Surfactants, emollients and rheological Additivespptx

Department of Pharmaceutical Sciences R.T.M.N.U Nagpur
Presentation on – Surfactants Emollients & Rheological Additives used in
Cosmetics
Presented by – Nilesh Punjaram Muttalwad M. Pharm 2nd sem
Guided by – Dr. Rita Wadetwar mam

Contents of this template
Questions
1.Enlist Various Building Blocks for Cosmetic Formulation and Explain in
Brief Surfactants?
2.Write a Note on Rheologocal additives and it’s Applications.
3.Write a brief introduction on surfactants .
4.Explain in brief about Emollients and classify it.

1.Surfactants
2.Emollients
3.Rheological Additives
4.References
• Introduction
• Classification
• Applications
• Introduction
• Classification
• Applications
• Introduction
• Classification
• Applications
Contents

• A Surface active agent (surfactants) is a substance which lowers the
surface tension of the medium in which it is dissolved and /or the
interfacial tension with other phases.
Surfactants
• All surface active agents have a structural feature in common: they are
all amphipathic molecule: that is, the molecule has two distinct parts-a
hydrophobic unit and a hydrophilic unit.
• A surfactant molecule is composed of a hydrophilic head and a
hydrophobic tail.
• The head can be an anionic, a cationic, a zwitterion, or a non-ionic group
while the tail is a nonpolar hydrocarbon chain.

According to the nature of the hydrophilic group surfactants are classified as:
• Anionic
• Cationic
• Non ionic
• Ampholytic
CLASSIFICATION OF SURFACTANTS

• Those surfactants in which surface active ion is negatively charged in
solution, are anionic surfactants.
• Anionic groups may be directly connected to hydrophobic part or these
may be connected through ester, ether, amide, or amidine links.
ANIONIC SURFACTANTS
Eg; Sodium dodecyl sulphate

a. Surfactants having anionic groups connected directly to the hydrophobic
unit.
Eg fatty acid soaps, alkyl sulphonates, alkyl sulphates, alkyl aryl
sulphonates,alkyl phosphates.
b. Surfactants having anionic groups connected through ester links
Eg: monoglyceride sulphates, dialkyl sulphosuccinate, polyethylene glycol
ester, sulphates isoethionates.
c. Surfactants having anionic groups connected through ether links. Eg, alkyl
ether sulphates,phenol ether sulphates, alkyl ether carboxylates

d. Surfactants having anionic groups connected through amide links.
Eg: alkalonamide sulphates, taurines, sarcosinates.
e. Surfactants having anionic groups connected through amidine links.
Eg:imidazole sulphates.

• Those surfactants in which surface active ion is positively charged in
solution, are cationic surfactants.
CATIONIC SURFACTANTS

• Quarternary ammonium salts in which nitrogen is directly attached to the
hydrophobic part. Eg: alkyl trimethhyl ammonium salts, dialkyl dimethyl
ammonium salts, alkyl dimethhyl benzyl ammonium salts, ethoxylated
alkyl-dimethhyl ammonium salts.
• Surfactants in which the cationic group separated from the hydrophobic
group. Fg: Quarternized amides of ethylene diamine, Quartemized amides
of polyethylenediamine.
Nitrogenous Surfactants

Non nitrogenous surfactants
Eg; sulphonium salts, phosphonium salts.
• Surfactants in which cationic group is located in a heterocyclic ring.
e.g; Alkyl pyridinium salts, alkyl morpholinium salts, alkyl imidazolinium
salts.
• Dicationic surfactant.
e.g; Quarternised diamine salts.

• Hydrophilic part of the molecule is made up of multiple uncharged polar
groups. Eg: Hydroxyl groups or ether linkages in ethylene oxide chains
NON IONIC SURFACTANTS

Three types
1. Alkanolamines.
Eg.fatty acid alkanolamine, fatty acid dialkanolamine.
2. Polyethylene glycol derivatives.
Eg. Alkyl polyglycol ether, alkyl aryl polyglycol ethers, thioethers
3.Polyethylenimine derivatives.
Eg. Alkylpolyethyleneimine, polyethyleneimine amides

AMPHOTERIC (ZWITTER-IONIC) SURFACTANTS
• Able to form a surface active ion with both positive and negative
char
Three types
1.Alkylamino acids.
E.g. Alkyl ẞ aminopropionates, betaines.
2. Acylaminoacids.
Eg. Acyl ẞ amino propionates, acyl peptides
3. Alkylimidazolines

• Many cosmetics are emulsions in which surfactants have been used as the
emulsifying agents.
• Three types of surfactants usually used as emulsifying agents: anionic,
cationic and non anionic.
APPLICATIONS OF SURFACTANTS
1. EMULSIFICATION PURPOSES:
ANIONICS:
• Widely used for emulsification purposes especially in the formulation of
hand creams and lotions.
E.g Fatty acid soaps, polyol fatty acid monoesters containing fatty acid soaps,
sulphuric esters etc.

i. These are substantive to proteins at acid pH
ii. These tend to produce emulsions with acid pH
iii. They have germicidal properties if not inactivated by anionics or
incompatible materials.
CATIONICS:
• Not widely used as emulsifying agents in cosmetics.
• Following properties should be kept in mind:

NON-IONIC SURFACTANTS:
E.g:
Polyoxyethylene fatty alcohol ethers (eg, polyoxyethylene lauryl alcohol).
Polyoxyethylene fatty acid esters (eg: polyoxyethylene stearate)
polyoxyethylene sorbitan fatty acid esters (eg: polyoxy ethylene sorbitan
monostearate)
Sorbitan fatty acid ester (eg: sorbitol monostearate)
• Compatible with large number of cosmetics because they do not ionise in
solutions. Therefore they are compatible with both anionic and cationic
surfactants.

• They also used in cosmetics for the emulsifying properties such as
lanoline, cholesterol, saponins.
• Today they largely replaced by synthetic detergents. However lecithin
which is a phospholipid is still being used today in the preparation of
milky lotion and creams Lecithin is obtained from egg yolk and soya
bean..
NATURAL SURFACTANTS
2.FOAMING AND CLEANSING PURPOSE
• For this purpose, surfactants are used mostly in shampoo, in which the
principleingredients are surfactants. For foaming and cleansing,
anionics, cationic, non-ionicand amphoteric surfactants are used.

ANIONIC SURFACTANTS
• This is the most widely used type of surfactant for laundering,
dishwashing liquids and shampoos because of its excellent cleaning
properties.
• In shampoo the anions such as alkaline sulphonates and alkaline
benzenesulphonate and fatty acids soaps are not used.
• a- olefinic sulphonates, alkyl sulphate are very popularly used in
shampoo fordetergency and foaming properties.
• Sulphosuccinates are known for the mild effects and less irritant to eyes
and used in mild shampoo as auxillary surfactants.
• Methyl taurides, and acyl peptides may be used.

CATIONIC SURFACTANTS
• They are not good foaming agents or detergents.
• They are also irritant to eyes and interact with protiens, thus they
cause dirt re-deposition onhair shaft.
• They can be used as additives for germicidal properties upto 5% in
shampoo.
Eg-alkyltrimethyl ammoniums, sterile dimethyl benzyl ammonium, cetyl
pyridinium salts.

NON-IONIC SURFACTANTS:
• They are good detergents and can be used as principle surfactants.
• Polyglyceryl ethers have good detergency and foaming properties.
• They are mild in nature and do not irritate the eye mucosa.
• Other non-ionics such as fatty acid alkanolamide are not used as
detergents but produce conditioning effects.
• Few other non-ionics used for other purposes for increasing the
stability and viscosity.
• Eg:- pluronics, sorbitol esters, ethoxylated fatty alcohols.

• Mainly used in mild shampoos such as baby shampoo because of their
mildness to skin and eye.
• They are known to have conditioning properties.
• Eg:- n-alkyl amino acids and betaines and imidazoline derivatives.
• N-alkyl amino acids are best foaming agents used in mildly alkaline pH.
Betaines are cationic in acidic pH and anionic in alkaline pH.
• They are stable over a wide range of pH(2-12). They are also
compatible with cationics, anionics, and non-ionics.
AMPHOTERIC SURFACTANTS

• All surfactants have good wetting properties.
• For the purpose of enhancing wetting, the short chain alkyl aryl
sulphonates, alkyl ethyl sulphates are often used for improving wetting
properties.
3.WETTING AGENTS:
4. SOLUBILISATION:
• Surfactants when used above CMC are known to have solubilising
properties.
• For incorporating perfumes in cosmetics or certain additives which
requires solubilisation.

COMMONLY USED SURFACTANTS:
Sodium lauryl sulphate (can be derived from coconuts) Produces High Foam;
easy to thicken. Strong Anionic Surfactant; can cause irritation.
Decyl Glucoside (derived from sugar) Anionic Surfactant; gentle on the skin.
Glyceryl Cocoate (derived from vegetables)
Disodium lauryl sulphosuccinate (derived from coconuts), Foaming agent,
Mild Decyl Polyglucoside (vegetable derived, used in baby shampoos for its
gentleness)
Cetearyl alcohol (derived from coconut oil) Amphoteric Surfactant

EMOLLIENTS
• Emollients are medical moisturising treatments applied directly to the skin
to soothe and hydrate it.
• They cover the skin with a protective film to trap in moisture.

• Emollients are often used to help manage dry, itchy or scaly skin conditions
such as eczema, psoriasis and ichthyosis.
• They help to repair the damaged natural barrier of the skin, also protect
from irritation and infections and can reduce redness, swelling and
itching.
• They help prevent patches of inflammation and flare-ups of these
conditions.

• Lanolin and its derivatives
• Lanolin is a nautral wax
• It helps to maintain the epidermis in a normal condition
• Its hydrophobic and adhesive character makes it an excellent occlusive
agent and a good emollient
AGENTS USED IN EMOLLIENTS
Lanolin derivatives are
Lanolin alcohol
Modified lanolins: Liquid lanolins
Esterified lanolin alcohol
Acetylated lanolin alcohol.
Polyoxyalkylene lanolins

STEROLS
Cholesterol is the only sterol used It lessen the irritating and defatting action
of emollient.
It helps emollient to penetrate into the epidermis and impart slepyness to skin
PHOSPHOLIPIDS
They are complex fat soluble substance They act as an emollient
Example: Lecitin, excellent emulsifier, emollient as well as surfactant

FATTY ACID
Stearic acid is the only one of choice Its helps to retain consistency of the end
product
FATTY ACID ESTERS
They leave a thin oily film on the skin which is greasy because of their oily
and low viscocity characteristic.
Example: Butyl stearate, isopropyl stearate, Isopropyl palmitate, polyesters
(like glyceryl
monostearate)
FATTY ALCOHOLS
They produce occlusive films that help to induce hydration of skin
Example: Cetyl and stearyl alcohols

Types of Emollients
Spray Bath Additives
Soap Substitutes
Ointments Lotions
Creams

CREAMS
• These are not particularly greasy.
• They are absorbed quite quickly so do not stain clothes.
• They are good for daytime use.
Examples:
Diprobase cream Hydromol cream
Oilatum cream Aveeno cream Cetraben
E45 cream Doublebase
Containing antibacterial: Dermol 500
Containing urea: Calmurid Hydromol extra
Examples for shower(cleansing): Dermol shower, E45 Shower

OINTMENTS
• These are greasy and are particularly useful for very dry or itchy skin
because they hydrate the skin better than creams.
• They do take longer to be absorbed and may make your clothes greasy.
• .Some people prefer to use these at night.
Examples:50% white soft paraffin in liquid paraffin (50/50 mix)
Epaderm
Hydromol
Emulsifying ointment
WARNING: Skin products containing white soft paraffin and emulsifying
ointment are easily ignited with a naked flame or a cigarette.

LOTIONS
They are good for hairy or damaged areas of skin (such as weeping
eczema)
They are thin and can spread easily
But they’re not very moisturising
Example:
Dermocalm lotion

Soap Substitutes
• Soap dries the skin and can make it itchy. Use soap substitutes for all
washing. These cleanse the skin effectively BUT do not lather like soap.
• Many creams and ointments may be used as soap substitutes.
Examples:
Cetraben
Wash E45
Diprobase cream
Emulsifying ointment
Hydromol ointment
Epaderm.
Dermol 500 (which contains antibacterial)

SPRAY
• They are good for hard-to-reach area.
• They are also used for sore or infected skin that shouldn’t be touched.
• They are quickly absorbed.
• A spray formulation easier to apply.
• Example: Emollin spray

• Bubbles (like soap) can irritate and dry skin. Emollient bath additives
should be added to the bath water to help to moisturise your skin and
leave a fine film on skin after bathing.
• TAKE CARE as they will make the bath slippery.
BATH ADDITIVES
Examples:
Oilatum Balneum Diprobath
Bath E45 Hydromol
Aveeno bath oil
With antimicrobials: Oilatum plus (with anti microbial)
Dermol 600

RHEOLOGICAL ADDITIVES
• Rheology is the science of flow.
• Every time a lotion is poured, a cream squeezed from a tube or a lipstick
applied, rheology is involved.
• Even when products are at rest, it plays an important part in controlling
stability of suspension.
• Understanding a formulation’s rheological needs enables, to create the
best possible products

• The rheology of a system is described in terms of its viscosity.
• Viscosity is the resistance to flow and defined as the force applied by the
resulting rate.
• Shear stress is the force per unit area applied and shear rate is the resulting
velocity gradient.

• A material which maintains a constant viscosity, regardless of shear rate,
has Newtonian flow (Fig.2). Dilatant flow (Fig.2) is a form where
viscosity increases with shear, sometimes encountered in highly
pigmented/filled systems.

• The rate of recovery of a system when stress is removed is also very
important. When a shear thinning system shows delayed viscosity
recovery, it is described as thixotropic (Fig.3).

• Pseudoplastic flow (Fig. 4), also known as shear thinning behaviour, and
typical of many commercial systems, is when viscosity decreases with
increasing shear rate.

Rheological Additives for Cosmetics
• Rheological additives can be broadly divided between aqueous-phase
thickeners and non-aqueous-phase thickeners.
• But it is important to remember the advantages of oil phase viscosity
modification that can greatly improve emulsion based products.
• ELEMENTIS Specialties additives for cosmetics are based on naturally
occurring materials: highly refined and beneficiated hectorite clay or
castor oil derivative

1. Aqueous-phase thickeners
• The Rheoluxe family of rheology modifiers are non-ionic polymeric
thickeners designed specifically for the personal care market.
• Rheoluxe consists of urethane based and Polyether Polyol based
associative thickeners with superior performance in difficult systems
such as those containing high salt levels or with extremes in pH.
• Due to its structure, Rheoluxe is soluble in water, but associates with
lipophilic materials to build viscosity.
• Rheoluxe Associative Thickeners

• The Rheoluxe range of products provides viscosity control in all types of
emulsion systems, creating an exceptional sensory profile.
• Supplied as easy to handle solutions, Rheoluxe can be added at any point
in the production process.
• Rheoluxe is heat stable, although cold process systems are possible.
• Use – To Stabilize Emulsion

Associative thickeners – mechanism of action
• Associative thickeners increase the viscosity of aqueous systems through
a system of molecular associations and interactions.
• The thickeners consist of water soluble polymeric chains modified with
hydrophobic caps.
• The hydrophobic caps of the polymer associate, that is build a structured
network with other hydrophobes in the formula.
• This results in micelle type structures that form a network resulting in
significant viscosity build.

HECTORITE
• Hectorite is a unique swelling clay offering several advantages. Hectorite’s
special properties, compared with bentonite, are:
• lower iron content
• lighter colour
• higher swelling capacity
• greater gel strength
• No crystalline silica
• Due to its small size, platelet shape and large surface area, hectorite is able
to form strong, stable viscous gels.
• Use – Stabilizes gel and emulsions

2.Non-Aqueous-Phase Additives
• Surfactants can influence hydrophilic clays.
• The rheological behaviour of hydrophilic clays..
• Non-ionic surfactants, if they are highly ethoxylated, can adsorb onto the
clay surface.
• This rarely causes problems either in flow control or activity of the
formulation. Anionic surfactants can act as dispersing agents and weaken
the gel structure. Alternatives that eliminate or minimise any problems
can normally be found. Cationic surfactants interact strongly and should
be avoided.

• Organic and silicone-based liquids used in oil and wax-based cosmetics,
and as the non-aqueous-phase in emulsions, benefit greatly from
ELEMENTIS Specialties rheological additives.
• Outstanding rheological properties are developed using BENTONE
organoclay rheological additives in their powder form or, even better, with
BENTONE GEL additives, their predispersed forms.

• thermostable viscosity control
• thixotropic flow
• suspension control of pigments and actives
• emulsion stabilisation
• silky skin feel
ADVANTAGES

• Hectorite is now reacted with special vegetable quaternary ammonium
salts to produce organoclays able to thicken and gel organic liquids.
• The correct choice of BENTONE additive is determined largely by the
polarity of the system to be thickened.
BENTONE organophilic Clays
• BENTONE organoclays form thixotropic gels by developing hydrogen
bond bridges between the edges of adjacent platelets as shown in
Figure

BENTONE GEL
• BENTONE GEL additives are optimally dispersed and activated
predispersions of ELEMENTIS Specialties organoclays.
• Benefits include:
• optimally dispersed.
• high-shear dispersion not necessary.
• no polar activation required.
• easy to handle and use.
• can be added at any appropriate and convenient stage in
manufacture.
• A wide range of gels made from various cosmetics oils, esters and solvents
are available.

• The use of a BENTONE GEL enables to achieve the maximum efficiency
from the organoclay without the need for careful shearing and activation.
• On the production scale, time is saved and the highest degree of
reproducibility attained, leading to potential cost savings.

APPLICATIONS
Mascara
Eye shadow
KEY PROPERTIES
Non-animal origin
Rheological control
Predictable, reproducible and stable viscosity control
Shear-thinning viscosity
Excellent suspension of pigments and actives
Controlled alignment of special-effect pigments
Thermostable viscosity raises apparent melting point and ensures cost-
efficient use of UV filters
Emulsion stabilization [w/o and o/w ]

Thixcin R Rheological Additive
• For the highest degree of thixotropy in aliphatic liquids, Thixcin R
additive is the product to use.
• In addition to its effective rheological properties, it gives water
repellence, stabilises emulsions and acts as a stiffening agent in lipsticks
and ointments.
• It can also be used as a dry binder in pressed powder systems.
• It is a castor oil derivative.
• It requires temperature-controlled activation within the range 55-60°C
(130-140°F) and high-shear mixing to develop its full structure.

• maintain homogeneity in molten and setting stages
• gain improved pay-out
• increase high-temperature integrity.
• eliminate oil migration.
• reduce “creasing” around lips and eyes.
APPLICATION
 Stick products (lipstick and antiperspirant)
 Mascara
• improve film-build
• increase water-resistance
• eliminate oil migration

• Eliminate ultrafine Tio2 skin-whitening problems
• Enhance sun protection factor (SPF).
• Optimise use of sunscreen actives.
• Reduce separation and settlement.
 Emulsions
• Elivate drop-point temperature of water-in-oil creams.
• Eliminate syneresis.
• Improve emulsion stability.
• Enable cold-process emulsification.
• Create novel viscosity effects
 UV Sunscreen

• Uniform distribution of active ingredients.
• Soft and dry skin feel.
• Significant less whitening.
 Antiperspirants aerosols

References
• Sharma PP.Cosmetics- Formulation, manufacturing and quality control.5th
ed.2014, P:94-103)
• Harry’s cosmeticology p.633-640.
• Images and Definitions from Wikipedia.
• Refered Slideshare
• Official website of Elementis.

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