Hair Care Products
Assoc. Prof. Dr.Pleumchitt Rojanapanthu
Pharmacy Department,
Faculty of Pharmacy Mahidol University,
Bangkok, Thailand
1
Hair Care Products :
Shampoos
Hair sprays
Conditioners
Hair gels
“2 in 1” shampoos
Perming solutions
Hair dyes., etc.
2
Shampoos
Purpose of shampoo is to clean hair
Customer also expect a dense and
luxurious lather
Basic or primary surfactants are
backbone of the cleansing products
are necessary
3
Shampoos
Shampoos can be made in various physical
form:


Liquids, creams, paste, aerosol and dry
majority are liquids, either clear or pearlised
The principle constituents of most liquid
shampoos can be classified as :



Primary detergents
Secondary detergents
Thickeners
4
Shampoos
(con.)
• Foamers
• foam stabilizers and booster
• Perfumes
• Preservatives
• Diluents (usually water)
• conditioning agents
5
Shampoos
(con.)
• Other additives (functional or
otherwise)
• pearlisers / opacifiers
• colours
Remark : many ingredients are
multifunctional and therefore do
not clearly fall into any one
category
6
Shampoos
(con.)
The surfactants used in a shampoo need
to be selected on the basis of a whole
range of properties including:
•
•
•
•
costs
foam height
foam texture
detergency
7
Shampoos
(con.)
•
•
•
•
•
•
•
irritancy
ease of handling and mixing
compatibility with other ingredients
color
odor
purity
biodegradability
8
Surfactants

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Basic anionic surfactants
(Primary, anionic surfactants)
Mild anionic surfactants
(Secondary, anionic surfactants)
Amphoteric surfactants
Nonionic surfactants
Cationic surfactants
9
Basic surfactants
1. Alky ether sulfates (R- (OCHCH2)xSO4M)
are most widely used surfactants
Exhibit well balanced properties
Excellent foamer, through the foam
structure is relatively coarse
Low CMC (critical micelle
concentration) ideal for cleansing
preparation
10
Basic surfactants (con.)
Ideal behavior regarding foam and
detergency
Be easily thickened with salt
Show good water solubility
Skin and eye compatibility is
acceptable
Lauryl ether sulfate / sod. Laureth sulfate
11
2. Alkyl sulfates (R-SO4m)
The first synthetic surfactant
Still most popular
Excellent foamer
Producing rich and creamy foam
12
3. a- Olefin sulfonates
A mixture alkene of sulfonates and
hydroxy alkane sulfonates
Milder than alkyl sulfonate
Similar irritation to the alkyl ether sulfate
Stable both in acidic and alkali pH values
13
Mild Anionic Surfactants
(Secondary surfactants)
The purpose is to improve skin and
eye compatibility of the formulation
Mild surfactant usually show
reduction of foaming and cleansing
compared with basic surfactant
14
Sulfosuccinate
Derivative of sulfosuccinic acid both mono
and diesters
Most popular derivative used in Europe is
disodium laureth sufosuccinate
Good foamer and relatively cheap
Instability in both low and high pH value
Stable at pH 6-6.5
15
Cocoyl isethionate
(RCOOH-CH2-CH2-SO3Na)
Mainly used as a surfactant in syndet bars
Improve skin compatibility
Excellent skin compatibility and emolliency
properties
Using in baby products and in facical wash
formulations
Maximum stability at pH 5-7
16
Alkyl ether carboxylates
(R-(OCH2-CH2)x-OCH2-COOM)
Mild surfactant, reduce foaming and
cleansing
Skin compatibility is similar to that of
alky; ether sulfate
Stable at low pH value
17
Magnesium surfactant
Have significantly better skin compatibility >
Sod., amm. and amine neutralized
Show high foaming and excellent cleansing
properties
Their applicational properties are practically
unchanged compared with the sodium foam
Magnesium ion increase the resistant of microbe
18
Alkyl phosphate
Mono alkyl phosphate is good surfactant
Show high foam with mildness to skin
Suitable for mild shampoo and show both
Di- and tri- are known as emulsifier
19
Amphoteric surfactants
The charge changes as a function of pH
value of the formulation
Build complex with anionic surfactant
Exhibit milder properties than individual
20
Alkyl betaines
Can be cationic or anionic depend on pH
At pH 5-7 as in shampoo, they form ionic complex
with anionic surfactant
Improve the skin compatibility of an anionic
formulation
The size of micelle
viscosity
Can improve foaming of a formulation (often use
for thickening the formulation)
Improve structure of the foam finer and creamy
21
Alkylamido betaines
Amino betaines are milder than alkyl
betaines
Lower price
Much more often use in cosmetics
22
Acylamphoglycinates and
acylamphopropionates
Most important products are coco
derivative
Good skin compatibility
Show some conditioning properties in
shampoos
Excellent foamer but is not stable in hard
water
23
Amino oxides
Amino oxides are never anionic
Show cationic, non-ionic depend on pH in
combination with anionics can act as a
foam booster and improve the foam
structure
Good thickener for ionic surfactant
Are good conditioning agents in hair
rinsing
24
Non-ionic surfactant
Ethoxylated products
Poor foaming used in shampoo
Often adds as solubilizers for perfume
Extraordinary mildness, used as the main
surfactant in ‘non-sting’ baby-shampoo
25
Alkyl polyglycoside (APG)
Not as good as anionic surfactant
Shows good foaming properties
Excellent skin compatibility
Normally use for secondary surfactant
26
Shampoos (con.)
“frequent use” shampoos contain higher
levels of milder secondary surfactants


many secondary surfactants exhibit lower
irritation to skin and eyes
small addition of secondary surfactant can
lead to a significant decrease irritation
27
Evaluation of Detergents
as Shampoo Bases
Ease of spreading
 Lathering power
 Efficient soil removal
 Ease of rinsing

28
Evaluation of Bases
Ease of combing wet hair
 Lustre of the hair
 Speed of drying
 Ease of combing and setting the
dry hair
 Safety of shampoo

29
Detergency
Detergency : the removal of dirt, involving
the following processes :
 ability to wet both the dirt and substrate
 reducing the interfacial tension
 dispersing the dirt particles
30
Shampoos Additives
Thickeners
High viscosity is very important both for
Product stability
Handling
The product should have viscosity
between 400 and 4000 m Pas
31
Thickeners (con.)
Pearlescent products should have
minimum viscosity of 2,000 m pas it
avoid precipitation
Ether sulfate + electrolytes (Cl-)
viscosity by the size of the micelle
Alkanolamide
formulation
the cloud point of the
32
Thickeners (con.)
Using the special high molecular
weight thickener ; PEG 6,000, PEG 120
It is either product, remain stable
against hydrolysis at higher
temperature or extreme pH values
Polymer thickener
Natural gum
Cellulose derivative
33
Foam stabilizer

In the present of oil, such as
sebum,
Monoethanolamines are the most
effective
34
Pearlescent agents
Ethylene glycol mono and ditearate
(EGMS,EGDS) are most often used in
surfactant formulations.
They have to be incorporate at high
temperature (70 -75)
Ready – made liquid pearlescent bases are
now popular
35
Conditioning agents
Shampoo with anionic surfactants leave
hair difficult to comb while wet
flyaway when comb after drying
Addition of conditioning agents
wet – combability
static charge
36
Conditioning agents (con.)
Cationic surfactants show good properties
but incompatable with anionic surfactants
Using quaternized polymer
: quaternize hydroxyethyl cellulose
(Poly quaternize 10) compatible with
most anionic surfactant
Show excellent conditioning properties
37
Conditioning agents (con.)
Impart manage-ability and body to hair
very low concentrations are sufficient
Due to its very high substantively to hair,
very low concentrations (0.5%) are
sufficient
High concentration may lead to overconditioning and build up on the hair
38
Conditioning agents (con.)
Small amount of fatty component : fatty
alcohol, monoglyceride can support
condition effect of shampoo
Silicone can be very effective conditioners,
but are very difficult to incorporate and
may act as antifoaming agents
39
Thickeners and foam
stabilizers
 Alkalonamides or their alternatives
 Polymeric materials
 Electrolytes
Many of these ingredients are multifunctional, and
most product use more than one.
40
Thickeners (con.)
Some surfactants systems are difficult
to thicken not responding well to
electrolyte additions
most surfactants systems are nonNewtonian, exhibit
shear – thinning
shear – thickening
time – dependence
time – independence
yield point
etc.
41
Thickeners (con.)
Ultimate test viscosity should be carefully
considered
Various raw materials manufactures have
developed
 PEG derivatives
 Polymeric material : natural gums
Gum-thickened product have a
different Rheology to otherwise similar
electrolyte-thickened product
42
Thickeners (con.)
Temperature effect is less for gum systems
than for an electrolyte-thickened system
This can be useful when formulating for
climates where the product might be
subjected to large temperature variations
in storage, distribution and use
43
Thickeners (con.)
Gum will often stabilize foam by
strengthening the film at the air/liquid
interfaces in the matrix of bubbles
Making foam feel denser (creamy) in use
It is sometimes apparent as soon as the
shampoo is poured into the hand
44
Some disadvantages
high cost
lengthened processing time (with higher
energy consumption if hot process is
used)
difficulty of making viscosity adjustment
This problem can often overcome by using a
small amount of electrolyte for final viscosity
adjustments.
45
Effect of electrolyte on viscosity of
surfactant systems
ionic density of the solution
consequent effect on micelle size and shape
Adding an electrolyte with the same cation as
that of primary anionic surfactant in the system
e.g: amm.chloride  amm.lauryl sulfate
sod. chloride  sod.lauryl ether
sulfate
46
Effect of electrolyte (con.)
Addition of electrolyte beyond a certain point
will cause thinning, quite rapid and 
The maximum in viscosity depends on:
Concentration
presence of alkalotamides
level of free fatty alcohol
effect of the perfumes
47
Effect of electrolyte (con.)
Maximum viscosity occurs at low
concentration of electrolyte when free fatty
ether and alkalonamides are present
Due to formation of mixed micelles
Should have experimental for the relationship
of viscosity and electrolyte concentration
48
Preservatives
Ensure that the products contain no
pathogenic …
Variety of preservatives are available:
parabens
Imidazolidinyl ureas
2-Bromo-2-nitropropane-,1,3-diol
5-Bromo-5-noitro-1,3-dioxane
Dimethyl dimethylol (DMDM)
hydantoin
49
Preservatives (con.)

Methyl chloroisothiazodlione and
methylisothiazodlione
Pohenoxethanol
 Drazolidinyl urea
 Methy dibromoglutatonitrile
 Questernium – 15
 Sodium iodate
 Glutaraldehyde

50
Preservatives (con.)
Many surfactants used for shampoo
manufacture are already preserved
Addition of preservatives must be taken into
account
Challenge test of the finished product must
be performed
51
Opacifier and pearliser
Opacification of shampoos usually for
aesthetic reason
An occasionally a useful technique to use
when the product can’t be made
completely clear
52
Opacifier (con.)
Opacification may be achieved simply by
Adding a small of fine, intensely white
polymer dispersion
For ease of dispersion and subsequent
product stability dilution of the opacifer to
a 10% solution with water before addition
to the main mix
53
Three common used ways achieving
Pearlescence using stearate
Buying a ready made pearlised base (need
dilution before adding)
Adding the chosen pearlising agents to the
hot mix (most commonly ethylene glycol
mono-desperate)
Buying a highly concentrated pearlising agent
in a liquid or semi-liquid form that may be
added as a cold mix
54
Factors affecting the appearance
of the ‘pearl’
1. Composition of stearate ester
2. Presence of alkanolamides and other
materials
3. Rate of cooling
4. Shear rate of stirring
5. Composition of the base
55
Conditioning agents
The majority of active conditioning agents
are cationic surfactants, incompatible with
anionic surfactants which are the basis of
nearly all shampoos
The properties of both cationic and
anionic can be modified
56
Variety other materials have been used as
conditioning agents in shampoo
Various vegetable oil
Vitamin
Lanolin and its derivative
Herbal extracts
Some specialty silicone
57
Color

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Using color which meet both EC and US
specifications whenever possible
Higher purity colors are more expensive
than technical grades
Color stability should be considered
Color fading can be minimize by adding a
suitable UV absorber
58

Water
soluble absorbers usually work best in
shampoos
 Bensophenone-4 and 2 (0.05-0.1%)
Color should be added in solution, not as
solid material
Aqueous solution color required
preservative

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59
Sequestrants

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
Such as EDTA (ethylene diamine tetraacetic acid) salts added in low level
To aid rinsing in hard water
To boost the efficiency of preservative
60
Anti-build-up shampoos

Are formulate to help remove
excess build-up of conditioning
agents and styling aids
61
Hair conditioners
Conditioning

Means many things to many people :
Reduction of fly-away
 Gloss
 Sheen
 Manageability
 Ease of handling
 Simply general overall appearance

62

Conditioner should impart the
condition of the hair as follow :

Improved wet and dry combing

Reduced fly-away (antistatic)

Increase gloss and volume

Improve curled retention

Repair the damage of hair shaft

Increase moisturing
63
Basic ingredients in the formulation
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Primary surfactants (nearly always
cationic)
Polymers
Bodying agents
Auxiliary emulsifiers
Oily components
Other ‘active’ ingredients
64
Conditioners (con.)
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Thickeners
Perfumes
Preservative
Diluents (usually water)
Colors
Other non-functional ingredient
65
Cationic surfactants

The most common active ingredients:


quaternary ammonium compound (quats)
properties related to charge density

Highly charged cationic will be more strongly
attracted to the negatively charged hair
surface
66
Cationic surfactants (con.)


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On the hair surface, the number, shape
and size of the fatty chain in mol. are
determinants
Two fatty acid chains > lubricity than
one chain
Long chain > effective lubricant than
short chain
67
Bodying agents


Conditioners are perceived to be
more effective when thick and
creamy
Using high level of fatty alcohol
along with other waxy esters
68
Auxiliary emulsifiers

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Some quats are good emulsifiers, some are
not
Incompatibility with anionic surfactants
Surfactants emulsion stability can’t be
obtained with cationic alone
Non-ionic surfactants are in used
Choosing 2 surfactants : should consider
HLB (Hydrophilic Lipophilic Balance)
69
Oil components

Should be considered the effect of oil on
:
Ease of manufactures
 Product stability

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Using at typically low level, less affecting
stability
Small quantities of exotic oil with
attractive names may be included
70
Thickeners

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Salt solution are in used
Add only very small amount at a time (viscosity
will peak at low concentration than in shampoo)
Add salt solution when emulsion is cold
(maximum 30 oC)
Use dilute salt solution (10% max) add very slow
with continue stirring
Small amount of salt solution with high-shear
mixing
Try a small batch and scale up carefully
71
Manufacturing

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Using two phases method
Heating oil and water phases
Combining together
Cooling process
According to high water phase /oil
ratio
Only part of water is heated is formed
a concentrate emulsion
 Adding the rest of water at cold stage

72
Clear Conditioners


Using aqueous solution of quarts, polymers,
or both
Conditioning other active ingredients such
as :



Parthenol, water-soluble silicone derivative
Thickening by electrolyte as shampoo
Developing quite strong lather
73
“2-in-1” shampoos
- contain both cleansing and high
levels of conditioning agents
- over 20% shampoos are sold of
this type
- silicone is the basic substance
derive from natural substances
74
How 2-in-1 formulations work: (1) surfactant molecules
(blue)and conditioner particles (pink) surround the hair;
each conditioner particle is trapped inside a crystal 'cage'
75
(2) The surfactant molecules are attracted to the
dirt on the hair surface and lift it away, leaving
the hair clean
76
(3) When the hair is rinsed, the conditioner particles are
released from their 'cages'; they are not washed away
but, because of their electrical charge (+), they are drawn
towards the (-) charges of the hair
77
4) They cling to the hair, smoothing out any roughness
on the surface and protecting the cuticle
78
Hair thickener

Hair can be made thicken by





Causing it to swell
Coating it to increase its diameter
Hair will be swollen in water / more under
alkali conditions
Powerful humectants may be used to
increase moisture content of hair
Application of panthenol solution cause the
swelling of hair
79
Styling aids
Hair Sprays, Hair gels

Various description terms :


Light hold, medium hold, strong hold, ultra
hold, mega hold
The main ingredients in hair sprays are
:
Polymer
 Plastizer
 Perfume

Solvent
 Neutralizer
 Other addition

80
Polymers



Ideal hair spray polymer should be
soluble in ethanol
Hydrophilic enough is be easily
removed from hair by shampooing
Hydrophilic enough to compatible
hydrocation propellants
81
Polymers (con.)




Should give powerful hold without
brittleness
Easily remove by combing or brushing
Must be good adhesion and not sticky
For example :
Vinyl pyrrolidone derivative
 Vinyl acetate
etc.

82
Solvent

Non-aerosol product

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
Ethanol alone or slightly dilute with water
Excellent solvent for most resins
The addition of water to solvent system
may be necessary:




To improve water solubility of ingredients
To retard evaporation salt
To reduce cause
To prevent perception from on acid-resin based
system
83
Plasticizers

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

Using to modify the properties of polymer flim
Making it more flexible
Only small quantities are normally required
(0.5% of dry weight polymer)
For examples:





Ester
Various silicone
Protein
Polyol
Lanolin derivatives
84
Neutralizer
Calculated from the acid value of
the resin
 Can be obtained from polymer

85
Hair Gels


Majority of gels on the market are aqueous/
aqueous alcoholic
Carboxyvinyl polymer are the most
important/ carbomer 940
•
•
•
•
Create the clear gel foam
Have some fixative power
Contribute to overall hold of the formulation
As a primative film former
86
Hair gels (con.)

Carbomer 940 gives the clearest gel
• Degrades by UV light: loss of viscosity
and clarity
• Overcome by adding UV absorber
• Sensitive with metal ion => catalyst gel to
be degrade
• Addition of EDTA is an effective way
87
Permanent Waving
Mode of action is as follows:



Reduction of –S-S- bonds between cystine
amino acid groping on an adjacent
polypeptides chains
Reassignments of hair into its new position
Reforming of the –S-S- bonds by oxidation
the various –SH residues will be linked into
new partners on the adjacent chains
88
Factor affecting the efficacy of
the product


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Processing time
Processing temperature
Concentration of reducing agent
Ratio of lotion to hair quantities
Penetration of the lotion
pH
The nature and the condition of untreated
hair
89
Permanent waving





Waving lotion are available in various physical
foams
Clear, cloudy liquid, cream or lotion, gel or
thickened liquid
Using low conductivity, demineralised water
Using equipment made of 316 grade stainless steel
or prolypropylene for all contact parts
Avoiding heavy metal contamination which may
be decompose the products and produce
discoloration
90
Permantent waving (con.)


The addtion of sequestrans is needed
Emulsion type or gel-type product:
• Required hot processing
• Thioglycollate should be added last after
cooling the mix
91
Permantent waving (con.)

The products can be extreme:
• The products is at high pH and strong reducing
• The sulfphide odour emitted during processing
of the hair are very hard to mask
92
Neutralisation




The reforming of the –S-S- bonds by oxidation
Oxidation is commonly carried out by hydrogen
peroxide (easier using than the other oxidizing
agent)
With a surfactant added to enhance penetration
The solution may be clouded or produced in form
of a pourable emulsion
93
Neutralisation (con.)




Bromated, the second most popular type of
neutralizer
Since both waving lotion and neutralizers
Usually have guite extreme pHs and exhibit
considerable redox potential
They are not particularly susceptible
microbiological contamination
94
Effect of Air and Sunlight
95
Hair dyes

Temporary, semi-permanent,
permanent dyes
Temporary dyes
 Any soluble colors can be used
 The color does not penetrate to the hair
shaft
 Complete removable by a single shampoo
96
Hair dyes (con.)

Another mean is by using color spray
organic and inorganic pigments can be
suspended in gum-thickened or
emulsion base
97
Semi-permanent dyes




Using dyestuffs whose cationic
characteristic gives them a natural affinity
of hair
Metallised dyes are not very compatible
with salt
The blend of amphoteric, cationic, non-ionic
surfactants with low salt levels is preferred
Performance may be enhanced by the
inclusion of solvents
98
Semi-permanent dyes (con.)


Water causes considerable swelling of the
hair shaft
Aqueous solution with some solvents cause
even more
leading is greatly increasd dye uptake
 Hair has more pores near the end than the root
 Treated hair has more porous than untreated hair
99
Permanent hair dyes


Permanent or oxidation dyes
Consist of two parts
- A dye intermediate solution and
oxidizing agent
- The latter always being
hydrogenperoxide
Dye intermediates are blended of primary
intermediates and coupling agents or modifiers
in a suitable base
100
Permanent hair dyes (con.)



During the permanent dying of hair, the dye
intermediate solution and oxidizing solution
are mixed and applied to the hair
The primary intermediate are gradually
oxidized
Then undergo coupling reaction with
modifier
101
Permanent hair dyes (con.)




The primary intermediate are all small
molecules can penetrate the hair shaft,
particularly the wet, alkali conditions
during the hair application
The oxidation and coupling reactions
produce much larger molecules
Many of which are then “trapped” in the
hair shaft
Thereby making the effect permanent
102
Some general remarks about
product development:
1. Make sure that the discussion is clear,
the brief should include, as minimum :
• Require performance parameters
in as much detail as possible
103
General remarks (con.)
*
*
*
*
Benchmark product, unless the
development is in a completely
new area
Guidelines on costs
Purpose claims
The required timing
104
General remarks (con.)
1. Do not produce a Rolls Royce when a mini
would be sufficient
2. Do not use new raw materials if one from
existing stocks will do
3. Specification often appear virtually
identical alternative sources of supplier
should be investigated
105
General remarks (con.)
4. Ensure reproducibility on scale up making
use of suitable plant and equipment
5. Keep formulations as simple as possible
6. Try to develop products which can be made
as cheap as possible:
• with minimum energy requirement
• minimum time for processing
106
107