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The primary function of shampoo is to clean hair

scalp.
THE TERM:

and

The word comes from the Hindi to press.

Originally used in English for massaging
It still describes part of process of a Turkish bath.

The first shampoos contained soaps (Sodium,

potassium
and ammonium salts of oleic and
coconut fatty acids), but these days they are based on
non-soap detergent (synthetic detergents have replaced
soaps as the primary surfactant in shampoos because
of their superior performance in hard water).

The first large-scale development of non-soap

detergent took place in Germany during the First
World War (because fats were in short supply)

The technology of complex shampoo emulsion

has also become more important as a result of the
development of effective two in one
shampoo,
which clean and condition hair at
the same
time.

1. Should easily spread over the hair.

2. Produce a rich, creamy lather and stable
3.
4.
5.
6.

foam which easily rinsed out with water.

After drying, the hair should be left in
lustrous condition and easily manageable.
Surfactant level must be relatively high 1020%.
Viscosity at least 2000 cps
Must exhibit low skin and eye irritation.
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1. If they used with hard water or low pH,

they leave the hair with dull, tacky coating.

2. Soap solutions are alkaline, causing
roughening of scales of the cuticle, giving
rise to dullness and fly effect.
(Amine soap gives neutral solutions).
Nowadays, most shampoos are based on
synthetic detergent.
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The alkyl and alkyl ether sulfate represent two most widely used
classes of surfactant for the formulation of shampoos.
1. Alkyl sulphates
C12H25O.SO3 Na+ SLS
C12H25O.SO3HN(CH2CH2OH)3 TLS

They are usually mixture,C12 lauryl, C14 myristyl,

C16 cetyl, C18 stearyl.
Coconut oil contains 50% each of C12 and C14.
Lauryl produces the most lather and myristyl the richest lather.
alkyl sulphate clean the hair well, and leave it shiny, but they tend
to strip the hair, leaving it unmanageable.

2. Ether sulphates

C12H25 (OCH2CH2)n O.SO3Na +

Foaming potential decreases with the increase of
the number of (OCH2CH2) group, while mildness
and solubility increases. The optimum is 2-3.
They are generally more soluble than alkyl
sulphates.

3. Miscellaneous anionic surfactant

They are not widely used but incorporated with
primary ones as secondary surfactants, or used in
specialty product.
E.g. sulfosuccinates , linear alkylbenzene sulfonate .

Cationic surfactant in shampoo formulations is more limited than

that of surfactant classes.
They are not as effective detergents due to their ability to strongly
bind to hairs negatively charge surface, and not efficiently removed
during rinsing.

Cetrimide is an example
CH3
|
C16H33 N+ CH3 Br
|
CH3

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Shampoos containing only one of the previous

types of detergents tends to be harsh, and its
therefore necessary to add an auxiliary
detergent, usually weak detergents which:
Increase the viscosity of the shampoo.
2. Stabilize the foam.
3. Have conditioning effect on the hair.
4. Increase the solubility of the primary
detergent.
1.

For example, polyoxyehtylene lauryl ether

C12H25 (OCH2CH2)23

THE MAIN THREE TYPES OF NON-IONIC

DETERGENTS:

1. Fatty alkanolamaides ( The ethanol amides)

They work as foam and viscosity enhancers. The main

component is the uncharged nonionic amide.
The major concern in formulating with alkanolamides is the
potential for free amine, particularly diethanolamine (DEA), to
form carcinogenic n-nitrosamines.
E.g. lauric diethanolamide
O

CH2CH2OH
C11H23C-N
CH2CH2OH

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2. Amine oxide
Are prepared by the oxidation of tertiary amines with
hydrogen peroxide. They are best known for their ability
to enhance foam characteristic, and provide thick,
creamy, more stable lather at moderately acidic pH.
CH3
|
CH3 (CH2)11 N O
|
CH3

e.g. Lauryldimethylamine oxide

Nonionic surfactant are generally not used as primary

surfactants in shampoos due to inferior foaming

characteristics, which result from their large surface area per
molecule and the lack of charge on the surface films in
nonionic foams.
The advantage of the use of nonionic is their ability to reduce
eye irritation and sting.

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Ampholytes
(Amphotrics)
- They have very low irritation potential and are almost completely nonstinging to the eyes.
- Can be formulated in many types of shampoos.
- Should avoid low pH when formulating because the amphotric become
positively charged since this can result in increased irritation.
CH3
|
_
C12H25 N + CH 2COO
|
CH3

N- lauryl betaine

Many additives associated with shampoos are added to provide various

additional benefits to the product; some are critical and others are
optional.
1. Viscosity modifiers
- Auxiliary detergents and conditioning polymers can provide a thickening effect to a
shampoo.
- Salts increase viscosity of detergent solutions, NaCl 1-2%, Ammonium chloride at
pH well below 7 to avoid liberation of ammonia,
salting out mechanism (bellshaped curve).
- Cellulose derivatives (0.5-1.5%)

2. Weak organic acids

A shampoo having the same pH as hair would do the least damage.
Hair pH = 5-6
,
S. Detergent pH = 6-8
An addition of citric acid will decrease pH to optimum pH 5.5

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3.

Opacifiers
The opacifying agent are usually stearates (stearic acid,
magnesium stearate, ethylene glycol monostearate), are used in
less than 1% concentration to give creamy appearance.

4.

Antioxidants/ Sequestrants / UV Absorber

Antioxidants are included in shampoo formulation to avoid

oxidation of unsaturated components, such as vegetable oil.

Sequestering agent is included in shampoo to prevent
discoloration and to improve the performance of the anti
microbial agents by forming soluble complex with metal ions.
Shampoo in clear packaging should contain a UV absorber, e.g.
benzophenone-4, to protect against color fading and other
reasons upon prolonged exposure to light.
5.

Preservatives

Are essential component of a shampoo formulation to protect

against microbial growth.
E.g. parabens.

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1.

Shampoos are also involved in damage of hair, either directly; through

removal of structural components of the hair fibers, of indirectly;
through removal of protective deposits on the hair.

Direct damage:

Studies indicated that the nonkeratinious regions of the hair, which

include the endocuticle, or inner portion of the cuticle, and the cell
membrane complex are susceptible to damage by surfactant molecules.
Exposure to shampoos can have deleterious effect on hair structure
over time.

2.

Indirect damage:

It is a result of fiber abrasion occurring when hairs are rubbed against

each other during cleaning. More important is the removal of sebum
from the fiber surface during shampooing (sebum act as natural
lubricant for hair).

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Shampoo formulations are classified into four

basic functions:
Cleaning, mild (or baby), conditioning, and
antidandruff.

Mild or baby shampoos is required to allow only

minimal eye, scalp, and skin irritant.
They often contain mild surfactant systems, such
as nonionics and amphotrics.

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Cleansing shampoo
Ingredient

Ammonium lauryl sulfate

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Cocamide DEA

Cocamidopropyl betain

Fragrance

0.7

Preservative

0.5

Citric acid

0.3

Ammonium chloride

0.2

Color

0.001

Water

q.s
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Baby shampoo
Ingredient

PEG-80 sorbitan
laurate
Sodium trideceth
sulfate
Sodium
lauroamphoacetate
PEG-120 methyl
glucose dioleate
Cocamidopropyl
hydroxysultaine
Fragrance

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0.7

Preservative

0.5

Color

0.01

Water

q.s

5
5
2
1

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Does hair need conditioner?

Conditioners are formulated to impart conditioning to
hair, for example; improve combing, softness, and
manageability, in addition to the usual cleaning benefits.

Physical damaging effect:

Wind, weather, ultraviolet radiation, brushing and
combing.

Chemical damaging effects:

1. Shampoos which remove natural lipids
2. Dyeing require preliminary bleaching
3. Bleaching with alkaline hydrogen peroxide
Drastic treatment which cause severe weakening of
the hair fibers and loss of elasticity
4. Permanent waving
Where peroxide and thioglycollate attack the
disulphide and peptide bonds of keratin.

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 Conditioning term is difficult to define

The process of conditioning involves at least

four functions:
1.
2.
3.
4.

Rendering the hair manageable, easy to comb and

set.
Preserve its natural appearance and luster.
Exerting a softening effect.
Giving BODY to the hair.

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Oil adheres to hair fibers body + luster +

lubrication
Excessive greasiness can be overcome by applying
the lipid in the form of diluted O/W emulsion and
by using high melting point lipids, such as
cetostearyl alcohol.

Vegetable oil, lanolin and its soluble derivatives

(POE or quaternaries), synthetic esters, sebum
substitutes, Octyl stearates and Squalene

Silicones have high refractive indices, and are

therefore good luster producing compounds.

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Keratin contains more acid groups than basic groups, and

therefore tend to attract positively charged molecules and
ions.
1. Cationic compounds (quaternary ammonium compounds), a

typical example cetrimide

2. Amidoamides (tertiary amines).a typical example
stearamidopropyl dimethylamine lactate
3. Alkanolamide, example Coconut diethanolamides
4. Ampholytes, example N- alkylbetaines as anti irritant.
5. Polyvinylpyrolidone (PVP).

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The conditioning effects of weak acids have been

known since ancient times (lemon juice, vinegar)
1.They dissolve calcium and magnesium deposits.
2.Neutralize excess alkali after bleaching or

permanent waving.
3.Precipitate the soluble keratin products resulted
from the rupture of peptide bonds by the action of
peroxide or thiglycollate.
A suitable lipid mixture is emulsified with cationic

surfactant O/W and a small quantity of weak

organic acid and protein can be added.

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Proteins are actually mixture of:

1.Proteins
2.polypeptides
3.peptide
4.amino acids

We can prepare them by hydrolyzing protein usually

with enzyme Collagen, Milk, Oats, Wheat, Soya.

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Cosmetic process

Bleaching
Waving

without protein

with protein

Cuticle removed

Cuticle intact

Extensive damage

Swelling, but no
damage

Its recommended that protein hydrolsates are used

before, with or after the chemical process.

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Absorption of protein fragments has

been demonstrated in several ways:
1.Treatment with

methionine was found

to retain radioactivity after rinsing.
2.Stronger color and ninhydrin, transverse
section stained more deeply
3.Hydroxyprolin of collagen ( analysis)
Undamaged
Absorbed

Moderately
bleached

Bleached
water

0.08%

0.2%

3.0%

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Ingredient

concentration %

Primary surfactant

12-20

Dehydrogenated tallow Phthalic

acid amide

4-7

Dimethicone

0.5-3

Cocamide DEA

1-5

Miscellaneous

q.s

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