INTODUCTION TO SURFACTAN

FOR COSMETICS & HOUSEHOLD GUIDANCE

DISPERSED SYSTEMS Foams and emulsions

By : Mala Pidiyanti
CV Lidah Buaya, Magelang. 2013
 Definition : Surfactants are compounds that stabilize
mixtures of oil and water by reducing the surface tension at the
interface between the oil and water molecules.
Surfactants are AMPHIPHILIC in nature. amphi which means "double" .
amphiphilic = double affinity as a polar-apolar duality
Hydrophilic = Lipophobe Polar, hight affinity
Hydrophobe = lipophile Non Polar, alkyl chain

PHOBE Greek roots phobos (fear)

PHIL Greek roots philos (Love)

Tail or hydrophobic group which has little affinity for water this group is
usually hydrocarbon (alkyl) chain
Head or hydrophilic group which has strong affinity for water & can be
neutral or charged.
The primary performance function of surfactants is the
lowering of interfacial tension. Some examples:

Cleansing
Lowering tension between dirt/oil , water, and your skin or
hair

Emulsions
Lowering tension between the oil phase and the water
phase

Dispersions
Lowering tension between particles and water or oil
 CLASSIFICATION OF SURFACTANTS
1. Anionic Surfactants : mostly SOAP, sulfonates or sulfates
2. Nonionic Surfactants : mostly ethoxylated, fatty acid ester
3. Cationic Surfactants : mostly quaternary ammoniums
4. Amphoteric or zwitterionic : mostly betaines and amino acid
derivatives

A new class of surface active substance

1. Polymeric surfactants or surface active polymers
2. Silicone Surfactan
- Term Siliphilic (silicone loving) and Siliphobic (silicone hating)
 SURFACTAN CRITERIA FOR PERSONAL CARE OR
HOUSEHOLD PRODUCT FORMULATION
1. Application : Household, skin care, body care, hair care
Brochure
2. Category : Primary, Secondary, Tertiary
3. Foamability : Foam Booster, antifoam
4. Level of Irritant : Irritant, Mild, very mild
Mildness: nonionics > amphoterics > anionics > cationics

5. Foam character : big bubble, small bubble, dense bubble

6. After feel effect : dry, soft, powdery feel, etc
7. Electrolyte response : thickening effect, cloudy, no effect
8. Level of use
 ANIONIC SURFACTANTS
1. SOAPS AND OTHER CARBOXYLATES
3 NaOH + (C17H35COO)3C3H5 3 C17H35COONa + CH2OH-CHOH-CH2OH
Triglyceride sodium stearate Glycerol
Tryglyceride is animal origin : Tallow, Lard
Monoglyceride used in industrial is commonly vegetable origin
C12 : 0 = Lauric Acid C18 : 0 = Stearic Acid
C14 : 0 = Myristic Acid C18: 1 = Oleic Acid
C16 : 0 = Palmitic Acid C18 : 2 = Linoleic Acid
C18 : 3 = Linolenic Acid

NaOH Resulting solid soap for barsoap

KOH, Resulting liquid soap
C16-C18 : Hard soap, low foam, whitish and do not produce skin irritation or
dryness
C12 C14 : Less hard, high foam, less whitish, cause dryness
 SOAP Making Oil Chart, Castille Soap
Base oil, butter or Soft, hard or Properties in soap usage
fat brittle
Coconut oil Hard large fluffy bubbles, highly cleansing, high amounts can be 15-30%
too drying, makes a white bar
Palm oil Hard a great base oil, makes a hard long lasting bar, stabilizes 25-50%
lather
Olive oil Soft/Hard makes a very gentle and mild bar, low lotion-like lather, 25-50%
low cleansing, great for babies and elder folks skin, some
people say that high amounts of olive oil make for a slimy
or snotty feel in the shower
Lard Hard a great base oil, makes a hard bar with a low creamy lather, 25-50%
makes a white bar, stabilizes lather
Tallow (beef) Hard a great base oil, makes a hard bar with a low creamy lather, 25-50%
stabilizes lather
Palm Kernel oil Brittle similar to coconut oil, large fluffy bubbles, highly 15-30%
cleansing but milder than coconut oil
Shea butter Hard makes a hard bar of soap, seems to add a silky feel to the 5- 15%
lather, stabilizes lather
Castor oil Soft helps suspend/hold the lather from coconut oil, adds 5-10%
creaminess, high amounts will cause a bar of soap to be
sticky and have a drag when using it in the shower
 ANIONIC SURFACTANTS
2. SULFATE
e.g., : sodium lauryl surfate , sodium laureth sulfate (Texapon, ECOSOL, IMEX), ,
Di-sodium Ricinoleate sulfate

3. SULFONATE
e.g., : linear alkylbenzene sulfonates (LAS), ABS, sodium laureth sulfosucinate
(Makanate EL)
 ANIONIC SURFACTANTS

4. OTHER ANIONIC SURFACTANTS

I. ORGANO PHOSPHORED SURFACTANTS

e.g., : Potasium Laureth Phospate (Dermalcare 213L/K)

II. SARCOSIDES OR ALCYL AMINO ACIDS

e.g., : Sodium lauroil sarcosinate (Crodasinic LS 30), Cocamide DEA, Cocamide

MEA

The most used synthetic product is lauryl sarcosinate, which is both a strong
bactericide and a blocking agent of hexokinase (putrefaction enzyme). Since it
is not cationic, it is compatible with anionic surfactants, and it is used in tooth
paste and "dry" shampoos for carpets and upholstery.
 NONIONIC SURFACTANTS
NONIONIC SURFACTANTS : Mostly For Cream Emulsion

1. ETHOXYLATED ALCOHOLS AND ALKYLPHENOLS

general formula RXH, that can ionize as RX-.
e.g., : Ethoxylated Linear Alcohols, Ethoxylated Alkyl Phenols, Cetyl Alcohol,
oleth-20 , steareth-2(Brij )
2. FATTY ACID ESTERS
e.g., : Glycerol monostearate , PEG-100 glyceryl stearate (commecial name :
Simulsol), sorbitan esters (comercial name : Span, Tween)
3. NITROGENATED NONIONIC SURFACTANTS
e.g., ; Tertiary amine oxides, ethoxylated imide
 NONIONIC SURFACTANTS
Advantages of Nonionic type surfactants :

1. As a class they are usually the least irritating

2. They are compatible with all the other type surfactants
3. They are compatible with salts
4. They are compatible at the widest pH range
5. They are pre-formed
6. As a class they are the most versatile
 CATIONIC SURFACTANS
1. QUATERNARY COMPOUNDS or QUATS.
They are not good detergents nor foaming agents, and they cannot be mixed in
formulations which contain anionic surfactants, with the exception of non
quaternary nitrogenated compounds, or when a catanionic complex synergetic
action is sought.

Quartenary compound (quats) Benzalkonium Chloride

The quats kill bacterial spores but rahter than inhibit their growth. They form a
residual antimicrobial film after being applied to surfaces. They attached to the
bacteria and cause the cytoplasmic membrane to leak, damaging and kill the
bacteria. The quats are low in toxicity, non iriitant to skin and can be neutralized
or made ineffective by using any anionic detergent.
Quat sanitizers are generally more effective in the alkaline pH range. However the
effect of pH may vary with bacterial species, with gram-negative bacteria being
more susceptible to quats in the acid pH range and gram-positive microbes in the
alkaline range.
Confusion in the marketplace

Bacteriostatic
Means stops bacterial growth examples are sulfamethoxazole which
blocks nucleic acid synthesis or chloramphenicol which blocks amino acid
synthesis. Such agents prevent bacteria reproducing but do not necessarily
kill them outright so they can still produce toxins and/or spoil foods.

Bactericidal
Agents kill bacteria rather than just inhibit their growth. We tend to use
quaternary ammonium compounds (quats) to do this in cleaning products
but there are others such as triclosan which uses a chlorinated phenol (and
so it is less soluble in water).

Antibacterial
Means whatever you want it to. It is a woolly, non specific term and does not
carry the specificity or weight of the two alternatives above
 CATIONIC SURFACTANS
Quats inactivated by anionic detergents (soaps), by many nonionic
detergents, and by calcium, magnesium, ferric, and aluminum ions. Also, they
are not recommended to be used in hard water. Effective levels are at 200
ppm. However, an increase in alkalinity through formulation with compatible
detergents may enhance the bactericidal activity of the quats

2. OTHER CATIONIC SURFACTAN

Cationic class contains aromatic or saturated heterocycles is N-dodecyl
pyridinium chloride or 1-hexadecyl piridium Chloride (INCI: Cetyl Piridium
Chloride) is used as batericide and fungicide. If a second hydrophilic group is
added (amide, ethylene oxide) the product is the both a detergent and a
bactericide. is compatible with anionic formulas since it is not stricly cationic.

They also found as antistatic agents in fabric softeners and hair rinse
formulas. E.g., Ester quats-sunqat TE 90 (softening agent), CTAC or BTAC as
anti static agent
 CATIONIC SURFACTANS
3. NITROGENATED SURFACTANTS WITH A SECOND HYDROPHILE
Cationic surfactants cannot be mixed in general with anionics, since they
react with one another to produce insoluble catanionic compounds. This is
quite a practical problem since most inexpensive formulas contain anionics of
the sulfonate or sulfate ester type, and it would be desirable to add to them
some cationic substance for softening pupose.
The incompatibility problem is circumvented by using a nitrogenated
surfactant of the amine type, i.e. with no actual positive ion, whose water
solubility is enhanced by incorporating a second polar group.
3.1 ALKANOL-AMIDES
They are among the best foam boosters available at neutral and alkaline
pH, with additional corrosion inhibition properties at neutral pH. Fatty acid
alkanol-amides are commonly used as foaming and wetting agents in hand
dish-washing detergents, shampoos and bar soaps, particularly the diethanol-
lauryl (coco) amide. E.g., : Cocamide DEA, cocamide MEA
 AMPHOTERIC SURFACTAN
Amphoteric or zwitterionic surfactants have two
functional group, one anionic and one cationic. In
most cases it is the pH which determines which
of the groups would dominate. with a minimum
of interfacial activity and a concomitant
maximum of water solubility

Amphoteric surfactants, particularly the aminoacid

ones are quite biocompatible, and are used in
pharmaceuticals and cosmetics.
 AMPHOTERIC SURFACTAN
1. AMINO PROPIONIC ACIDS
The general formula for amino propionic acids is RN+-CH2-CH2-COO- . Their
isoelectric point is around pH = 4. They are soluble in acid or alkaline
solutions. They adsorb on skin, hair, and textile fibers. They are used as
antistatic and lubricants for hair and fabrics. The dodecyl amino propionic
acid is used in cosmetics as wetting agent and bactericide. At high pH it is
good detergent and foaming agent. However, due to their carboxylic acid
groups, these surfactants are sensitive to divalent cations.

2. IMIDO PROPIONIC ACIDS

Their general formula is HOOC-CH2-CH2-RN+H-CH2-CH2-COO-. Their
isoelectric point is around pH = 2-3. They are thus more water soluble than
the previous ones. They are used as textile softeners. Dicarboxylic compounds
of alkyl imidazole, in which the alkyl group is located on the carbon placed
between the nitrogen atoms, are used in cosmetics and de luxe soap bars.
 AMPHOTERIC SURFACTAN
3. QUATERNIZED COMPOUNDS
Quaternized compound have similar structures. The most important are
betaines and sulfobetaines or taurines, which have a single methylene group
between the acid and the quaternary ammomium.

These surfactants are amphoteric at neutral and alcaline pH, and cationic
at acid pH (at which the carboxylic acid is not ionized). Since the nitrogen
atom is quaternized, these surfactants always display a positive charge. They
tolerate a high salinity, particularly divalent cations, e.g. calcium and
magnesium. They are the most used class of amphoteric surfactants. They are
found in softeners for textiles, hair rinse formulas, and corrosion inhibition
additives. They are good foam boosters because of their cationic
characteristics. Sulfobetaines have an anionic group (sulfonate) which
tolerates calcium ions, and are used as lime soap dispersing agents (LSDA) in
de luxe soap bars and detergents.
 Polymeric surfactants
These surfactants have many uses, in particular as colloid and nanoemulsion
dispersants, wetting agents, detergents.
There are two main configurations: "block" and "graft, where H and L
represent hydrophilic and lipophilic monomer units.

The result is a macromolecular surfactant. Although the hydrophilic and

lipophilic parts are quite separated, the polymer polarity segregation is not that
obvious since both groups are slightly polar
However most polimeric surfactants belong to the second (graft) type,
particularly synthetic products such as polyelectrolytes which are not strictly
surfactants or are not used for their surfactant properties
Polymeric surfactants, an example :

1. CMC

2. Aristoflex AVC

3. Hostacerin SAF : Mineral oil, isopropyl palmitate,

trilaureth-4 phosphate, rapeseed oil sorbitol esters, ammonium
acryloyldimethyltaurate/VP copolymer
 SILICONE SURFACTAN
Advantage :
Improved surface tension reduction 20 dynes/cm2 rather than the
30+ dynes/cm2
Wetting in water, and oil based systems.
Emulsification properties
Film forming properties
Irritation mitigation
Improve skin feel

Dimethicone Copolyol
The silicone soluble portion is shown in red, the water soluble portion
is shown in blue
Dimethicone Copolyol (DMC)

INCI Name MW Surface Tension

PEG-8 Dimethicone 800 21.9 Dynes/cm2
PEG-8 Dimethicone 6353 28.1 Dynes/cm2
PEG-8 Dimethicone 12.500 31.0 Dynes/cm2

Silicone surfactants are no longer silicone surfactants* when the amount

of silicone in the molecule is too low to effect surface tension. At that point
the molecules simply become fatty surfactants that have silicone attached.
Lower molecular weight DMC have faster wetting times, products can be
easily selected that provide both efficient wetting and low ocular irritation.
Unfortunately, many DMC are poor wetting agents. This is due to the fact that
most commercial products have a molecular weight in excess of 2500.
PEG-8-PG-coco-Glucoside Dimethicone :

The sugar (APG) portion of the molecule provides good foam and a high
degree of substantivity to hair and skin. it provides an outstanding skin feel
when applied from body wash formulations. These products show that they
provide foaming and slip while actually lowering the irritation of
formulations. They show excellent toxicological properties as well as an ability
to mitigate irritation in harsh formulations
APPLICATIONS
Skin Care Products: creams, lotions, tonics, shower gels, etc.
Hair Care Products: shampoos, conditioners, hair tonics, hair creams, etc.
Sun Care Products: pre and post sun care creams, lotions, gels, etc.
Make-up Products: foundations, lipsticks, etc.
Health Care
LATIHAN SOAL