Kozmetička sredstva na tekstilu: kozmetotekstilije · koriste ciklodekstrini koji su blagi prema koži, a s kozmetičkim sred-stvom mogu stvoriti kompleks koji se raznim tehnikama

I. MATIJEVIĆ i sur.: Kozmetička sredstva na tekstilu: kozmetotekstilije, Tekstil 65 (1-2) 1-12 (2016.) 1

Kozmetička sredstva na tekstilu: kozmetotekstilije

Iva Matijević, mag.ing.techn.text.Prof.dr.sc. Sandra Bischof, dipl.ing.Prof.dr.sc. Tanja Pušić, dipl.ing.Sveučilište u Zagrebu Tekstilno-tehnološki fakultetZavod za tekstilno-kemijsku tehnologiju i ekologijuZagreb, Hrvatskae-mail: [email protected] 27.7.2015.

UDK 677.07:668.58:677.016Pregled

Zahtjevi današnjice nameću sve veću potražnju za inovativnim i viskoučin-kovitim tekstilijama koje mogu olakšati i poboljšati stil života. Iz razloga što su kozmetički proizvodi široko dostupni te dodatno što njihova primjena ponekad zahtijeva izdvajanje puno vremena, proizašla je ideja o jednostavnoj aplikaciji kozmetičkih proizvoda na tekstil. Način vezanja tekstila i kozmetičkog sredstva omogućava kontrolirano otpuštanje kozmetičkog sredstva s tekstila. Svrha obrade je postići otpuštanje aktivnih tvari u željenom trenutku ili određenom vremenskom razdoblju uz istovremeno postizanje zadovoljavajuće postojanosti na pranje. Pritom je kemizam otpuštanja problematika kojoj treba posvetiti posebnu pažnju. U ovom radu je detaljnije opisan pojam kozmetičkog tekstila ili kozmetotekstilija, prikazana je njihova podjela, namje-na, a dodatno je obrađena i problematika otpuštanja aktivnih tvari i posto-janosti obrade. Na kraju je dan osvrt na moguće smjerove razvoja ove sve popularnije završne obrade tekstilnih materijala kojima tekstil dobiva do-datna svojstva i postaje proizvod visoke vrijednosti.Ključne riječi: kozmetotekstilije, kozmetički pripravci, mikrokapsule, visoko-učinkovite tekstilije

1. Uvod

Tekstil i kozmetika su među najstari-jim proizvodima koje je čovjek ikad napravio, ali povezivanje tekstila i kozmetike u obliku kozmetotekstilija je relativno novi koncept primjene i istraživanja koji je veoma značajan za 21. stoljeće [1].Najzanimljiviji način „pohrane“ koz-metičkog sredstva je onaj u mikro-kapsuli zbog mogućnosti kontroli-ranog otpuštanja aktivnog sredstva. Iako se mikrokapsule spominju i ra-nije za razne primjene u tekstilnoj industriji, tek se 1990-ih spominje

upotreba za kozmetičke svrhe. Jedan od primjera su mikrokapsule koje sadrže eterična ulja. Takve mikro-kapsule nanesene na tekstiliju tije-kom nošenja, uslijed kojeg dolazi do mehaničkih pritisaka i trenja, otpu-štaju miris ili daju neki drugi efekt ovisno o vrsti eteričnog ulja [2].Za kozmetičku primjenu često se koriste ciklodekstrini koji su blagi prema koži, a s kozmetičkim sred-stvom mogu stvoriti kompleks koji se raznim tehnikama veže za teksti-liju [3, 4].Napredak u razvoju kozmetoteksti-lija je relativno spor iz razloga koji je

još uvijek prisutan - postizanje želje-ne učinkovitosti i postojanosti obra-de u isto vrijeme. Jedan od problema je osjetljivost, odnosno nestabilnost mnogih kozmetičkih sastojaka, npr. parfemi su lako hlapljivi, dok je ve-ćina vitamina osjetljiva na povišenu temperaturu.Razvoj i proizvodnja učinkovitih kozmetotekstilija koje pružaju do-datne vrijedne pogodnosti za potro-šače tijekom nošenja nije nimalo jednostavan zadatak. Glavni zadatak je zadržati kozmetičko sredstvo na tekstiliji nakon provedenog ciklusa pranja te omogućiti njegovo kontro-

I. MATIJEVIĆ i sur.: Kozmetička sredstva na tekstilu: kozmetotekstilije, Tekstil 65 (1-2) 1-12 (2016.)2

lirano otpuštanje. Ipak, ne smije se pretjerati sa željom da se kozmetičko sredstvo ne skida sa tekstilije prili-kom ciklusa pranja jer u tom slučaju postaje upitno otpuštanje sredstva na kožu. Mikrokapsuliranjem lako hlap-ljivih sredstava, kao što su eteričana ulja, te odabirom materijala, za sti-jenke mikrokapsula određenih svoj-stava može se utjecati na kontrolira-no otpuštanje kozmetičkog sredstva, npr. nepropusnost, osjetljivost na pritisak ili trenje i sl. [2].Kod aplikacije mikrokapsula na tek-stil preporučuje se korištenje veziv-nih sredstava (bindera) radi pobolj-šanja postojanosti na pranje [2, 5].Različiti pristupi su poduzeti za rje-šavanje izazova kontroliranog otpu-štanja pri čemu je, povijesno, glavni fokus interesa obično bio na neot-puštanju u pranju, a premalo pažnje se posvetilo mehanizmu prijenosa na kožu [6].Za razumijevanje važnosti kozmeto-tekstilija, potrebno je poznavati naj-veći organ ljudskog tijela, kožu. Pro-sječna površina kože je 1,8 m2 i na nju otpada 15 % mase cijelog tijela što ukazuje koliko je važna i briga za nju. Dijeli se na tri glavna dijela: epi-dermu, dermu i hipodermu. Ciljani sloj kože za kozmetiku je epiderma (sl.1), koji se nalazi iznad svih osta-lih slojeva, i u direktnom je dodiru s

okolinom. Ovaj sloj se sastoji od sta-nica koje se neprestano mijenjaju sve dok se ne napravi najviši sloj koji se naziva rožnati sloj (lat. stratum cor-neum). Udio vode je različit, naime u temeljnom sloju (lat. stratum basa-le) on iznosi 75 %, a u rožnatom 15% [6-9].Koža je zdrava i lijepa jedino kada je uravnotežena. Preduvjeti za zdravu kožu su: određen sadržaj vlage, mo-gućnost samozaštite, elastičnost kože te mogućnost obnavljanja stanica [10]. Ljudska koža je nepropusna ba-rijera koja daje snažnu zaštitu od vanjskih utjecaja i tvari, uključujući bakterije, gljivice, viruse, alergene, prašinu i velike molekule. U gornjem sloju, postoji više od 90 % višesloj-nog keratinocita. Rožnati sloj, vanj-ski sloj epiderme, pruža iznimno učinkovitu barijeru kod kontrolira-nog ulaska kozmetičkog sredstva, no zbog jedinstvenog sastava i strukture čini i veliku barijeru na koži od utje-caja okoline i sprečava dehidraciju tijela [11].

2. Defi nicija kozmetotekstilija

Prema priručniku [12] koji se temelji na regulativi Europske komisije (EC) No 1223/2009 za kozmetičke proiz-vode [13], „…tekstil može biti „pri-

jenosno sredstvo“ za isporuku tvari ili mješavina tvari na ljudsku kožu koje se oslobađaju tijekom vremena na različite površinske dijelove ljud-skog tijela, osobito na ljudsku kožu, a koje imaju posebne funkcije kao što su čišćenje kože, davanje mirisa, pro-mjenu izgleda kože, zaštitu, korekciju tjelesnih mirisa ili općenito održanje u dobrom stanju.Kozmetički tekstili su spoj kozme-tičkog sredstva ili mješavine sredsta-va i tekstilnog supstrata. Kozmetič-ko sredstvo ili mješavine sredstava, mogu biti prirodnog ili sintetičkog podrijetla. Da bi neko aktivno sred-stvo ili mješavina sredstava, koje se nanosi na tekstil uopće bilo kozme-tičko sredstvo mora zadovoljavati uvjet otpuštanja na kožu. Naime, sredstva koja se ne otpuštaju na kožu ne smatraju se kozmetičkim proizvo-dom, niti se tekstili na koja su nane-sena aktivna sredstva koja se ne ot-puštaju na kožu smatraju kozmeto-tekstilijama [12].Europski odbor za standardizaciju (CEN - European Committee for Standardization) je 2005. godine ime-novao radnu skupinu (WG) za pro-blematiku kozmetotekstilija, CEN/TC 248/WG 25 [1]. Radna skupina WG 25 je bila odgovorna za razvoj normi za kozmetičke tekstile. WG-25 je identifi cirao neka područja u koji-ma je neophodna normizacija i u skladu s time je imenovano pet pod-skupina za rad na različitim područ-jima kozmetotekstilija. Tako Europ-ski odbor za standardizaciju donosi i normu za kozmetičke tekstile: CEN/TR 15917:2009: Textiles – Cosmeto-textiles (HRI CEN/TR 15917:2010: Tekstil - Kozmetički tekstili) [14]. Normativne reference koje su ne-ophodne, a navode u navedenoj nor-mi su:• HRN EN ISO 3175-1:2010: Tek-

stil - Profesionalna njega, kemij-sko čišćenje i mokro čišćenje tka-nina i odjevnih predmeta - 1. dio: Ocjenjivanje učinka čišćenja i završne obrade (ISO 3175-1:2010; EN ISO 3175-1:2010),

Sl.1 Shematski prikaz epiderme [8]

Rožnati sloj

Mrtve staniceispunjene skeratinom

Lameralnegranule

Keratinocit

Merkelovastanica

Senzornineuron

Svijetli sloj

Zrnati sloj

Nazubljeni sloj

Temeljni sloj

Melanocit

Derma


• HRN EN ISO 3758:2008: Tekstil - Označavanje njege primjenom simbola (ISO 3758:2005; EN ISO 3758:2005),

• HRN EN ISO 6330:2003/A1:2009 enpr: Tekstilije – Postupci pranja i sušenja u kućanstvu u svrhu ispi-tivanja tekstila (ISO 6330:200/Amd 1:2008; EN ISO 6330:2000/A1:2009),

• HRN EN ISO 22716:2008: Koz-metika - Dobra proizvođačka praksa (DPP) - Smjernice za dobru proizvođačku praksu (ISO 22716:2007; EN ISO 22716:2007).

Poželjno je primjenjivati navedene normativne reference te se usklađi-vati sa standardima kao što su Oeko--Tex® 100 i Oeko-Tex® 1000. Time se osigurava visoka kvaliteta tekstila prije nego što se kozmetičko sred-stvo uopće aplicira na njega i kozme-totekstilije kao gotovog proizvoda. Potrebno je provoditi individualne testove na kozmetičkim sredstvima u kemijskoj industriji, a nakon izrade gotovog proizvoda (kozmetoteksti-lija) potrebno je testirati cijeli proiz-vod uz pomoć općih bioloških testo-va koji su slični antimikrobnim testo-vima. Kozmetotekstilija mora proći testiranja prema normi HRN EN ISO 10993-10:2013: Biološka procjena medicinskih proizvoda - 10. dio: Is-pitivanja za iritaciju i osjetljivost kože (ISO 10993-10:2010; EN ISO 10993-10:2013) te OE CD metode (OECD 405, 406, 407 & 471) [1, 6].

2.1. Kozmetička sredstva

Defi nicija kozmetičkog proizvoda kao aktivnog sredstva prema spomenutoj direktivi čl. 1 u službenom prijevodu glasi: „Kozmetički proizvod” je bilo koja tvar ili pripravak koji je namije-njen dodiru s različitim vanjskim di-jelovima ljudskog tijela (koža, kosa, nokti, usnice i vanjski spolni organi) ili sa zubima i sluznicom u usnoj šup ljini, isključivo ili prvenstveno da ih se očisti, namiriši ili zaštiti kako bi ih se održalo u dobrom stanju, pro-mijenilo njihov izgled ili popravilo tjelesne mirise.

U Europskoj uniji od 11.7.2013. di-rektiva za kozmetičke proizvode (EU) Cosmetics Directive 76/768/EEC, zamijenjena je uredbom Regu-lation (EC) No 1223/2009 “Cosmetic Products Regulation” [13].Glavni kozmetički sastojci potječu od anorganskih i sintetičkih kemika-lija, od tvari životinjskog porijekla (hitozan, skvalen) i biljnih derivata (aloe vere, voća, eteričnih ulja, cvi-jeća, vitamina itd.) [1, 15].Ovisno o učinku koji se želi postići na koži, npr. revitalizacija, hidrataci-ja, zaštita kože, smanjenje i sprječa-vanje nastanka akni, mrlja, ekcema itd., mogu se koristiti različiti biljni pripravci. Oni pružaju željeni efekt za ciljanu kozmetičku namjenu, ili više njih, jer svaki od pripravaka naj-češće ima više područja djelovanja. Zeleni čaj djeluje kao hvatač slobod-nih radikala, tj. ima antioksidativna svojstva te revitalizira kožu, pove-ćava mikrocirkulaciju kože, a dodat-no pruža i zaštitu od UV zračenja [10, 16].Eterična ulja su hlapljivi, prirodni i kompleksni sastojci koje karakterizi-ra snažan miris a nastaju od aromat-skih biljaka kao sekundarni meta-boliti. Najčešće se dobivaju ispara-vanjem ili hidro destilacijom, a prvo su ih razvili Arapi u srednjem vijeku. Znajući za njihova antiseptička (anti-bakterijska, antivirusna i antifungal-na) svojstva koristila su se kod bal-zamiranja, čuvanja hrane i kao anti-mikrobna, analgetska sedativna, pro-tuupalna, spazmolitička sredstva te kao sredstva za lokalnu anesteziju. I danas se koriste za slične svrhe, me-đutim sve se više proučavaju i više se zna o mehanizmima njihovog djelovanja, naročito antimikrobnog [17]. Zbog navedenih svojstava često se primjenjuju za kozmetičke teksti-le [18]. Najčešće spominjana eterič-na ulja koja se koriste za kozme-tičke tekstile su ulje lavande, ružma-rina, čajevca, grejpa, bergamota itd. [2, 19].Eterična ulja lavande (Lavandula an-gustifolia), muškatne kadulje (Salvia sclarea L.), sandalovine (Santalum) i

slatke naranče (Citrus sinensis) dje-lotvorna su i sigurna za ublažavanje anksioznog poremećaja [20]. Ružma-rin (Rosmarinus offi cinalis L.) je bilj-ka koja ima veliku medicinsku i aro-matsku vrijednost. Eterično ulje ruž-marina ima antiproliferativnu, anti-oksidativnu i antibakterijsku aktiv-nost [21]. Ulje lavande se koristi samo po sebi kao lijek i kao dodatak nekim lijekovima i u kozmetici [22], dok se mirisnom stimulacijom lavan-de i ružmarina povećava aktivnost vezivanja slobodnih radikala i sma-njuje razinu kortizola u slini [23]. Mirisna stimulacija eteričnog ulja od grejpa utječe na autonomnu neuro-transmisiju i na krvni tlak [24]. Ber-gamot (Citrus bergamia, Risso) je voće najpoznatije po svom eteričnom ulju (BEO) koje se koristi u aromate-rapiji za smanjenje simptoma stresom uzrokovane anksioznosti i blagih po-remećaja raspoloženja, a istražuje se i njegov utjecaj na smanjenje bolova uzrokovanih tumorom [25]. Iako se eterična ulja koriste u tradicionalnoj medicini još od davnih vremena, zbog potencijalno velikog antikance-rogenog djelovanja, još uvijek nije u potpunosti objašnjen mehanizam nji-hovog djelovanja, pa se na tom po-dručju provode intenzivna istraživa-nja [26].Eterična ulja su poznata i po svojim brojnim biološkim učincima među kojima se ističe antibakterijsko djelo-vanje [15, 27-29]. Neka od njih dje-luju na poboljšanje cirkulacije krvi u mozgu, djeluju umirujuće ili osvježa-vaju umorni organizam. Stoga se aro-materapija, terapija eteričnim uljima intenzivno razvija posljednjih deset-ljeća, a bazira se na dobro utvrđenim znanstvenim činjenicama. Provodi se udisanjem para eteričnih ulja iz miri-snih lampi ili direktnim kontaktom s kožom. Razvijanje proizvoda, među kojima su i kozmetički tekstili, koji bi omogućili drugačiji vid kontinu-irane aromaterapije predstavlja veliki izazov i napredak u primjeni bioak-tivnih tvari prirodnog podrijetla u una-pređenju i očuvanju ljudskog zdravlja [27]. Jedan od izazova je odabir naj-


prikladnijeg tekstilnog supstrata kako bi se postiglo što bolje vezivanje, ali i otpuštanje eteričnog ulja s obzirom na primjenu kozmetotekstilija. Na-dalje, pažljiv odabir primijenjenih procesa završnog oplemenjivanja na tkanini ili odjevnom predmetu, npr. izbjeljivanje, bojadisanje itd. jer se na taj način može štetno utjecati na traj-nost i učinkovitost apretiranih eterič-nih ulja [18].

2.2. Tekstilni supstratKao podloga za nanašanje kozme-tičkih pripravaka mogu se koristiti tkanine, pletiva ili netkane tekstilije. Tekstilni supstrat, ovisno o prirodi vlakna, može biti biorazgradljiv ili nerazgradljiv. Također, pojedinačna vlakna mogu sadržavati biološki ak-tivna sredstva, lijekove u strukturi te aktivna sredstva koja mogu biti kova-lentno vezana na funkcionalne sku-pine vlakna. U primjeni su i netkani tekstili proizvedeni procesom elek-troispredanja koje posljednjih godina nude mogućnost primjene lijekova i kozmetičkih sredstava za različite biomedicinske i medicinske aplikaci-je [30, 31].Kada se govori o tekstilnim supstra-tima koji imaju sposobnost otpušta-nja aktivnih tvari uvjet je da su na vlakna/materijal prethodno naneseni pripravci koji mu daju medicinska ili „wellness“ svojstva. Tekstilni sup-strat može biti obrađen s bioaktivnim sredstvima u prisutnosti odgovaraju-ćih fi zičkih ili kemijskih modifi kato-ra kako bi se pospješilo kovalentno vezivanje sredstva na tekstil [32, 33]. Općenito se na tekstilni supstrat ak-

tivna sredstva fi zički adsorbiraju, apsorbiraju, naslojavaju, vežu u obli-ku mikrokapsula ili kovalentno ko-njugiraju [6].Kod netkanih tekstila od nanovla-kana dobivenih elektroispredanjem, aktivno sredstvo se može dodati i u otopinu prije ispredanja. Moguće je podešavanje promjera i orijentirano-sti vlakana kako bi se postigla želje-na mehanička svojstva i željeni način otpuštanja aktivnog sredstva podeša-vanjem parametara procesa elektro-ispredanja, npr. električnim potenci-jalom, protokom polimerne otopine, razmakom između bubnja i sakuplja-ča niti [6].

3. KozmetotekstilijeU raznim literaturama [1, 34-36] au-tori klasifi ciraju kozmetotekstilije na osnovi različitih koncepata, naj-češće na temelju njegovog utjecaja na ljudsko tijelo i metode nanašanja na tekstilni supstrat.Prema utjecaju na ljudsko tijelo, mogu biti podijeljene na kozmetotekstili-je za:• mršavljenje [6],• hidrataciju [15, 36],• energizaciju [36],• za miris [34, 37],• osvježenje i opuštanje [22, 35],• revitalizaciju [16, 38],• zaštitu od UV zraka [16, 20],• poboljšanje čvrstoće i elastičnosti

kože [38].Različita kozmetička sredstva pri-mjenjuju se na tekstil različitim teh-nikama u različitim fazama proiz-vodnje kako bi se postigao kozmetič-

ki učinak. Odabir postupka ili tehni-ke ovisi o prirodi kozmetičkog sred-stva i o prirodi tekstila, kao i o ko-ličini kozmetičkog sastojka koja će se dodati. Na temelju postupka, od-nosno oblika nanašanja kozmetičkog sredstva na tekstil slijedi ova podje-la [6]:• mikroinkapsuliranje,• kompleksiranje,• naslojavanje,• cijepljenje,• dodatak kozmetičkih sredstava

tijekom proizvodnje (npr. koeks-truzija).

Usporedba odabranih postupaka ve-zivanja kozmetičkih sredstva s tek-stilijom s obzirom na područje pri-mjene, mogućnost prihvata sredstva, otpornost na pranje i prijenos na kožu, prikazana je u tab.1.U dosadašnjem razvoju kozmetotek-stilija naglasak je stavljen na prona-lazak različitih aktivnih tvari i me-toda nanašanja, no najveći problem predstavlja praćenje mehanizma kon-troliranog otpuštanja aktivnih tvari. Stoga, razvijanje kozmetotekstilija nameće različite tehničke izazove kao što su npr. odabir prigodnog koz-metičkog sredstva, ravnomjerna ras-podjela, neprimjetno uklapanje u tka-ninu na takav način da se učinak od-vija uz što manje izgubljene aktivne tvari tijekom njege tekstilije - pranja. Najčešće primjenjivana tehnologija koja se koristi za ciljano, tj. kontro-lirano otpuštanje aktivne tvari je mi-kroinkapsuliranje [6].Nadalje, za razumijevanje vezivanja kozmetičkih pripravka i tekstila, ne-ovisno o obliku nanašanja (mikro-

Tab.1 Usporedba primjenjivanih načina nanašanja kozmetičkih sredstava na tekstil [6]

Postupak Područje primjene Mogućnost prihvata sredstva Otpornost na pranje Prijenos

na kožu

Mikroinkapsulacija Vrlo široko, ali uglavnom na sredstva ne topljiva u vodi Visoka Dobra, ovisi o vrsti

veziva Dobar

Kompleksiranje (npr. ciklodekstrin) Veoma specifi čno, za mali broj sredstava Srednje do visoka Dobra Ograničen

Naslojavanje Široko. Nije primjenjivo za osjetljiva ili hlapljiva sredstva Veoma visoka Dobra, ovisi o vrsti

vlakna i tipu veziva Dobar

Koekstruzija Veoma limitirano do ekstremno robustnih sredstva Niska do srednja Izvrsna Neznatan


kapsule, kompleksi s ciklodekstri-nom itd.), a sa svrhom dobivanja tekstila s novim funkcionalnim svoj-stvima, potrebno je obratiti pažnju i na zeta potencijal tekstila. Poznato je da elektrovodljivost i pH otopine utječu na elektrokinetički naboj tek-stilnog materijala [39]. Dodatno, iz-bor sredstava za mokre obrade tako-đer utječe na promjene naboja obra-đenog materijala, pri čemu on može biti viši ili niži od naboja materijala u početnoj fazi [40, 41].

4. Tehnologije vezivanja kozmetičkih sredstva za tekstilni supstrat

4.1. Primjena mikrokapsula – mikroinkapsuliranje

Koncept mikroinkapsulacije smatra se da potječe iz 1930-ih godina kada se koristila tehnika nanašanja prska-njem (engl. spray-drying) [42]. Teh-nologiju mikroinkapsuliranja koristi-la je i NASA u ranim 1980-im radi upravljanja toplinskim svojstvom od-jeće, naročito za upotrebu kod sve-mirskih odijela. Inkapsulirali su se materijali s promjenom faza (engl. phase-change materials - PCMs), sa željom da se smanje ekstremne razli-ke u temperaturi kojima su astronau-ti izloženi tijekom misija u svemiru [43]. Nakon toga dolazi do širenja primjene ove tehnologije u gotovo sva područja ljudskog djelovanja i potreba [44, 45]. U posljednjih 25 godina intenzivno se istražuje pri-mjena mikrokapsula u poljoprivred-noj, prehrambenoj, kozmetičkoj i tekstilnoj industriji [46, 47].Mikroinkapsulacija je tehnika kojom se izoliraju čestice u (tekućem, kru-tom ili plinovitom stanju) unutar ovoj-nice (ljuske) te se dobivaju proizvodi sfernog oblika, mikro ili nanometar-ske veličine. Ovojnica štiti aktivnu tvar, tj. jezgru od vanjskog okruže-nja. Ova tehnologija se uglavnom koristi u zaštitne svrhe [46, 48, 49].Mikrokapsule su čestice u rasponu veličine 1–1000 μm koje sadrže ak-tivnu tvar (u tekućem ili krutom sta-nju) okruženu prirodnom, semi-sin-

tetičkom ili sintetičkom polimernom ovojnicom (membranom). Sastoje se od dva dijela, odnosno od jezgre i ovojnice [10, 46, 50]. Struktura mi-kročestica se općenito može klasifi -cirati na više načina: kao mikrokap-sula s jednom jezgrom okruženu slo-jem - ovojnicom, tj. stijenkom mate-rijala; nadalje, kao mikrosfera s ras-pršenom jezgrom u kontinuiranoj mreži matrice; te kao složenije struk-ture, tj. višeslojne mikrokapsule ili višeljusne mikrosfere, sl.2 [48].Za izradu jezgre se najčešće koriste materijali u obliku otopine, disperzi-je ili emulzije. Kompatibilnost mate-rijala jezgre s ovojnicom je važan kriterij za povećanje učinkovitosti mikroinkapsulacije i često se provo-di prethodna obrada materijala jezgre kako bi se poboljšala kompatibilnost. Veličina jezgre ima veliku ulogu kod difuzije, propusnosti i/ili kontrolira-nog otpuštanja. Inkapsulirati se može širok izbor materijala, ovisno o zah-tjevima: pigmenti, bojila, monome-ri, katalizatori, sredstva za stvrdnja-vanje, usporivači gorenja, omekšiva-či [46].Mikrokapsule imaju mnogo predno-sti zanimljivih za širu primjenu:• zaštita nestabilnih, osjetljivih ma-

terijala od okoline u kojoj se kori-ste,

• bolja mogućnost procesiranja (po-boljšana topljivost, disperzivnost, protočnost),

• samoodržanje sprječavanjem re-akcije razgradnje (oksidacija, de-hidracija),

• kontrolirano, kontinuirano ili vre-mensko oslobađanje,

• maskiranje mirisa ili okusa,• imobilizacija enzima i mikroorga-

nizama,

• kontrolirana i ciljana dostava lije-kova,

• rukovanje tekućinom kao kruti-nom [46].

Kozmetički pripravci često su osjet-ljivi na toplinu, skloni su oksidaciji ili lako dolazi do njihove promjene. Mikroinkapsuliranjem ili vezivanjem u komplekse omogućava se njihova zaštita, odnosno sprječava se degra-dacija oksidacijom ili promjena tije-kom sušenja i/ili toplinskih procesa te skladištenja. U slučaju primjene hlapljivih sastojka sprječava se ispa-ravanje i produljuje im se vijek traja-nja, što je izuzetno važno kod pri-mjene parfema i eteričnih ulja [6].

4.1.1. Postupci mikroinkapsuliranjaRazličiti se postupci koriste za in-kapsuliranje mikročestica pa ih se može podijeliti na fi zikalne i kemij-ske (tab.2) [11, 30, 42, 46, 51, 52].Izbor tehnike mikroinkapsuliranja ovisi o tvarima koje se primjenjuju, o njihovoj veličini, biokompatibilno-sti i biorazgradljivosti, fi zikalno-ke-mijskim svojstvima (tvari u jezgri i ovojnici), o predloženom mehaniz-mu otpuštanja aktivne tvari iz jezgre te o troškovima procesa [48]. Izbor tehnike ovisi i o sljedećim parame-trima:– za koju svrhu će se mikrokapsule

koristiti;– inertnosti prema sredstvu koje se

inkapsulira i sredstvu za ovojnicu;– zatijevanom vremenu otpuštanja

inkapsuliranog sredstva;– optimalnoj koncentraciji aktivnog

sredstva za inkapsulaciju;– mehanizmu otpuštanja aktivnog

sredstva iz mikrokapsule (npr. pH, pritisak, topljivost, vrijeme i agi-tacija (mućkanje);

Sl.2 Različite morfologije mikročestica dobivenih mikroinkapsuliranjem: (a) mikrokapsula, (b) mikrosfera, (c) i višeslojna mikrokapsula (d) višeljusna

i višejezgrena mikrosferna

(a) (b) (c) (d)


– načinu otpuštanja aktivnog sred-stva (kontinuirano, trenutno ili kontrolirano otpuštanje);

– veličini čestica, gustoći i zahtje-vima stabilnosti inkapsuliranog sredstva;

– cijeni mikrokapsula, preparata ili aplikacije s obzirom na krajnji proizvod.

Visoka cijena mikroinkapsulacije još je uvijek najveći problem za tržište iako u mnogo slučajeva cijena kraj-njeg proizvoda zadovoljava s obzi-rom na vrijednost proizvoda [10, 46].Između tehnika prikazanih u tab.2 dvije se najčešće koriste za mikro-inkapsuliranje aktivnog materijala: prskanje i koacervacija. Oba procesa dijele gledište "zelene kemije" pri-

mjenom u prvom redu biljnih pro-teina te ostalih obnovljivih i bioraz-gradljivih sirovina. Važno je naglasi-ti da te dvije tehnike ne zahtijevaju korištenje organskih otapala [48].

4.1.2. Čimbenici koji utječu na učinkovitost mikroinkapsulacije

Učinkovitost inkapsulacije mikroče-stica, mikrokapsula ili mikrosfera ovisi o utjecaju različitih parametara. Na sl.3 su prikazani čimbenici koji utječu na učinkovitost inkapsulacije. Poželjna je slaba topljivost (netoplji-vost) polimera u organskim otapali-ma, dobra topljivost organskih otapa-la u vodi, visoka koncentracija po-limera, niski stupanj omjera disperz-

ne faze i kontinuirane faze (engl. dispersed phase/continuous phase; DP/CP) te brz učinak uklanjanja u otapalu. Navedena savojstva su pred-uvjet brzom skrutnjavanju mikroče-stica i postizanju visokog učinka in-kapsulacije [51].

4.1.3. Primjena mikrokapsula u tekstilu

Mikroinkapsulacija može imati zna-čajnu ulogu u postizanju dulje trajno-sti i učinkovitosti inkapsuliranog sredstva, kao i eliminaciji loših miri-sa, ali i otpuštanju ugodnih mirisa. Može se reći da je primjena mikro-kapsula na tekstilnim materijalima uspješna kada mikrokapsule opstanu na materijalu nakon višestrukih ci-klusa pranja i sušenja kojima su pod-vrgnute, što je jedan od većih zahtje-va. Kako bi korisnik bio zadovoljan, mikrokapsule moraju djelovati do-voljno dugo, gotovo koliko je i rok trajanja tekstilnog materijala, npr. mirisne poliuretanske mikrokapsule za muška odijela jedan su od uspješ-nih primjera [37]. Uz to, primje-na mikrokapsula ne smije imati ne-gativni utjecaj na svojstva tekstila, npr. čvrstoću, opip, udobnost i dr. [49, 53].Mikrokapsule se, osim za poboljša-nje mirisa i dezodorirajuće djelova-nje, mogu koristiti i kao prijenosnici mirisa za posebne svrhe, npr. aroma-terapiju. Mirisi i arome se odavno koriste u narodnoj medicini. Pojam aromaterapija se prvi put spominje u kasnim 1920-im godinama i pripi-suje se R.M. Gattefosseu. Učenje o međuodnosu između psihologije i aroma (mirisa) koje izazivaju spe-cifi čne osjećaje i emocije 1982. je nazvano aromakologijom (engl. aro-machology). Vjeruje se da je srž aro-materapije u simulaciji mirisnih putova u mozgu, posebno u limbič-kom sustavu jer određene arome uzrokuju osjećaje opuštanja, uzbu-đenja, senzualnosti, sreće, zadovolj-stva i sl. [53].Izbor materijala za ovojnicu mikro-kapsule je veoma važan i uglavnom

Tab.2 Metode mikroinkapsuliranja

Fizikalne metode Kemijske metodePrskanje-sušenje Odvajanje faza koacervacijomPrskanje-hlađenje Isparavanje otapalaAtomizacija rotirajućim diskom Ekstrakcija otapalaPremazivanje fl uidnim slojem Polimerizacija na granici fazaKoekstruzija sa stacionarnom mlaznicom Jednostavna i složena koacervacijaCentrifugalni proces s više otvora In-situ polimerizacijaKoekstruzija s potopljenim mlaznicama Tehnologija liposomaCentrifugalna ekstruzija NanokapsulacijaPremaz zračnom suspenzijom Polimerizacija matrice

Sl.3 Čimbenici koji utječu na učinak inkapsulacije [51]

Dobra topljivost polimerau organskom otapalu

Niska topljivost organskogotapala u vodi

Niska koncentracija polimera

Visok stupanj DP/CP

Sporo uklanjanje u otapalu

Sporo skrutnjavanje Brzo skrutnjavanje

INKAPSULACIJE INKAPSULACIJE

Slaba topljivost polimerau organskom otapalu

Visoka topljivost organskogotapala u vodi

Visoka koncentracija polimera

Niski stupanj DP/CP

Brzo uklanjanje u otapalu


se defi nira prema fi zičkim svojstvi-ma okoline u kojoj se mikrokapsula koristi jer određeni sustavi zahtijeva-ju čvršću kapsulu da se sprječi pre-uranjeno otpuštanje aktivne tvari iz jezgre [34, 37, 53, 54].Česta je upotreba liposoma za ovoj-nicu mikrokapsula jer omogućavaju prodiranje aktivnih tvari kroz barije-re kože. Liposomi su umjetni mjehu-rići koji se sastoje od vodene jezgre okružene jednim ili više dvosloja fosfolipida. Jednostavno se spajaju s prirodnim slojevima kože dopušta-jući aktivnim sredstvima da efektiv-no penetriraju, štiteći aktivno sred-stvo od raspada prije samog penetri-ranja u dvoslojni sustav kože (sl.4) [55, 56].Jedna od područja istraživanja pri-mjene liposoma u tekstilu je i u po-stupku bojadisanja vune, gdje po-spješuju prijenos bojila i njihovo vezivanje u vlaknu, uz smanjenje oštećenja vlakana u odnosu na po-stupke konvencionalnog bojadisanja vune [53]. Dodatno se njihovom pri-mjenom smanjuje onečišćenje okoli-ša. Liposomi (kao nekontaminirani biološki materijali) su biorazgradljivi te u odnosu na konvencionalna po-moćna sredstva imaju dodatnu pred-nost za nove tehnologije [57]. Tako-đer su prihvatljivi kao pomoćna sred-stva u postupcima pranja i njege te izbjeljivanja tekstila [58].

4.2. Primjena kompleksnih spojeva – kompleksiranje

Kompleksiranje je nastajanje kom-pleksnih spojeva između dvaju ili više vrsta iona ili molekula [59]. Ukoliko se kompleksiranje koristi u području kozmetotekstilija, tj. za potrebe vezivanja sredstva na tekstil, tada se najčešće odnosi na stvaranje inkluzijskih kompleksnih spojeva, npr. ciklodekstrina s velikim brojem organskih tvari.Ciklodekstrini su prirodni ciklički oligosaharidi koji nastaju tijekom enzimske razgradnje škroba. Najpo-znatiji i industrijski dostupni su obli-ci α-, β- i γ- ciklodekstrin s 6, 7 i 8 D- glukozidnih podjedinica, koji čine šuplju strukturu koja ima polar-ne hidroksilne skupine i hidrofobnu unutrašnjost. D-glukozidne jedinice su kovalentno vezane na ugljikove atome C1 i C4 (sl.5). Polumjer šup-ljina varira od 0,5 do 0,85 nm [10, 60, 61]. U tim šupljinama se mogu smjestiti aktivne tvari. Za stvaranje kompleksa, između aktivne tvari (tzv. gosta) i šupljine, tj. ciklodek-strina (tzv. domaćina), nije važno hoće li cijela aktivna tvar stati u šup-ljinu, dovoljno je da stane jedan dio [62, 63].Na tekstilu se najčešće primjenjuje β-CD zbog jednostavne proizvodnje, izraženog promjera šupljine, cijene i

jednostavnosti vezivanja na tekstilnu površinu. Komercijalno dostupan de-rivat β-CD je monoklorotriazinil. Ciklodekstini se smatraju vrlo važ-nim pomoćnim sredstvima prihvat-ljivim za okoliš jer su biorazgradljivi i netoksični. Ciklodekstrini mogu tvoriti inkluzijske komplekse s veli-kim brojem organskih tvari. Zbog toga se mogu dobiti tekstili s novim funkcionalnim svojstvima sa znatno smanjenom brzinom otpuštanja ak-tivnih tvari [60, 61, 64, 65].Ovi materijali mogu kompleksirati razne tvari, tako mogu vezati i tvari koje stvaraju neugodan miris tijela ili se mogu koristiti za oslobađanje par-fema ili otpuštanje kozmetičkih sa-stojaka na kožu [61].Postoji nekoliko načina vezivanja CD-a na tekstilnu površinu. Fizikal-ne metode sastoje se od otapanja de-rivata CD-a s hidrofobnim lancima u polimernoj otopini prije formiranja samog vlakana. CD-i imaju tenden-ciju migriranja na površinu, tvoreći raspoložive šupljine za inkluzije. Ke-mijske metode uključuju: 1. sinteze derivata CD-a s ionskim bočnim sku-pinama koje su u međusobnom dje-lovanju s ionskim skupinama veza-nim za vlakna; 2. sinteze reaktivnih derivata CD-a koji se cijepe na tek-stiliju uz pomoć veziva (detaljnije u poglavlju 4.4.) [3, 10, 66].Trajno učvršćivanje (fi ksiranje) ci-klodekstrina na vlakana jedan je od atraktivnih mogućnosti kemijske modifi kacije tekstilnih materijala [6].Kompleksi se mogu vezati za tek-stiliju uz pomoć vezivnog sredstva

Sl.4 Fuzija liposoma s barijerom kože i otpuštanje aktivnih tvari u kožu: a) liposom prije doticaja s kožom, b) fuzija liposoma s kožom i prodiranje inkapsuliranog sredstva u kožu, c) sjedinjenje fosfolipidnog dvosloja s kožom [55]

Sl.5 Struktura β-ciklodekstrina sa 7 glukozidnih podjedinica [10]

a)

c)

b)


(umreživača). Prema literaturi za ovu su upotrebu najprikladniji reaktivni poliuretani, ali se često koriste i u vodi topljivi polimeri kao što je škrob i modifi cirani škrob, karboksi metil celuloza, sintetički lateks (poli-izopreni), stiren-butadien, polivinil-acetat i aminoaldehidne smole [3, 6].CD stvaranju komplekse s raznim molekulama uključujući i one koje imaju kozmetički učinak, npr. men-tol, kofein ili α-tokoferol (vitamin E) (sl.6) [6, 67]. Istraživanja o postoja-nosti vitamina E, provedena na pa-mučnim i viskoznim materijalima, su pokazala da je postojanost funkcio-nalizacije vitamina E direktno ovisna o pH vrijednosti kupelji prilikom njege. Najbolja postojanost je po-stignuta u slučaju kad je pH<8, dok je u slučaju pH³8 postojanost neza-dovoljavajuća [68].

4.3. Naslojavanje

Naslojavanje je jedna od najjedno-stavnijih metoda direktnog nanaša-nja aktivnog sredstva na površinu tekstilije. Nanašanje se može prove-sti uranjanjem tekstilije u kupelj u kojoj se nalazi aktivno sredstvo ili naslojavanjem mikro ili nano česti-cama ili kapsula. Učinkovitost nana-šanja aktivnih tvari će jako ovisiti o vrsti vlakna i o aktivnom sredstvu. Na primjer, aktivna sredstva s većim afi nitetom će lako formirati tanki sloj na površini polimera. U mnogim će slučajevima naslojene tkanine otpu-stiti znatnu količinu aktivnih tvari neposredno nakon in vivo implanta-cije. Ovaj nedostatak je veoma nepo-pularan kada se želi postići postupno, tj. produljeno, otpuštanje aktivnog sredstva. Kako bi se izbjegao taj pro-

blem, tekstilija se naslojava s apretu-rom koja se sastoji od mikrokapsula i vezivnog sredstva jer se tako može značajno smanjiti početno naglo ot-puštanje i oslobađanje aktivnog sred-stva koje isključivo ovisi o prirodi mikro/nanokapsule. Jedna od mo-gućnosti u slučaju obrade sintetskih vlakana (npr. PA vlakno) je pret-hodno naslojavanje vlakna otopinom aktivnog sredstva te se ovaj proces ponavlja kako bi se postiglo kontro-lirano otpuštanje aktivnog sredstva u produljenom vremenu. Sljedeći primjer je naslojavanje nanočestica srebra u svrhu dobivanja antibakte-rijske površine. Dodatna učinkovi-tost se pospješuje primjenom ultra-zvuka i ionskog zračenja. Slobodni radikali stvoreni na površini vlakna nakon izlaganja energetskom zrače-nju tvore stabilne kovalentne veze sa srebrom, što rezultira materijalom s učinkovitom antibakterijskom povr-šinom [6].

4.4. Cijepljenje

Iako se najčešće opisuje kovalentno cijepljenje (engl. grafting) mikro-kapsula, posebno na prirodnim vlak-nima, najčešća vrsta vezivanja uk-ljučuje korištenje veziva (bindera) specifi čno pogodnih za kozmetičke i tekstilne sustave uz naglasak na dobru kompatibilnost s kožom. Često korištene vrste veziva su umreženi silikoni, poliakrilati, polietilen-vinil-acetati i poliuretani. Određena koli-čina veziva, obično 0,25 % do 4,0 % (suhe tvari po masi tkanine), je po-trebna za učinkovito vezivanje mi-krokapsule, kompleksa ili nanesenih čestica na vlakna kako bi se smanjio njihov gubitak tijekom njege teksti-

lija. Brzina otpuštanja naslojenih kozmetičkih sredstava može biti pri-lagođena variranjem količine i vrste veziva koje se koristi. Velike količine veziva koja u potpunosti pokrivaju mikrokapsulu daju bolju zaštitu od pucanja tijekom trošenja i usporava-ju oslobađanje kozmetičkih sredsta-va na kožu. Dodatna uloga veziva i mogućih drugih aditiva je dati odjev-nom predmetu konvencionalna svoj-stva kao što su otpornost na prljavšti-nu i otpornost na vlagu [6, 69].

5. Otpuštanje kozmetičkog sredstva

Nakon što se kozmetičko sredstvo na neki od navedenih načina inkorporira u tekstilni materijal, važno je ra-zumjeti i postupak njegovog otpušta-nja. Naime, ponekad je primarni cilj da se aktivno sredstvo potpuno otpusti u određenom trenutku, a ponekad je cilj da otpuštanje bude postupno tije-kom vremena, kako bi proizvod što dulje zadržao željenu funkcionalnost.Otpuštanje aktivnog sredstva se kon-trolirano i postupno može potaknuti mehaničkim djelovanjem (npr. tre-njem), otapanjem, biorazgradnjom, difuzijom, toplinom, promjenom pH vrijednostia ili enzimatskom aktiv-nošću. Kod mikrokapsula kao nosio-ca aktivnih tvari izbor mehanizma i ovojnice mikrokapsule ovisi o ko-načnoj primjeni proizvoda s obzirom na fi zikalnu i kemijsku stabilnost, koncentraciju, potrebnu veličinu če-stica, mehanizam otpuštanja i troško-ve proizvodnje. Stoga se mikrokap-sule koriste u raznim područjima: u prehrambenoj, biomedicinskoj, far-maceutskoj, kozmetičkoj, tekstilnoj industriji i poljoprivredi [48, 50].

Sl.6 Vitamin E (a-tokoferol: a) kemijska formula); b) shematski prikaz kompleksa vitamina E i ciklodekstrina

a) b)


Aktivna tvar difundira kroz ovojnicu mikrokapsule određenom brzinom (sl.8). Oslobađanje aktivnog sredstva se može klasifi cirati na temelju dru-gih mehanizama, kao što su erozija (produkt se postupno otapa u mem-branskim ovojnicama), difuzija (npr. ulje difundira izvan sustava), eks-trakcija (mehaničke sile tijekom žva-kanja ili obrada povećane površine ulja) i puknućem (spremnik sustava pukne pod utjecajem mehaničkih ili osmotskih sila). Puknuće stijenke može biti inicirano na različite nači-ne: mehanički, otapanjem, taljenjem, toplinskim ili UV/VIS zračenjem, biorazgradnjom, enzimatskom de-gradacijom, bubrenjem stijenki [50].Na brzinu difuzije u polimernoj ma-trici te na otpuštanje nekog aktivnog sredstva ili osmozu utječu pojedina svojstva polimerne mreže, kao što su: duljina i oblik polimernog lanca, fl eksibilnost, mobilnost, sorpcijska i desorpcijska svojstva, stupanj plasti-fi ciranja ili potencijalne interakcije između polimera i aktivne tvari [11, 30, 31, 50, 70].

6. Učinkovitost i ispitivanje kozmetotekstilija

Učinkovitost kozmetičkog proizvoda defi nira količina aktivne tvari potreb-ne za ostvarivanje željenog učinka na koži. Npr. djelovanje na vlažnost i mršavljenje zahtijeva veliku količinu aktivnih tvari na koži kako bi se spo-znali rezultati, a s druge strane miri-sno djelovanje zahtijeva veoma malu količinu kako bi se postigao željeni učinak. Kozmetički tekstili mogu imati produljeni učinak ovisno o konstrukciji mikrokapsula, tekstilije itd. Veoma je teško spriječiti otapa-

nje u vodi topljivih tvari tijekom pra-nja. To zahtijeva mnogo truda u odre-đivanju receptura, mikroinkapsulaci-ji i sl. Korištenjem proizvoda za ob-novu tekstila, npr. sprejeva, može se produljiti njihovu učinkovitost, npr. kozmetotekstilija s efektom mršav-ljenja koja prilikom nošenja i pranja gubi učinak može se obnoviti ponov-nim nanašanjem. Drugi aspekt koji je potrebno uzeti u obzir je dizajn koz-metotekstilije. Potrebno je uskladiti kompoziciju i konstrukciju tekstil-nog supstrata, dizajn odjeće i završnu obradu kako bi se postigla maksimal-na učinkovitost. Na tekstilnom sup-stratu veće plošne mase očuvanje kozmetičke učinkovitosti, npr. vlaže-nje kože, može se očekivati od 5 do 10 dana nošenja ako se ručno pere ili blago pere u stroju za rublje [6]. Pri-mjeri kozmetičkih tekstila za mršav-ljenje imaju nansene odgovarajuće kozmetičke preparate na tekstil. Vje-rojatnije će takvi tekstili davati dobre rezultate ako su konstruirani kao ela-stične tajice s određenim stupnjem nemedicinske kompresije ili kao uske traperice. Takav dizajn omogu-ćava dobar kontakt između tekstila i kože s problematičnim područjima čime se postiže i efekt masaže i koja omogućava adekvatan prijenos koz-metičkog preparata s tekstilnog sup-strata na kožu [6].Moguće je subjektivno i objektivno ocjenjivanje kozmetotekstilija za is-pitivanje različitih kozmetičkih uči-naka: kemijska svojstva, toksičnost, prisustvo vitamina E, efi kasnost, ana-liza mirisa, trajnost, označavanje [1].Za određene učinke se mogu primi-jeniti objektivne, a za neke subjektiv-ne metode vrednovanja kozmetotek-stilija. Objektivne metode vrednova-

nja kozmetotekstilija kojima se ispi-tuje koža su: korneometrija (uz Cor-neometer®), koja se koristi za ispiti-vanje efekta hidratacije kože; in vivo optička tehnika geometrije ljudske kože (uz Dermatop®, FOITS), koja se koristi za ispitivanje efekta hrapa-vosti kože i određivanje promjena kod transepidermalnog gubitka vode (uz Tewameter®), koja se koristi za ispitivanje funkcije barijere kože. Za vrednovanje efekata kao što su ras-hlađivanje i mršavljenje (anticelulit-ni efekt) koriste se subjektivne meto-de kao što su testiranja krajnjih po-trošača putem upitnika i/ili razgovo-rom [6].

7. ZaključakKozmetički sektor se kontinuirano razvija kroz primjenu novih sirovina, prirodnih pripravaka, izradom recep-tura s raznim aktivnim i pomoćnim tvarima. Primjena kozmetičkih pri-pravaka na tekstil je otvorila novo područje istraživanja, proizvodnje i primjene, čime kozmetički tekstili znače inovaciju u tehničkom, bioteh-ničkom i medicinskom području. Zanimanje znanstvenika je usmjere-no na istraživanje mogućnosti ugrad-nje kozmetičkih pripravaka u tekstil-ne proizvode visoke dodane vrijed-nosti i duljeg životnog ciklusa. U skladu s time razvijaju se postupci obrade, kontroliraju mehanizmi ot-puštanja i validiraju metode ob-jektivnog i subjektivnog vrednova-nja učinkovitosti kozmetotekstilija. Razvoj, unapređenje i komercijaliza-cija kozmetotekstilija iziskuje konti-nuiranu suradnju istraživača, proiz-vođača i krajnjeg korisnika.

Zahvala: Rad doktorandice Ive Ma-tijević je fi nancirala Hrvatska za-klada za znanost unutar projekta 9967ADVANCETEX: Advanced tex-tile materials by targeted surface modification. Mišljenja, nalazi i zaključci ili preporuke navedeni u ovom materijalu odnose se na autore i ne odražavaju nužno stajališta Hr-vatske zaklade za znanost.

Sl.8 Difuzija i kontrolirano otpuštanje aktivne tvari

Vezivnosredstvo

Tekstilnovlakno

Otpuštanjeaktivnog sredstvana kožu


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SUMMARYCosmetic preparations on textiles: Cosmetotextiles

I. Matijević, S. Bischof, T. PušićCurrent requirements ask for innovative and high-performance textiles which could improve our life style and make it more comfortable. The facts that cosmetic products are widely available and their application and use are some-times time-consuming, have given rise to idea of applying them to textiles in a simpler but effi cient manner. Proper manner of attaching a cosmetic prepara-tion on a textile substrate would enable its controlled release through a period of time. This treatment is aimed at simultaneous release of active substance at desirable moment or in a given time frame, and at achievement of satisfactory durability in washing. The chemistry of the release is a problem that should be particularly dealt with in this context.This paper offers a defi nition of cos-metotextiles; division and their purpose are defi ned, while the problems of active substance release and fastness of the treatment have been also explained. Finally, a review of the possible development trends has been given for these increasingly popular fi nishing treatments of textiles, which offer additional properties to textiles and give textile products high added value.Key words: cosmetotextiles, cosmetic preparations, microcapsules, high-per-formance textilesUniversity of Zagreb, Faculty of Textile TechnologyDepartment of Textile Chemistry and EcologyZagreb, Croatiae-mail: [email protected]

Received July 27, 2015

Kosmetische Mittel auf Textilien - KosmetotextilienAlltagsanforderungen drängen eine wachsende Nachfrage nach innovativeren und hochleistungsfähigen Textilien auf, die den Lebensstil erleichtern und verbessern. Da kosmetische Produkte weit und breit verfügbar sind und dere Verwendung manchmal sehr viel Zeit in Anspruch nimmt, hat sich die Idee entwickelt, kosmetische Produkte auf Textilwaren aufzubringen. Textilware in Kombination mit kosmetischen Produkten ermöglicht deren kontrollierte Freisetzung. Das Ziel dieses Verfahrens ist die Freisetzung von aktiven Sub-stanzen im gewünschten Moment oder in einer bestimmten Zeitspanne, wobei eine zufriedenstellende Waschbeständigkeit erzielt wird. Dabei spielt der Che-mismus der Freisetzung eine bedueutende Rolle, der besondere Aufmerksam-keit gewidmet werden sollte. Der Begriff der Kosmetotextilien ist in diesem Artikel ausführlich beschrieben, deren Aufgliederung und Verwendung sind dargestellt, und zusätzlich sind auch die Problematik der Freisetzung von ak-tiven Substanzen und die Verarbeitungsstabilität dargelegt. Schliesslich wird ein Rückblick auf mögliche Entwicklungstendezen dieser immer beliebteren Endausrüstung von Textilwaren gegeben, wodurch Textilien zusätzliche Ei-genschaften erhalten und zu einem hochwertigen Erzeugnis werden.

I. MATIJEVIĆ et al.: Cosmetic preparations on textiles: Cosmetotextiles, Tekstil 65 (1-2) 13-24 (2016.) 13

Cosmetic preparations on textiles: Cosmetotextiles

Iva Matijević, mag.ing.techn.text.Prof. Sandra Bischof, Ph.D.Prof. Tanja Pušić, Ph.D.University of Zagreb Faculty of Textile TechnologyDepartment of Textile Chemistry and EcologyZagreb, Croatiae-mail: [email protected] July 27, 2015

UDC 677.07:668.58:677.016Review

Current requirements ask for innovative and high-performance textiles which could improve our life style and make it more comfortable. The facts that cos-metic products are widely available and their application and use are sometimes time-consuming, have given rise to idea of applying them to textiles in a simpler but effi cient manner. Proper manner of attaching a cosmetic preparation on a textile substrate would enable its controlled release through a period of time. This treatment is aimed at simultaneous release of active substance at desirable moment or in a given time frame, and at achievement of satisfactory durability in washing. The chemistry of the release is a problem that should be particu-larly dealt with in this context. This paper offers a defi nition of cosmetotextiles; division and their purpose are defi ned, while the problems of active substance release and fastness of the treatment have been also explained. Finally, a review of the possible development trends has been given for these increasingly popu-lar fi nishing treatments of textiles, which offer additional properties to textiles and give textile products high added value.Key words: cosmetotextiles, cosmetic preparations, microcapsules, high-performance textiles

1. IntroductionTextiles and cosmetics were among the fi rst products man created. How-ever, joining textiles and cosmetics in the form of cosmetotextiles is a rela-tively new concept of applying them together and the investigations per-formed promise a high impact in the 21st century [1].The most interesting method of stor-ing a cosmetic preparation is con-structing a microcapsule, as it offers the means of controlled release of the active substance. Although microcap-sules have been mentioned for some

time in various applications in textile industry, they were not used for cos-metic applications before 1990s. One of the examples is microcapsules containing essential oils. These mi-crocapsules are applied to textiles, which implies mechanical pressures and friction, with fragrance released or some other effect achieved, de-pending on the type of the essential oil used [2]. Cyclodextrins are often used in cosmetic applications, as they have a mild impact on skin, while they are able to create a complex with a cosmetic preparation, which can be

attached to textiles using various techniques [3, 4].Development of cosmetotextiles has been relatively slow and the main reason for that is still present today –inability to achieve targeted effec-tiveness and washing durability at the same time. One of the problems is the sensitivity, or instability, of numerous cosmetic compounds, e.g. perfumes or fragrances are highly volatile, while most vitamins are sensitive to high temperatures.To develop and manufacture an effi -cient cosmetotextile product, such

I. MATIJEVIĆ et al.: Cosmetic preparations on textiles: Cosmetotextiles, Tekstil 65 (1-2) 13-24 (2016.)14

that would offer additional valuable properties to be realised in wearing, is by no means a simple task. Key targets are to keep the cosmetic prep-aration on the textiles after a washing cycle and enable controlled release of the active substance in it. However, the target of keeping the cosmetic preparation on textiles in washing cycles should not be overdone, as the primary function is to release it onto the skin, and it should not be endan-gered. Microencapsulation of highly volatile compounds, such as essential oils, together with a proper selection of the materials with adequate prop-erties for the microcapsule walls, can achieve controlled release of cosmet-ic preparations, i.e. impermeability and at the same time sensitivity to pressure or friction [2]. The use of binders is recommended when micro-capsules are applied to a textile sub-strate, as it considerably improves washing fastness results [2, 5].Various approaches have been tried to solve the problem of controlled release. Historically, the focus of in-terest has been on preventing release in washing, while not enough atten-tion has been paid to the mechanism of transferring the cosmetic prepara-tion onto the skin [6].To be able to understand the impor-tance of cosmetotextiles, it is neces-

sary to be familiar with the biggest organ of our body – the skin. The average surface area of human skin is 1.8 m2 and it constitutes 15% of the overall body mass, which indicates that taking care of the skin is of ut-most importance for our health. The skin is divided into three principal parts: epidermis, dermis and hypo-dermis. Epidermis is the target layer of the skin when cosmetics are con-cerned (Fig.1). It is the upper layer of the skin, above all the other layers, and is in a direct contact with the en-vironment. Epidermis consists of cells that are in constant shuffl ing and change, until the upmost layer is con-stituted, called a horny layer (Lat.stratum corneum). Water content dif-fers from layer to layer. In the basal layer (Lat.stratum basale) it is 75%, while in the horny layer it reaches only15% [6 -9].Skin is healthy and attractive only when it is well balanced. Prerequi-sites for a healthy skin are: particular water content in the skin, ability of self-protection, skin elasticity, as well as the ability to renew cells [10]. Hu-man skin is an impermeable barrier which protects the organism from foreign, outside, substances, includ-ing bacteria, fungi, viruses, allergens, dust and some other big molecules. The uppermost layer contains more

than 90% of multilayer keratocytes. The horny layer, the outer epidermis layer, offers a highly effi cient barrier for the controlled entry of the cos-metic product. However, due to the unique composition and structure it also constitutes a signifi cant barrier on the skin, protecting the body from the impacts of the environment and prevents dehydration [11].

2. Defi ning cosmetotextilesAccording to a manual [12] based on a European Commission (EC) regula-tive No 1223/2009 for cosmetic prod-ucts [13], „…textile can be a „acarry-ing agent“ in delivering substances or mixtures of substances to human skin, released in a particular time pe-riod to different surface areas of hu-man body, particularly to human skin, which have specialised func-tions, such as skin cleaning, adding fragrances, changing the appearance of the skin, correcting bodily scents or keeping skin in good health in gen-eral.“Cosmetotextiles are complexes con-sisting of cosmetic preparations, or their mixtures, and textile substrates. Cosmetic preparation, or mixture of preparations, can be of natural or syn-thetic origin. For an active prepara-tion or a mixture applied to a textile substrate to be considered a cosmetic agent at all, it is necessary that it should possess the ability to be re-leased to the skin. Preparations that are not released to the skin are not considered cosmetic products, nor are the textiles with active substances applied to them that are not released to the skin, classifi ed as cosmetotex-tiles [12].The European Committee for Stan-dardization (CEN) appointed a work-ing group (WG) in 2005, a kind of task force to deal with the problems of cosmetotextiles, CEN/TC 248/WG 25 [1]. The working group WG 25 was responsible for the development of standards associated with cosme-totextiles. WG-25 identifi ed some areas where standardisation was nec-essary and appointed accordingly fi ve

Fig.1 Schematic of epidermis [8]

Stratum corneum

Dead cells fi lledwith keratin

Lamellargranules

Keratinocyte

Merkel cell

Sensoryneuron

Stratum lucidum

Stratumgranulosum

Stratum spinosum

Stratum basale

Melanocyte

Dermis


sub-groups to work in different areas of cosmetotextiles. The standard was accepted by the European Committee for Standardization CEN/TR 15917:2009: Textiles – Cosmetotex-tiles [14]. Necessary normative refer-ences cited in the above standard are:• HRN EN ISO 3175-1:2010: Tex-

tile– Professional care, dry-clean-ing and wetcleaning of fabrics and garments – Part 1: Assessment of performance after cleaning and fi nishing (ISO 3175-1:2010; EN ISO 3175-1:2010)

• HRN EN ISO 3758:2008: Tex-tiles. Care labelling code using symbols (ISO 3758:2005; EN ISO 3758:2005)

• HRN EN ISO 6330:2003/A1:2009 enpr: Textiles – Domestic washing and drying procedures for textile testing (ISO 6330:200/Amd 1:2008; EN ISO 6330:2000/A1:2009)

• HRN EN ISO 22716:2008: Cos-metics–Good Manufacturing Practices (DPP) –Guidelines for good manufacturing practice (ISO 22716:2007; EN ISO 22716:2007)

It is recommendable to use the above normative references and harmonise them with the norms such as Oeko-Tex® 100 and Oeko-Tex® 1000. This would ensure high quality of textiles prior to applying a cosmetic prepara-tion onto it, as well as high standard of cosmetic textiles as a fi nished product. It is necessary to perform individual tests on cosmetic prepa-rations in chemical industry, while, after the cosmetic textile product has been completed, it is also necessary to test the product using general bio-logical tests, similar to antimicrobial tests conventionally performed. Cos-metic textiles are supposed to pass through all the tests following the standard HRN EN ISO 10993-10:2013: Biological evaluation of medi-cal devices, Part 10 Tests for irritation and skin sensitization (ISO 10993-10:2010; EN ISO 10993-10:2013) as well as the OECD methods (OECD 405, 406, 407 & 471) [1, 6].

2.1. Cosmetic agentsCosmetic product is as an active agent defi ned according to the above Directive, Article 1, offi cially as fol-lows: „Cosmetic product is any sub-stance or preparation intended to be in touch with various parts of human body (skin, hair, lips and outer sexual organs), or with teeth and mucous membranes within the mouth cavity, exclusively or primarily to clean them, odorise them or protect them, so as to keep them in good condition, change their appearance or improve bodily odours“. The EU has replaced the Cosmetic Directive 76/768/EEC from 11.7.2013 by the Regulation (EC) No. 1223/2009, entitled “Cos-metic Products Regulation” [13].Basic cosmetic ingredients have their origin in inorganic and synthetic chemicals, animal (citosan, squalane) and vegetable derivatives (aloevera, various fruits, essential oils, fl owers, vitamins, etc.) [1, 15].Various plant preparations can be used in preparing cosmetic products, depending upon the target effect on the skin, e.g. revitalisation, hydration, skin protection, reduction and preven-tion of acnes, spots, eczema. They of-fer achieving the targeted effect for a particular cosmetic purpose, or more of them as preparations are most often active in more than one area. Green tea acts as a free radical scavenger, i.e. has antioxidative properties and revit-alises the skin in this way, improves microcirculation in the skin and ad-ditionally offers protection from UV irradiation [10, 16].Essential oils are volatile, complex natural compounds, with characteris-tic fragrance, obtained from aromatic plants as secondary metabolites. They are mostly obtained by the pro-cesses of evaporation or hydrodestil-lation. Being familiar with their anti-septic, e.g. antibacterial, antiviral and antifungal properties, Arabs in Mid-dle Ages used these oils for embalm-ing, food preparation and as antimi-crobial analgetics, in treating various infl ammations, as spasmolytics, as well as local anaesthetics. The prop-

erties expected from essential oils have not been changed much until the present days. However, we know more about the mechanisms of their activity, especially in the antimicro-bial area [17]. Due to the above prop-erties they are quite often used for cosmetotextiles [18]. Essential oils that are most often used for this pur-pose are lavender, rosemary, tea tress (melaleuca alternifolia), grapefruit, bergamot, etc. [2, 19].Essential oils obtained from lavender (Lavandula angustifolia), clary sage (Salvia sclarea L.), sandal (Santalum) and sweet orange (Citrus sinensis) are effi cient and secure for the pur-pose of easing anxiety disorder [20]. Rosemary (Rosmarinus offi cinalis L.) is a plant of high medical and aro-matic value. Rosemary essential oil functions as an antiproliferative, an-tioxidative and antibacterial agent [21]. Lavender oil is used as a remedy itself and as an additive to other rem-edies and in cosmetics [22] while in-haling lavender and rosemary in-creases the activity of bonding free radicals and reduces the level of cor-tisol in saliva [23]. Fragrant stimula-tion by grapefruit essential oil im-pacts positively autonomous neuro-transmission and blood pressure [24]. Bergamot (Citrus bergamia, Risso) is a fruit well known by its essential oil (BEO) that is used in aromatherapy to ease the symptoms of stress-cause anxiety and mild mood disorders, while the impact of this oil on pains caused by cancers is being investi-gated [25]. Although essential oils have been used in traditional medi-cine throughout history, due to their high potential as anti cancer thera-peutical agents, there is still no suf-fi ciently detailed explication of their mechanisms and investigations in this area are currently underway [26].Essential oils are known, among oth-er things, for their numerous biologi-cal effects, among which antibacte-rial activity has gained special atten-tion [15, 27 -29]. Some of the essen-tial oils exhibit a wide scope of other effects on human organism, some of


them improving blood circulation in the brain, some act as tranquilisers or refresh tired organism. This is why essential oils based aromatherapy has been widely accepted in the course of past few decades. Aromatherapy is conducted by inhaling essential oil vapours from fragrant lamps or by contact of the oil with the skin. De-veloping products that would enable another manner of continuous aroma-therapy is a challenge and constitutes a signifi cant area of development in the application of natural bioactive substances for the improvement and preservation of health [27]. One of the challenges is the selection of proper textile substrate, so as to achieve optimal bonding as well as the release of the essential oil in the course of using cosmetotextiles. Ad-ditionally, careful selection of fi nal fi nishing processes to be implement-ed on the fabric or garment, e.g. bleaching, dyeing, etc., can also be of key importance, as these processes can have a detrimental effect on the durability and effectiveness of the es-sential oils used in fi nishing [18].

2.2. Textile substrateTextile substrates onto which cos-metic preparations are applied can be woven fabric, knitted fabrics or non-wovens. Depending on the nature of the fi bres used, the textile substrate can be biodegradable or non-biode-gradable. Individual fi bres can also contain biologically active agents, medical agents in their structure and active agents that can be covalently bonded to functional groups of the textile substrate involved. Nonwoven textiles have also been used manufac-tured by electrospinning, and have offered the possibility of applying medical and cosmetic preparations for various biomedical and health-care applications [30].When textile with the ability of rele-asing active substances are conside-red, the prerequisite for their use is that preparations giving health-care or „wellness“ properties have previo-usly been applied to the fi bres or fa-

bric. Textiles can be treated with bi-oactive agents with adequate physical or chemical modifi ers present, so as to improve and enhance covalent bonding of these agents to the textile. Generally, active agents are adsor-bed, absorbed, coated, encapsulated or covalently conjugated onto the textile substrate [6].When using nonwoven textiles obta-ined by electrospinning of nano fi -bres, active ingredients can be added into the spinning solution prior to spinning. Fibre diameter and orienta-tion can be controlled by adjusting parameters of the electrospinning process, e.g. electric potential, polymer solution fl ow, the distance between the drum and filament collector, with the aim of obtaining targeted mechanical properties and targeted rate and manner of releasing the active substance from the substra-te [6].

3. CosmetotextilesVarious literature references [1, 34-36] classify cosmetotextiles using different bases and concepts, most often using the impacts on human body as a basis of classifi cation, or the method of applying them onto textile substrates.On the basis of the impact on human body, cosmetotextiles can be divided into:• weight-loss cosmetotextiles [6],• skin hydration cosmetotextiles

[15, 36],• energising cosmetotextiles [36],• fragrance and perfume contain-

ingcosmetotextiles [34, 37],• refreshment and relaxation cos-

metotextiles [22, 35],• revitalisation cosmetotextiles [16,

38],• UV ray protection cosmetotextiles

[16, 20],• cosmetotextiles improving skin

strength and elasticity [38].Various cosmetic agents are applied on textile substrates using different application techniques, at various pro-duction stages, with the aim of achiev-

ing optimal cosmetic effect. The se-lection of application process or tech-nique depends on the nature of cos-metic preparation and on the nature of textiles in question, as well as on the amount of the cosmetic agent to be applied. The procedures of applying cosmetic preparations onto textile substrates can be divided into [6]:• microencapsulation,• complexation,• coating,• grafting,• adding cosmetic agent in the man-

ufacturing process (e.g. coextru-sion).

Tab.1 gives a comparison of the se-lected processes of applying cosmet-ic agents onto textiles, based on the area of application, the ability of re-ceiving the preparations, washing fastness and transfer to the skin of the wearer.The development of cosmetotextiles until now has been mostly aimed at fi nding and constructing various ac-tive ingredients and substances and inventing methods of their applicati-on. However, major issue is still mo-nitoring the mechanism of the active substances controlled release. This puts into the focus of interest various technical challenges, such as the se-lection of adequate cosmetic agent, uniform distribution of the agent, in-conspicuous integration into the fa-bric to be used. The aim is to achieve the effect with as little loss of the ac-tive agent as possible in the course of textile care and washing cycles. Microencapsulation is most often used for a purposeful, i.e. controlled release of active cosmetic agents [6].Additional attention should be paid to zeta potential of the textiles, in order to understand the bonding mecha-nism of textiles to a cosmetic prepa-ration, independent of the form and manner of its application (microcap-sules, complexes with cyclodextrin etc.). The aim is to obtain textiles with new functional properties. It is well known that conductivity and so-lution pH have a signifi cant impact on the electrokinetic charge of tex-tiles [36]. The selection of the fi n-


ishes for wet treatments can also im-pact the changes in electrical charge of the material treated, while the charge can be higher or lower than the charge of the material in the initial phases of the treatment [40, 41].

4. Technology of bonding cosmetic agents to textile substrate

4.1. Bonding of microcapsules – microencapsulation

The earliest concept of microencap-sulation appeared in 1930s, when the technique of spray-drying was fi rst used [42]. The technology of micro-encapsulation was used by NASA in early 1980s to control garment ther-mal properties, particularly for space suits. Phase-change materials (PCMs) were encapsulated, with the aim to reduce extreme temperature differ-ences the astronauts were exposed to during their space missions [43]. The use of microencapsulation was not restricted to NASA but included all the parts of men’s activities and needs [44, 45]. Microcapsules have been intensively investigated for the last 25 years in various areas: agriculture, food industry, cosmetic and textile industry [46, 47].Microencapsulation is a technique used to isolate some particles (in liq-uid, solid or gaseous state) within an envelope (shell or capsule) in order to get a spherical shape product, of mi-cro- or nanometre size. The shell pro-tects the active substance within, i.e. the core, from outer infl uences. The technique is mostly used as a protec-tive measure [46, 48, 49].

Microcapsules are particles ranging in size from 1 to 1–1000 μm, contain-ing an active substance (in liquid or solid phase), surrounded by natural, semi synthetic or synthetic polymer envelope (membrane). They consist of two parts, the core and the shell [10, 46, 50]. Microparticle structure can generally be described in various ways: as a microcapsule with a single core surrounded by a layer – enve-lope, i.e. a wall of material; as a mi-crosphere with dispersed core in a continuous matrix network; or as a more complex structure, i.e. multi-layer microcapsule, or multishell mi-crosphere (Fig.2) [48].The core of a microcapsule is most often composed of materials in the form of a solution, dispersion or emulsion. Compatibility of the core material and the envelope (capsule) is an important factor in improving microencapsulation effectiveness, thus core material is often pretreated to ensure better compatibility. Core size plays an important role in diffu-sion, permeability and/or controlled release. A wide range of materials can be encapsulated, for various purpos-es. These can be pigments, dyes, monomers, catalysts, curing agents, fl ame retardants, softeners etc. [46].

When widely used, microcapsules have a number of interesting advan-tages:• protection of unstable, sensitive

materials, from the environment in which they are used,

• easier processibility (increased solubility, dispesibility and fl ow-ing properties),

• self-preservation through preven-tion of decomposition reaction (oxidation, dehydration),

• controlled, continuous or timed release,

• masking odours and tastes,• immobilisation of enzymes and

microorganisms,• controlled and targeted delivery of

medicines,• handling liquids as if they were

solids [46].Numerous cosmetic compounds are sensitive to heat, prone to oxidation or change. Microencapsulation or bonding into complexes enables the protection of sensitive cosmetic in-gredients from detrimental infl uenc-es, such as degradation by oxidation or by polymerisation during drying and/or thermal treatments and gar-ment storing. These processes pre-vent evaporation of volatile com-pounds and prolong their lifetime,

Tab.1 Comparison of the processes of applying cosmetic agents onto textiles [6]

Process Area of application Ability of receiving the preparation Washing fastness Transfer to

the skin

Microencapsulation Very wide, but primarily to compounds not soluble in water High Good, depending on the type

of bonding agent Good

Complexation (e.g. cyclodextrin)

Highly specifi c, for a limited range of preparations Medium to high Good Limited

Coating Wide. Not applicable for sensitive and volatile agents Very high Good, depending on the

fi bre type and bonding agent Good

Coextrusion Limited to extremely robust preparations Low to medium Excellent Insignifi cant

Fig. 2 Different morphologies of microparticles obtained by microencapsulation: (a) microcapsule, (b) microsphere, (c) multilayer microcapsule and (d) multishell

and multicore microsphere

(a) (b) (c) (d)


which is of high importance when using perfumes and essential oils [6].

4.1.1. The processes of microencapsulation

Various processes are used to encap-sulate microparticles. They can be divided into physical or chemical (Tab.2) [11, 30, 42, 46, 51, 52].The selection of microencapsulation technique to be used for a particular process depends upon the size, bio-compatibility and biodegradation of the particles, physical-chemical prop-erties of the core and coating (cap-sule), the application of microparti-cles, the mechanism proposed for the release of the active core, as well as upon the costs of the process [48].

The selection of the technique also depends upon the following param-eters:– microcapsules purpose;– inertness towards the encapsulat-

ed agent and towards the shell;– process conditions in order to pre-

venten capsulated agent to be re-leased too early;

– optimal concentration of the ac-tive substance for encapsulation;

– the mechanism of releasing active substance from the microcapsule (e.g. pH, pressure, solubility, time and agitation (stirring);

– what manner of release is pre-ferred: continuous, sudden or con-trolled;

– particle size and density require-ments for stability of the encapsu-lated agent;

– costs of the capsules, substance in it and/or application, as compared to the cost of the fi nal product. High cost of microencapsulation is still one of the outstanding problems for the market, although in many cases the costs of the fi nal product are quite adequate to its value [10, 46].

Two techniques out of these present-ed in Table 2 are most often used to encapsulate active materials: spray-ing and coacervation. Both of them respect the concept of „green chem-istry“ through using primarily plant proteins, as well as other renewable and biodegradable sources. It is im-portant to note that both techniques employ no organic solvent through-out the process [48].

4.1.2. Factors infl uencing microencapsulation effi ciency

The effi ciency of encapsulation for microparticles, microcapsules or mi-crospheres depends on various pa-rameters that infl uence it. Figure 3 shows the parameters and factors that impact encapsulation effi ciency. It can be seen that favourable parame-ters are low polymer solubility in or-ganic solvents, high solubility of or-ganic solvents in water, high polymer concentration, low ratio of dispersed phase/continuous phase (DP/CP), as well as a rapid effect of removal in a solvent. All of these are prerequisites for rapid stiffening (curing) of mic-roparticles, which results in high en-capsulation effi ciency [51].

4.1.3. The use of microencapsulation in textiles

Microencapsulation can play a sig-nifi cant role in achieving prolonged durability and effi ciency of the en-capsulated agent, as well as in remov-ing bad odours and delivering pleas-ant ones. Microencapsulation on textiles is considered successful if microcapsules remain on the material after multiple washing and drying

Tab.2 Microencapsulation methods

Physical methods Chemical methodsSpray drying Coacervation Phase separation Spray chilling Solvent evaporationRotary disk atomization Solvent extractionFluid bed coating Interfacial polymerisationStationary nozzle coextrusion Simple and complex coacervationMultiorifi ce - Centrifugal Process In situ polymerisationSubmerged nozzle coextrusion Liposome technologyPolyacrylonitrile coating (PAN) NanoencapsulationAir-Suspension Coating Matrix polymerization

Fig.3 Factors infl uencing encapsulation effi ciency [51]

High polymer solubility inorganic solvents

Low organic solventsolubility in water

Low polymer concentration

High DP/CP ratio

Slow removal in a solvent

Slow microparticlestiffening (curing)

Rapid microparticlestiffening (curing)

LOW ENCAPSULATIONEFFICIENCY

HIGH ENCAPSULATIONEFFICIENCY

Low polymer solubility inorganic solvents

High organic solventsolubility in water

High polymer concentration

Low DP/CP ratio

Rapid removal in a solvent


cycles. This precisely presents one of the key problems this technology is faced with. Microcapsules should act long enough, optimally as long as the working life of the textile material, to make the user satisfi ed. One of the most successful examples are poly-urethane fragrant microcapsules for men’s suits [37]. Additionally, the process of microencapsulation should not have a detrimental impact on the properties of textiles, e.g. handle and comfort [49, 53].Apart from improving the odour and deodorising, microcapsules can also be used as a means of transferring odours for special purposes, e.g. for aromatherapy. Fragrances and aro-mas have been used in popular medi-cine for centuries. The expression „aromatherapy“ was mentioned for the fi rst time in late 1920s, by R.M. Gattefosse. The study of the relation between psychology and aromas (scents) that cause specifi c feelings and emotions was named aromachol-ogy in 1982. It is believed that the key of aromatherapy is in stimulating olfactory paths in the brain, particu-larly in the limbic system, as particu-lar aromas (scents) cause the feelings of relaxation, excitement, sensuality, happiness, welfare or bliss [53].Selection of the material for micro-capsule shell is highly important and is mostly dictated by the physical properties of the environment where the microcapsule is used, as some systems ask for fi rmer capsules so as to prevent or regulate premature re-lease of the active substance [34, 37, 53, 54].Liposomes are often employed as shells for the encapsulation of active substances, as they enable active sub-stances to penetrate skin barriers –stratum corneum and stratum spino-sum. Liposomes are artifi cial bubbles consisting of aqueous core surround-ed by one or more phospholipide lay-ers and are easily attached to natural skin layers, enabling active substanc-es to effectively penetrate the skin, protecting at the same time the active substance from any degradation or

decomposition prior to the penetra-tion of the double-layer skin system (Fig. 4) [55, 56].One of the most frequent usages of liposomes in textile is the process of dyeing. Liposomes are being investi-gated and applied as carriers, appro-priate to reduce the degradation ef-fects in conventional wool dyeing [53]. Employing microencapsulation with liposomes in wool dyeing re-duces environment pollution as well. Liposomes, as uncontaminated bio-logical material are biodegradable, as opposed to conventional synthetic auxiliaries, and they are considered to have additional advantages to be used by new technologies [57]. Addition-ally, liposomes are also used in textile washing and bleaching [58].

4.2. Bonding of complex supstances – complexation

Complexation involves chemical bonding of two or more species, ions or molecules [59]. If it is employed in the area of cosmetotextiles, i.e. to bond a substance to a textile sub-strate, complexation usually deals with creating inclusive compounds, e.g. cyclodextrins with a high content of organic substances.Cyclodextins are natural cyclic oligo-saccharides created during the enzy-matic decomposition of starch. The best known and available to the in-

dustry are the forms of α-, β- and γ- cyclodextrins, with 6, 7 and 8 D- glu-coside units of hollow structure, pos-sessing polar –OH groups and hydro-phobic inner part. D- glucoside units are covalently bonded to carbon at-oms C1 and C4 (Fig.5). The diameter of the hollows varies from 0.5 to 0.85 nm [10, 60, 61]. These hollows can be used to accommodate active sub-stances. It is not necessary that the whole of the active substance is ac-commodated into the hollow to create a complex of the active substance (so called guest) and the hollow, i.e. cy-clodextrin (so called host), a part of it is quite suffi cient [62, 63].β-CD is most often used on textiles, due to its simple manufacture, pro-nounced diameter of the hollow, low costs and simple manner of bonding

Fig. 4 Fusing liposomes with skin barrier and releasing active substances into the skin: a) liposome prior to contacting skin, b) fusing liposome with skin

and penetration of encapsulated agent into the skin, c) phospholipid layer and skin merging [55]

Fig.5 Cyclodextrin structure with 7 glucoside subunits [10]

a)

c)

b)


to textile surface. Commercially available β–CD derivative is mono-chlorotriazine. Cyclodextrins are im-portant auxiliaries, environmentally friendly, as they exhibit no toxicity and are completely biodegradable. Cyclodextrins can make inclusive compounds with a number of other organic substances. This is how tex-tile fabrics can be manufactured in-cluding new functional properties, with considerably reduced rate of ac-tive substance release [60, 61, 64].These materials can captivate com-pounds such as body odours, using an inclusion complex, or can be used to release fragrances or deliver cosmet-ic substances onto the skin [61].There are various ways of bonding CD to a textile surface. Physical methods consist of soluting CD de-rivative with hydrophobic chains in a polymer solution prior to fi bre form-ing. CDs tend to migrate to the sur-face, forming hollows available for inclusions. Chemical methods in-clude: (1) CD derivative synthesis with ionic side groups, which interact with ionic groups bonded to the fi bre, and (2) synthesis of CD reactive de-rivatives that are split on the textiles with the help of a curing agent (more details can be found in chapter 4.4.) [3, 10, 66].Fixing cixlodextrins permanently onto fi bres is one of the most attrac-tive possible innovations in modify-ing textile materials [6].Complexes can be bonded to any tex-tile using a bonding (curing) agent. Literature references indicate reactive polyurethanes as the most appropriate for this purpose, although, in practice, water-soluble polymers are often used as well, such as starch and modifi ed

starch, carboxy methyl cellulose, syn-thetic latex, styrene-butadiene, poly-vinyl acetate or acrylic latex and ami-noaldehyde resins [3, 6].The other cyclodextrin-based ap-proach is the application of cell-shaped molecules, consisting of six to eight glucose units, obtained by en-zymatic decomposition of starch. They more readily create protective complexes with various molecules, including those that have a cosmetic effect, e.g. menthol, caffeine, or α-tocopherol (vitamin E) (Fig. 6) [6, 67]. The investigations of vitamin E stability, performed on cotton and viscose fabrics, showed that the sta-bility of vitamin E functions was di-rectly dependent on pH values of the bath in textile care. The highest sta-bility was achieved when pH was <8, while the stability was not satisfac-tory with pH ³8 [68].

4.3. CoatingCoating is one of the simplest meth-ods for direct application of an active substance onto a textile surface. Coating can be done by immersing textiles into a solution containing the active substance, or by coating with micro/nano particles or capsules. The effi ciency of active substance appli-cation will in most part depend on the type of the fi bres used and on the ac-tive substance in question. For ex-ample, active substances with higher affi nity will readily form a thin layer on the surface of the polymer. Coated fabrics will quite often release con-siderable amount of active substance immediately after in vivo implanta-tion. This disadvantage is quite detri-mental if the goal is to release the active substance gradually, i.e. in a

longer period of time. To avoid the problem, the textile is treated with a coating consisting of microcapsules and a bonding agent. This consider-ably reduces initial sudden release and freeing of the active substance, which depends exclusively on the na-ture of the micro/nanocapsule used. One of the possibilities in treating synthetic fi bres (e.g. PA fi bre) is to pre-coat the fi bre with a solution of the active substance, with the process repeated to achieve controlled release of the active substance during a pro-longed period of time. Another ex-ample is coating fi bres with silver nanoparticles, with the aim of obtain-ing an antibacterial surface. Effi cien-cy is improved by applying ultra-sound and ionic irradiation to the fi -bres. Free radicals created on the fi bre surface after the exposure to energy radiation form stable covalent bonds with silver nanoparticles, creating an effective antibacterial surface [6].

4.4. GraftingAlthough covalent grafting of micro-capsules is most often described, es-pecially on natural fi bres, the most often encountered type of bonding includes using binders, specifi cally adapted for cosmetic and textile sys-tems, with the accent on proper com-patibility to the skin. Crosslinked silicones are often used, as well as polyacrylates, polyethylene-vinyl-acetates and polyurethanes. To bond microcapsules complexes or particles applied effi ciently, a defi nite amount of binder is necessary, generally from 0.25% to 4.0% (of the dry substance to the fabric mass) in order to reduce their loss in the course of textile care cycles. The rate of cosmetic agents

Fig.6 Vitamin E (a-tocopherol: a) chemical formula); b) schematic representation of thevitamin E andcyclodextrin complex

a) b)


release can be controlled by varying the amount and type of the binder used. Higher amounts of binder, cov-ering the microcapsule completely, offer better protection from breaking in use and slow down the release of cosmetic agents onto the skin. Addi-tionally, binders and some other ad-ditives can offer some conventional, but still important, properties to the article of clothing involved, such as soil resistance and moisture resis-tance [6, 69].

5. Cosmetic agent releaseAfter the cosmetic agent has been in-corporated into the textile material, it is important to defi ne and understand the manner of its release. Primary aim is sometimes to release the active agent completely at a particular mo-ment, while sometimes it is supposed to be slowly released, so that the product retains its functionality as long as possible.Controlled and gradual release of the active agent can also be initiated by mechanical actions (e.g. by friction), by soluting, biodegradation, diffu-sion, heat, changes in pH or by enzy-matic activity. The selection of the mechanism and shell of the micro-capsule depend upon the end-use of the product, having in mind its phys-ical and chemical stability, concentra-tion, particle size, release mechanism and manufacturing costs. This is why it is possible to use microcapsules for various applications: in food industry, biomedicine, for pharmaceuticals, cosmetics, as well as in textile indus-try and agriculture [48, 50].Active substances diffuse through the microcapsule shell at a particular rate (Fig. 8). Release of the active sub-stance can be classifi ed according to some other mechanisms, such as ero-sion (the product is gradually dis-solved in the membrane envelopes), diffusion (e.g. oil diffuses out of the system), extraction (mechanical forc-es in chewing or treatment of the in-creased oil surface) or fracture (sys-tem container fractures under the impact of mechanical or osmotic

forces). Wall fracture can be initiated in various manners: mechanically, by solution, by melting, thermally or UV/VIS irradiation, by biodegrada-tion, enzymatic degradation or wall swelling [50].Some properties of the polymer net-work used, such as the chain, fl exibil-ity, mobility, sorption and desorption properties, plasticising degree or po-tential interaction between the poly-mer and the active substance in-volved, impact the rate of diffusion in the polymer matrix and the rate of releasing the active substance, i.e. osmosis. [11, 30, 31, 50, 70].

6. Effi ciency and cosmetotextile testing

Cosmetic product effi ciency is de-fi ned by the amount of active sub-stance necessary to achieve the target effect on the skin. For example, ef-fects such as humidity and weight loss ask for a considerable amount of active substances on the skin to show any measurable results, while fra-grances, on the other hand, require a small amount of the active substance to achieve the targeted effect. They can have a prolonged effect, depend-ing upon the microcapsule and textile construction. It is extremely complex task to prevent water-soluble sub-stances from dissolving during wash-ing. The application of products for regeneration of textiles, i.e. sprays containing active substances, cosme-totextileeffi cient performance can be prolonged. For example, cosmetotex-tiles with the weight-loss effect that is lost in wearing and washing can be renewed by the re-application of the active agent. Another aspect that should be taken into account is the

cosmetotextile design. Design and construction of the textile substrate, garment design and fi nishing should be aligned to achieve maximum ef-ficiency. Heavier textile substrate could offer prolonged and retained cosmetic effect for some 5 to 10 days of wearing, e.g. skin moisturising, provided hand washing or mild ma-chine washing are employed [6]. An-other example are cosmetotextiles offering weight-loss effect as a result of wearing/activity of adequate cos-metotextiles. These will probably exhibit good results if they are con-structed as elastic tights with a par-ticular degree of non-medical com-pression or as tight jeans. Such a construction offers good contact be-tween the textile and problematic ar-eas of the skin, probably also gives a massage effect and enables adequate transfer of the cosmetic substance from the textile substrate onto the skin [6].Cosmetotextiles can be evaluated ei-ther subjectively or objectively when testing various cosmetic effects. Chemical properties can be tested, together with toxicity, the presence of vitamin E, effi ciency, scent analysis, durability or marking [1].Some effects of cosmetotextiles can be evaluated by objective and some by subjective methods. Objective methods of evaluating cosmetotex-tiles test the skin and include: corne-ometry (Corneometer®), used to test skin hydration effect; in vivo optic technique of human skin geometry (FOITS, Dermatop®), used to test the effect of skin roughness and deter-mine the changes at trans-epidermal water loss (Tewameter®), used to test skin barrier function. The effects such as cooling and weight-loss (anti-cel-

Fig.8 Diffusion and controlled release of active substance

Binder

Textilefi bre

Active substancerelease onto theskin


lulite effect) are evaluated using sub-jective methods, such as testing the end-users through questionnaires and/or interviews [6].

7. ConclusionCosmetic sector has been continu-ously developed by using new raw materials, natural preparations, as well as by designing and formulating new active and auxiliary substances. The application of cosmetic prepara-tions onto textiles has opened a new area of investigation, production and application, so that cosmetotextiles now present an innovation in techni-cal and bio-technical areas and in medicine. The interest of scientists is aimed at investigating the possibili-ties of incorporating cosmetic prepa-rations into textile products of high added value and longer life cycle. Processing methods have been devel-oped accordingly, mechanisms of release controlled, and methods test-ed for objective and subjective evalu-ation of cosmetotextiles effi ciency. Obviously, the development, im-provements and commercialisation of cosmetotextiles ask for a continu-ous cooperation of researchers, man-ufacturers and end-users.

Acknowledgement: The work of Iva Matijević, Ph.D. was fi nanced by the Croatian Science Foundation, within the framework of the project 9967 ADVANCETEX: Advanced textile materials by targeted surface modifi -cation. Opinions, fi ndings, results, conclusions or suggestions and re-commendations contained in this pa-per are authors’ view points and do not necessarily refl ect the viewpoints of the Croatian Science Foundation.

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Documents

Kozmetička sredstva na tekstilu: kozmetotekstilije · koriste ciklodekstrini koji su blagi prema koži, a s kozmetičkim sred-stvom mogu stvoriti kompleks koji se raznim tehnikama