J. Appl. Csmetl. 28, 1-11 (Jnury /Mrch 201 O) The Effect f Ethxylates f Maracuja and Almnd Oils n the Perfrmance and Physicchemical Prperties f Shwer Gels Marian W. Sutek, Katarzyna Pytlas Radm Technical University, Department f Chemistry, Faculty f Physical and lnrganic Chemistry. Radm - Pland Received: Nvember, 2009. Key wrds: Ethxylates f maracuja and almnd ils; Shwer gel; Cefficient f vìscsìty; Famability; Emulsifiability f dirt; Misturising; Summary Shwer gels are the mst ppular grup f bath csmetics. Their share n bth the Plish and Eurpean market has been cnstantly grwing. Apart frm cleansing prperties, the gels exhibit ther prperties, such as misturizing and sftening the skin, giving it a nice scent and prviding relaxatin. While preparing shwer gel frmulatins it is imp 1ant t use thse raw materials which d nt nly cleanse but als care fr the bdy. Such prperties can be btained by adding vegetable raw materials with cleansing and refattening abilities t traditinal frrnulatins f bath csrnetics. Particular attentin shuld be paid t new nninic surfactants such as ethxylates f vegetable ils. Due t the presence f an ethylene xide chain, the materials are sluble in a hydrphilic medium withut lsing the prpe11ies f an il. In view f the caring, nurishing and refattening prperties f maracuja and almnd ils, an attempt has been made t use their ethxylates (INCI: PEG-60 Maracuja Glycerides, PEG-60 Almnd Glycerides) as effective ingredients affecting physicchemical and perfrmance characteristics f shwer gels. The results f this study shw that shwer gels cntaining the selected vegetable il ethxylates have cmparable r better prperties than cmmerciai prducts.
The Effect f Ethxylates f Maracuja and Almnd Oils n the Perfrmance and... Riassunt I gel-dccia rappresentan il grupp più nt di csmetici da bagn e la lr presenza è in cstante aument sia nel mercat placc che in quell eurpe. A parte la lr azine detergente, grazie all'us di particlari materie prime utili per la cura del crp, questi gel pssiedn prprietà idratanti ed emll ienti, che, smmate alla lr prfumazine, dnan un interessante effett rilassante. Per le lr prprietà emllienti e seb-prtettive, particlarmente utili sn gli etssilati di diversi li vegetali, in quant la presenza nella lr mlecla della catena ssietilenica li rende particlarmente idrfili senza che perdan le nte prprietà degli li. A quest scp sn stati utilizzati gl i etssilati di maracuja e di li di mandrle (INCI: PEG-60 Maracuja Glycerides, PEG-60 Almnd Glycerides) per frmulare gel-dccia ad azine nutriente e seb-nrmalizzante. I risultati dell studi cndtt dimstran cme i gel-dccia frmulati cn questi etssilati presentin migliri caratteristiche rispett ai cmuni prdtti presenti sul mercat. 2
Sulek MW, Pytlas K. INTRODUCTION Due primarily t their versatility and cmfrt in use, shwer gels are nw the mst ppular grup f liquid bath preparatins (1-7). Shwer gels are clear, slightly palescent r "milky" liquids whse viscsity makes them easy t apply. Apart frm remving dirt frm the suiface f the skin, the preparatins ught t m i sten, sften, grease and cnditi n the skin, give it a pleasant scent and prvide a feeling f freshness. It shuld als be easy t rinse them ff the skin. Besides, they shuld prduce fam when applied and be neutra! t the human bdy. Bath preparatins have a s)jghtly acidic reactin (5-9). Shwer gels cntain bth synthetic and naturally ccurring raw materials ( 1-5). The key rle is played by surface-active agents (surfactants). The aninic surfactants used are primarily sulfates f fatty alchls and their ethxylates, sulfsuccinates, cndensates f fatty acids with amin acids, prteins r their hydrlysates. The amphteric surfactants used are alkylamide betaines and imidazle derivatives, whereas the nninic surfactants used are diethanlamides, ethxylated fatty alchls and ethxylated vegetable ils. Other cmpunds added t gel frmulatins include viscsity mdifiers (electrlytes, plymers), humectants, refatteners, plant extracts, sequestrants, fragrances (essential i ls) and preservati ves. Particular attentin shuld be paid t ethxylates f vegetable ils which are mre and mre ften used as cmpnents f bth bath and bdy care preparatins (9). The generai frmula f ethxylated vegetable ils is: CH- O-(CH CH O)x-C-R I 2 1 2 0 CH-0-(CH CH O)y-C-R I 2 2 Il CH20- (CH 2 CH 2 0)z- C- R where: x + y + z = m - average degree f plyaddìtìn f ethylene xìde, R - fatty acid radical. They are a grup f nninic surface-active agents which are used as slubilizers and refatteners in washing preparatins and als as emllients, emulsifiers and cemulsifiers in emulsin systems (9). MATERIALS ANO METHODS Materials Tw kinds f ethxylates f vegetable ils were selected: frm maracuja (INCI: PEG-60 Maracuja Glycerides) and frm almnds (INCI: PEG-60 Almnd G lycerides). Bth f them are csmetic raw materials prduced by Crda [9]. The starting pint fr the preparatin f ur wn gel frmulatins were typical shwer gel frmulatins (2-5). The mdel frmu latin cnsists f a basic aninic surfactant (INCI: Sdium Laureth Sulphate), auxilliary surfactants frm a grup f nninic cmpunds (INCI: Ccamide DEA) and frm a grup f amphteric cmpunds (INCI: Ccamidprpyl Betaine), sdium ch lride (INCI: Sdium Chlride) as the mst cmmn viscsity mdifier in this type f prducts, as well as a fragrance cmpsitin, a preservative, a ph regulatr (INCI: Citric Acid) and water (Table I). Seven preparatins cntaining maracuja il ethxylates and seven preparatins cntaining almnd il ethxylates were prepared. The preparatins differed in the cncentratin f ethxylates. Additinally, a base preparatin wi thut ethxylates was prepared. Bth dmestic and imprted cmmerciai prducts have been used as reference preparatins. Their cmpsitin includes bth synthetic and naturally ccurring ingredients. They are ppular medium- and high priced high-quality prducts whse sales figures have been steadily increasing. 3
The Effect f Ethxylates f Maracuja and Almnd Oils n the Perfrmance and... TABLEI Shwer gel frmulatin cntaining maracuja il ethxylates (INCI: PEG-60 Maracuja Glycerides) and almnd il ethxylates (INCI: PEG-60 Almnd Glycerides). Z-0 Z- 1 Z-2 Z-3 Z-4 Z-5 Z-6 Z-7 Z-8 Z-9 I Z-10 I Z-11 I Z-12 I Z-13 I Z-14 INCI name wt % A ua li IO 100 Sdium Laureth Sul fle Ccamide DEA I 2.5 Ccamidprpyl Betaine --+-- 0.01 PEG-60 Marncuja Glycerides I I l"ll' 1, I, I PEG-60 Almnd G lyccridcs Sdium Chlride Parfum Clur Citric Acicl Preservative I I 10-0.01 I I I I I I I I I 'l, I 1, I,, q.s. O.I O.I up IO ph -6.5 O.I 0.05 Mefhds This paper investigates the effect f the type and cncentratin f vegetable il ethxylates n selected physicchemical and perfrmance characteristics f shwer gels, i.e. viscsity, famability, ability t remve dirt and ability t retain cnstant skin hydratin. The investigatin results btained were cmpared with thse fr the cmmerciai prducts and, based n that, the preparatins with the best prperties were selected. The cefficienf f viscsity The cefficient f viscsity (11) is ne f the mst imprtant perfrmance characteristics f bath preparatins. The preparatins shuld nt flw dwn the bdy but be easily spread, s the 11 value shuld be prperly selected. This value shuld als be taken int accunt when designing the packaging t guarantee prper gel dsage. The measurements f viscsity f shwer gels were carried ut with a Brkfield RVDV - I+ viscmeter at a rtatinal speed f the spindle f 5 rpm at 20 C which mst precisely reflects applicatin cnditins f such preparatins (9). Famabilify Famability is anther imprtant parameter affecting the quality f bath preparatins. The 4
Sulek MW Pyttas K. vlume f fam and its stability enhance aesthetic qualities f bathing and the cnsumers tend t assciate rich fam with a gd cleansing actin. Shwer gels shuld exhibit high famability in a relatively shrt time but high stability is nt necessary as shwering is nta lng prcess and fam shuld be easily rinsed ff the bdy. The fambility prperties f shwer gels were studied by means f the Rss-Miles fam test (7-8). The test cnsists in measuring the fam vlume prduced by puring ut a I% aqueus slutin f a shwer gel frm a separating funnel nt the surface f the slutin f the same cncentratin in a measuring cylinder. The quantities measured included fam vlume after JOs frm its frmatin (famability) and als after I and I O minutes. Based n the latter quantities, the cefficient f fam stability X was defined by: X = V 2 100 [%] vi where: V 1 - fam vlume measured after l min, cm 3 V 2 - fam vlume measured after 10 min, cm 3 Emulsifiability f dirt The abil ity f shwer gels t remve dirt was evaluated. T he tests were based n a mdified methd fr determining the emulsifiability f fats in a wash bath btained frm the preparati ns examined r frm the cmmerciai gels (7). The max imum quantity f il emulsified by l % slutins f the preparatins examined was a measure f the ability t remve dirt. Misturizing The degree f skin hydratin was evaluated by measuring the capacity resistance f the hrny layer f the epiderrnis (crnemeter CM 825) (12). The tests were carried ut n a clean, degreased skin, which was a reference pint. After applying the preparatins and washing them ff, slcin hydratin was measured in 15 minute intervals fr up t 90 minutes. The results were cmpared with the degree f hydratin f the skin which had nt been treated with any preparatin. The measurement result was defined in arbitrary units ( 12). RESULTS The cefficient f viscsity The effect f the cncentratin f sdium chlride (INCI: Sdium Chlride) as ne f the mst cmmn viscsity mdifiers used in bath preparatins n the viscsity cefficient values f shwer gels was analyzed (Fig. I). The grey shaded area in the diagrams describes the range f viscsity cefficient values fr cmmerciai shwer gels (7000-12000 mpa s, at rtatinal speed f 5 rpm). When the cncentratin f the electrlyte (NaCI) increased, the cefficient f dynamic viscsity als increased reaching a maximum and this was fllwed by a decrease in the value being measured. The highest viscsity values (ca. 47000 mpa's) were btained fr the preparatin withut vegetable il ethxylates at 2% NaCI. Even a small additin f ethxylates (O.O I%) cnsiderably reduced the maximum value fri (l.9% NaCI) t 37400 mpa.s fr PEG-60 Maracuja Glycerides and t 42800 mpa s fr PEG-60 Almnd Glycerides. The viscsity cefficient value decreased with an increase in the cncentratin f ethxylates and the maximum shifted twards higher cncentratins f the electrlyte. The results btained were used t determine the minimum cncentratin f sdium chlride at which the viscsity cefficients f the preparatins cntaining ethxylates are cmparable with thse fr cmmerciai prducts (7000-12000 mpa s, at rtatinal speed f 5 rpm). 5
The Effect qf Ethxylates f Maracuja and Almnd Oi/s n the Perfrmance and... 60000 50000... ;,, ~ 40000 ~ 30000 u... :> 20000 10000 ~... ~.~... 0.5 L5 2 2.5 3 Cncentratin (%] 3.5 4 4.S a - 5 ---+- r. cncentratin f ethxylates -a--0.01% cncentratin f ethxylates -.!!r-0.05% cncentratin f ethxylates,.._0.1% cncentratin f ethxylates --0.5% cncentratin f ethxylates ---&--- 1% cncentratin f ethxylates -+- 5% cncentratin f ethxylates --10% cncentratin f ethxylates 60000 50000 ;,, "' ~ 40000 ~ 30000.... ~ 20000 :> 10000L'< ~~~~.... ~ 8 TM: 0.5 L5 2 2.5 3 3.5 4 4.5 5 Cncentratin (%] ---+- r. cncentratin f ethxylates -a--0.01% cncentratin f ethxylates ----&- 0.05% cncentratin f ethxylates,.._0.1% cncentj:atin f ethxylates --0.5% cncentratin f ethxylates ---&--- 1% cncentj:atin f ethxylates -+- 5% cncentj:atin f ethxylates - -10% cncentj:atin fethxylates b Fig. l Depe11de11ce f dynamic viscsiry f shwer gels c11taini11g: a - maracuja il ethxylates (PEG-60 Maracuja Glycerides), b - al111011d il ethxylates (PEG-60 Almnd G/ycerides) 0 11 cnce11tratin f electrlyte (NaCI). Brkfield RVDV I+ viscmeter, RV-type spindles, rtatinal speed - 5 rpm. Measure111e1111e111pera111re: 20 C. Famability The results f the famability tests n shwer gels (fam vlume and its stability index) are shwn in Fig. 2. The grey shaded areas shw the value range fr fam vlume (370-445 cm 3 ) and its stability indices (90-100%) fr cmmerciai prducts. The cncentratin f vegetable ils slightly affects the famability f shwer gels and the results btained are cmparable with the values f fam vlume and fam stability indices fr cmmerciai prducts. 6
Sulek M W, Pytlas K. TABLE III Cncentratin f electrlyte (NaCI) in shwer gel frmulatins. PEG-60 Maracuja Glycerides [ % ] 0.01 0.05 0.1 0.5 1 5 10 NaCI [ %] l 1,1 1,1 1,1 1,2 1,4 2,2 2,6 PEG-60 Almnd Glycerides [%] 0.01 0.05 0.1 0.5 1 5 10 NaCI [%] 1 1 l 1 1,1 1,3 1,8 2,5 600 500 80 1., >< ~ 400 '<l 60 "'.9 ~ ~ 300 ;;i. > 40 ~ ~ 200 ~ ""' 100 20 ""' ---<>-- Fam vlume --p am stability index 0.01 0.05 0.1 0.5 1 5 10 Cncentratin [%] a 1 600 500 '~ ~~ ~ ~~~~'~ 80 ~ ~ 400 ><., 60 '<l i=.9.2 300 ~ > ;;i ~ 200 ""'., 40 {l... 20 ~ 100 ---<>-- Fam vlume --F am stability index ""' 0.01 0.05 0.1 0.5 1 5 10 e nc entrati n [.%] Fig. 2 Dependence f famabi/ity cmd fam stability index f shwer gels n cnce111rcain f' a - maracuja il ethxylate (PEG-60 Maracuja Glycerides), b - almnd il ethxylate (PEG-60 A/111011d Glycerides). Rss-Mi/es methd. Measureme/11 temperature: 2(J'C. b "' 7
The Effect f Ethxylates f Maracuja and Almnd Oils n the Perfrmance and... In the case f the preparatin withut ethxylates, the vlume f fam was 390 cm 3 and its stability index was 98%. With an increase in the cncentratin f PEG-60 Maracuja Glycerides the fam vlume increased slightly up t 440 cm 3 fr l / ethxylate and then it decreased. A graduai increase in the fam vlume was bserved fr shwer gels cntaining PEG-60 Almnd Glycerides. The fam stability index shwed an upward trend frm 94% t 100% with an increase in the cncentratin f ethxylates. Emulsifiabilify f dirf The ability t remve dirt frm the surface f the skin is an imprtant criterin that must be satisfied by bath preparatins. Shwer gels shuld remve sweat and dirt frm the su1face f the skin but they shuld nt degrease it excessively. The emulsificatin f a mdel ily stain was examined in arder t evaluate the ability t remve dirt frm the surface f the skin. The maximum mass (in grams) f emulsified rapeseed il added t the wash bath was a measure f cleansability. The results btained are shwn in Fig. 3. They were cmpared with cmmerciai prducts whse emulsifiabil ity f dirt ranged frm 1.4 t 2.8 g f the mdel staining (rapeseed il). It is shwn in the diagrams by the shaded area. 'Ò tèì 3 ~ 2.5 "' Oil ~~ 2 Q) ~ 'Ò e:., 1.5 i i I e.5 ~ I._. L...I L...I L...I L...I L...I L...I L...I O.DI 0.05 O,I 0.5 5 IO Cncentratin [%] a 'Ò 3 tèì -5 2.5~~~~~.~~ e "' Oil ~~ 2 Q) Q) 'Ò ~ ~ L5 e ~ i ~ I., e.5 t: I L...I L...I L...I L...1 L...I, L...I L...I L...I O.DI 0.05 O.I 0.5 5 IO Cncentratin [%] b Fig. 3 E111ulsifiability f ily stains by shwer gels as a f1111cri11 f cncenrrarin f ethxylates: a - PEG-60 Maracuja Glycerides, b - PEG-60 Almnd Glycerides. 8
Sulek MW P)ttts K. Ali the preparatins evaluated were capable f remving dirt within the range f the maximum values f the mass f the emulsified ily stain bserved fr cmmerciai prducts. The value fr the preparatin withut ethxylates was 2.2 g. The emulsifiability f the ily stain increased with an increase in the cncentratin f vegetable il ethxylates. The highest emulsifiability was bserved fr the preparatins cntaining I / f the cmpunds analysed - 2.6 g f rapeseed il. Misturizing A measurement f skin hydratin as a functin f time was made after applying shwer gels (Fig. 4). The results btained were cmpared with thse fr cmmerciai prducts fr which the leve) f skin hydratin ranged frm 28 t 42 arbitrary units (see the shaded area in Fig. 4). 50 -:i~.!!.. 40 <:.:i "' 30 -li È ~ 20... :: 10!;D a 15 30 45 60 --+- dryskin --+--0% cncentrat.in f ethxylates -a-.01r. cncentrat.in f ethxylates --e,-0.05% cncentrat.in f ethxylates --X-0.1% cncentrat.in f ethxylates ~0.5% cncentrat.in f ethxylates --1% cncentrat.in f ethxylates --5% cncent~at.in f ethxylates --+-10% cncentrat.in f ethxylates 75 90 Time [mìn) a 50 ;::i ~ 40 <:.::i -li "' 30 >...s:: ~ 20 'ti.,!;d Q 10 15 30 45 60 Time [min) 75 90 --+- dry skin --+--0% cncentrat.in f ethxylates --e- 0.01% cncentrat.in f ethxylates --&-0.05% cncentrat.in f ethxylates --X-0.1% cncentrat.in f ethxylates ~0.5% cn centrat.in f ethxylates --1% cncentrat.in f ethxylates --5% cncentrat.in f ethxylates --+-10% cncentrat.in f ethxylates b Fig. 4 Depende11ce f degree f ski11 hydratin n cnce11trati11 f eth;1.y/ates in shwer gels and time after rheir applicatin: a - PEG-60 Maracuja Glycerides, b - PEG-60 Almnd Glycerides. Cmemeter CM 825 frm Curage + Khazaka electr11ic. Temperature 20 C 9
The Effect f Ethxylates f Maracuja and Almnd Oils n the Perfrmance and... The hydratin f dry skin during the 90-minute test was at the leve! f 28-32 arbitrary units. The applicatin f the ethxylate-free shwer gel increased skin hydratin up t the leve! f 33-37 a.u.. An imprvement in skin hydratin was bserved with an increase in the cncentratin f vegetable il ethxylates (up t I%) in shwer gels. It remained at a steady leve! r tended t increase slightly. In the case f preparatins cntaining PEG-60 Maracuja Glycerides, the maximum skin hydratin was btained after applying shwer gels cntaining 0.1-J % ethxylates and reached 35-45 a.u.. The best prperties f maintaining a cnstant leve! f water in the epidermis were bserved far preparatins cntaining 0.5-1 % PEG-60 Almnd Glycerides. The hydratin ranged frm 40 t 45 (sufficiently misturized skin) and it was higher than the leve! f skin hydratin bserved after the applicatin f cmmerciai shwer gels. lates maintained the degree f hydratin at the highest leve!, which was higher than the degree f hydratin after applicatin f cmmerciai prducts. This study shws that the cncentratin f vegetable il ethxylates has a cnsiderable influence n the quality f shwer gels. The applicatin f l % vegetable il ethxylates in shwer gels seems t be the mst favurable. The applicatin f the preparatins cntaining 5 and 10% ethxylates is the least favurable due t the high cncentratin f the electrlyte required t btain apprpriate viscsity f the final prduct. DISCUSSION Vegetable il ethxylates are csmetic raw materials which cmbine prperties f ils and water slubility. Additin f ethxylates t shwer gels favurably affects their famability and ability t remve dirt. They deserve particular attentin due t their mild interactin with the skin including refattening in bath preparatins. Frmulatins f shwer gels cntaining ethxylates were prepared n the basis f earlier studies (6-7). Selected perfrmance characteristics f the preparatins based n ur wn frmulatins were cmparable r better than thse fr cmmerciai prducts. The cefficient f viscsity, famability and cleansing prperties were cmparable with cmmerciai prducts within the whle range f cncentratins f vegetable il ethxylates. The biggest differences were bserved in misturizing abilities f shwer gels tested. The preparatins cntaining 1 % ethxy- 10
Sulek MW, Pytlas K. References 1) Mitsui T. (1988) New Csmetic Science, Elsevier Science B.V., pp. 446-457. 2) Butler H, Hunting ALL. (2000) Pucher's Perfumes, Csmetics and Saps, 1Q h Editin, Kluwer Academic Publisher, pp. 101-149. 3) Williams DF, Schmitt WH. (1992) Chemistry and Technlgy f the Csmetics and Ti letries Industry. Blackie Academic & Prfessinal, Glasgw. 4) Barel AO, Paye M, Maiback HJ. (2001) Handbk f Csmetic Science and Technlgy, Wydawnictw: Marce! Dekkers INC, New Yrk. S) Lai KY, Reever RE. (1997) Liquid Detergents. Liquid Saps, Smfactant Science Series, Vlume 67, Clgate-Palmlive Cmpany, New Yrk. 6) Sutek MW, Pytlas K, Szczesniak A. (2007) Influence f ethxylatin degree f lauryl alchl n quality f shwer gels, Current Trends in Cmmdity Science, Pznan, August 27-29, 2007, Vi. I, The Pznan University fecnmics Publishing Huse. 7) Wasilewski T, Klimaszewska E. (2007) Rle f misturising agents in quality imprvement f shwer gels, Pfish Jurnal j Cmmdity Science Wyd. Plitechnika Radmska, ITeE-PIB, 1: 62-72. 8) PN-ISO 696:1994, Srdki pwierzchniw czynne. Oznaczanie zdlnsci piantw6rczych zmdyfikwarni metdq Rss-Miles'a. 9) Crvl Maracuja (2004) Extic water sluble emllient & mildness additive. Crda Chemicals Eurpe Persna) Care, 01 /04 DCl29/I, pp. 1-7, www.crda.cm. 10) Wasilewski T, Sutek MW. (2006) The influence f micelle shape, size and the rganizatin degree n the viscsity f cleansing prducts, J. Plish Sciety f Csmetic Chemists, 1:14-20. 11) Brkfield Catalg (2008) "Slutins fr a Viscus Wrld. Viscmeters, Rhemeters & Texture Analyzers fr Labratry and Prcess Applicatins", pp. 6-39. 12) Curage + Khazaka electrnic GmbH, The Crnemeter CM 825, J 2/2003. Authrs' Address: Marian W. Sufek, Katarzyna Pytlas Radm Technical University Department f Chemistry Faculty f Physical and lnrganic Chemist ul. B. Chrbreg 27 26-600 Radm - Pland e-mail: rektrb@pr. radm. pi e-mail: k.pytlas@pr.radm.pl 11