dandruff agents, film formers, swelling agents, further UV light-protective factors, antioxidants, hydrotropic agents, preservatives, insect repellents, self-tanning agents, solubilisers, perfume oils, colourants, bacteria-inhibiting agents and the like.
Super-Fatting Agents
Substances suitable for use as super-fatting agents are, for example, lanolin and lecithin and also polyethoxylated or acrylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the latter simultaneously acting as foam stabilisers.
Surfactants
Examples of suitable mild surfactants, that is to say surfactants especially well tolerated by the skin, include fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and/or di-alkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, □-olefin sulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines and/or protein fatty acid condensation products, the latter preferably being based on wheat proteins.
Consistency Regulators/Thickeners and Rheology Modifiers
Silicium dioxide, magnesium silicates, aluminium silicates, polysaccharides or derivatives thereof for example hyaluronic acid, xanthan gum, guar-guar, agar-agar, alginates, carraghenan, gellan, pectines, or modified cellulose such as hydroxycellulose, hydroxypropylmethylcellulose. In addition polyacrylates or homopolymer of reticulated acrylic acids and polyacrylamides, carbomer (carbopol types 980, 981, 1382, ETD 2001, ETD2020, Ultrez 10) or Salcare range such as Salcare SC80 (steareth-10 allyl ether/acrylates copolymer), Salcare SC81 (acrylates copolymer), Salcare SC91 and Salcare AST (sodium acrylates copolymer/PPG-1 trideceth-6), sepigel 305(polyacrylamide/laureth-7), Simulgel NS and Simulgel EG (hydroxyethyl acrylate/sodium acryloyldimethyl taurate copolymer), Stabilen 30 (acrylates/vinyl isodecanoate crosspolymer), Pemulen TR-1 (acrylates/C10-30 alkyl acrylate crosspolymer), Luvigel EM (sodium acrylates copolymer), Aculyn 28 (acrylates/beheneth-25 methacrylate copolymer), etc.
Polymers
Suitable cationic polymers are, for example, cationic cellulose derivatives, for example a quaternised hydroxymethyl cellulose obtainable under the name Polymer JR 400 from Amerchol, cationic starches, copolymers of diallylammonium salts and acrylamides, quarternised vinylpyrrolidone/vinyl imidazole polymers, for example LUViquat® (BASE), condensation products of polyglycols and amines, quaternised collagen polypeptides, for example lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat®L/Grünau), quaternised wheat polypeptides, polyethyleneimine, cationic silicone polymers, for example amidomethicones, copolymers of adipic acid and dimethylaminohydrdxypropyldiethylenetriamine (Cartaretin/Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride (Merquat 550/Chemviron), polyaminopolyamides, as described, for example, in FR-A-2 252 840, and the crosslinked water-soluble polymers thereof, cationic chitin derivatives, for example of quaternised chitosan, optionally distributed as microcrystals; condensation products of dihaloalkyls, for example dibromobutane, with bisdialkylamines, for example bisdimethylamino-1,3-propane, cationic guar gum, for example Jaguar C-17, Jaguar C-16 from Celanese, quaternised ammonium salt polymers, for example Mirapol A-15, Mirapol AD-1, Mirapol AZ-1 from Miranol. As anionic, zwitterionic, amphoteric and non-ionic polymers there come into consideration, for example, vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers and esters thereof, uncrosslinked polyacrylic acids and polyacrylic acids crosslinked with polyols, acrylamidopropyl-trimethylammonium chloride /acrylate copolymers, octyl acrylamide/methyl methacrylatetert butylaminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, vinylpyrrolidone/dimethylaminoethyl methacrylate/vinyl caprolactam terpolymers and also optionally derivatised cellulose ethers and silicones. Furthermore the polymers as described in EP 1093796 (pages 3-8, paragraphs 17-68) may be used.
Biogenic Active Ingredients
Biogenic active ingredients are to be understood as meaning, for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes.
Deodorising Active Ingredients
As deodorising active ingredients there come into consideration, for example, antiperspirants, for example aluminium chlorohydrates (see J. Soc. Cosm. Chem. 24, 281 (1973)). Under the trade mark Locron® of Hoechst AG, Frankfurt (FRG), there is available comercially, for example, an aluminium chlorohydrate corresponding to formula Al 2 (OH)5Cl×2.5H 2 O, the use of which is especially preferred (see J. Pharm. Pharmacol. 26, 531 (1975)). Besides the chlorohydrates, it is also possible to use aluminium hydroxyacetates and acidic aluminium/zirconium salts. Esterase inhibitors may be added as further deodorising active ingredients. Such inhibitors are preferably trialkyl citrates, such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and especially triethyl citrate (Hydagen CAT, Henkel), which inhibit enzyme activity and hence reduce odour formation. Further substances that come into consideration as esterase inhibitors are sterol sulfates or phosphates, for example lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and esters thereof, for example glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, adipic acid monoethyl ester, adipic acid diethyl ester, malonic acid and malonic acid diethyl ester and hydroxycarboxylic acids and esters thereof, for example citric acid, malic acid, tartaric acid or tartaric acid diethyl ester. Antibacterial active ingredients that influence the germ flora and kill or inhibit the growth of sweat-decomposing bacteria can likewise be present in the preparations (especially in stick preparations). Examples include chitosan, phenoxyethanol and chlorhexidine gluconate. 5-chloro-2-(2,4-dichlorophenoxy)-phenol (Triclosan, Irgasan, Ciba Specialty Chemicals Inc.) has also proved especially effective.
Anti-Dandruff Agents
As anti-dandruff agents there may be used, for example, climbazole, octopirox and zinc pyrithione. Customary film formers include, for example, chitosan, microcrystalline chitosan, quaternised chitosan, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, polymers of quaternary cellulose derivatives containing a high proportion of acrylic acid, collagen, hyaluronic acid and salts thereof and similar compounds.
Antioxidants
In addition to the primary light-protective substances it is also possible to use secondary light-protective substances of the antioxidant kind that interrupt the photochemical reaction chain triggered when UV radiation penetrates the skin or hair. Typical examples of such antioxidants are amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and derivatives thereof, imidazoles (e.g. urocanic acid) and derivatives thereof, peptides, such as D,L-carnosine, D-carnosine, L-carnosine and derivatives thereof (e.g. anserine), carotinoids, carotenes, lycopene and derivatives thereof, chlorogenic acid and derivatives thereof, lipoic acid and derivatives thereof (e.g. dihydrolipoic acid), aurothioglycose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, lauryl, palmitoyl, oleyl, linoleyl, cholesteryl and glyceryl esters thereof) and also salts thereof, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and also sulfoximine compounds (e.g. buthionine sulfoximines, homocysteine sulfoximine, buthionine sulfones, penta-, hexa-, hepta-thionine sulfoximine), also (metal) chelating agents (e.g. hydroxy fatty acids, palmitic acid phytic acid, lactoferrin), hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EDDS, EGTA and derivatives thereof, unsaturated fatty acids and derivatives thereof (e.g. linolenic acid, linoleic acid, oleic acid), folic acid and derivatives thereof, ubiquinone and ubiquinol and derivatives thereof, vitamin C and derivatives (e.g. ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (e.g. vitamin A palmitate) and also coniferyl benzoate of benzoin resin, rutinic acid and derivatives thereof, glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butyl hydroxytoluene, butyl hydroxyanisole, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, superoxide dismutase, N-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]sulfanilic acid (and salts thereof, for example the disodium salts), zinc and derivatives thereof (e.g. ZnO, ZnSO4), selenium and derivatives thereof (e.g. selenium methionine), stilbene and derivatives thereof (e.g. stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of those mentioned active ingredients. HALS (=“Hindered Amine Light Stabilizers”) compounds may also be mentioned.
Further synthetic and natural antioxidants are listed e.g. in patent WO 0025731:
Structures 1-3 (page 2), structure 4 (page 6), structures 5-6 (page 7) and compounds 7-33 (page 8-14).
The amount of antioxidants present is usually from 0.001 to 30% by weight, preferably from 0.01 to 3% by weight, based on the weight of the UV absorbing composite powder of the invention.
Hydrotropic Agents
To improve the flow behaviour it is also possible to employ hydrotropic agents, for example ethoxylated or non ethoxylated mono-alcohols, diols or polyols with a low number of carbon atoms or their ethers (e.g. ethanol, isopropanol, 1,2-dipropanediol, propyleneglycol, glyerin, ethylene glycol, ethylene glycol monoethylether, ethylene glycol monobutylether, propylene glycol monomethylether, propylene glycol monoethylether, propylene glycol monobutylether, diethylene glycol monomethylether; diethylene glycol monoethylether, diethylene glycol monobutylether and similar products). The polyols that come into consideration for that purpose have preferably from 2 to 15 carbon atoms and at least two hydroxy groups. The polyols may also contain further functional groups, especially amino groups, and/or may be modified with nitrogen. Typical examples are as follows: glycerol, alkylene glycols, for example ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and also polyethylene glycols having an average molecular weight of from 100 to 1000 Dalton; technical oligoglycerol mixtures having an intrinsic degree of condensation of from 1.5 to 10, for example technical diglycerol mixtures having a diglycerol content of from 40 to 50% by weight; methylol compounds, such as, especially, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol; lower alkyl-glucosides, especially those having from 1 to 8 carbon atoms in the alkyl radical, for example methyl and butyl glucoside; sugar alcohols having from 5 to 12 carbon atoms, for example sorbitol or mannitol; sugars having from 5 to 12 carbon atoms, for example glucose or saccharose; amino sugars, for example glucamine; dialcohol amines, such as diethanolamine or 2-amino-1,3-propanediol.
Preservatives
Suitable preservatives include, for example, Methyl-, Ethyl-, Propyl-, Butyl-parabens, Benzalkonium chloride, 2-Bromo-2-nitro-propane-1,3-diol, Dehydroacetic acid, Diazolidinyl Urea, 2-Dichloro-benzyl alcohol, DMDM hydantoin, Formaldehyde solution, Methyldibromoglutanitrile, Phenoxyethanol, Sodium Hydroxymethylglycinate, Imidazolidinyl Urea, Triclosan and further substance classes listed in the following reference: K. F. DePolo—A short textbook of cosmetology, Chapter 7, Table 7-2, 7-3, 7-4 and 7-5, p 210-219.
Bacteria-Inhibiting Agents
Typical examples of bacteria-inhibiting agents are preservatives that have a specific action against gram-positive bacteria, such as 2,4,4′-trichloro-2′-hydroxydiphenyl ether, chlorhexidine (1,6-di(4-chlorophenyl-biguanido)hexane) or TCC (3,4,4′-trichlorocarbanilide). A large number of aromatic substances and ethereal oils also have antimicrobial properties. Typical examples are the active ingredients eugenol, menthol and thymol in clove oil, mint oil and thyme oil. A natural deodorising agent of interest is the terpene alcohol farnesol (3,7,11-trimethyl-2,6,10-dodecatrien-1-ol), which is present in lime blossom oil. Glycerol monolaurate has also proved to be a bacteriostatic agent. The amount of the additional bacteria-inhibiting agents present is usually from 0.1 to 2% by weight, based on the solids content of the preparations.
Perfume Oils
There may be mentioned as perfume oils mixtures of natural and/or synthetic aromatic substances. Natural aromatic substances are, for example, extracts from blossom (lilies, lavender, roses, jasmine, neroli, ylang-ylang), from stems and leaves (geranium, patchouli, petitgrain), from fruit (aniseed, coriander, carraway, juniper), from fruit peel (bergamot, lemons, oranges), from roots (mace, angelica, celery, cardamom, costus, iris, calmus), from wood (pinewood, sandalwood, guaiacum wood, cedarwood, rosewood), from herbs and grasses (tarragon, lemon grass, sage, thyme), from needles and twigs (spruce, pine, Scots pine, mountain pine), from resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials also come into consideration, for example civet and castoreum. Typical synthetic aromatic substances are, for example, products of the ester, ether, aldehyde, ketone, alcohol or hydrocarbon type. Aromatic substance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether; the aldehydes include, for example, the linear alkanals having from 8 to 18 hydrocarbon atoms, citral, citronellal, citronellyl oxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal; the ketones include, for example, the ionones, isomethylionone and methyl cedryl ketone; the alcohols include, for example, anethol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenyl ethyl alcohol and terpinol; and the hydrocarbons include mainly the terpenes and balsams. It is preferable, however, to use mixtures of various aromatic substances that together produce an attractive scent. Ethereal oils of relatively low volatility, which are chiefly used as aroma components, are also suitable as perfume oils, e.g. sage oil, camomile oil, clove oil, melissa oil, oil of cinnamon leaves, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, labolanum oil and lavandin oil. Preference is given to the use of bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenyl ethyl alcohol, hexyl cinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, boisambrene forte, ambroxan, indole, hedione, sandelice, lemon oil, tangerine oil, orange oil, allyl amyl glycolate, cyclovertal, lavandin oil, muscatel sage oil, damascone, bourbon geranium oil, cyclohexyl salicylate, vertofix coeur, iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romillat, irotyl and floramat alone or in admixture with one another.
Colourants
There may be used as colourants the substances that are suitable and permitted for cosmetic purposes, as compiled, for example, in the publication “Kosmetische Färbemittel” of the Farbstoffkommission der Deutschen Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pages 81 to 106. The colourants are usually used in concentrations of from 0.001 to 0.1% by weight, based on the total mixture.
Other Adjuvants
It is furthermore possible for the cosmetic preparations to contain, as adjuvants, anti-foams, such as silicones, structurants, such as maleic acid, solubilisers, such as ethylene glycol, propylene glycol, glycerol or diethylene glycol, opacifiers, such as latex, styrene/PVP or styrene/acrylamide copolymers, complexing agents, such as EDTA, NTA, alaninediacetic acid or phosphonic acids, propellants, such as propane/butane mixtures, N 2 O, dimethyl ether, CO 2 , N 2 or air, so-called coupler and developer components as oxidation dye precursors, reducing agents, such as thioglycolic acid and derivatives thereof, thiolactic acid, cysteamine, thiomalic acid or mercaptoethanesulfonic acid, or oxidising agents, such as hydrogen peroxide, potassium bromate or sodium bromate.
Suitable insect repellents are, for example, N,N-diethyl-m-toluamide, 1,2-pentanediol or insect repellent 3535; suitable self-tanning agents are, for example, dihydroxyacetone and/or erythrulose or dihydroxy acetone and/or dihydroxy acetone precursors as described in WO 01/85124 and/or erythrulose.
Polymeric Beads or Hollow Spheres as SPF Enhancers
The combination of the UV-absorbing composite powder of the invention and a UV-absorber combination, disclosed above, with SPF enhancers, such as non-active ingredients like Styrene/acrylates copolymer, silica beads, spheroidal magnesium silicate, crosslinked Polymethylmethacrylates (PMMA; Micopearl M305 Seppic), can maximize better the UV protection of the products. Holosphere additives (Sunspheres® ISP, Silica Shells Kobo.) deflect radiation and the effective path length of the photon is therefore increased. (EP0893119). Some beads, as mentioned previously, provide a soft feel during spreading. Moreover, the optical activity of such beads, e.g. Micropearl M305, cans modulate skin shine by eliminating reflection phenomena and indirectly may scatter the UV light.
Cosmetic or Pharmaceutical Preparations
Cosmetic or pharmaceutical formulations are contained in a wide variety of cosmetic preparations. There come into consideration, for example, especially the following preparations:
skin-care preparations, e.g. skin emulsions, multi-emulsions or skin oils; cosmetic personal care preparations, e.g. facial make-up in the form of day creams or powder creams, face powder (loose or pressed), rouge or cream make-up, eye-care preparations, e.g. eyeshadow preparations, mascara, eyeliner, eye creams or eye-fix creams; lip-care preparations, e.g. lipsticks, lip gloss, lip contour pencils, nail-care preparations, such as nail varnish, nail varnish removers, nail hardeners or cuticle removers; light-protective preparations, such as sun milks, lotions, creams or oils, sunblocks or tropicals, pre-tanning preparations or after-sun preparations; skin-tanning preparations, e.g. self-tanning creams; insect-repellents, e.g. insect-repellent oils, lotions, sprays or sticks;
Presentation Forms of the Cosmetic Composition
The final formulations listed may exist in a wide variety of presentation forms, for example:
in the form of liquid preparations as a W/O, O/W, O/W/O, W/O/W or PIT emulsion and all kinds of microemulsions, in the form of a gel, in the form of an oil, a cream, milk or lotion, in the form of a powder, a lacquer, a tablet or make-up, in the form of a stick, in the form of a spray (spray with propellent gas or pump-action spray) or an aerosol, in the form of a foam, or in the form of a paste.
Of special importance as cosmetic preparations for the skin are light-protective preparations, such as sun milks, lotions, creams, oils, sunblocks or tropicals, pretanning preparations or after-sun preparations, also skin-tanning preparations, for example self-tanning creams. Of particular interest are sun protection creams, sun protection lotions, sun protection milk and sun protection preparations in the form of a spray or sun-protection foams.
For example, especially the following cosmetic formulations may be used:
a1) spontaneously emulsifying stock formulation, consisting of the UV absorber according to the invention, PEG-6-C10oxoalcohol and sorbitan sesquioleate, to which water and any desired quaternary ammonium compound, for example 4% minkamidopropyl dimethyl-2-hydroxyethylammonium chloride or Quaternium 80 is added; a2) spontaneously emulsifying stock formulation consisting of the UV absorber according to the invention, tributyl citrate and PEG-20-sorbitan monooleate, to which water and any desired quaternary ammonium compound, for example 4% minkamidopropyl dimethyl-2-hydroxyethylammonium chloride or Quaternium 80 is added; b) quat-doped solutions of the UV absorber according to the invention in butyl triglycol and tributyl citrate; c) mixtures or solutions of the UV absorber according to the invention with n alkylpyrrolidone.
Other typical ingredients in such formulations are preservatives, bactericides and bacteriostatic agents, perfumes, dyes, pigments, thickening agents, moisturizing agents, humectants, fats, oils, waxes or other typical ingredients of cosmetic and personal care formulations such as alcohols, poly-alcohols, polymers, electrolytes, organic solvents, silicon derivatives, emollients, emulsifiers or emulsifying surfactants, surfactants, dispersing agents, antioxidants, anti-irritants and anti-inflammatory agents etc.
The instant invention will be further illustrated with reference to the following examples. However, these examples are intended to illustrate the invention and are not to be construed to limit the scope of the invention. That is, the type and ingredient of the cosmetic composition covered by the instant invention will not be limited to those disclosed in the following examples and the cosmetic composition may comprise any ingredient commonly added or used for manufacturing cosmetic products with no limitation.
EXAMPLE 1
Purified water 500g was put in a 1L-beaker and the core particles, spherical silica having an average size of 3 μm (SUNSPHERE®, Asahi Glass SI-Tech. Co., Ltd.) 90 g was added thereto with stirring by a dispersing mixer. A commercially available aqueous dispersion of the compound of formula (1) (MBBT) containing 50% MBBT in micronized form with an average particle size <200 nm (TINOSORB® M, Ciba Specialty Chemicals, Basel, Switzerland) was used. An aqueous dispersion containing 10% TINOSORB® M 100 g was added to the beaker and the mixture was stirred well. Then, 5% aqueous aluminum sulfate 100 g was added to the mixture and further stirred. After that, pH of the mixture was adjusted to neutral and the mixture was further stirred.
After that, the mixture was centrifuged to dehydrate and the obtained particles were washed with ethanol to remove water soluble ingredients in TINOSORB® M other than the water insoluble UV absorber (MBBT). This step was repeated twice and then, the particles were dried at 120° C. for 10 hours to give 100 g of composite particles consisting of the core particles and about 5 wt % MBBT adsorbed to the surface of the core particles.
EXAMPLE 2
Purified water 500 g was put in a 1L-beaker and the core particles, spherical silica with an average size of 3 μm (SUNSPHERE®, Asahi Glass SI-Tech. Co., Ltd.) 89.5 g were added thereto with stirring by a dispersing mixer. An aqueous dispersion containing 14% TINOSORB® M 100 g was added to the beaker and the mixture was stirred well. Then, 3.5% aqueous aluminum sulfate 100 g was added to the mixture and further stirred. After that, pH of the mixture was adjusted to neutral and the mixture was further stirred.
After that, the mixture was treated according to the same manner as Example 1 to give 100 g of composite particles consisting of the core particles and about 7 wt % MBBT adsorbed to the surface of the core particles.
EXAMPLE 3
Purified water 500 g was put in a 1L-beaker and the core particles, spherical silica with an average size of 3 μm (SUNSPHERE®, Asahi Glass SI-Tech. Co., Ltd.) 85 g was added thereto with stirring by a dispersing mixer. An aqueous dispersion containing 20% TINOSORB® M 100 g was added to the beaker and the mixture was stirred well. Then, 5% aqueous aluminum sulfate 100 g was added to the mixture and further stirred. After that, pH of the mixture was adjusted to neutral and the mixture was further stirred.
The mixture was treated according to the same manner as Example 1 to give 100 g of composite particles consisting of the core particles and about 10 wt % MBBT adsorbed to the surface of the core particles.
EXAMPLE 4
Purified water 500 g was put in a 1L-beaker and the core particles, spherical silica with an average size of 3 μm (SUNSPHERE®, Asahi Glass SI-Tech. Co., Ltd.) 70 g was added thereto with stirring by a dispersing mixer. An aqueous dispersion containing 40% TINOSORB® M 100 g was added to the beaker and the mixture was stirred well. Then, 10% aqueous aluminum sulfate 100 g was added to the mixture and further stirred. After that, pH of the mixture was adjusted to neutral and the mixture was further stirred.
After that, the mixture was treated according to the same manner as Example 1 to give 100 g of composite powder consisting of the core particles and about 20 wt % MBBT adsorbed to the surface of the core particles.
Comparative Example 1
Purified water 500 g was put in a 1L-beaker and the core particles, spherical silica with an average size of 3 μm (SUNSPHERE®, Asahi Glass SI-Tech. Co., Ltd.) 94 g was added thereto with stirring by a dispersing mixer. An aqueous dispersion containing 10% TINOSORB® M 100 g was added to the beaker and the mixture was stirred well. Then, 1% aqueous aluminum sulfate 100 g was added to the mixture and further stirred. After that, pH of the mixture was adjusted to neutral and the mixture was further stirred.
The mixture was centrifuged to dehydrate. Upon the dehydration, white liquid that seemed to contain MBBT was removed. Then, the particles were washed with ethanol and the filtrate was also white liquid. The amount of the resulting particles was 96 g.
Comparative Example 2
Purified water 500 g was put in a 1L-beaker and the core particles, spherical silica with an average size of 3 μm (SUNSPHERE®, Asahi Glass SI-Tech. Co., Ltd.) 98 g was added thereto with stirring by a dispersing mixer. 2% aqueous aluminum sulfate 100 g was added thereto and the mixture was further stirred. After that, pH of the mixture was adjusted to neutral and the mixture was further stirred. Then, the mixture was centrifuged to dehydrate and the particles were dried at 120° C. for 10 hours to give 100 g of composite powder.
Comparative Example 3
Purified water 500 g was put in a 1L-beaker and the core particles, spherical silica with an average size of 3 μm (SUNSPHERE®, Asahi Glass SI-Tech. Co., Ltd.) 40 g was added thereto with stirring by a dispersing mixer. An aqueous dispersion containing 80% TINOSORB® M 200 g was added to the beaker and the mixture was stirred well. Then, 20% aqueous aluminum sulfate 100 g was added to the mixture and further stirred. After that, pH of the mixture was adjusted to neutral and the mixture was further stirred.
The mixture was treated according to the same manner as Example 1 to give 100 g of composite particles.
Test Example 1
UV-Protecting Effect I (UV-Absorbing Property)
Each of the composite powders comprising the composite powder particles obtained in Examples 1-4 and Comparative Examples 1-3 was weighted and mixed with trioctanoine so that the weight ratio of the composite powder:trioctanoine was 3:7. The mixture was stirred with dispersing mixer at 3000 rpm for 10 minutes to give dispersion. The absorption spectrum of each dispersion over the wavelength range of 280-400 nm was determined with a spectrophotometer (UV-3010; HITACHI, Ltd.). Results are shown in FIG. 1 .
Test Example 2
UV-Absorbing Effect II (In Vitro SPF Determination)
Each of the composite powders obtained in Examples 1-4 and Comparative Example 1-3 was weighted and mixed with vaseline so that the weight ratio of the composite powder:vaseline was 25:75. The mixture was homogenized in a mortar to give uniform paste. The paste was uniformly applied on Transpore Tape (Sumitomo 3M) in an amount of 2 mg/cm 2 and in vitro SPF was determined with SPF Analyzer UV-1000S (Labsphere). Result are shown in Table 1 below.
Test Example 3
Texture Evaluation
The texture of each composite powder of Examples 1-4 and Comparative Examples 1-3 in view of the touch of the powder is smooth, squeaky or rough was evaluated by 5 panelists according to the five scores shown below:
Five Absolute Evaluation
1: Bad and uncomfortable texture 2: Slightly bad and uncomfortable texture 3: Normal (comparative to the untreated core particles) 4: Slightly good and comfortable texture 5: Good and comfortable texture
The average values were taken and shown in Table 1 using the following marks:
++: 4 or above +: 3 or above and less than 4 −: 2 or above and less than 3 −−: less than 2
Results of Test Examples 2 and 3
TABLE 1 Test Ex. 2 Test Ex. 3 Example 1 2.59 ++ Example 2 3.32 ++ Example 3 4.32 ++ Example 4 7.42 + Com. Ex. 1 1.01 ++ Com. Ex. 2 0 ++ Com. Ex. 3 10.42 −−
According to FIG. 1 showing the result of test example 1, the UV absorbance of Examples 1-4 and Comparative Example 3 were increased with the amount of the MBBT adsorbed to the surface of the core particles. Although the powder of comparative Example 1 was manufactured using the same amount of MBBT as that of Example 1, the powder of Comparative Example 1 exhibited less UV absorbance than Example 1. This fact exemplifies that the metal salt like aluminum sulfate is essential for manufacturing the composite powder of the invention. In the Test Example 2, similar result as the Test Example 1 was obtained.
According to the result of Test Example 3, the composite powder of comparative example 3 comprising 40 wt % of MBBT provided uncomfortable and rough feeling besides its high UV absorbing property.
EXAMPLE 5
Purified water 500 g was put in a 1L-beaker and core particle, mica with an average size of 17 μm 70 g was added thereto with stirring by a dispersing mixer. An aqueous dispersion containing 40% TINOSORB® M 100 g was added to the beaker and the mixture was stirred well. Then, 10% aqueous aluminum sulfate 100 g was added to the mixture and further stirred. After that, pH of the mixture was adjusted to neutral and the mixture was further stirred.
The mixture was treated according to the same manner as Example 1 to give 100 g of composite powder consisting of the core particles and about 20 wt % MBBT adsorbed to the surface of the core particles.
EXAMPLES 6 AND 7, COMPARATIVE EXAMPLES 4-6
Two-Way Cake Foundation
The composite powder obtained in Example 3 or 4 was used to give two-way cake foundation with the ingredients shown in Table 2 below. The evaluation according to Test Examples 2 and 3 were conducted and results are shown in Table 2.
Preparation:
Powder ingredients (1)-(11) were mixed and pulverized by means of a Henschel mixer. Oil ingredients (12)-(16) were mixed in a separate container and added to the powder ingredients. The mixture was kneaded uniformly, then pulverized with an atomizer and the obtained powder was put in an aluminum dish and pressed to give two way cake foundation.
TABLE 2 Ingredients of the two way cake foundation amount(wt %) Comp. Comp. Comp. Comp. Ingredients Ex. 6 Ex. 7 Ex. 4 Ex. 5 Ex. 6 Ex. 7 (1) methicone treated talc balance balance balance balance balance balance (2) methicone 6 6 6 6 6 6 treated titanium dioxide (3) methicone 20 20 20 20 20 20 treated mica (4) methione 36 36 36 36 36 36 treated sericite (5) Composite powder 10 Ex. 3 (6) Composite Powder 10 Ex. 4 (7) Micronized 3 5 3 titanium dioxide (8) Micronized zinc 5 5 oxide (9) methicone 1 1 1 1 1 1 treated yellow iron oxide (10) methicone 0.5 0.5 0.5 0.5 0.5 0.5 treated red iron oxide (11) methicone 0.1 0.1 0.1 0.1 0.1 0.1 treated black iron oxide (12) Dimethicone 6 6 6 6 6 6 1000 cs (13) Octyl methoxy 3 3 3 3 3 3 cinnamate (14) squalane 3 3 3 3 3 3 (15) Preservative 0.2 0.2 0.2 0.2 0.2 0.2 (16) antioxidant 0.1 0.1 0.1 0.1 0.1 0.1 total 100.0 100.0 100.0 100.0 100.0 100.0
TABLE 3
Comp.
Comp.
Comp.
Comp.
Ex. 6
Ex. 7
Ex. 4
Ex. 5
Ex. 6
Ex. 7
in vitro SPF
20.4
25.4
15.2
20.3
18.2
28.0
texture
++
++
++
−
±
−
As is apparent from table 3 above, the two way cake foundations of Examples 6 and 7 exhibited excellent UV protecting effects. The compositions of comparative examples 5-7 also exhibited an excellent UV-protecting effect but the texture was bad and provided bluish color upon applied to the face. According to the results, the two way foundations of the examples 6 and 7 are excellent in both of UV-protecting property and texture.
EXAMPLE 8
Pressed Powder
TABLE 4 Ingredients amount (wt %) (1) talc balance (2) polymethyl 10 methacrylate (7 μm)* (3) sericite 30 (4) scaly-shaped silica** 3 (5) composite powder 10 Ex. 4 (6) preservative suitable amount (7) colorant suitable amount (8) octyl methoxy 3 cinnamate (9) squalane 2 (10) Preservative suitable amount (11) antioxidant suitable amount (12) perfume suitable amount *Matsumoto Microsphere ® M-100 (Matsumoto Yushi Seiyaku Co., Ltd) **SUNLOVELY ® C (Asahi Glass SI-Tech. Co., Ltd.)
Preparation:
Powder ingredients (1)-(7) were mixed and pulverized, and put in a Henschel mixer. The oil ingredients (8)-(11) were added into the mixer and kneaded to give an uniform mixture. The mixture was then pulverized with an atomizer, put in an aluminum dish and pressed to give pressed powder.
Evaluation:
The obtained pressed powder had a smooth and comfortable texture and an in-vitro SPF of 17.
EXAMPLE 9
Oil Based Cake Foundation
TABLE 5 Ingredients amount (wt %) (1) methicone treated talc 5.3 (2) methicone treated titanium dioxide 8 (3) composite powder Ex. 5 15 (4) methicone treated sericite 28.2 (5) methicone treated iron oxide red 0.5 (6) methicone treated iron oxide yellow 1.8 (7) methicone treated iron oxide black 0.2 (8) candelilla wax 1 (9) carnauba wax 1 (10) ceresin 1.5 (11) cyclopentasiloxane 14 (12) isononyl isononanate balance (13) polyglyceryl-2 diisostearate 2 (14) dextrin palmitate* 1 (15) octyl methoxy cinnamate 3 (16) Preservative suitable amount (17) antioxidant suitable amount *Rheopearl ™ KL(Chiba Seifun Co., Ltd.)
Preparation:
Powder ingredients (1)-(7) were mixed and pulverized in a Henschel mixer. Oil ingredients (8)-(17) were mixed and heated to melt and dissolved. The powder ingredients were added to the oil ingredients, the mixture was dispersed uniformly and put in a container, gradually cooled to the room temperature to give oil based cake foundation.
The obtained oil based cake foundation had a smooth and comfortable texture and an in-vitro SPF of 20.
EXAMPLE 10
Stick Type Foundation
TABLE 6 Ingredients amount (wt %) (1) dimethicone 18 (2) cyclopentasiloxane 30 (3) octyl methoxy cinnamate 5 (4) diisostearyl malate 4 (5) candelilla wax 6 (6) hydrogenated jojoba wax 4 (7) cetyl dimethicone copolyol 2 (8) sorbitan sesquiisostearate 0.5 (9) antioxidant suitable amount (10) Preservative suitable amount (11) perfume suitable amount (12) methicone treated colorant 0.5 (13) methicone treated titanium 3.5 dioxide (14) methicone treated talc 2 (15) methicone treated mica 2 (16) polymethyl methacrylate 2 (17) composite powder Ex. 2 10 (18) purified water balance (19) sodium citrate 0.3 (20) butyleneglycol 3 (21) glycerin 2 (22) Preservative suitable amount
Preparation:
Powder ingredients (12)-(17) were mixed in a Henschel mixer. Oil ingredients (1)-(11) were weighted, put in a container and heated to melt. Ingredients (18)-(22) were weighted and put in another container and dissolved by heating to give an aqueous solution. The mixture of the powder ingredients was added to the oil ingredients and the resulting mixture was dispersed uniformly. Then the aqueous solution was added thereto, and the mixture was emulsified and defoamed. Thus obtained mixture was put in a mold and cooled gradually to give the desired stick foundation.
Evaluation:
The obtained stick foundation had a smooth and comfortable texture and an in-vitro SPF of 17.
EXAMPLE 11
W/O Emulsion Foundation
TABLE 7 Ingredients amount (wt %) (1) POE-10 dimethicone(HLB = 4.5) 0.80 (2) Polyglyceryl polyricinoleate 0.50 (3) neopentyl glycol dicaprate 3.00 (4) squalane 1.00 (5) pentaerythrityl tetraethylhexanoate 2.00 (6) stearoyl inulin* 1.00 (7) octyl methoxy cinnamate 4.00 (8) cyclopentasiloxane 15.40 (9) Preservative suitable amount (10) antioxidant suitable amount (11) perfume suitable amount (12) silicone treated titanium dioxide 4.00 (13) silicone treated talc 3.68 (14) composite powder Ex. 3 6.00 (15) silicone treated colorant 1.00 (16) purified water balance (17) butylene glycol 6.00 (18) glycerin 1.00 (19) sodium chloride 1.00 (20) Preservative suitable amount *Rheopearl ™ ISK(Chiba Seifun Co., Ltd.)
Preperation:
Powder ingredients (12)-(15) were mixed in a Henschel mixer, added to oil ingredients (1)-(11), and the resulting mixture was kneaded uniformly. Ingredients (16)-(20) were heated in a separate container to provide an aqueous solution. The mixture wherein powder ingredients were dispersed in the oil ingredients, was added to the aqueous solution and the mixture was emulsified. The emulsion was cooled gradually to the room temperature to give the desired W/O emulsion foundation.
Evaluation:
The obtained W/O emulsion foundation had a smooth and comfortable texture and an in-vitro SPF of 18.
EXAMPLE 12
Cheek Blush
TABLE 8 Ingredients amount (wt %) (1) talc balance (2) sericite 60.9 (3) micronized titanium 3.0 dioxide (4) composite powder of 17.5 claim 5 (5) colorant suitable amount (6) octyl methoxy 3.0 cinnamate (7) octyl palmitate 5.0 (8) Preservative suitable amount (9) antioxidant suitable amount
Preparation:
Powder ingredients (1)-(5) were mixed by a Henschel Mixer and oil ingredients (6)-(9) were dissolved by heating. Both mixtures were mixed and pulverized with an atomizer. The resulting powder was put in a dish and pressed to give the desired pressed cheek color blush.
The obtained pressed cheek color blush had a smooth and comfortable texture and an in-vitro SPF of 25.
EXAMPLE 13
Sunscreen Cream
TABLE 9 Ingredients amount (wt %) (1) PEG-10 dimeticone 3 (2) cyclopentasiloxane 15.8 (3) neopentylglycol dicaprate 5 (4) squalane 5 (5) dextrin palmitate* 1.5 (6) octyl methoxy cinnamate 3 (7) preservative suitable amount (8) antioxidant suitable amount (9) Micronized titanium dioxide 58% 20 dispersion** (10) composite powder Ex. 3 5 (11) purified water balance (12) butyleneglycol 4 (13) peservative suitable amount (14) sodium chloride 1 *Rheopearl ™ ISK(Chiba Seifun Co., Ltd.) **Cosmeserve ™ WP-58MP(V) (Dainippon Kasei Co., Ltd.)
Preparation:
Oil ingredients (1)-(8) were dissolved by heating and ingredients (9) and (10) were added thereto. The mixture was dispersed uniformly by an agitator. Ingredients (11)-(14) were put in a separate container and heated to give an aqueous solution. Said aqueous solution was added to the mixture of ingredients (1)-(10) and dispersed to give emulsion, the mixture was cooled to room temperature to give sunscreen cream. Thus obtained sunscreen cream was highly transparent and had a smooth and comfortable texture and an in-vitro SPF of 50.
EXAMPLE 14
Lipstick
TABLE 10 Ingredients amount (wt %) (1) carnauba wax 2.00 (2) candelilla wax 5.00 (3) ceresin 6.00 (4) microcrystalline wax 2.00 (5) cholesteryl hydroxystearate 1.50 (6) diisostearyl malate 12.00 (7) glyceryl triisostearate balance (8) neopentyl glycol dicaprate 8.15 (9) octyldodecanol 12 (10) pentaerythritol-fatty acid ester 12 (11) octyl methoxy cinnamate 3 (12) antioxidant suitable amount (13) peservative suitable amount (14) colorant suitable amount (15) composite powder of Example 5 5.00 (16) Pearl Lustre Pigments 5.00
Preparation:
Oil ingredients (1)-(13) were mixed and dissolved to give an uniform solution, ingredients (14)-(16) were added thereto and dispersed uniformly. The mixture was defoamed, poured in a mold and cooled. Thus obtained stick was mounted in a suitable container to give lipstick.
The obtained lipstick had a smooth and comfortable texture and an in-vitro SPF of 10.
EXAMPLE 15
Pore Minimizer Makeup Base
TABLE 11 Ingredients amount (wt %) (1) octyl methoxy cinnamate 5 (2) methylphenylpolysiloxane 30.15 (3) stearylalcohol 9 (4) dextrin palmitate* 7.4 (5) preservative suitable amount (6) antioxidant suitable amount (7) cyclopenta siloxane balance (8) Composite powder Example 4 10 (9) porous silica** 20 *Rheopearl ™ KL(Chiba Seifun Co., Ltd.) **SUNSPHERE ® L-51 (Asahi Glass SI-Tech. Co., Ltd.)
Preparation:
Oil ingredients (1)-(7) were dissolved to give uniform solution. Ingredients (8) and (9) were added thereto and dispersed uniformly. The mixture was defoamed and poured in a suitable container and cooled gradually to room temperature to give pore minimizing make up base. The make up base had a smooth and comfortable texture and an in-vitro SPF of 20 (in vitro).
EXAMPLE 16
Loose Powder
TABLE 12 Ingredients amount (wt %) (1) talc balance (2) titanium dioxide 1 (3) lauroyl lysine* 3 (4) composite powder Ex. 4 10 (5) Micronized titanium dioxide 5 (6) Preservative suitable amount (7) colorant suitable amount (8) squalane 1 (9) preservative suitable amount (10) antioxidant suitable amount (11) perfume suitable amount *Amihope ® LL(Ajinomoto Co., Inc.)
Preparation:
Powder ingredients (1)-(7) were pulverized and mixed, and put in a Henschel mixer. The oil ingredients (8)-(11) were added thereto and the mixture was kneaded uniformly. Thus obtained uniform mixture was pulverized with an atomizer and the obtained powder was put in an aluminum dish and pressed to give pressed loose powder.
The pressed loose powder had a smooth and comfortable texture and an in-vitro SPF of 15.
The contents of the references cited in the instant specification are herein incorporated by reference.
1.PublishNumber: US-2007104662-A1
2.Date Publish: 20070510
3.Inventor: SATONAKA KENYA
YOSHIOKA TAKATSUGU
MOTOKI TAKASHI
YAMAGATA TOMOHIRO
4.Inventor Harmonized: SATONAKA KENYA(JP)
YOSHIOKA TAKATSUGU(JP)
MOTOKI TAKASHI(JP)
YAMAGATA TOMOHIRO(JP)
5.Country: US
6.Claims:
(en)An ultraviolet-absorbing composite powder comprising a plurality of composite powder particles, wherein the composite powder particle consists of an inorganic or organic core particle having an average particle diameter of 0.5-100 μm, and a compound of formula (1):
which is adsorbed to the surface of the core particle is provided. The composite powder of the invention exhibits an excellent UV ray protecting property as well as smooth and comfortable texture, and is useful for manufacturing cosmetic products.
7.Description:
(en)FIELD OF THE INVENTION
The instant application relates to a composite powder having core particle and benzotriazol UV absorber coating which is coated on the surface of the core particle, and cosmetic composition comprising the same.
ART RELATED
Ultraviolet light is divided into UV-C (200-280 nm wavelength) which is absorbed by the ozone layer, UV-B (280-320 nm) which causes sunburn, and UV-A (320-400 nm) which promotes suntan after exposure. According to recent studies, UV-A and UV-B cause harmful effects including not only sunburn and suntan but also pigment deposition, dry skin, skin roughness and skin aging. In addition, depletion of the ozone layer results in increased UV radiation reaching the Earth's surface, which in turn can lead to a greater chance of overexposure to UV radiation and the related effects to the skin. There are increasing desire for cosmetics with UV-protecting property.
Organic ultraviolet absorbers, which have been used for protecting against UV radiation, have various problems in using the same for manufacturing cosmetic products, for examples, (1) being less soluble to oils, especially silicone oils, which are conventionally used in cosmetics; (2) usually cause sticky feelings to the skin; (3) being less stable against light; (4) discoloration and/or unpleasant odor occurs upon time. On the other hand, conventionally used inorganic UV absorbers have problems such as (1) cause squeaky feeling, (2) result in white appearance when applied to the skin and (3) act as light catalyst. Due to those problems, the amount of the inorganic UV absorbers being added to cosmetic product has been limited. In addition, many conventional cosmetic products with UV protecting property comprises sole UV absorber and there are no products having UV protecting properties against wide range of UV rays including UV-A and UV-B.
A new UV absorber which is excellent in light stability and can protect against wide range UV rays, 2,2′-methylenebis[6-(2H-benzotriazolyl-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] has been developed (see U.S. Pat. No. 5,225,951, the contents of which is herein incorporated by reference). In this specification, the compound is abbreviated as “MBBT”. This organic UV absorber is insoluble to water as well as to oils used in cosmetic products and provides the UV protecting effect by absorbing, scattering and reflecting UV rays. The UV protecting effect based on the UV ray scattering and reflecting may vary depending on the particle size of the compound and particle size range of 150-200 nm is optimal. In addition, combined use of MBBT with another UV absorber will synergistically increase the UV protecting property of the compound.
U.S. Pat. No. 6,235,271, the contents of which is herein incorporated by reference, discloses a product comprising micronized MBBT of the optimal particle size dispersed in water. Said aqueous dispersion of micronized MBBT is used conveniently for manufacturing cosmetic product and has been available on market (TINOSORB® M, Ciba Specialty Chemicals, Basel, Switzerland). However, said product cannot be used for manufacturing non-aqueous formulation. In addition, MBBT particles will aggregate when a salt is added to the dispersion and the UV protecting action of the aggregated MBBT will decrease significantly. For manufacturing water in oil type emulsion, salts such as sodium sulfate and sodium chloride are added to stabilize the emulsion and therefore, it was difficult to manufacture water in oil emulsion with the aqueous dispersion of MBBT. In addition, a large amount of MBBT in a cosmetic composition may cause unpleasant texture of the product.
Japanese Patent Application Laid Open No. 2004-168913 proposes incorporating MBBT particles in a polymer matrix which is soluble in organic solvents. However, the MBBT particles tend to aggregate upon incorporating the same into the polymer matrix and therefore, hardly maintain the optimal particle size. Accordingly, the resulting product could not provide enough UV-protecting effect.
SUMMARY OF THE INVENTION
An object of the application is to provide a transparent composite powder which has excellent ultraviolet-absorbing ability and is comfortable to wear. A further object of the application is to provide a cosmetic composition having a high ultraviolet-protecting property comprising said composite powder.
The instant application provides a composite powder comprising a plurality of composite powder particles, wherein the composite powder particle consists of an inorganic or organic core particle having an average particle diameter of 0.5-100 μm, and a compound of formula (1):
which is coated on the surface of the core particle. The benzotriazol type ultraviolet-absorber of formula (1) is insoluble in water or oils used for manufacturing cosmetic compositions.
Further, the instant application provides a cosmetic composition comprising the above described composite powder. Preferably, the cosmetic composition further comprises a methoxy cinnamate derivative such as octyl methoxy cinnamate and isoamyl methoxy cinnamate or butyl methoxydibenzoylmethane (BMDBM). By the combined use of the composite powder of the invention and a methoxy cinnamate derivative or BMDBM, the photostability of the methoxy cinnamate derivative or BMDBM can be enhanced and the ultraviolet protecting property of the cosmetic composition will be synergistically increased.
Further more, the instant application provides a method for manufacturing the composite powder of the invention, which comprises the step of mixing the core particles and the compound of formula (1) in an aqueous solvent under the presence of an aqueous soluble salt of a metal selected from the group consisting of Al, Mg, Ca, Zn, Zr and Ti whereby the compound of formula (1) adsorbs to the surface of the core particles.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 depicts the graph showing the result of test example 1.
FIG. 2 is an electron micrograph of the composite powder obtained in example 1.
FIG. 3 is an electron micrograph of the composite powder obtained in Example 5.
BEST MODE FOR CARRYING OUT THE INVENTION
The compound of formula (1), a benzotriazole type UV absorber, is preferably in the form of fine particles having an average particle diameter of equal to or less than 200 nm, more preferably, 150-200 nm. Higher UV protecting property of the resulting composite powder can be achieved by employing the particles within said size range. The compound of formula (1) is available on market and TINOSORB® M (Ciba Specialty Chemicals, Basel, Switzerland) can preferably used in this invention. TINOSORB® M is an aqueous dispersion containing 50% of powdery compound of formula (1) having an average particle diameter of 200 nm or less.
The inorganic or organic core particle having an average particle diameter of 0.5-100 μm may be any material used for manufacturing cosmetic products. For example, inorganic particles such as talc, kaolin, sericite, white mica, bronze mica, black mica, synthetic mica, red mica, lithia mica, vermiculite, magnesium carbonate, calcium carbonate, diatomite, magnesium silicate, calcium silicate, aluminum silicate, barium silicate, barium sulfate, strontium silicate, metal tungstate, silica, hydroxyapatite, zeolite, boron nitride and ceramics powder, organic particles such as nylon powder, silicone powder, polyethylene powder, polystyrene powder, benzoguanamine powder, polyethylene tetrafluoride, distyrene benzene polymer powder, epoxy powder, acrylic powder, microcrystalline cellulose and urethane powder, as well as white pigments such as titanium oxide, micro titanium dioxide, zinc oxide and micro zinc oxide. Among them, talc, mica, sericite, kaolin and barium sulfate are preferably used. Lamellar particles are especially useful since the resulting composite particles will have uneven surface which provide less supecular reflection and cause less glossy-finish. When spherical particles such as silica or cellulose are used as core particles, the surface of the resulting composite particle becomes uneven due to the treatment with the compound of formula (1) and therefore, the composite powder having a higher diffuse reflection property can be obtained and the cosmetic composition comprising said composite powder can provide an excellent power to minimize the appearance of skin pores.
The average particle diameter of the core particles is preferably 0.5-100 μm, more preferably, 1-50 μm. When the average particle size is less than 0.5 μm, the composite powder with the good properties cannot be obtained using the benzotriazole UV-absorber having an average particle size of 200 nm or less. In contrast, when the particle diameter of the core particles is 100 μm or more, the texture of the resulting composite powder becomes unpleasant.
The composite powder of the invention may be manufactured by mixing the core particles and the compound of formula (1) in an aqueous solvent under the presence of an aqueous soluble salt of a metal selected from the group consisting of Al, Mg, Ca, Zn, Zr and Ti whereby coating the core particle by the compound of formula (1). According to the method of the invention, the particles of the compound of formula (1) are adsorbed to the surface of the core particles in an oriented manner. Examples of the aqueous soluble salt of a metal selected from the group consisting of Al, Mg, Ca, Zn, Zr and Ti used in the instant method may include aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum calcium sulfate, magnesium chloride, magnesium sulfate, magnesium nitrate, calcium sulfate, calcium chloride, calcium nitrate, calcium acetate, zinc chloride, zinc nitrate, zinc sulfate, zinc acetate, zirconium sulfate, zirconium chloride, titanium oxysulfate and titanium tetrachloride. Among the above, aluminum sulfate is especially useful in view of its availability. The metal salts may be used as aqueous solutions thereof.
Upon manufacturing the composite powder of the present invention, the amount of the benzotriazole type UV-absorber of formula (1) may be 1 wt % or more, and 35 wt % or less, especially, 3-30 wt % based on the total amount of the core particles and the UV absorber. By adjusting the amount of the UV-absorber, the resulting composite powder can exhibit good UV protecting effect as well as good and comfortable texture.
According to the method for manufacturing the composite powder of the invention, the amount of the salt of a metal selected from the group consisting of Al, Mg, Ca, Zn, Zr and Ti per one part by weight of the compound of formula (1) may preferably be ¼ part by weight or more so that the particles of the benzotriazole type UV-absorber are adsorbed well to the surface of the core particles, and 2 parts by weight or less in view of the comfortable texture of the resulting composite powder, and especially, ½-1 part by weight.
The composite powder of the invention consists of plurality of composite powder particles that comprises core particles and compound of formula (1) adsorbed thereto in an oriented manner. The details of the surface treatment is not specifically limited and may be carried out based on known procedures. For example, the core particles are dispersed in water and 1-35 wt % of the compound of formula (1), based on the total amount of the core particles and the compound of formula (1), is added to the dispersion and stirred vigorously. The oriented adsorption of a part of the benzotriazole compound to the surface of the core particles occurs during this stage. Then, an aqueous soluble salt of a metal selected from the group consisting of Al, Mg, Ca, Zn, Zr and Ti in an amount of ¼-2 parts by weight per one part by weight of the compound of formula (1) in the form of aqueous solution is added to the mixture. By adding the aqueous solution of the salt, the oriented adsorption of the particles of the compound of formula (1) to the surface of the core particles is completed. Thus obtained mixture is then dehydrated and washed by centrifugation or the like, and dried at 80-120° C. to give the desired composite powder having UV ray protecting property.
Thus obtained composite powder of the invention has the structure wherein particles of the insoluble benzotriazole UV absorber of formula (1) are adsorbed uniformly to the surface of the core particle and the UV absorber particles are not aggregated each other. Due to the structure, the composite particle behaves as if it is primary particle consisting of single particle. Accordingly, the composite powder of the invention comprising plurality of the composite particles is highly transparent, has smooth and comfortable texture, and provides an excellent UV ray protecting property. The composite powder of the invention is preferably used for manufacturing cosmetic products.
The composite powder of the invention may be used without further processing or the surface of the composite particle may include treated with a hydrophobic agent to give hydrophobic powder. Examples of hydrophobic agents for the hydrophobic treatment may be silicone agent, fatty acid, fatty acid soap and fatty acid ester. Examples of silicone agents may include silicone oils such as methylhydrogenpoly siloxane, dimethylpoly siloxane and methylphenylpoly siloxane, alkyl silanes such as methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane and octyltrimethoxysilane, fluoroalkyl silanes such as trifluoromethylethyltrimethoxysilane and heptadecafluorodecyl trimethoxysilane. Examples of fatty acids may include palmitic acid, isostearic acid, stearic acid, lauric acid, myristic acid, behenic acid, oleic acid, rosin acid and 1,2-hydroxystearic acid. Examples of fatty acid soaps may include aluminum stearate, calcium stearate and aluminum 1,2-hydroxystearate. Examples of fatty acid esters may include dextrin fatty acid ester, cholesterol fatty acid ester, sucrose fatty acid ester and starch fatty acid ester. The hydrophobic treatment of the composite powder of the invention may be carried out with one or more of the hydrophobic agents as above and according to a conventionally known method.
The instant invention further provide a cosmetic composition comprising the composite powder of the invention. The cosmetic composition of the present invention may comprise further ingredients which are added to conventional cosmetic products, if desired. Examples of the ingredients other than the composite powder of the invention may include solid/half solid oil such as vaseline, lanoline, ceresin, microcrystalline wax, carnauba wax, candelilla wax, higher fatty acid and higher alcohol, fluid oil such as squalan, fluid paraffin, ester oil, diglyceride, triglyceride, silicone oil, olive oil, avocado oil and mink oil, fluoride oils such as perfluoro polyether, perfluorodecalin and perfluorooctane, water- and oil-soluble polymer, surface active agent, inorganic and organic pigments, silicone, metal soap, lecithin, amino acid, collagen, polymer, inorganic or organic pigment whose surface is treated by fluoride compound, colorant such as tar color and natural color, ethanol, antiseptic agent, antioxidant, dye, thickener, pH adjustor, flavoring agent, UV absorber, moisturizing agent, blood circulation improver, cool feeling agent, bactericide, skin activating agent and water. Those ingredients may be added to the cosmetic composition of the invention as long as they deteriorate the object of the invention.
The cosmetic composition of the present invention may preferably comprise an additional UV absorbing agent selected from a methoxy cinnamate derivative such as octyl methoxy cinnamate or isoamyl methoxy cinnamate and butyl methoxydibenzoylmethane (BMDBM). By the combined use of the composite powder and a methoxy cinnamate derivative or BMDBM, a synergistic UV-protecting property can be provided to the resulting composition. Preferably, the additional UV absorbing agent is a methoxy cinnamate derivative, especially, octyl methoxy cinnamate.
The octyl methoxy cinnamate used in the instant invention is a transparent pale yellow liquid with weak characteristic odor and is a UV-B absorber widely used for manufacturing cosmetic products. The compound is commercially available, for example PARSOL® MCX (DSM Nutritional Products), Uvinul® MC-80 (BASF), NOMUCORT® TAB (Nisshin Oillio) and Escarole® (ISP). Isoamyl methoxy cinnamate is also available on market as Neo Heliopan® E1000 (H&R).
The cosmetic composition of the invention may further comprise one or more additional UV filter substances and adjuvants shown in the table below:
Suitable UV filter substances and adjuvants which can be additionally used with the UV Ray absorbing composite powder according to the present invention No. Chemical Name CAS No. 1 (+/−)-1,7,7-trimethyl-3-[(4- 36861-47-9 methyiphenyl)methylene]bicyclo- [2.2.1]heptan-2-one; p-methyl benzylidene camphor 2 1,7,7-trimethyl-3- 15087-24-8 (phenylmethylene)bicyclo[2.2.1]heptan-2- one; benzylidene camphor 3 (2-Hydroxy-4-methoxyphenyl)(4- 1641-17-4 methylphenyl)methanone 4 2,4-dihydroxybenzophenone 131-56-6 5 2,2′,4,4′-tetrahydroxybenzophenone 131-55-5 6 2-Hydroxy-4-methoxy benzophenone; 131-57-7 7 2-Hydroxy-4-methoxy benzophenone-5-sulfonic 4065-45-6 acid 8 2,2′-dihydroxy-4,4′-dimethoxybenzophenone 131-54-4 9 2,2′-Dihydroxy-4-methoxybenzophenone 131-53-3 10 Alpha-(2-oxoborn-3-ylidene)toluene-4- 56039-58-8 sulphonic acid and its salts (Mexoryl SL) 11 1-[4-(1,1-dimethylethyl)phenyl]-3-(4- 70356-09-1 methoxyphenyl)propane-1,3-dione (Avobenzone) 12 Methyl N,N,N-trimethyl-4-[(4,7,7-trimethyl- 52793-97-2 3-oxobicyclo[2,2,1]hept-2- ylidene)methyl]anilinium sulphate (Mexoryl SO) 22 3,3,5-Trimethyl cyclohexyl-2-hydroxy 118-56-9 benzoate; homosalate 23 Isopentyl p-methoxycinnamate; isoamyl 71617-10-2 methoxy cinnamate 27 Menthyl-o-aminobenzoate 134-09-8 28 Menthyl salicylate 89-46-3 29 2-Ethylhexyl 2-cyano,3,3-diphenylacrylate; 6197-30-4 octocrylene 30 2-ethylhexyl 4-(dimethylamino)benzoate 21245-02-3 31 2-ethylhexyl 4-methoxycinnamate; octyl 5466-77-3 methoxy cinnamate 32 2-ethylhexyl salicylate 118-60-5 33 Benzoic acid,4,4′,4′′-(1,3,5-triazine- 88122-99-0 2,4,6-triyltriimino)tris-, tris(2- ethylhexyl)ester; 2,4,6-Trianilino-(p- carbo-2′-ethylhexyl-1′-oxl)-1,3,5-triazine (Octyl Triazone) 34 4-aminobenzoic acid 150-13-0 35 Benzoic acid, 4-amino-, ethyl ester, 113010-52-9 polymer with oxirane 38 2-phenyl-1H-benzimidazole-5-sulphonic 27503-81-7 acid; phenylbenzimidazolsulfonic acid 39 2-Propenamide, N-[[4-((4,7,7-trimethyl-3-oxobicyclo[2.2.]hept- 147897-12-9 2-ylidene)methyl]phenyl]methyl)-, homopolymer 40 Triethanolamine salicylate 2174-16-5 41 3,3′-(1,4-phenylenedimethylene)bis[7,7- 90457-82-2 dimethyl-2-oxo-bicyclo[2.2.1]heptane-1 methanesulfonic acid] (Cibafast H) 42 Titanium dioxide 13463-67-7 44 Zinc oxide 1314-13-2 45 2,2′-Methylene-bis-[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3- 103597-45-1 tetramethylbutyl)-phenol](Tinosorb M) 46 2,4-bis{(4-(2-ethylhexyloxy)-2-hydroxy]- 187393-00-6 phenyl)-6-(4-methoxyphenyl)-(1,3,5)- triazine (Tinosorb S) 47 1H-Benzimidazole-4,6-disulfonic acid, 2,2′- 180898-37-7 (1,4-phenylene)bis-, disodium salt 48 Benzoic acid, 4,4′-[[6-[[4-[[(1,1-dimethylethyl)amino]carbonyl]- 154702-15-5 phenyl]amino]1,3,5-triazine-2,4-diyl]diimino]bis-, bis(2-ethylhe- xyl)ester; diethylhexyl butamido triazone (Uvasorb HEB) 49 Phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3- 155633-54-8 [1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]-; drometrizole trisiloxane (Mexoryl XL) 50 Dimethicodiethylbenzalmalonate; Polysilicone 15 (Parsol SLX) 207574-74-1 51 Benzenesulfonic acid, 3-(2H-benzotnazol-2-yl)-4-hydroxy-5-(1- 92484-48-5 methylpropyl)-, monosodium salt (Tinogard HS) 52 Benzoic acid, 2-[4-(diethylamino)-2- 302776-68-7 hydroxybenzoyl]-, hexyl ester (Uvinul A Plus) 53 1-Dodecanaminium, N-[3-[[4-(dimethylamino)benzoyl]amino]- 156679-41-3 propyl]N,N-dimethyl-, salt with 4-methylbenzenesulfonic acid (1:1) (Escalol HP610) 54 1-Propanaminium, N,N,N-trimethyl-3-[(1-oxo-3-phenyl-2- 177190-98-6 propenyl)amino]-, chloride 55 1H-Benzimidazole-4,6-disulfonic acid, 2,2′- 170864-82-1 (1,4-phenylene)bis- 56 1,3,5-Triazine, 2,4,6-tris(4- 7753-12-0 methoxyphenyl)- 57 1,3,5-Triazine, 2,4,6-tris[4-[(2- 208114-14-1 ethylhexyl)oxy]phenyl]- 58 1-Propanaminium, 3-[(3-[3-(2H-benzotriazol- 340964-15-0 2-yl)-5-(1,1-dimethylethyl)-4- hydroxyphenyl]-1-oxopropyl]amino]-N,N- diethyl-N-methyl-, methyl sulfate (salt) 59 2-Propenoic acid, 3-(1H-imidazol-4-yl)- 104-98-3 60 Benzoic acid, 2-hydroxy-, [4-(1- 94134-93-7 methylethyl)phenyl]methyl ester 61 1,2,3-Propanetriol, 1-(4-aminobenzoate) 136-44-7 (Glyceryl PABA) 62 Benzeneacetic acid, 3,4-dimethoxy-a-oxo- 4732-70-1 63 2-Propenoic acid, 2-cyano-3,3-diphenyl-, 5232-99-5 ethyl ester 64 Anthralinic acid, p-menth-3-yl ester 134-09-8 65 2,2′-bis(1,4-phenylene)-1H-benzimidazole- 349580-12-7, 4,6-disulphonic acid mono sodium salt or Disodium phenyl dibenzimidazole tetrasulfonate (Neo Heliopan AP) 66 1,3,5-Triazine-2,4,6-triamine, N,N′-bis[4- 288254-16-0 [5-(1,1-dimethylpropyl)-2- benzoxazolyl]phenyl]-N″-(2-ethylhexyl)- (Uvasorb K2A) 67 68 sterols (cholesterol, lanosterol, phytosterols), as described in WO0341675 69 mycosporines and/or mycosporine-like amino acids as described in WO2002039974, e.g. Helioguard 365 from Milbelle AG, isolated mycosporine like amino acids from the red alga porphyra umbilicalis (INCI: Porphyra Umbilicalis )that are encapsulated into liposomes,) 70 alpha-lipoic-acid as described in DE 10229995 71 synthetic organic polymers as described in EP 1371358, [0033]-[0041] 72 phyllosilicates as described in EP 1371357 [0034]-[0037] 73 silica compounds as described in EP1371356, [0033]-[0041] 74 inorganic particles as described in DE10138496 [0043]-[0055] 75 latex particles as described in DEfl0138496 [0027]-[0040] 76 1H-Benzimidazole-4,6-disulfonic acid, 2,2′- 180898-37-7 (1,4-phenylene)bis-, disodium salt; Bisimidazylate (Neo Heliopan APC) 77 78 79 E or Z isomer or mixture of E/Z isomers 80 81 Di-2-ethylhexyl-3,5-dimethoxy-4-hydroxy- benzalmalonate (Oxynex ST, EMD Chemicals, as described in U.S. Pat. No. 20040247536) 82 2,4,6-Tris-1,1′,4′,1″-terphenyl-4-yl- 1,3,5-triazine
The form or product type of the instant cosmetic composition is not specifically limited and may be in the form of make up products such as powdery foundation, cream foundation, oil base foundation, two-way foundation, stick type foundation, loose powder, eye shadow, cheek blush and lipstick, skin care products such as lotion, emulsion and cream as well as body cosmetics such as body powder and baby powder.
As water- and oil-containing emulsions (e.g. W/O, O/W, O/W/O and W/O/W emulsions or microemulsions) the preparations contain, for example, from 0.1 to 30% by weight, preferably from 0.1 to 15% by weight and especially from 0.5 to 10% by weight, based on the total weight of the composition, of one or more UV absorbers including the composite powder of the invention, from 1 to 60% by weight, especially from 5 to 50% by weight and preferably from 10 to 35% by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30% by weight, especially from 1 to 30% by weight und preferably from 4 to 20% by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90% by weight, especially from 30 to 90% by weight, based on the total weight of the composition, of water, and from 0 to 88.9% by weight, especially from 1 to 50 % by weight, of further cosmetically acceptable adjuvants.
The cosmetic or pharmaceutical compositions/preparations according to the invention may also contain one or one more additional compounds as described below.
Fatty Alcohols
Guerbet alcohols based on fatty alcohols having from 6 to 18, preferably from 8 to 10 carbon atoms including cetyl alcohol, stearyl alcohol, cetearyl alcohol, oleyl alcohol, octyldodecanol, benzoate of C12-C15 alcohols, acetylated lanolin alcohol, etc.
Esters of Fatty Acids
Esters of linear C6-C24 fatty acids with linear C3-C24 alcohols, esters of branched C6 C13carboxylic acids with linear C6-C24 fatty alcohols, esters of linear C6-C24 fatty acids with branched alcohols, especially 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C6-C22 fatty alcohols, especially dioctyl malates, esters of linear and/or branched fatty acids with polyhydric alcohols (for example propylene glycol, dimer diol or trimer triol) and/or Guerbet alcohols, for example caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and technical-grade mixtures thereof (obtained, for example, in the pressure removal of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or in the dimerisation of unsaturated fatty acids) with alcohols, for example, isopropyl alcohol, caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linoyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and technical-grade mixtures thereof (obtained, for example, in the high-pressure hydrogenation of technical-grade methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as monomer fractions in the dimerisation of unsaturated fatty alcohols).
Examples of such ester oils are isopropylmyristate, isopropylpalmitate, isopropylstearate, isopropyl isostearate, isopropyloleate, n-butylstearate, n-hexyllaurate, n-decyloleate, isooctylstearate, iso-nonylstearate, isononyl isononanoate, 2-ethylhexylpalmitate, 2-hexyllaurate, 2-hexyldecylstearate, 2-octyldodecylpalmitate, oleyloleate, oleylerucate, erucyloleate, erucylerucate, cetearyl octanoate, cetyl palmitate, cetyl stearate, cetyl oleate, cetyl behenate, cetyl acetate, myristyl myristate, myristyl behenate, myristyl oleate, myristyl stearate, myristyl palmitate, myristyl lactate, propylene glycol dicaprylate/caprate, stearyl heptanoate, diisostearyl malate, octyl hydroxystearate, etc.
Other Adjuvants
Alpha glucosylrutin (CAS No. 130603-71-3), 2-butyloctyl o-hydroxybenzoate (CAS No. 190085-41-7), vitamin E (CAS No. 1406-18-4), vitamin E acetate (CAS No. 58-95-7), diethylhexyl 2,6- naphthalate, di-n-butyl adipate, di(2-ethylhexyl)-adipate, di(2-ethylhexyl)-succinate and diisotridecyl acelaat, and also diol esters, such as ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di(2-ethylhexanoate), propylene glycol diisostearate, propylene glycol dipelargonate, butanediol diisostearate and neopentyl glycol dicaprylate. Esters of C6-C24 fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, saturated and/or unsaturated, especially benzoic acid, esters of C2-C12dicarboxylic acids with linear or branched alcohols having from 1 to 22 carbon atoms or polyols having from 2 to 10 carbon atoms and from 2 to 6 hydroxy groups, or iminodisuccinic acid and imiondisuccinic acid salts [CAS 7408-20-0] or latex particles, aloe vera, chamomile, ginko biloba, ginseng, coenzyme Q10, laminaria ochroleuca extract, magnolia oborata extract, melalenca alternifolia leaf oil, rubus idaeus seed oil, vaccinium macrocarpon seed oil, pumpkin seed extract, pumpkin seed oil, grape seed extract, carnosine, alpha-arbutin, madecassoside, termino-laside, tetrahydrocurcuminoids (THC), mycosporines, mycosporine like amino acids from the red alga porphyra umbilicalis, mycosporine-like amino acids (as described in WO2002039974), cis-9-octadecenedioic acid, lipoic acid, laurimino dipropiomic acid tocopheryl phosphates (LDTP), microcrystalline cellulose (MCC), polycarbonates as described in WO 0341676, sterols (cholesterol, lanosterol, phytosterols), as described in W00341675 and linear poly-alpha-glucans as described in U.S. Pat. No. 6,616,935, the contents of those references are herein incorporated by reference.
Natural or Synthetic Triglycerides Including Glyceryl Esters and Derivatives
Di- or tri-glycerides, based on C6-C18 fatty acids, modified by reaction with other alcohols (caprylic/capric triglyceride, wheat germ glycerides, etc.). Fatty acid esters of polyglycerin (polyglyceryl-n such as polyglyceryl-4 caprate, polyglyceryl-2 isostearate, etc. or castor oil, hydrogenated vegetable oil, sweet almond oil, wheat germ oil, sesame oil, hydrogenated cottonseed oil, coconut oil, avocado oil, corn oil, hydrogenated castor oil, shea butter, cocoa butter, soybean oil, mink oil, sunflower oil, safflower oil, macadamia nut oil, olive oil, hydrogenated tallow, apricot kernel oil, hazelnut oil, borago oil, etc.
Waxes including esters of long-chain acids and alcohols as well as compounds having wax-like properties, e.g., carnauba wax, beeswax (white or yellow), lanolin wax, candellila wax, ozokerite, japan wax, paraffin wax, microcrystalline wax, ceresin, cetearyl esters wax, synthetic beeswax, etc. Also, hydrophilic waxes as Cetearyl Alcohol or partial glycerides.
Pearlescent Waxes
Alkylene glycol esters, especially ethylene glycol distearate; fatty acid alkanolamides, especially coco fatty acid diethanolamide; partial glycerides, especially stearic acid monoglyceride; esters of polyvalent, unsubstituted or hydroxy-substituted carboxylic acids with fatty alcohols having from 6 to 22 carbon atoms, especially long-chained esters of tartaric acid; fatty substances, for example fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon atoms, especially laurone and distearyl ether; fatty acids, such as stearic acid, hydroxystearic acid or behenic acid, ring-opening products of olefin epoxides having from 12 to 22 carbon atoms with fatty alcohols having from 12 to 22 carbon atoms and/or polyols having from 2 to 15 carbon atoms and from 2 to 10 hydroxy groups, and mixtures thereof.
Hydrocarbon Oils
Mineral oil (light or heavy), petrolatum (yellow or white), microcrystalline wax, paraffinic and isoparaffinic compounds, hydrogenated isoparaffinic molecules as polydecenes and polybutene, hydrogenated polyisobutene, squalane, isohexadecane, isododecane and others from plant and animal kingdom.
Silicones or Siloxanes (Organosubstituted Polysiloxanes)
Dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones, and also amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/or alkyl-modified silicone compounds, which at room temperature may be in either liquid or resinous form. Linear polysiloxanes, dimethicone (Dow Corning 200 fluid, Rhodia Mirasil DM), dimethiconol, cyclic silicone fluids, cyclopentasiloxanes volatiles (Dow Corning 345 fluid), phenyltrimethicone (Dow Corning 556 fluid). Also suitable are simethicones, which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units with hydrogenated silicates. A detailed survey by Todd et al. of suitable volatile silicones may in addition be found in Cosm. Toil. 91, 27 (1976).
Fluorinated or Perfluorinated Oils
Perfluorhexane, dimethylcyclohexane, ethylcyclopentane, polyperfluoromethylisopropyl ether.
Emulsifiers
Any conventionally usable emulsifier can be used for the compositions. Emulsifier systems may comprise for example: carboxylic acids and their salts: alkaline soap of sodium, potassium and ammonium, metallic soap of calcium or magnesium, organic basis soap such as Lauric, palmitic, stearic and oleic acid etc. Alkyl phosphates or phosphoric acid esters, acid phosphate, diethanolamine phosphate, potassium cetyl phosphate. Ethoxylated carboxylic acids or polyethyleneglycol esters, PEG-n acylates. Linear fatty alcohols having from 8 to 22 carbon atoms, branched from 2 to 30 mol of ethylene oxide and/or from 0 to 5 mol propylene oxide with with fatty acids having from 12 to 22 carbon atoms and with alkylphenols having from 8 to 15 carbon atoms in the alkyl group. Fatty alcohol polyglycolether such as laureth-n, ceteareth-n, steareth-n, oleth-n. Fatty acid polyglycolether such as PEG-n stearate, PEG-n oleate, PEG-n cocoate. Monoglycerides and polyol esters. C12-C22 fatty acid mono- and di-esters of addition products of from 1 to 30 mol of ethylene oxide with polyols. Fatty acid and polyglycerol ester such as monostearate glycerol, diisostearoyl polyglyceryl-3-diisostearates, polyglyceryl-3-diisostearates, triglyceryl diisostearates, polyglyceryl-2-sesquiisostearates or polyglyceryl dimerates. Mixtures of compounds from a plurality of those substance classes are also suitable. Fatty acid polyglycolesters such as monostearate diethylene glycol, fatty acid and polyethylene glycol esters, fatty acid and saccharose esters such as sucro esters, glycerol and saccharose esters such as sucro glycerides. Sorbitol and sorbitan, sorbitan mono- and di-esters of saturated and unsaturated fatty acids having from 6 to 22 carbon atoms and ethylene oxide addition products. Polysorbate-n series, sorbitan esters such as sesquiisostearate, sorbitan, PEG-(6)-isostearate sorbitan, PEG-(10)-sorbitan laurate, PEG-17-dioleate sorbitan. Glucose derivatives, C8-C22 alkyl-mono and oligo-glycosides and ethoxylated analogues with glucose being preferred as the sugar component. O/W emulsifiers such as methyl gluceth-20 sesquistearate, sorbitan stearate/sucrose cocoate, methyl glucose sesquistearate, cetearyl alcohol/cetearyl glucoside. W/O emulsifiers such as methyl glucose dioleate/ methyl glucose isostearate. Sulfates and sulfonated derivatives, dialkylsulfosuccinates, dioctyl succinate, alkyl lauryl sulfonate, linear sulfonated parafins, sulfonated tetraproplyne sulfonate, sodium lauryl sulfates, amonium and ethanolamine lauryl sulfates, lauyl ether sulfates, sodium laureth sulfates, sulfosuccinates, aceyl isothionates, alkanolamide sulfates, taurines, methyl taurines, imidazole sulfates. Amine derivatives, amine salts, ethoxylated amines, oxide amine with chains containing an heterocycle such as alkyl imidazolines, pyridine derivatives, isoquinoteines, cetyl pyridinium chlorure, cetyl pyridinium bromide, quaternary ammonium such as cetyltrimethylbroide amonium broide (CTBA), stearylalkonium. Amide derivatives, alkanolamides such as acylamide DEA, ethoxylated amides such as PEG-n acylamide, oxydeamide. Polysiloxane/polyalkyl/polyether copolymers and derivatives, dimethicone, copolyols, silicone polyethylene oxide copolymer, silicone glycol copolymer. Propoxylated or POE-n ethers (Meroxapols), Polaxamers or poly(oxyethylene)m-block-poly(oxypropylene)n-block(oxyethylene). Zwitterionic surfactants that carry at least one quaternary ammonium group and at least one carboxylate and/or sulfonate group in the molecule. Zwitterionic surfactants that are especially suitable are betaines, such as N alkyl-N,N dimethylammonium glycinates, cocoalkyldimethylammonium glycinate, N acylaminopropyl N,N dimethylammonium glycinates, cocoacylaminopropyldimethylammonium glycinate and 2 alkyl-3-carboxymethyl-3-hydroxyethylimidazolines each having from 8 to 18 carbon atoms in the alkyl or acyl group and also cocoacylaminoethylhydroxyethylcarboxymethylglycinate, N-alkylbetaine, N-alkylaminobetaines. Alkylimidazolines, alkylopeptides, lipoaminoacides, self emulsifying bases and the compounds as described in K. F. DePolo, A short textbook of cosmetology, Chapter 8, Table 8-7, p 250-251.
Non ionic emulsifiers such as PEG-6 beeswax (and) PEG-6 stearate (and) polyglyceryl-2 isostearate [Apifac], glyceryl stearate (and) PEG-100 stearate. [Arlacel 165], PEG-5 glyceryl stearate [arlatone 983 S], sorbitan oleate (and) polyglyceryl-3 ricinoleate. [Arlacel 1689], sorbitan stearate and sucrose cocoate [arlatone 2121], glyceryl stearate and laureth-23 [Cerasynth 945], cetearyl alcohol and ceteth-20 [Cetomacrogol Wax], cetearyl alcohol and colysorbate 60 and PEG-150 and stearate-20 [Polawax GP 200, Polawax NF], cetearyl alcohol and cetearyl polyglucoside [Emulgade PL 1618], cetearyl alcohol and ceteareth-20 [Emulgade 1000NI, Cosmowax], cetearyl alcohol and PEG-40 castor oil [Emulgade F Special], cetearyl alcohol and PEG-40 castor oil and sodium cetearyl sulfate [Emulgade F], stearyl alcohol and steareth-7 and steareth-10 [Emulgator E 2155], cetearyl alcohol and steareth-7 and steareth-10 [Emulsifying wax U.S.N.F], glyceryl stearate and PEG-75 stearate [Gelot 64], propylene glycol ceteth-3 acetate [Hetester PCS], propylene glycol isoceth-3 acetate [Hetester PHA], cetearyl alcohol and ceteth-12 and oleth-12 (Lanbritol Wax N 21), PEG-6 stearate and PEG-32 stearate [Tefose 1500], PEG-6 stearate and ceteth-20 and steareth-20 [Tefose 2000], PEG-6 stearate and ceteth-20 and glyceryl stearate and steareth-20 [Tefose 2561], glyceryl stearate and ceteareth-20 [Teginacid H, C, X].
Anionic emulsifiers such as PEG-2 stearate SE, glyceryl stearate SE [Monelgine, Cutina KD], propylene glycol stearate [Tegin P], cetearyl Alcohol and Sodium cetearyl sulfate [Lanette N, Cutina LE, Crodacol GP], cetearyl alcohol and sodium lauryl sulfate [Lanette W], trilaneth-4 phopshate and glycol stearate and PEG-2 stearate [Sedefos 75], glyceryl stearate and sodium lauryl Sulfate [Teginacid Special]. Cationic acid bases such as cetearyl alcohol and cetrimonium bromide.
The emulsifiers may be used in an amount of, for example, from 1 to 30% by weight, especially from 4 to 20% by weight and preferably from 5 to 10% by weight, based on the total weight of the composition.
When formulated in O/W emulsions, the preferably amount of such emulsifier system could represent 5% to 20% of the oil phase.
Adjuvants and Additives
The cosmetic/pharmaceutical preparations, for example creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments, may in addition contain, as further adjuvants and additives, mild surfactants, super-fatting agents, consistency regulators, thickeners, polymers, stabilisers, biogenic active ingredients, deodorising active ingredients, anti-dandruff agents, film formers, swelling agents, further UV light-protective factors, antioxidants, hydrotropic agents, preservatives, insect repellents, self-tanning agents, solubilisers, perfume oils, colourants, bacteria-inhibiting agents and the like.
Super-Fatting Agents
Substances suitable for use as super-fatting agents are, for example, lanolin and lecithin and also polyethoxylated or acrylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the latter simultaneously acting as foam stabilisers.
Surfactants
Examples of suitable mild surfactants, that is to say surfactants especially well tolerated by the skin, include fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and/or di-alkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, □-olefin sulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides, alkylamidobetaines and/or protein fatty acid condensation products, the latter preferably being based on wheat proteins.
Consistency Regulators/Thickeners and Rheology Modifiers
Silicium dioxide, magnesium silicates, aluminium silicates, polysaccharides or derivatives thereof for example hyaluronic acid, xanthan gum, guar-guar, agar-agar, alginates, carraghenan, gellan, pectines, or modified cellulose such as hydroxycellulose, hydroxypropylmethylcellulose. In addition polyacrylates or homopolymer of reticulated acrylic acids and polyacrylamides, carbomer (carbopol types 980, 981, 1382, ETD 2001, ETD2020, Ultrez 10) or Salcare range such as Salcare SC80 (steareth-10 allyl ether/acrylates copolymer), Salcare SC81 (acrylates copolymer), Salcare SC91 and Salcare AST (sodium acrylates copolymer/PPG-1 trideceth-6), sepigel 305(polyacrylamide/laureth-7), Simulgel NS and Simulgel EG (hydroxyethyl acrylate/sodium acryloyldimethyl taurate copolymer), Stabilen 30 (acrylates/vinyl isodecanoate crosspolymer), Pemulen TR-1 (acrylates/C10-30 alkyl acrylate crosspolymer), Luvigel EM (sodium acrylates copolymer), Aculyn 28 (acrylates/beheneth-25 methacrylate copolymer), etc.
Polymers
Suitable cationic polymers are, for example, cationic cellulose derivatives, for example a quaternised hydroxymethyl cellulose obtainable under the name Polymer JR 400 from Amerchol, cationic starches, copolymers of diallylammonium salts and acrylamides, quarternised vinylpyrrolidone/vinyl imidazole polymers, for example LUViquat® (BASE), condensation products of polyglycols and amines, quaternised collagen polypeptides, for example lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat®L/Grünau), quaternised wheat polypeptides, polyethyleneimine, cationic silicone polymers, for example amidomethicones, copolymers of adipic acid and dimethylaminohydrdxypropyldiethylenetriamine (Cartaretin/Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride (Merquat 550/Chemviron), polyaminopolyamides, as described, for example, in FR-A-2 252 840, and the crosslinked water-soluble polymers thereof, cationic chitin derivatives, for example of quaternised chitosan, optionally distributed as microcrystals; condensation products of dihaloalkyls, for example dibromobutane, with bisdialkylamines, for example bisdimethylamino-1,3-propane, cationic guar gum, for example Jaguar C-17, Jaguar C-16 from Celanese, quaternised ammonium salt polymers, for example Mirapol A-15, Mirapol AD-1, Mirapol AZ-1 from Miranol. As anionic, zwitterionic, amphoteric and non-ionic polymers there come into consideration, for example, vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers and esters thereof, uncrosslinked polyacrylic acids and polyacrylic acids crosslinked with polyols, acrylamidopropyl-trimethylammonium chloride /acrylate copolymers, octyl acrylamide/methyl methacrylatetert butylaminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, vinylpyrrolidone/dimethylaminoethyl methacrylate/vinyl caprolactam terpolymers and also optionally derivatised cellulose ethers and silicones. Furthermore the polymers as described in EP 1093796 (pages 3-8, paragraphs 17-68) may be used.
Biogenic Active Ingredients
Biogenic active ingredients are to be understood as meaning, for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes.
Deodorising Active Ingredients
As deodorising active ingredients there come into consideration, for example, antiperspirants, for example aluminium chlorohydrates (see J. Soc. Cosm. Chem. 24, 281 (1973)). Under the trade mark Locron® of Hoechst AG, Frankfurt (FRG), there is available comercially, for example, an aluminium chlorohydrate corresponding to formula Al 2 (OH)5Cl×2.5H 2 O, the use of which is especially preferred (see J. Pharm. Pharmacol. 26, 531 (1975)). Besides the chlorohydrates, it is also possible to use aluminium hydroxyacetates and acidic aluminium/zirconium salts. Esterase inhibitors may be added as further deodorising active ingredients. Such inhibitors are preferably trialkyl citrates, such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and especially triethyl citrate (Hydagen CAT, Henkel), which inhibit enzyme activity and hence reduce odour formation. Further substances that come into consideration as esterase inhibitors are sterol sulfates or phosphates, for example lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and esters thereof, for example glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, adipic acid monoethyl ester, adipic acid diethyl ester, malonic acid and malonic acid diethyl ester and hydroxycarboxylic acids and esters thereof, for example citric acid, malic acid, tartaric acid or tartaric acid diethyl ester. Antibacterial active ingredients that influence the germ flora and kill or inhibit the growth of sweat-decomposing bacteria can likewise be present in the preparations (especially in stick preparations). Examples include chitosan, phenoxyethanol and chlorhexidine gluconate. 5-chloro-2-(2,4-dichlorophenoxy)-phenol (Triclosan, Irgasan, Ciba Specialty Chemicals Inc.) has also proved especially effective.
Anti-Dandruff Agents
As anti-dandruff agents there may be used, for example, climbazole, octopirox and zinc pyrithione. Customary film formers include, for example, chitosan, microcrystalline chitosan, quaternised chitosan, polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers, polymers of quaternary cellulose derivatives containing a high proportion of acrylic acid, collagen, hyaluronic acid and salts thereof and similar compounds.
Antioxidants
In addition to the primary light-protective substances it is also possible to use secondary light-protective substances of the antioxidant kind that interrupt the photochemical reaction chain triggered when UV radiation penetrates the skin or hair. Typical examples of such antioxidants are amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and derivatives thereof, imidazoles (e.g. urocanic acid) and derivatives thereof, peptides, such as D,L-carnosine, D-carnosine, L-carnosine and derivatives thereof (e.g. anserine), carotinoids, carotenes, lycopene and derivatives thereof, chlorogenic acid and derivatives thereof, lipoic acid and derivatives thereof (e.g. dihydrolipoic acid), aurothioglycose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, lauryl, palmitoyl, oleyl, linoleyl, cholesteryl and glyceryl esters thereof) and also salts thereof, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and also sulfoximine compounds (e.g. buthionine sulfoximines, homocysteine sulfoximine, buthionine sulfones, penta-, hexa-, hepta-thionine sulfoximine), also (metal) chelating agents (e.g. hydroxy fatty acids, palmitic acid phytic acid, lactoferrin), hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EDDS, EGTA and derivatives thereof, unsaturated fatty acids and derivatives thereof (e.g. linolenic acid, linoleic acid, oleic acid), folic acid and derivatives thereof, ubiquinone and ubiquinol and derivatives thereof, vitamin C and derivatives (e.g. ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (e.g. vitamin A palmitate) and also coniferyl benzoate of benzoin resin, rutinic acid and derivatives thereof, glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butyl hydroxytoluene, butyl hydroxyanisole, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, superoxide dismutase, N-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]sulfanilic acid (and salts thereof, for example the disodium salts), zinc and derivatives thereof (e.g. ZnO, ZnSO4), selenium and derivatives thereof (e.g. selenium methionine), stilbene and derivatives thereof (e.g. stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of those mentioned active ingredients. HALS (=“Hindered Amine Light Stabilizers”) compounds may also be mentioned.
Further synthetic and natural antioxidants are listed e.g. in patent WO 0025731:
Structures 1-3 (page 2), structure 4 (page 6), structures 5-6 (page 7) and compounds 7-33 (page 8-14).
The amount of antioxidants present is usually from 0.001 to 30% by weight, preferably from 0.01 to 3% by weight, based on the weight of the UV absorbing composite powder of the invention.
Hydrotropic Agents
To improve the flow behaviour it is also possible to employ hydrotropic agents, for example ethoxylated or non ethoxylated mono-alcohols, diols or polyols with a low number of carbon atoms or their ethers (e.g. ethanol, isopropanol, 1,2-dipropanediol, propyleneglycol, glyerin, ethylene glycol, ethylene glycol monoethylether, ethylene glycol monobutylether, propylene glycol monomethylether, propylene glycol monoethylether, propylene glycol monobutylether, diethylene glycol monomethylether; diethylene glycol monoethylether, diethylene glycol monobutylether and similar products). The polyols that come into consideration for that purpose have preferably from 2 to 15 carbon atoms and at least two hydroxy groups. The polyols may also contain further functional groups, especially amino groups, and/or may be modified with nitrogen. Typical examples are as follows: glycerol, alkylene glycols, for example ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and also polyethylene glycols having an average molecular weight of from 100 to 1000 Dalton; technical oligoglycerol mixtures having an intrinsic degree of condensation of from 1.5 to 10, for example technical diglycerol mixtures having a diglycerol content of from 40 to 50% by weight; methylol compounds, such as, especially, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol; lower alkyl-glucosides, especially those having from 1 to 8 carbon atoms in the alkyl radical, for example methyl and butyl glucoside; sugar alcohols having from 5 to 12 carbon atoms, for example sorbitol or mannitol; sugars having from 5 to 12 carbon atoms, for example glucose or saccharose; amino sugars, for example glucamine; dialcohol amines, such as diethanolamine or 2-amino-1,3-propanediol.
Preservatives
Suitable preservatives include, for example, Methyl-, Ethyl-, Propyl-, Butyl-parabens, Benzalkonium chloride, 2-Bromo-2-nitro-propane-1,3-diol, Dehydroacetic acid, Diazolidinyl Urea, 2-Dichloro-benzyl alcohol, DMDM hydantoin, Formaldehyde solution, Methyldibromoglutanitrile, Phenoxyethanol, Sodium Hydroxymethylglycinate, Imidazolidinyl Urea, Triclosan and further substance classes listed in the following reference: K. F. DePolo—A short textbook of cosmetology, Chapter 7, Table 7-2, 7-3, 7-4 and 7-5, p 210-219.
Bacteria-Inhibiting Agents
Typical examples of bacteria-inhibiting agents are preservatives that have a specific action against gram-positive bacteria, such as 2,4,4′-trichloro-2′-hydroxydiphenyl ether, chlorhexidine (1,6-di(4-chlorophenyl-biguanido)hexane) or TCC (3,4,4′-trichlorocarbanilide). A large number of aromatic substances and ethereal oils also have antimicrobial properties. Typical examples are the active ingredients eugenol, menthol and thymol in clove oil, mint oil and thyme oil. A natural deodorising agent of interest is the terpene alcohol farnesol (3,7,11-trimethyl-2,6,10-dodecatrien-1-ol), which is present in lime blossom oil. Glycerol monolaurate has also proved to be a bacteriostatic agent. The amount of the additional bacteria-inhibiting agents present is usually from 0.1 to 2% by weight, based on the solids content of the preparations.
Perfume Oils
There may be mentioned as perfume oils mixtures of natural and/or synthetic aromatic substances. Natural aromatic substances are, for example, extracts from blossom (lilies, lavender, roses, jasmine, neroli, ylang-ylang), from stems and leaves (geranium, patchouli, petitgrain), from fruit (aniseed, coriander, carraway, juniper), from fruit peel (bergamot, lemons, oranges), from roots (mace, angelica, celery, cardamom, costus, iris, calmus), from wood (pinewood, sandalwood, guaiacum wood, cedarwood, rosewood), from herbs and grasses (tarragon, lemon grass, sage, thyme), from needles and twigs (spruce, pine, Scots pine, mountain pine), from resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials also come into consideration, for example civet and castoreum. Typical synthetic aromatic substances are, for example, products of the ester, ether, aldehyde, ketone, alcohol or hydrocarbon type. Aromatic substance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether; the aldehydes include, for example, the linear alkanals having from 8 to 18 hydrocarbon atoms, citral, citronellal, citronellyl oxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal; the ketones include, for example, the ionones, isomethylionone and methyl cedryl ketone; the alcohols include, for example, anethol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenyl ethyl alcohol and terpinol; and the hydrocarbons include mainly the terpenes and balsams. It is preferable, however, to use mixtures of various aromatic substances that together produce an attractive scent. Ethereal oils of relatively low volatility, which are chiefly used as aroma components, are also suitable as perfume oils, e.g. sage oil, camomile oil, clove oil, melissa oil, oil of cinnamon leaves, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, labolanum oil and lavandin oil. Preference is given to the use of bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenyl ethyl alcohol, hexyl cinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, boisambrene forte, ambroxan, indole, hedione, sandelice, lemon oil, tangerine oil, orange oil, allyl amyl glycolate, cyclovertal, lavandin oil, muscatel sage oil, damascone, bourbon geranium oil, cyclohexyl salicylate, vertofix coeur, iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romillat, irotyl and floramat alone or in admixture with one another.
Colourants
There may be used as colourants the substances that are suitable and permitted for cosmetic purposes, as compiled, for example, in the publication “Kosmetische Färbemittel” of the Farbstoffkommission der Deutschen Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pages 81 to 106. The colourants are usually used in concentrations of from 0.001 to 0.1% by weight, based on the total mixture.
Other Adjuvants
It is furthermore possible for the cosmetic preparations to contain, as adjuvants, anti-foams, such as silicones, structurants, such as maleic acid, solubilisers, such as ethylene glycol, propylene glycol, glycerol or diethylene glycol, opacifiers, such as latex, styrene/PVP or styrene/acrylamide copolymers, complexing agents, such as EDTA, NTA, alaninediacetic acid or phosphonic acids, propellants, such as propane/butane mixtures, N 2 O, dimethyl ether, CO 2 , N 2 or air, so-called coupler and developer components as oxidation dye precursors, reducing agents, such as thioglycolic acid and derivatives thereof, thiolactic acid, cysteamine, thiomalic acid or mercaptoethanesulfonic acid, or oxidising agents, such as hydrogen peroxide, potassium bromate or sodium bromate.
Suitable insect repellents are, for example, N,N-diethyl-m-toluamide, 1,2-pentanediol or insect repellent 3535; suitable self-tanning agents are, for example, dihydroxyacetone and/or erythrulose or dihydroxy acetone and/or dihydroxy acetone precursors as described in WO 01/85124 and/or erythrulose.
Polymeric Beads or Hollow Spheres as SPF Enhancers
The combination of the UV-absorbing composite powder of the invention and a UV-absorber combination, disclosed above, with SPF enhancers, such as non-active ingredients like Styrene/acrylates copolymer, silica beads, spheroidal magnesium silicate, crosslinked Polymethylmethacrylates (PMMA; Micopearl M305 Seppic), can maximize better the UV protection of the products. Holosphere additives (Sunspheres® ISP, Silica Shells Kobo.) deflect radiation and the effective path length of the photon is therefore increased. (EP0893119). Some beads, as mentioned previously, provide a soft feel during spreading. Moreover, the optical activity of such beads, e.g. Micropearl M305, cans modulate skin shine by eliminating reflection phenomena and indirectly may scatter the UV light.
Cosmetic or Pharmaceutical Preparations
Cosmetic or pharmaceutical formulations are contained in a wide variety of cosmetic preparations. There come into consideration, for example, especially the following preparations:
skin-care preparations, e.g. skin emulsions, multi-emulsions or skin oils; cosmetic personal care preparations, e.g. facial make-up in the form of day creams or powder creams, face powder (loose or pressed), rouge or cream make-up, eye-care preparations, e.g. eyeshadow preparations, mascara, eyeliner, eye creams or eye-fix creams; lip-care preparations, e.g. lipsticks, lip gloss, lip contour pencils, nail-care preparations, such as nail varnish, nail varnish removers, nail hardeners or cuticle removers; light-protective preparations, such as sun milks, lotions, creams or oils, sunblocks or tropicals, pre-tanning preparations or after-sun preparations; skin-tanning preparations, e.g. self-tanning creams; insect-repellents, e.g. insect-repellent oils, lotions, sprays or sticks;
Presentation Forms of the Cosmetic Composition
The final formulations listed may exist in a wide variety of presentation forms, for example:
in the form of liquid preparations as a W/O, O/W, O/W/O, W/O/W or PIT emulsion and all kinds of microemulsions, in the form of a gel, in the form of an oil, a cream, milk or lotion, in the form of a powder, a lacquer, a tablet or make-up, in the form of a stick, in the form of a spray (spray with propellent gas or pump-action spray) or an aerosol, in the form of a foam, or in the form of a paste.
Of special importance as cosmetic preparations for the skin are light-protective preparations, such as sun milks, lotions, creams, oils, sunblocks or tropicals, pretanning preparations or after-sun preparations, also skin-tanning preparations, for example self-tanning creams. Of particular interest are sun protection creams, sun protection lotions, sun protection milk and sun protection preparations in the form of a spray or sun-protection foams.
For example, especially the following cosmetic formulations may be used:
a1) spontaneously emulsifying stock formulation, consisting of the UV absorber according to the invention, PEG-6-C10oxoalcohol and sorbitan sesquioleate, to which water and any desired quaternary ammonium compound, for example 4% minkamidopropyl dimethyl-2-hydroxyethylammonium chloride or Quaternium 80 is added; a2) spontaneously emulsifying stock formulation consisting of the UV absorber according to the invention, tributyl citrate and PEG-20-sorbitan monooleate, to which water and any desired quaternary ammonium compound, for example 4% minkamidopropyl dimethyl-2-hydroxyethylammonium chloride or Quaternium 80 is added; b) quat-doped solutions of the UV absorber according to the invention in butyl triglycol and tributyl citrate; c) mixtures or solutions of the UV absorber according to the invention with n alkylpyrrolidone.
Other typical ingredients in such formulations are preservatives, bactericides and bacteriostatic agents, perfumes, dyes, pigments, thickening agents, moisturizing agents, humectants, fats, oils, waxes or other typical ingredients of cosmetic and personal care formulations such as alcohols, poly-alcohols, polymers, electrolytes, organic solvents, silicon derivatives, emollients, emulsifiers or emulsifying surfactants, surfactants, dispersing agents, antioxidants, anti-irritants and anti-inflammatory agents etc.
The instant invention will be further illustrated with reference to the following examples. However, these examples are intended to illustrate the invention and are not to be construed to limit the scope of the invention. That is, the type and ingredient of the cosmetic composition covered by the instant invention will not be limited to those disclosed in the following examples and the cosmetic composition may comprise any ingredient commonly added or used for manufacturing cosmetic products with no limitation.
EXAMPLE 1
Purified water 500g was put in a 1L-beaker and the core particles, spherical silica having an average size of 3 μm (SUNSPHERE®, Asahi Glass SI-Tech. Co., Ltd.) 90 g was added thereto with stirring by a dispersing mixer. A commercially available aqueous dispersion of the compound of formula (1) (MBBT) containing 50% MBBT in micronized form with an average particle size <200 nm (TINOSORB® M, Ciba Specialty Chemicals, Basel, Switzerland) was used. An aqueous dispersion containing 10% TINOSORB® M 100 g was added to the beaker and the mixture was stirred well. Then, 5% aqueous aluminum sulfate 100 g was added to the mixture and further stirred. After that, pH of the mixture was adjusted to neutral and the mixture was further stirred.
After that, the mixture was centrifuged to dehydrate and the obtained particles were washed with ethanol to remove water soluble ingredients in TINOSORB® M other than the water insoluble UV absorber (MBBT). This step was repeated twice and then, the particles were dried at 120° C. for 10 hours to give 100 g of composite particles consisting of the core particles and about 5 wt % MBBT adsorbed to the surface of the core particles.
EXAMPLE 2
Purified water 500 g was put in a 1L-beaker and the core particles, spherical silica with an average size of 3 μm (SUNSPHERE®, Asahi Glass SI-Tech. Co., Ltd.) 89.5 g were added thereto with stirring by a dispersing mixer. An aqueous dispersion containing 14% TINOSORB® M 100 g was added to the beaker and the mixture was stirred well. Then, 3.5% aqueous aluminum sulfate 100 g was added to the mixture and further stirred. After that, pH of the mixture was adjusted to neutral and the mixture was further stirred.
After that, the mixture was treated according to the same manner as Example 1 to give 100 g of composite particles consisting of the core particles and about 7 wt % MBBT adsorbed to the surface of the core particles.
EXAMPLE 3
Purified water 500 g was put in a 1L-beaker and the core particles, spherical silica with an average size of 3 μm (SUNSPHERE®, Asahi Glass SI-Tech. Co., Ltd.) 85 g was added thereto with stirring by a dispersing mixer. An aqueous dispersion containing 20% TINOSORB® M 100 g was added to the beaker and the mixture was stirred well. Then, 5% aqueous aluminum sulfate 100 g was added to the mixture and further stirred. After that, pH of the mixture was adjusted to neutral and the mixture was further stirred.
The mixture was treated according to the same manner as Example 1 to give 100 g of composite particles consisting of the core particles and about 10 wt % MBBT adsorbed to the surface of the core particles.
EXAMPLE 4
Purified water 500 g was put in a 1L-beaker and the core particles, spherical silica with an average size of 3 μm (SUNSPHERE®, Asahi Glass SI-Tech. Co., Ltd.) 70 g was added thereto with stirring by a dispersing mixer. An aqueous dispersion containing 40% TINOSORB® M 100 g was added to the beaker and the mixture was stirred well. Then, 10% aqueous aluminum sulfate 100 g was added to the mixture and further stirred. After that, pH of the mixture was adjusted to neutral and the mixture was further stirred.
After that, the mixture was treated according to the same manner as Example 1 to give 100 g of composite powder consisting of the core particles and about 20 wt % MBBT adsorbed to the surface of the core particles.
Comparative Example 1
Purified water 500 g was put in a 1L-beaker and the core particles, spherical silica with an average size of 3 μm (SUNSPHERE®, Asahi Glass SI-Tech. Co., Ltd.) 94 g was added thereto with stirring by a dispersing mixer. An aqueous dispersion containing 10% TINOSORB® M 100 g was added to the beaker and the mixture was stirred well. Then, 1% aqueous aluminum sulfate 100 g was added to the mixture and further stirred. After that, pH of the mixture was adjusted to neutral and the mixture was further stirred.
The mixture was centrifuged to dehydrate. Upon the dehydration, white liquid that seemed to contain MBBT was removed. Then, the particles were washed with ethanol and the filtrate was also white liquid. The amount of the resulting particles was 96 g.
Comparative Example 2
Purified water 500 g was put in a 1L-beaker and the core particles, spherical silica with an average size of 3 μm (SUNSPHERE®, Asahi Glass SI-Tech. Co., Ltd.) 98 g was added thereto with stirring by a dispersing mixer. 2% aqueous aluminum sulfate 100 g was added thereto and the mixture was further stirred. After that, pH of the mixture was adjusted to neutral and the mixture was further stirred. Then, the mixture was centrifuged to dehydrate and the particles were dried at 120° C. for 10 hours to give 100 g of composite powder.
Comparative Example 3
Purified water 500 g was put in a 1L-beaker and the core particles, spherical silica with an average size of 3 μm (SUNSPHERE®, Asahi Glass SI-Tech. Co., Ltd.) 40 g was added thereto with stirring by a dispersing mixer. An aqueous dispersion containing 80% TINOSORB® M 200 g was added to the beaker and the mixture was stirred well. Then, 20% aqueous aluminum sulfate 100 g was added to the mixture and further stirred. After that, pH of the mixture was adjusted to neutral and the mixture was further stirred.
The mixture was treated according to the same manner as Example 1 to give 100 g of composite particles.
Test Example 1
UV-Protecting Effect I (UV-Absorbing Property)
Each of the composite powders comprising the composite powder particles obtained in Examples 1-4 and Comparative Examples 1-3 was weighted and mixed with trioctanoine so that the weight ratio of the composite powder:trioctanoine was 3:7. The mixture was stirred with dispersing mixer at 3000 rpm for 10 minutes to give dispersion. The absorption spectrum of each dispersion over the wavelength range of 280-400 nm was determined with a spectrophotometer (UV-3010; HITACHI, Ltd.). Results are shown in FIG. 1 .
Test Example 2
UV-Absorbing Effect II (In Vitro SPF Determination)
Each of the composite powders obtained in Examples 1-4 and Comparative Example 1-3 was weighted and mixed with vaseline so that the weight ratio of the composite powder:vaseline was 25:75. The mixture was homogenized in a mortar to give uniform paste. The paste was uniformly applied on Transpore Tape (Sumitomo 3M) in an amount of 2 mg/cm 2 and in vitro SPF was determined with SPF Analyzer UV-1000S (Labsphere). Result are shown in Table 1 below.
Test Example 3
Texture Evaluation
The texture of each composite powder of Examples 1-4 and Comparative Examples 1-3 in view of the touch of the powder is smooth, squeaky or rough was evaluated by 5 panelists according to the five scores shown below:
Five Absolute Evaluation
1: Bad and uncomfortable texture 2: Slightly bad and uncomfortable texture 3: Normal (comparative to the untreated core particles) 4: Slightly good and comfortable texture 5: Good and comfortable texture
The average values were taken and shown in Table 1 using the following marks:
++: 4 or above +: 3 or above and less than 4 −: 2 or above and less than 3 −−: less than 2
Results of Test Examples 2 and 3
TABLE 1 Test Ex. 2 Test Ex. 3 Example 1 2.59 ++ Example 2 3.32 ++ Example 3 4.32 ++ Example 4 7.42 + Com. Ex. 1 1.01 ++ Com. Ex. 2 0 ++ Com. Ex. 3 10.42 −−
According to FIG. 1 showing the result of test example 1, the UV absorbance of Examples 1-4 and Comparative Example 3 were increased with the amount of the MBBT adsorbed to the surface of the core particles. Although the powder of comparative Example 1 was manufactured using the same amount of MBBT as that of Example 1, the powder of Comparative Example 1 exhibited less UV absorbance than Example 1. This fact exemplifies that the metal salt like aluminum sulfate is essential for manufacturing the composite powder of the invention. In the Test Example 2, similar result as the Test Example 1 was obtained.
According to the result of Test Example 3, the composite powder of comparative example 3 comprising 40 wt % of MBBT provided uncomfortable and rough feeling besides its high UV absorbing property.
EXAMPLE 5
Purified water 500 g was put in a 1L-beaker and core particle, mica with an average size of 17 μm 70 g was added thereto with stirring by a dispersing mixer. An aqueous dispersion containing 40% TINOSORB® M 100 g was added to the beaker and the mixture was stirred well. Then, 10% aqueous aluminum sulfate 100 g was added to the mixture and further stirred. After that, pH of the mixture was adjusted to neutral and the mixture was further stirred.
The mixture was treated according to the same manner as Example 1 to give 100 g of composite powder consisting of the core particles and about 20 wt % MBBT adsorbed to the surface of the core particles.
EXAMPLES 6 AND 7, COMPARATIVE EXAMPLES 4-6
Two-Way Cake Foundation
The composite powder obtained in Example 3 or 4 was used to give two-way cake foundation with the ingredients shown in Table 2 below. The evaluation according to Test Examples 2 and 3 were conducted and results are shown in Table 2.
Preparation:
Powder ingredients (1)-(11) were mixed and pulverized by means of a Henschel mixer. Oil ingredients (12)-(16) were mixed in a separate container and added to the powder ingredients. The mixture was kneaded uniformly, then pulverized with an atomizer and the obtained powder was put in an aluminum dish and pressed to give two way cake foundation.
TABLE 2 Ingredients of the two way cake foundation amount(wt %) Comp. Comp. Comp. Comp. Ingredients Ex. 6 Ex. 7 Ex. 4 Ex. 5 Ex. 6 Ex. 7 (1) methicone treated talc balance balance balance balance balance balance (2) methicone 6 6 6 6 6 6 treated titanium dioxide (3) methicone 20 20 20 20 20 20 treated mica (4) methione 36 36 36 36 36 36 treated sericite (5) Composite powder 10 Ex. 3 (6) Composite Powder 10 Ex. 4 (7) Micronized 3 5 3 titanium dioxide (8) Micronized zinc 5 5 oxide (9) methicone 1 1 1 1 1 1 treated yellow iron oxide (10) methicone 0.5 0.5 0.5 0.5 0.5 0.5 treated red iron oxide (11) methicone 0.1 0.1 0.1 0.1 0.1 0.1 treated black iron oxide (12) Dimethicone 6 6 6 6 6 6 1000 cs (13) Octyl methoxy 3 3 3 3 3 3 cinnamate (14) squalane 3 3 3 3 3 3 (15) Preservative 0.2 0.2 0.2 0.2 0.2 0.2 (16) antioxidant 0.1 0.1 0.1 0.1 0.1 0.1 total 100.0 100.0 100.0 100.0 100.0 100.0
TABLE 3
Comp.
Comp.
Comp.
Comp.
Ex. 6
Ex. 7
Ex. 4
Ex. 5
Ex. 6
Ex. 7
in vitro SPF
20.4
25.4
15.2
20.3
18.2
28.0
texture
++
++
++
−
±
−
As is apparent from table 3 above, the two way cake foundations of Examples 6 and 7 exhibited excellent UV protecting effects. The compositions of comparative examples 5-7 also exhibited an excellent UV-protecting effect but the texture was bad and provided bluish color upon applied to the face. According to the results, the two way foundations of the examples 6 and 7 are excellent in both of UV-protecting property and texture.
EXAMPLE 8
Pressed Powder
TABLE 4 Ingredients amount (wt %) (1) talc balance (2) polymethyl 10 methacrylate (7 μm)* (3) sericite 30 (4) scaly-shaped silica** 3 (5) composite powder 10 Ex. 4 (6) preservative suitable amount (7) colorant suitable amount (8) octyl methoxy 3 cinnamate (9) squalane 2 (10) Preservative suitable amount (11) antioxidant suitable amount (12) perfume suitable amount *Matsumoto Microsphere ® M-100 (Matsumoto Yushi Seiyaku Co., Ltd) **SUNLOVELY ® C (Asahi Glass SI-Tech. Co., Ltd.)
Preparation:
Powder ingredients (1)-(7) were mixed and pulverized, and put in a Henschel mixer. The oil ingredients (8)-(11) were added into the mixer and kneaded to give an uniform mixture. The mixture was then pulverized with an atomizer, put in an aluminum dish and pressed to give pressed powder.
Evaluation:
The obtained pressed powder had a smooth and comfortable texture and an in-vitro SPF of 17.
EXAMPLE 9
Oil Based Cake Foundation
TABLE 5 Ingredients amount (wt %) (1) methicone treated talc 5.3 (2) methicone treated titanium dioxide 8 (3) composite powder Ex. 5 15 (4) methicone treated sericite 28.2 (5) methicone treated iron oxide red 0.5 (6) methicone treated iron oxide yellow 1.8 (7) methicone treated iron oxide black 0.2 (8) candelilla wax 1 (9) carnauba wax 1 (10) ceresin 1.5 (11) cyclopentasiloxane 14 (12) isononyl isononanate balance (13) polyglyceryl-2 diisostearate 2 (14) dextrin palmitate* 1 (15) octyl methoxy cinnamate 3 (16) Preservative suitable amount (17) antioxidant suitable amount *Rheopearl ™ KL(Chiba Seifun Co., Ltd.)
Preparation:
Powder ingredients (1)-(7) were mixed and pulverized in a Henschel mixer. Oil ingredients (8)-(17) were mixed and heated to melt and dissolved. The powder ingredients were added to the oil ingredients, the mixture was dispersed uniformly and put in a container, gradually cooled to the room temperature to give oil based cake foundation.
The obtained oil based cake foundation had a smooth and comfortable texture and an in-vitro SPF of 20.
EXAMPLE 10
Stick Type Foundation
TABLE 6 Ingredients amount (wt %) (1) dimethicone 18 (2) cyclopentasiloxane 30 (3) octyl methoxy cinnamate 5 (4) diisostearyl malate 4 (5) candelilla wax 6 (6) hydrogenated jojoba wax 4 (7) cetyl dimethicone copolyol 2 (8) sorbitan sesquiisostearate 0.5 (9) antioxidant suitable amount (10) Preservative suitable amount (11) perfume suitable amount (12) methicone treated colorant 0.5 (13) methicone treated titanium 3.5 dioxide (14) methicone treated talc 2 (15) methicone treated mica 2 (16) polymethyl methacrylate 2 (17) composite powder Ex. 2 10 (18) purified water balance (19) sodium citrate 0.3 (20) butyleneglycol 3 (21) glycerin 2 (22) Preservative suitable amount
Preparation:
Powder ingredients (12)-(17) were mixed in a Henschel mixer. Oil ingredients (1)-(11) were weighted, put in a container and heated to melt. Ingredients (18)-(22) were weighted and put in another container and dissolved by heating to give an aqueous solution. The mixture of the powder ingredients was added to the oil ingredients and the resulting mixture was dispersed uniformly. Then the aqueous solution was added thereto, and the mixture was emulsified and defoamed. Thus obtained mixture was put in a mold and cooled gradually to give the desired stick foundation.
Evaluation:
The obtained stick foundation had a smooth and comfortable texture and an in-vitro SPF of 17.
EXAMPLE 11
W/O Emulsion Foundation
TABLE 7 Ingredients amount (wt %) (1) POE-10 dimethicone(HLB = 4.5) 0.80 (2) Polyglyceryl polyricinoleate 0.50 (3) neopentyl glycol dicaprate 3.00 (4) squalane 1.00 (5) pentaerythrityl tetraethylhexanoate 2.00 (6) stearoyl inulin* 1.00 (7) octyl methoxy cinnamate 4.00 (8) cyclopentasiloxane 15.40 (9) Preservative suitable amount (10) antioxidant suitable amount (11) perfume suitable amount (12) silicone treated titanium dioxide 4.00 (13) silicone treated talc 3.68 (14) composite powder Ex. 3 6.00 (15) silicone treated colorant 1.00 (16) purified water balance (17) butylene glycol 6.00 (18) glycerin 1.00 (19) sodium chloride 1.00 (20) Preservative suitable amount *Rheopearl ™ ISK(Chiba Seifun Co., Ltd.)
Preperation:
Powder ingredients (12)-(15) were mixed in a Henschel mixer, added to oil ingredients (1)-(11), and the resulting mixture was kneaded uniformly. Ingredients (16)-(20) were heated in a separate container to provide an aqueous solution. The mixture wherein powder ingredients were dispersed in the oil ingredients, was added to the aqueous solution and the mixture was emulsified. The emulsion was cooled gradually to the room temperature to give the desired W/O emulsion foundation.
Evaluation:
The obtained W/O emulsion foundation had a smooth and comfortable texture and an in-vitro SPF of 18.
EXAMPLE 12
Cheek Blush
TABLE 8 Ingredients amount (wt %) (1) talc balance (2) sericite 60.9 (3) micronized titanium 3.0 dioxide (4) composite powder of 17.5 claim 5 (5) colorant suitable amount (6) octyl methoxy 3.0 cinnamate (7) octyl palmitate 5.0 (8) Preservative suitable amount (9) antioxidant suitable amount
Preparation:
Powder ingredients (1)-(5) were mixed by a Henschel Mixer and oil ingredients (6)-(9) were dissolved by heating. Both mixtures were mixed and pulverized with an atomizer. The resulting powder was put in a dish and pressed to give the desired pressed cheek color blush.
The obtained pressed cheek color blush had a smooth and comfortable texture and an in-vitro SPF of 25.
EXAMPLE 13
Sunscreen Cream
TABLE 9 Ingredients amount (wt %) (1) PEG-10 dimeticone 3 (2) cyclopentasiloxane 15.8 (3) neopentylglycol dicaprate 5 (4) squalane 5 (5) dextrin palmitate* 1.5 (6) octyl methoxy cinnamate 3 (7) preservative suitable amount (8) antioxidant suitable amount (9) Micronized titanium dioxide 58% 20 dispersion** (10) composite powder Ex. 3 5 (11) purified water balance (12) butyleneglycol 4 (13) peservative suitable amount (14) sodium chloride 1 *Rheopearl ™ ISK(Chiba Seifun Co., Ltd.) **Cosmeserve ™ WP-58MP(V) (Dainippon Kasei Co., Ltd.)
Preparation:
Oil ingredients (1)-(8) were dissolved by heating and ingredients (9) and (10) were added thereto. The mixture was dispersed uniformly by an agitator. Ingredients (11)-(14) were put in a separate container and heated to give an aqueous solution. Said aqueous solution was added to the mixture of ingredients (1)-(10) and dispersed to give emulsion, the mixture was cooled to room temperature to give sunscreen cream. Thus obtained sunscreen cream was highly transparent and had a smooth and comfortable texture and an in-vitro SPF of 50.
EXAMPLE 14
Lipstick
TABLE 10 Ingredients amount (wt %) (1) carnauba wax 2.00 (2) candelilla wax 5.00 (3) ceresin 6.00 (4) microcrystalline wax 2.00 (5) cholesteryl hydroxystearate 1.50 (6) diisostearyl malate 12.00 (7) glyceryl triisostearate balance (8) neopentyl glycol dicaprate 8.15 (9) octyldodecanol 12 (10) pentaerythritol-fatty acid ester 12 (11) octyl methoxy cinnamate 3 (12) antioxidant suitable amount (13) peservative suitable amount (14) colorant suitable amount (15) composite powder of Example 5 5.00 (16) Pearl Lustre Pigments 5.00
Preparation:
Oil ingredients (1)-(13) were mixed and dissolved to give an uniform solution, ingredients (14)-(16) were added thereto and dispersed uniformly. The mixture was defoamed, poured in a mold and cooled. Thus obtained stick was mounted in a suitable container to give lipstick.
The obtained lipstick had a smooth and comfortable texture and an in-vitro SPF of 10.
EXAMPLE 15
Pore Minimizer Makeup Base
TABLE 11 Ingredients amount (wt %) (1) octyl methoxy cinnamate 5 (2) methylphenylpolysiloxane 30.15 (3) stearylalcohol 9 (4) dextrin palmitate* 7.4 (5) preservative suitable amount (6) antioxidant suitable amount (7) cyclopenta siloxane balance (8) Composite powder Example 4 10 (9) porous silica** 20 *Rheopearl ™ KL(Chiba Seifun Co., Ltd.) **SUNSPHERE ® L-51 (Asahi Glass SI-Tech. Co., Ltd.)
Preparation:
Oil ingredients (1)-(7) were dissolved to give uniform solution. Ingredients (8) and (9) were added thereto and dispersed uniformly. The mixture was defoamed and poured in a suitable container and cooled gradually to room temperature to give pore minimizing make up base. The make up base had a smooth and comfortable texture and an in-vitro SPF of 20 (in vitro).
EXAMPLE 16
Loose Powder
TABLE 12 Ingredients amount (wt %) (1) talc balance (2) titanium dioxide 1 (3) lauroyl lysine* 3 (4) composite powder Ex. 4 10 (5) Micronized titanium dioxide 5 (6) Preservative suitable amount (7) colorant suitable amount (8) squalane 1 (9) preservative suitable amount (10) antioxidant suitable amount (11) perfume suitable amount *Amihope ® LL(Ajinomoto Co., Inc.)
Preparation:
Powder ingredients (1)-(7) were pulverized and mixed, and put in a Henschel mixer. The oil ingredients (8)-(11) were added thereto and the mixture was kneaded uniformly. Thus obtained uniform mixture was pulverized with an atomizer and the obtained powder was put in an aluminum dish and pressed to give pressed loose powder.
The pressed loose powder had a smooth and comfortable texture and an in-vitro SPF of 15.
The contents of the references cited in the instant specification are herein incorporated by reference.
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