Polysaccharides in. Anju Bansal CP Kelco. Research Scientist- Personal care applications.

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Polysaccharides in Personal Care Applications Anju Bansal CP Kelco Research Scientist- Personal care applications anju.bansal@cpkelco.com

Topics to be discussed Polysaccharides and rheology Features of some selected Polysaccharides Concepts showing functional & sensorial attributes Conclusion & Questions

Polysaccharides Polysaccharides are relatively l complex carbohydrates. They are polymers made up of many monosaccharide joined together Range of rheology Gelled Sprayable Suspended d Flowable Squeezable

Polysaccharides & Interactions Non interacting molecules Tend to have a constant viscosity Seem thick when pouring but do not suspend well Give a rich appearing texture Examples : Cellulose Gum, Lamda carrageenan

Non interacting molecules

Polysaccharides & Interactions Molecules l with short-lived interactions ti Have a viscosity that decreases with increasing shear rate (pseudoplastic flow) Create high viscosity at low shear rates for good suspension Have low viscosity at higher rates for easy pouring Can appear to be lumpy or have thick-and-thin areas Examples: Xanthan gum

Short lived Interactions

Polysaccharides & Interactions Molecules with long-lived interactions Have a viscosity that decreases after being sheared Creates a gel that can be sheared, it may or may not rebuild Are usually pseudoplastic after being sheared Require good control in formulation and manufacturing Examples: Gellan gum, k carrageenan (K+) & l carrageenan (Ca+2)

Long lived Interactions

Polysaccharides for Personal care Xanthan gum Carboxymethyl cellulose Gellan gum Carrageenan Pectin

Xanthan Gum INCI : Xanthan gum Fermentation derived (Xanthomonas campestris) Cellulose l backbone with three sugar side chain Differentiating Properties: Smooth Flow Xanthan-Xanthan gum with smooth rheology. Pseudoplastic : forms networks (reversible) in aqueous systems Stable in extreme ph conditions (ph 3-11): e.g. AHA cream Stable in high h electrolyte l t medium: e.g. Clay masks, make-up Functional in difficult to thicken surfactant systems: e.g. Body-wash Provides improved thermal stability: e.g. Sunscreen Good alcohol tolerance: e.g. Hand sanitizer gel formulated with 62% v/v alcohol

Xanthan Gum Primary Structure Cellulose Backbone glucose glucose CH 2 H H CH 2 H H acetate H = CH 2 CCH H n Side Chain CM- H H mannose M = Na, K, 1/2 Ca pyruvate CM- CH 3 C CH 2 H H H H glucuronate mannose

Double-Helices in Various Xanthan Gum Products Smooth flow xanthan Regular xanthan

Smooth Xanthan gum vs. Regular Xanthan gum stringiness

Concept 1: Natural Face Wash Ingredients QTY(%W/W) QTY(%W/W) Water (Aqua) q.s. to 100 q.s. to 100 Smooth Flow Xanthan Gum 1.2 - Regular xanthan gum - 1.2 Glycerin 5.00 5.00 Disodium Cocoyl Glutamate 12 12 Decyl glucoside 10 10 Sodium cocoyl apple amino acids 4 4 Cocamidopropyl betaine 10 10 Aloe barbadensis leaf juice 0.4 0.4 Preservative qs q.s. qs q.s. Luffa Cylindrica fruit 0.2 0.2 Fragrance, color q. s. q. s.

Concept 1: Rheological Results Smooth Xanthan Gum Regular Xanthan Smooth Xanthan Regular Xanthan Gum More gloppy, gives tackiness smooth flow xanthan gum Low extentional viscosity, low stringiness, non tacky skin feel

Applications: Sunscreens (with Ti2/ Zn) Shower gel Natural Shampoo Alcohol Sanitizer Moisturisers BB creams Glycolic acid cream Gel mask and clay face packs Edible body massage lotion Depilatory Lotion Smooth flow Xanthan Gum

Cellulose gum INCI: Cellulose Gum Derived from Cellulose Carboxymethyl esters of anhydroglucose units Vary by: Molecular weight Degree of substitution Differentiating Properties: Viscosity depends on molecular weight. Low viscosity grades- Newtonian flow To achieve correct level of high shear viscosity- e.g. Mascara Provides smooth, thick viscosity- during pouring Promotes a richer skin feel Excellent solubility and film formation properties- e.g. Eyeliner Good Binding properties- e.g. Toothpaste Low molecular CMC for film delivery systems- e.g. Breath strips

Comparing Xanthan Gum and Cellulose gum 12 Yield Stress (Pa) Structure 5 10 4 8 3 Light Feel 2 Body 6 Yield Stress 1 4 2 Slip Non-Stringy 0 Keltrol Xanthan CGSFT gum Cellulose Cekol30K gum Keltrol Xanthan CG-SFT gum Cekol Cellulose 30K gum Using Brookfield Ultra Rheometer Preliminary Lab data nly Comparing aqueous gum solutions

Concept 2: Blueberry moisturizing lotion Ingredients QTY (%W/W) QTY (%W/W) Water (Aqua) q.s to 100 q.s to 100 Glycerin 3 3 Xanthan Gum (Smooth) 0.5 - Cellulose Gum - 0.75 Cetyl octanoate 4.5 4.5 Caprylic capric tryglyceride 5 5 Stearyl alcohol 0.5 0.5 Vitamin E acetate 0.2 0.2 Macadamia nut oil 4 4 Cetearyl livate (and) Sorbitan livate 3.5 3.5 Phenoxyethanol (and) capryl glycol (and) ethylhexylglycerin (and) hexylene glycol 0.8 0.8 Blueberry Fruit Extract 1 1 Aloe vera Juice 0.2 0.2 Fragrance 0.2 0.2 Viscosity with Xanthan gum: 15,000 cp @ 3rpm,LV3 with Cellulose gum:12,000 cp @ 3rpm,LV3

Concept 2: Rheological Results Comparing Blueberry lotion - Cekol 30000 and Keltrol CG-SFT 10 3 10 1 Pa s 10 2 Viscosity at high shear: Skin feel η 10 1 10 0 10-1 10 0 10-2 10-1 10 0 10 1 10 2 1/s 10 3 Shear Rate γ. Blueberry lotion-cekol 30k 3 Blueberry lotion-keltrol CG-SFT 1 Cellulose gum Flowable, smooth Xanthan Gum Higher G structured, non drip, keeps shape Cellulose Gum Less shear thinning Heavier skin feel Anton Paar GmbH Xanthan Gum (Smooth Flow) More shear thinning (pseudoplastic) Lighter skin feel

Cellulose gum Applications: Emollient cream for hand and feet Rich Creamy lotion Nourishing serum for dry skin Luxurious Body cream Smoothening Body lotion Acne treatment Films Age-spot treatment Film Ready to use face mask film

Gellan Gum INCI:Gellan gum Fermentation derived (Sphingomonas elodea), Four sugar repeating unit, with acyl groups Types: Low acyl: Hard/ brittle gels- Forms gels by cations-na, Ca, Mg, K High acyl: Soft/elastic gels Differentiating Properties: Provides true yield : Form long term interactions (network) in water system Ability to form Fluid Gels: Low viscosity sprayable liquid with suspension. Efficient use levels- 0.02-0.1% 020 Provides excellent suspending & stabilizing properties Excellent Sprayability: Due to Shear thinning & low extensional viscosity property - sunscreen-sprays Light skin-feel, Non-stringy flow: clean break from nozzle

(a) High Acyl Gellan Gum CH 3 C CH 2 H 2 0.5 C - M + CH 2 H H H 2 CH 3 H C CH 2 H H H H H n (b) Low Acyl Gellan Gum CH 2 H C - M + CH 2 H H H H CH 3 H H H H H n

Concept 3: Sprayable Sunscreen Ingredients QTY(%W/W) QTY(%W/W) Water (Aqua) q.s to 100 q.s to 100 Gellan Gum 0.025 - C14-22 Alcohol (and) C12-20 Alkyl Glucoside 2.5 2.5 Glycerin 2 2 ctyl Salicylate 5 5 Viatmin E acetate 0.30 0.30 ctyl Methoxycinnamate 7.5 7.5 C12-15 Alkyl Benzoate 3.5 3.5 Phenoxyethanol (and) capryl glycol (and) ethylhexylglycerin (and) hexylene glycol 0.8 0.8 Aloe vera juice 0.30 0.30 Chamomile Extract 0.50 0.50 Fragrance 0.2 0.2

Concept 3: Rheological Results Good Stability Gellan gum Viscosity Pa Control separation Control emulsion Gellan emulsion Shear rate 1/s Stability of Sunscreen spray at room temperature and elevated temperature

Concept 3: Rheological Results Sunscreen Spray Pattern Regular Xanthan gum Gellan gum

Gellan Gum Applications: Refreshing body milk Sunscreen Spray Moisturizing spray Eye cream Hair smoothening mist Air fresheners Body wash with beads Liquid hand foam

Carrageenan INCI: Carrageenan, Chondrus Crispus (EU) Extracted from red seaweeds Partially sulfated poly D-galactose Types: Iota, elastic gels -require ions Kappa, strong gels - require ions Lambda, viscosity only Differentiating Properties: Iota type forms elastic, transparent gels Gels are pseudoplastic/ thixotropic and impart lubrication Can provide structure Combination with Xanthan provides sensorial differentiation Good water binding property and syneresis control Innovative texture possible- Shower Gummies

Types of Carrageenan Kappa carrageenan Forms strong, brittle gels Iota carrageenan Forms elastic gels Lambda carrageenan Forms viscous solutions

Gelling mechanism Lambda Iota Kappa Solution Gel 1 Gel 2 Cooling

Concept 4: Seaweed-Mineral Gel Mask Ingredients QTY(%W/ W) QTY(%W/ W) Water Qs to 100 Qs to 100 Smooth Xanthan Gum 1.50 2.0 Carrageenan 0.50 - Arnica & Algae Extract 0.50 0.50 Aloe vera Juice 0.20 0.20 Sodium hyaluronate 0.1 1.00 Ginkgo biloba extract 1.00 1.00 Algae extract, Water 1.50 1.50 Glycerin 2.00 2.00 Sea salt 1.00 1.00 Fragrance/color q.s. q.s. Preservative q.s. q.s. Parsley Leaf 0.1 0.1

Concept 4: Rheological Results 10.000 10 1 Pa s 1.000 0.5-2 1/s Cling 100 η 10 1 0,1 0,01 10 0 0,001 0,01 0,1 1 10 100 1.000 1/s Shear Rate γ. Seaweed gel mask - Keltro CG-SFT 1 Xanthan gum + Carrageenan Seaweed gel mask - Keltro CG-SFT+Cenuvisco CI-123 1 Anton Paar GmbH -slightly higher viscosity -Cling at 0.5-2 1/s. Good pick-up. Xanthan gum + Carrageenan Higher G Better shape retention Cleaner break Xanthan gum Lower G -> less gel character

Seaweed Gel Mask: Texture Possibilities Xanthan gum Xanthan gum + Carrageenan

Gelled systems with Carrageenan Surfactants gelled using Carrageenan Depending on Carrageenan type, ratio and combination varied textures possible Soft elastic Shower gummies Rigid Shower gummies Cooling Gel films

Carrageenan Applications Shaving i cream Seaweed-minerals gel mask Body butter Natural toothpaste Personal Lubricant Shower jellies Shampoos Air freshener gels

INCI: Pectin Pectin Extraction from citrus peel, followed by alcohol precipitation- De-esterification Chemical Structure: partially methoxylated poly D-galacturonic acid Types: LM Pectin DE< 50 Differentiating properties Restores skin s natural ph Moisturizes skin Improves skin barrier function Stable at low ph (below 5) HM Pectin DE > 50 Can impart emollient skin feel, Newtonian rheology Non-irritating and non-sensitizing

Pectin: partially methoxylated poly D-galacturonic acid

Pectin Weak acid pka about 4 Low DE (more acid) High buffering R-CH + H - High DE (more ester) R-C - + H 2 sustained buffering R-CCH 3 + H - R-C - + CH 3 H Blend Combination of high and low DE provides both features

In Vivo Clinical Tests ph development over time with or without applying pectin 7.5 Soap washing and application of pectin containing media 7 ph 6.5 6 Reference Control Pectin Solution 5.5 5-10 40 90 140 190 240 290 340 390 Time (min) Conclusion: Highly significant ph buffering capacity Directional increase in barrier function protection Moisturizing i i effect of stratum t corneum

In Vivo Clinical Tests Institut d Epertise Clinique (IEC) - France Jan 2008 19 women in the age range 18 70, with hypersensitive, dry to extra-dry skin. 28 days study on the face compared to a placebo lotion Pectin Blend Pectin blend use level- 1.25% Conclusions: A statistical ti ti significant ifi decrease of trans epidermial i water loss by 20%, showing into evidence a protective effect on the skin and improvement of the skin barrier function.

Pectin Applications: Post-depilatory cream Diaper rash cream Dry skin balm After-shave cream Skin protection cream for mature skin Normalizing cream for acne prone skin Face wipes Products for sensitive skin Feminine hygiene products Lotionized tissue products

Texture kit with polysaccharides Structure 5 4 3 Slip 2 1 0 Consistency soak-in Non-Stringy

Combining Polysaccharides 1000 Varying polymer ratio in Blueberry lotion 100 G' G' 50/50 Gellan CMC 10/90 Gellan CMC G ' G'' 10 1 0.001 0.01 0.1 1 10 Strain Using Bohlin Instrument 50/50 Gellan CMC 10/90 Gellan CMC Preliminary Lab data nly

Combining Polysaccharides Structure 5 4 3 Slip 2 1 0 Consiste ncy soak-in Non- Stringy 50/50 Gellan CMC 0.15CMC+0.15HA 10/90 Gellan CMC 0.75CMC +0.05HA Preliminary Lab data nly Using Bohlin Instrument

Polysaccharides provide functional and sensorial benefits Gellan gum Carrageenan Smooth Xanthan gum Cellulose Gum Pectin Fluid gel stabilisation Sensorial enhancer, texturiser Less stringy, smooth flow Rich luxurious consistency Multifunctional ingredient for healthy skin

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