AVAILABLE INGREDIENTS TO THE FORMULATOR IN HOUSEHOLD LIQUID DETERGENTS AND PERSONAL CARE PRODDUCTS

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1 AVAILABLE INGREDIENTS TO THE FORMULATOR IN HOUSEHOLD LIQUID DETERGENTS AND PERSONAL CARE PRODDUCTS Marchesi Flavio, Azrak Giorgio - CISME Italy snc Via Giuseppe Marcora Milano (Italia) Abstract Current market needs for detergents and personal care products require more efficient cleaning performance and at the same time, bio-compatible to skin and Environmentally Friendly. These needs make producers of personal care and household detergents products look for raw materials from renewable natural origin that can be friendly to the skin and the environment without compromising washing efficiency. Formulators also have to consider additional requirements such as formula cost, biodegradability, skin bio-compatibility, aspect, viscosity, stability, foam density, etc.. For each of the single above mentioned characteristics already exists on the market several ingredients, which work positively on some aspects but often negatively on others, obliging the formulator to choose among several ingredients to establish a balanced compromise. INTRODUCTION Formulations of personal care and household detergents such as hand soaps, and hand dishwashing liquids are mainly based on surfactants named primary surfactants as well as additional surfactants named secondary surfactants or cosurfactants. The functionality purpose of secondary surfactants is to improve some characteristics in the basic formulae, such as detergency effectiveness, foam, viscosity, reduction in the skin irritation, skin feel during and after wash, etc.. In rinse-off products consumers require characteristics such as; excellent washing efficiency, good foaming proprieties (also in hard water), good viscosity / rheological behaviour (often considered by consumers an index of concentration), skin compatibility during and after wash, as well as acceptable cost. Putting together all such requirements and properties is the final goal of each formulator. For the purpose of satisfying the various characteristics needed in detergents and personal care products, several secondary surfactants have been introduced in the last ten years. Generally speaking each secondary surfactants acts in the formulation on some specific characteristics, but at the same time also has negative effects on other desired characteristics; for example, CocoDEA increases the viscosity of the formulation, and at the same time decreases the washing efficiency, and also creates a nitrosamine problem. Alternative substances are also available to increase the viscosity, such as synthetic polymers (acrilates, polyurethanes, carbomers ), or natural polymers such as xanthan gum for cosmetics applications, both types however show negative skin-feel and do not have any positive influence on washing efficiency. Some of them are solid such as CocoMEA, and require melting or dissolution with negative effects on handling and production cost.

2 The aim of this article is to draw the attention of the formulator to a new multifunctional secondary surfactant, for personal care and household products, easy to use and formulate, that offers several application advantages and can resolve different problems contemporarly. Its use in the formulation grants several application benefits, allowing the use of one single product instead of dissimilar ingredients which would also result in an increase in formula cost. Multifunctional co-surfactant DITEROL AL40. The functional characteristics of this secondary co-surfactant, composed of a synergic base of biodegradable surfactants mainly of natural origin, can be summarized in its ability to increase the washing efficiency, increase the foam stability and density, increase the viscosity when electrolytes are added, have an anti-smell (deodorant) function, and above all strongly reduce skin irritation caused by primary surfactants. DITEROL AL40 Belongs to a new generation of multifunctional co-surfactants, based on natural active ingredients derived from Italian olive oil, and from the metabolism of glucose and glycogen. INCI Name Sodium Peg-7 Olivoil Citrate C12-C14 Alkyl Lactate CAS number Apparence Pourable paste Colour Yellowish Odour Slightly olive Active matter 40 +/- 2% ph (1%sol) 6,5 7,5 This innovative product, manufactured and exported in industrial scale, does not show the disadvantages known by the products actually on the market which act on a single characteristics in the formulae, and interfere negatively on others therefore oblige the formulator to increase the quantity and number of additives to compensate for the negative effects that may arise in the finish product. In this article we will show the characteristics of Diterol AL40 and compare its performance to CocoDEA in formulations of personal care and liquid dishwashing detergents. We chose CocoDEA as a parameter of evaluation because like Diterol AL40 it is extremely cost effective in formulation, andits pros and cons are well known in industry world-wide, even though in recent years it has been phased out from formulation by major manufacturers due to its nitrosamine potential.

3 RHEOLOGICAL BEHAVIOUR IN PERSONAL CARE FORMULATION Viscosity of Diterol AL40, versus Diterol 87 at different % of NaCl SLES 10% a.m. + 2% w/w CocoDEA ( Diterol 87) SLES 10% a.m. + 2% w/w Diterol AL40 Figure Viscosity 20 C (cps) with Diterol 87 with Diterol AL40 0 1,5 2 2,5 3 3,5 4 %NaCl ( Brookfield sp.10 rpm 3 ) The above rheological behaviour is brought to extreme in a theoretical formulae based exclusively on SLES. In this abnormal case CocoDea increases the viscosity of SLES more than Diterol AL40. To obtain similar levels of viscosity with Diterol AL40, NaCl must be increased by about 0,4%.The solution with Diterol AL40 unlike CocoDea remains limpid even at higher concentrations of NaCl..Completely different behaviour is showed by Diterol AL40 when used in conventional blends ( table 2 ) The below table shows the viscosity of Diterol AL40 versus CocoDEA in a blend at different % of NaCl SLES 10% a.m. + 5% w/w Cocamidopropyl Betaine + 3% w/w Cocoyl Glutamate + 2% w/w Coco DEA (Diterol 87 ) SLES 10% a.m. + 5% w/w Cocamidopropyl Betaine + 3% w/w Cocoyl Glutamate + 2% w/w Diterol AL40

4 Figure viscosity 20 C (cps) w ith Diterol AL 40 w ith Diterol ( Brookfield sp.10 rpm 3 ) 0,5 1 1,5 2 %NaCl In a simple personal care formulation Diterol AL40 performs better than CocoDEA, in terms of viscosity. At equal viscosity Diterol AL40 requires about 0.4% lower concentration of NaCl FOAM CHARACTERISTICS The below table shows the foam of Diterol AL40 versus CocoDEA (Diterol 87) in a/m blend at different time laps. Figure foam ( ml) minutes w ith Diterol 87 w ith Diterol AL40

5 Foam volume and aspect has been detected in a graduated cylinder using 200 ml of 1g/l of a/m blend after 30 strokes in 30 second ( hard water 10 French degree). EVALUATION In personal care formulations at equal dosage and % of electrolyte higher viscosity is observed with Diterol AL40 with respect to CocoDEA (Diterol 87). Improved foam stability is also observed with Diterol AL40 with compact and dense bubbles. RHEOLOGICAL BEHAVIOUR IN DISHWASHING LIQUID DETEREGENT 10% a.m. Labsa + 3% a.m. SLES + 2% w/w Diterol AL40 10% a.m. Labsa + 3% a.m. SLES + 2% w/w CocoDEA ( Diterol 87) Rheological behaviours of dishwashing with CocoDEA and Diterol AL40 have been tested at difference percentages of electrolyte ( NaCl) as per Tab. 4 Figure 4. Viscosity mpas (sp10,rpm3) , ,5 %NaCl Diterol AL40 CocoDea In a standard dishwashing formulation Diterol AL40 shows better performance in terms of viscosity compared with CocoDEA,

6 FOAM CHARACTERISTICS The below table shows the foam of Diterol AL40 versus CocoDEA (Diterol 87) in a/m blend at different time laps Foam volume has been detected in a graduated cylinder using 200 ml of 1g/l of dishwashing product after 30 strokes in 30 second ( hard water 10 French degree ). Figure ml Diterol AL40 Coco dea ' 10' 20' minutes EVALUATION In a dishwashing-liquid formulae at equal dosage and % of electrolyte higher viscosity is observed with Diterol AL40 with respect to CocoDEA (Diterol 87). Improved foam stability is also observed with Diterol AL40 with compact and dense bubbles. IN VITRO EVALUATION OF SKIN IRRITATION POTENTIAL In vitro methods are an interesting alternative system to traditional vivo test to evaluate biological properties of topical products and cosmetics (according with European cosmetics rules that ask manufacturers to assess the product safety and effectiveness, without employing animals, BCD n 76/768/ECC of the 27/07/76, EC L.262 of the 27/09/1976; VI amendment Council Directive 76/768 EEC of the 14/06/1993 ECKL 151 of the 23/06/1993). Cytotoxicity assay can be carried out in order to evaluate in vitro the potential skin irritation of cosmetic ingredients or finished products on keratinocyte cultures. The in vitro test on skin-derived cells is a simplified but yet very informative model of the reaction that may occur in vivo. Products are directly applied locally on human skin or hair, often in contact with mucous membranes. The cytoxicity assay performed in this study was designed to evaluate the toxic dermal irritation potential of tested products using relevant human cell grow in vitro. Cytotoxicity test performed on human keratocites of fibroblasts in mono-layers have

7 been extensively used in the evaluation of eye and skin irritation potential of cosmetics and ingredients. The objectives of this assay is to assess quantitatively the effects of the products on the cell survival trough the MTT assay; this is a very simple colorimetric assay that allows to determinate the percentage of living cell within cell cultures. This method has been developed originally bu Mossman,. The key reagent is 3(4,5- dimethylthiazol-2-yl)-2,5-diphenil tetrazolium bromide or MTT. Mithocondrial dehydrogenases of viable cell cleave the tetrazolium ring, leading to the formation of purple crystals, salt of formazan. An increase or decrease in cell number results in a concomitant change in the amount of formazan formed, indicating the degree of cytotoxicity caused by the tested material.. IC50 ( Inhibiting concentration 50%) : concentration of test compound which causes a 50% decrease of cells survival as compared to untreated cells. The IC50 value ( Inhibition Concentration 50) is the concentration of test compound which induce a 50% decrease of cells growth / survival. It makes it possible to evaluate the potential irritating effect of the compound. With MTT we tested Lauryl Ether Sulphate( SLES) 13% a.m. on its own as well as in combination with 2% Diterol AL40 to evaluate the eventual decrease in terms of potential irritation Table 1. Product IC 50 mg/ml Judgement SLES 13% a.m. 0.8 Slightly irritant SLES 13% a.m.+ 2% Diterol AL40 w/w 5.1 Very good biocompatibility IC 50 < 1 mg/ml = irritating product IC 50 > 3 mg/ml = very good biocompatibility EVALUATION A blend of 13% a.m. SLES and 2% w/w Diterol AL40 resulted 6 times less cytotoxic than SLES on its own confirming Diterol AL40 ability to reduce potential irritation of primary surfactants. CONCLUSION A bio-compatible multifunctional co-surfactant derived from natural origin Combines the performance of low irritating surfactants with emollient and restructuring skin agents due to the presence of derivatives of olive oil and alkyl lactate whose benefits are well known and demonstrated in literature Reduces substantially the irritancy of commonly used surfactants. Excellent viscosity booster free of nitrosamine. Produces stable and compact foam granting a creamy sensation on application. In dosage above 3% it exhibits deodorant proprieties thanks to the anti bacteria action deriving from the hydrolysis of ester (sniff test) The deodorant effect is linked to the presence of lactate in formulation whose deodorant effect is well known and demonstrated in literature

8 Its presence in a liquid detergent helps the skin to restore its healthy aspect by avoiding the denaturation of proteins and the disorganisation of the horny layer. Easy to use and compatible with all primary surfactants Bibliography 1. Bothan P.A., Earl L.K, Fentem J.H. Rouuet R. Van De Sandt J.J.M ( 1998) Alternative methodsfor skin irritation testing : the current status ATLA Kupper, T.S. (1990) Immune and inflammatory processes in the cutaneous tissue: mechanisand speculatuion Jour..Clin.Invest 3. Norma UNI EN ISO Valutazione biologica dei sispositivi medici- Prove per la citotossicità in vitro Settembre S.Amari, A.Amari, C.Schubert, Olive oils surfactants, B&T Milano Genova C., Zatta A.,Deiana L., Montesion F. Mono-branched alkyl lactate as a rheological improver for body and personal care formulations Condea Italy K.F.De Polo, Textbook of Cosmetology, Verla 5. Azrak G. Marchesi F. Secondary multifunctional surfactant based on natural origin raw material. Cisme Italy Patent MI2008A001860

European Market Natural Personal Care Products The market has been growing at a fast rate. - Growing consumers demand for natural/organic personal car

European Market Natural Personal Care Products The market has been growing at a fast rate. - Growing consumers demand for natural/organic personal car Innovation Seminars April 14th, 2015 AMISOFT ECS-22W Amino Acid Based Surfactant for Natural Cosmetics & Sulfate-Free Personal Care Products In-Cosmetics 2015 Nana Haraya Cosmetic Group Ajinomoto Co.,