Modern formulation concepts with actual raw materials

Transcription

1 FH Prof. Dr. G. Kutz Zurich, Modern formulation concepts with actual raw materials Prof. Dr. Gerd Kutz Lippe and Höxter Zurich,

2 FH Prof. Dr. G. Kutz Zurich, verview: formulation concepts Rich/valuable perceived skin feel ils, leo-gels Submicronemulsions Foams W/-emulsions (lotion/creams) /W-emulsions (lotion/creams) Gel(s)-creams fresh/light low viscosity high

3 FH Prof. Dr. G. Kutz Zurich, verview: leading substances Lipids Hydrogenated Polydecene Bis-Diglyceryl-Polyacyladipate-2 Dicaprylyl Carbonate Emulsifiers Inulin Lauryl Carbamate Sodium Surfactin Glyceryl Cocoate Citrate Lactate (and) Glyceryl Isostearate Polymers Hydroxypropyl Starch Phosphate Propylene Glycol Laurate and Ethyl Cellulose and Propylene Glycol Isostearate Ammoniumacryloyldimethyltaurate/ VP Copolymer PEG-180/Laureth-50/TMMG Copolymer PEG/PPG-25/25 Dimethicone

4 FH Prof. Dr. G. Kutz Zurich, Raw materials: general requirements - Safe - Pure, i.e. few by-products -Stable - xidation -Light - Hydrolysis - Free of own smell - Colourless - Accepted by law - Multi-functionally, e.g. in the sense of a documented, comprehensible effectiveness - Formulation advantage regarding - production technology and/or - product realization and/or - sensory characteristics

5 FH Prof. Dr. G. Kutz Zurich, Lipids Functions Effects Solvent ( active substance carrier ) Dispersing agent ( base ) Hydrophobic agent Sensory profile, in particular: - smoothing - increase of the elasticity Stabilisation of the barrier function (TEWL ) Moisture-retention (Corneometry ) Penetration- effecting

6 FH Prof. Dr. G. Kutz Zurich, Lipids Hydrogenated Polydecene - colourless, neutral odour liquid content: > 98,5 % C 30 : % C 40 : % C 50 : 9-25 % C 60 : 1-7 % ** Directive 2004/45/EC of Specification/Description C H 3 C 10n H 20n+2, n= 3-7 E 907 CH3 H(C 3 C 10 H 21 ) x Hydrogenated poly-1-decene x=1-5 CH 3 As glazing agent for sugar confectionary and dried fruits *Directive 2003/11/EC of on food additives other than colours and sweeteners sets out a list of authorised miscellaneous additives, the food stuffs in which they may be used and their conditions of use

7 FH Prof. Dr. G. Kutz Zurich, Lipids Bis-Diglyceryl Polyacyladipate-2 Acetoglycerides C H 3 H H H H H 3 C H 3 C H 3 C H H 3 C H C H 3 H CAS-No.: DMF-Nr.: C H 3 H 3 C E 472a Acetic esters of mono- and diglycerides of edible fatty acids H

8 Lipids Bis-Diglyceryl Polyacyladipate-2 Test conditions: water resistance Rinsed skin surface Type of colour 18cm³ Food colour Applied amount of colour 60mg Rinsing volume 2 L before Water temperature 30 +/- 2 C Drying time of colour 2, 5 minutes Application time 10 minutes Test product applied 2mg/cm² Number of test persons 11 after FH Prof. Dr. G. Kutz Zurich,

9 BDPA Control Paraffinum (PL) Lanolin (L) L. Alc./PL 1/4 ACG/PL 1/4 Lipids Bis-Diglyceryl Polyacyladipate-2 BDPA/ACG/PL 1/1/8 Food colour washed off [%] BDPA/PL 1/4 BDPA/ACG 1/ FH Prof. Dr. G. Kutz Zurich,

10 Lipids Dicaprylyl Carbonate C H 3 CH 3 skin perception (smoothness) Slow spreadability oil components Fast spreadability oil components Medium spreadability oil components Ideal combination of oil components Smoothness slope time FH Prof. Dr. G. Kutz Zurich,

11 University of of Applied Sciences Lipids Hydrodispersion gel (emulsifier- free) INCI Sodium Polyacrylate Pentaerythrityl Distearate Dicaprylyl Carbonate Coco-Caprylate/Caprate Aqua [%] 1,0 1,0 5,0 5,0 ad 100,0 FH Prof. Dr. G. Kutz Zurich,

12 Lipids /W lotion INCI Cetearyl Glucoside, Cetearyl Alcohol Potassium Cetyl Phosphate Pentaerythrityl Distearate Caprylic/Capric Triglyceride Dicaprylyl Carbonate Dibutyl Adipate ctyldodecanol Glycerol Sodium Polyacrylate, Hydrogenated Polydecene, PPG-5 Laureth-5 Perfume/Preservative, Actives Aqua University of of Applied Sciences [%] 1,0 1,0 12,0 6,5 4,3 6,0 10,0 2,0 q.s ad 100,0 FH Prof. Dr. G. Kutz Zurich, ,0

13 Emulsifiers (Poly-) Glucose H H H 3 C H H n H H H Lauryl Glucoside, Cetearyl Glucoside, Cetearyl Wheat Bran Glycosides (and) Cetearyl Alcohol H (Poly-) Fructose H 3 C HN H H H H Inulin Lauryl Carbamate H H H H H FH Prof. Dr. G. Kutz Zurich, n

14 FH Prof. Dr. G. Kutz Zurich, Emulsifiers Inulin Lauryl Carbamate Specification/Description - white, crystalline powder - content: > 97 % - Mol mass: ~ water solubility: ~ 4% - surface tension (2%): 53mN/m - used concentration: 0,2-1% - used ph-value: can be used in cold - processing applications - no pre-dispersing necessary - compatible with usual structure building agents - high salt concentration possible - high pressure homogenisation to prepare nano-emulsions

15 FH Prof. Dr. G. Kutz Zurich, Emulsifiers Nano-emulsions (/W) Dimethicone 20,0% Caprilic/Capric Triglycerides 20,0% Jojoba il 20,0% Polydecene 20,0% Inulin Lauryl 2,4% 2,4% 2,4% 2,4% Carbamate Water 77,6% 77,6% 77,6% 77,6%

16 Emulsifiers Sprayable Antiperspirant INCI [%] Inulin Lauryl Carbamate 1,0 Sodium Magnesium Silicate 1,0 Aluminium Chlorohydrate (25% sol.) 50,0 Distarch Phosphate 4,0 Isostearyl Isostearate 8,5 Cyclomethicone and PPG-15 Stearyl 12,5 Ether Sorbitan Isostearate 1,0 Preservative, Perfume q.s Aqua ad 100,0 FH Prof. Dr. G. Kutz Zurich,

17 FH Prof. Dr. G. Kutz Zurich, Emulsifiers Sodium Surfactin H3C CH 3 H 3 C H 3 C HN HN NH - CH 3 CH 3 - HN NH Specification/Description H 3 C CH 3 HN NH CH 3 CH 3 - white powder - water soluble> 50% - bio tenside - Bacillus subtilis C H 3 C H 3

18 FH Prof. Dr. G. Kutz Zurich, Emulsifiers Sodium Surfactin - effective emulsifier in low concentration - favourably toxicological characteristics, in particular concerning irritation potential - reduction of the irritative effect of some substances - inhibition of skin permeation of some unwanted substances - Incompatible with polyvalent metal ions, in particular Ca 2+ and Mg 2+ - avoid lower ph-value than 6,5

19 Emulsifiers Transparent gel INCI Jojoba il Glycerol Sodium Surfactin [%] 80,0 20,0 1,0 /W-cream INCI Squalane live il Jojoba il Cetearyl Alcohol Sodium Surfactin Glycerol 1,3 Butylene Glycol Carbomer Xanthan Gum Sodium Hydroxide (10% in water) Aqua [%] 8,0 3,0 1,0 1,0 1,0 6,0 1,0 0,4 0,2 ph > 6,5 ad 100,0 FH Prof. Dr. G. Kutz Zurich,

20 FH Prof. Dr. G. Kutz Zurich, Emulsifiers Lactoglyceride/Citroglyceride Fatty acids Alpha hydroxy acids C H 3 C H 3 H 3 C H H H H H H H 3 C H H Glyceryl Stearate Citrate Glyceryl Citrate Lactate Linolate leate Glyceryl Laurate Citrate Lactate Glyceryl Cocoate Citrate Lactate Glyceryl Cocoate Citrate Lactate (and) Glyceryl Isostearate E 472 b/c Glycerol H H H

21 FH Prof. Dr. G. Kutz Zurich, Emulsifiers Glyceryl Cocoate Citrate Lactate (and) Glyceryl Isostearate - /W- emulsifier und emollient - hot and/or cold - production - liquid -oil soluble - emulsion, lotion, cream - used concentration 2-3 % - sensory favourably

22 Emulsifiers Skin cream ( cold production ) INCI [%] Glyceryl Cocoate/Citrate/Lactate and 3,0 Glyceryl Isostearate Butylene Glycol Dicaprylate/Dicaprate 4,0 Diethylhexyl Carbonate 4,0 C12-C13 Alkyl Lactate 3,0 Caprylic/Capric/Succinic Triglyceride 2,0 Propylene Glycol Dicaprylate/Dicaprate 1,0 Glycerol 4,0 Hydroxypropyl Starch Phosphate 5,0 Aqua ad 100,0 FH Prof. Dr. G. Kutz Zurich,

23 Polymers Si-based C- based Native (Partial-) Synthetic Synthetic Polysiloxan-Polyalcyl- Polyether-Copolymers Albumin Casein Gelatine Gum arabica Gellan Gum Xanthan Gum Hydroxypropyl Starch Phosphate Methylcellulose Hypromellose Ethylcellulose Ammonium Acryloyldimethyltaurate/ VP Copolymer PEG-180/Laureth-50/ TMMG Copolymer Polyacrylate Polyalcylacrylate Crosspolymers Poloxamers FH Prof. Dr. G. Kutz Zurich,

24 FH Prof. Dr. G. Kutz Zurich, Polymer Hydroxypropyl Starch Phosphate H - H H H H CH 3 H - H H H H H P - - Specification/Description - white powder - pre-swelled ( pregelatinized ) -granulated - cold/ hot water soluble - addition to oil- and/or water phase possible - nonionic, tolerates also high salt concentration - sensory worth-increasing

25 Polymer Anti-Perspirant cream INCI [%] Aluminium Chlorohydrate (50% sol.) 20,0 Hydroxypropyl Starch Phosphate 4,0 Dicaprylyl Ether 3,0 Coco-Caprylate/Caprate 2,5 Glycerin (99,5%) 2,0 ctyldodecanol 0,5 Ceteareth-12 1,0 Ceteareth-20 1,0 Cetearyl Alcohol 0,5 Glyceryl Laurate 1,0 Cetyl Palmitate 0,5 Aqua ad 100,0 FH Prof. Dr. G. Kutz Zurich,

26 FH Prof. Dr. G. Kutz Zurich, Polymers (Compound) Propylene Glycol Laurate (> 50%) and Ethyl Cellulose (5-9,9%) and Propylene Glycol Isostearate (5-9,9%) Isostearyl Alcohol (> 50%) and Butylene Glycol Cocoate (25-50%) and Ethyl Cellulose (1-4,9%) Specification/Description - weakly yellow, viscose liquid - used concentration 2-6% - hot - and/or cold processable - emulsifier- free /W- emulsions - water resistant formulations - very good compatibility - sensory favourably

27 FH Prof. Dr. G. Kutz Zurich, Compounds US Patent 6,187,323; Aiache, Jean-Marc; et al Stable gel mixture in the form of a mixture of oleogel and aqueous gel, process for its preparation, pharmaceutical and cosmetic compositions comprising it,... INCI Macrogolglycerololeate Propylene Glycol Isostearate Ethyl Cellulose Sesame il Ethanol BHA, BHT, Fragrance [%] 82,5 8,5 6,0 1,0 0,5 1,5 INCI Carbomer Aqua, Ethanol (6:5, weight ratio) [%] 0,3 99,7 10% leogel + 90 % Hydrogel = 100 % Bi-gel (Emulsion!)

28 FH Prof. Dr. G. Kutz Zurich, Polymer Ammonium Acryloyldimethyltaurate/VP Copolymer Specification/Description H 3 C CH 3 n m N NH H 3 C H3C S - NH white powder, partly-neutralized - used concentration: 0,5-1 % - used ph-value: /W system and/or emulsifier- free systems - sensory favourably, cause not sticking

29 FH Prof. Dr. G. Kutz Zurich, Polymer Ammonium Acryloyldimethyltaurate/VP Copolymer Commercial product: Aqua, Glycerin, Distarch Phosphate, Alcohol Denat., Ethylhexyl Methoxycinnamate, Glyceryl Stearate Citrate, Caprylic/Capric Tri-glyceride, Myristyl Myristate, ctyldodecanol, Tocopheryl Acetate, Titanium Dioxide, Maris Sal, Aluminum Chlorohydrate, Cetearyl Alcohol, Dimethicone, Ammonium Acryloyldimethyltaurate/VP Copolymer, Sodium Carbomer, Alumina, Tetrasodium Iminodisuccinate, Silica, Sodium Polyacrylate, BHT, Butylene Glycol, Ethylhexylglycerin, Phenoxyethanol, Methylparaben, Propylparaben, Iodopropynyl Butyl-carbamate, Parfum, Alpha-Isomethyl Ionone, Citronellol, Hexyl Cinnamat, Benzyl Salicylate, Butylphenyl Methylpropional, Linalool, CI US Patent Application Lanzendorfer, G., et al Claim 1: A cosmetic or dermatological gel cream of the oil-in- water type, comprising up to 90% by weight of a water phase, up to 20% by weight of a liquid phase, based on the total weight of the preparation, up to 5% by weight of one or more emulsifiers, also comprising up to 5% by weight of one or more ammonium acryloyldimethyltaurates/vinylpyrrolidone copolymers.

30 FH Prof. Dr. G. Kutz Zurich, Polymer PEG-180/Laureth-50/TMMG Copolymer Specification/Description -dry sheds - content: 100% - Mol mass: ~ used concentration: 1 5 % (0,4-2 %) - used ph-value: > 5,5 - nonionic, hydrophobic modified polymer - thickener of the water phase - in particular containing surfactant systems

31 Polymer PEG-180/Laureth-50/TMMG Copolymer EP A1 Riedel, H., et al Self foaming, foamy, after-foaming or foamable cosmetic or dermatological preparations with a content of nonionic polymers thickener. Foamy /W-cream INCI [%] Stearic acid 3,0 Cetylalcohol 8,5 PEG-20- Stearate 8,5 Talc and Silica aa ad 4,0 Carbomer 0,2 Magnesium Aluminium Silicate 0,5 Paraffin and Glycerol aa ad 10,0 Isohexadecane 2,0 PEG-180/Laureth-50/TMMG 0,5 Copolymer Propellant q.s Aqua and Sodium Hydroxide ad 100,0 FH Prof. Dr. G. Kutz Zurich,

32 FH Prof. Dr. G. Kutz Zurich, Polymers PEG/PPG-25/25 Dimethicone CH 3 CH 3 CH 3 CH 3 CH 3 Si Si Si Si CH 3 CH 3 CH 3 n (CH 2 ) m 2 CH 3 Specification/Description - clear, yellowish liquid -HLB-value: ~11 CH 2 CH 2 16 CH 3 CH CH 2 16 H

33 FH Prof. Dr. G. Kutz Zurich, Polymers PEG/PPG-25/25 Dimethicone IPM 1 = clear single phase systems 2 = 3 phase systems 3 = 2 phase systems 4 = (floating) emulsions 5 = cloudy, white systems E 1 H

34 FH Prof. Dr. G. Kutz Zurich, Polymers Skin care cream INCI [%] PEG/PPG- 25/25 Dimethicone 2,5 Dimethicone 100 2,4 Cetyl Alcohol 2,0 Trimethylsiloxysilicate 1,0 Isopropyl Palmitate 4,0 Glyceryl Stearate 3,0 Stearic Acid 1,0 Glycerol and Alcohol aa ad 10,0 Propylene Glycol 2,0 Carbomer 0,2 Aqua and Sodium Hydroxide (adjust ph =6) ad 100,0

35 FH Prof. Dr. G. Kutz Zurich, Polymers Skin care cream n = 8 women years old 127,9 127,0 125,6 120 Corneometervalue (%) * = highly significant different to the blank at α = 0,05 Time (min)

36 FH Prof. Dr. G. Kutz Zurich, New raw materials: General Characteristics - Multi-functionally, e.g. in the sense of a documented, comprehensible effectiveness - Formulation advantage regarding - production technology and/or - product realization and/or - sensory characteristics

37 FH Prof. Dr. G. Kutz Zurich, Literature Zocchi, G., Skin-Feel Agents, in Handbook of Cosmetic Science and Technology, edited by Barel, A.., Paye, M., Maibach, H.J., Marcel Dekker Verlag, New York, 2001 CTFA International Cosmetic Ingredient Dictionary and Handbook, 10th Edition, 2004 Commission Directive 2004/45/EC amending Directive 96/77/EC laying down specific purity criteria on food additives other than colours and sweeteners ( ) Köhler, J., Galenische Entwicklung eines Insektenrepellents mit verbesserter Haftfestigkeit, Dissertation, Bonn, 2001 Verordnung zur Neuordnung lebensmittelrechtlicher Vorschriften über Zusatzstoffe vom Mitchell, C., Nefkens, S., Ansmann, A., Brüning, S., Issberner, U., Formulation Design by Texture Modification, 51. Sepawa Kongress, Conference Proceedings, , 2004 Zeidler, U., Über das Spreiten von Lipiden auf der Haut, Fette-Seifen-Anstrichmittel, 87, (10), , 1985 Rochl, E.L., Brand, M.H., A Quantitative Description of Emolliency, Seifen-Öle-Fette-Wachse, 117, (4), , 1991

38 FH Prof. Dr. G. Kutz Zurich, Literature Gassenmeier, T., Busch, P., Sensory Assessment of Lipids in Leave-n and Rinse-ff Products, in Cosmetic Lipids and the Skin Barrier, edited by Förster, T., Marcel Dekker Verlag, New York, 2002 W 02/0579 A1, Decorative Cosmetic Preparations Containing Dialkylcarbonate and Metal xides, Kutz, G., Bruns, C., Hennig S., Enga, M., Current ingredients in semi-solid formulations and their effects on skin hydration, transepidermal water loss and water resistance, Abstract, 5 th World Meeting on Pharmaceutics Biopharmaceutics and Pharmaceutical Technology, Geneva, 2006 Kutz, G., Hennig, S., Rac, D., Scheppler, P., PPG/PEG- 25/25 Dimethicone: Was leistet es?, SÖFW- Journal, 130, (1/2), 35-44, 2004 Stevens, C.V., et al., Polymeric surfactants based on Inulin, a polysaccharide extracted from Chicory. 1. Synthesis and interfacial properties, Biomacromolecules, 2, , 2001 W/ A1, Hydrophobically Modified Saccharide Surfactants, Tadros, T., Booten, K., Levecke, B., Hydrophobically Modified Inulin: A Novel Polymeric Surfactant and Emulsion Stabilizer, Cosmetic and Toiletries, 119, (4), 51-60, 2004 Booten, K., Levecke, B., Polymeric, carbohydrate-based surfactants and their use in personal care applications, SÖFW-Journal, 130, (8), 10 16, 2004 DE A1, Emulsion mit substituierten Sacchariden, Arima, K., Kakinuma, A., Tamura, G., Surfactin, a cristalline peptilipid surfactant produced by Bacillus subtilis, Biochem. Biophys. Res. Commun., 31, , 1968