Sie sind auf Seite 1von 42

75

Shampoo and
Conditioner Science
Robert Y. Lochhead
University of Southern Mississippi
Shampoos and conditioners are the highest volume of products
sold in personal care. In this chapter, we will consider the science
that underpins the functioning of these product types. Te principal
function of shampoos is to cleanse the hair. However, since the
introduction of two-in-one shampoos in the 1970s, it has not
been sufcient for a shampoo to merely cleanse the hair. Modern
shampoos should at least cleanse, condition, make the hair easier
to style, and fragrance the hair with a pleasant, lingering smell.
Modern conditioners should lower the friction between hair fbers to
allow easier grooming and alignment of the hair fbers while leaving
them glossy and avoiding lankness.
Te science of shampoos and conditioners is still evolving and
in addition to describing fundamentals, this chapter attempts
to take the reader to the frontiers of research in shampoo and
conditioner science.
Introduction
Located within the hair follicle is a sebaceous gland that
continuously excretes an oily material, known as sebum, onto
the hair and scalp. Tis substance consists of compounds such as
fatty acids, hydrocarbons, and triglycerides, and serves as natures
conditioning treatmentproviding lubrication and surface
Practical Modern Hair Science
www.Alluredbooks.com CHAPTER 3
Shampoo and Conditioner Science
76
hydrophobicity, while potentially replenishing components of
the cell membrane complex. However, afer a day or so, buildup
of this substance begins to result in a greasy look and feel.
Moreover, particulate dust and dirt adhere readily to this sebum
layer. In modern cultures such sebum-soiled hair is deemed to
be undesirable, and therefore, it should be removed on a regular
basis by a facile process. Tis process is, of course, shampooing.
Sebum cannot be removed by water because oil and water do not
mix. Aqueous shampoos can remove oily soil from the hair surface
because shampoos contain surface-active agents, commonly
abbreviated as surfactants. Te molecules of these surface-active
agents self-assemble into micelles, which are the agents that
solubilize oily soils.
To understand how surfactants work, it is necessary to consider
the exact process that leads to oil and water being incompatible.
Tere are two diferent possibilities for substances to be insoluble
in water. In one case, substances have stronger intermolecular
cohesion than water. Tis is why substances like sand, clay, and
glass are insoluble in water; the molecules of sand attract each
other more strongly than the molecules of water and this attraction
leads to the sand being insoluble. Tis reason for the insolubility is
exactly opposite to the reasons for the insolubility of hydrophobic
substances such as oils. Te intermolecular forces between the oil
molecules are weaker than the intermolecular bonds between water
molecules and the oils are expelled from water. Tis expulsion arises
largely from entropy and the efect has been coined hydrophobic
interaction.
1,2
From the time of the Phoenicians, it has been known
that oil spreads to calm troubled waters. Tis efect arises from the
fact that the spread oil has a lower surface tension than the water. At
this point it is appropriate to consider the efect known as surface
tension. Molecules in the bulk of liquids are attracted on all sides
by their neighboring molecules. However, molecules at the surface
are subjected to imbalanced forces because they are attracted by the
underlying liquid molecules, but there is essentially no interaction
with the vapor/gas molecules on the other side of the liquid/vapor
Chapter 3
77
boundary. Tis imbalance leads to a two-dimensional force at the
surface, namely surface tension. Te surface tension is numerically
equal to the surface free energy.
3
Te magnitude of surface tension
directly correlates with the strength of the intermolecular forces.
Water has hydrogen bonds, dipole-dipole interaction, and dispersion
forces between its molecules, and as a consequence the surface
tension of water is rather high72 mN/meter at room temperature.
On the other hand, only dispersion forces are present between the
molecules of alkanes. As a consequence, the surface tension of
alkanes is relatively lowranging 2030 mN/meter.
Surfactants comprise molecules that contain two parts: a
hydrophobic segment that is expelled by water and a hydrophilic
segment that interacts strongly with water. Such molecules are said
to be amphipathic (amphi meaning dual and pathic from the
same root as pathos which can be interpreted as sufering). Tus,
a surfactant molecule sufers both oil and water. Tis dual nature
confers interesting properties on surfactants in aqueous solution.
At very low concentrations, the surfactant is expelled to the surface,
a process called adsorption. Tis adsorption causes the surfactant
concentration at the surface to be much higher than the surfactant
concentration in the bulk of the solution. At extremely low
concentrations, when the surfactant molecules on the surface are
located too far apart to efectively interact with each other, Traubes
Rule applies. Traubes Rule states that the ratio of the surface
concentration to the bulk concentration increases threefold for each
CH
2
group of an alkyl chain.
4
Tis ratio is called the surface excess
concentration.
5
According to this rule, soap with a dodecyl chain
should have a surface excess concentration that is more than a half-
million times its concentration in the bulk solution. At extremely
low concentrations, the surfactant molecules on the surface act as a
two-dimensional gas. As the concentration increases, the surfactant
molecules begin to interact, but they are still mobile within the
plane; they behave as two-dimensional liquids. At even higher
concentrations, as the surfactant saturates the surface, the chains
orient out of the surface plane and the chain-chain interactions
Shampoo and Conditioner Science
78
cause the surfactant to behave as a two-dimensional solid. Irving
Langmuir was awarded the 1932 Nobel Prize in Chemistry for
measuring this efect and explaining it on a molecular basis.
6

When a surfactant adsorbs to saturate an aqueous surface, the
surface is largely composed of the surfactants hydrophobic groups;
this means that the surface essentially has low surface energy. As a
consequence of the low surface energy, the surface area is easier to
expand to a flm. Tis means that the system is easier to foam, since
aqueous foams really consist of water flms with entrapped gas. If
the foam surface is structured by the adsorbed surfactant, then foam
stability can be achieved.
7

Surfactant Micelles
Relatively large aggregates form within solution just beyond
the concentration at which the surface becomes saturated with
surfactant.
8
Tese aggregates are surfactant micelles in which
the hydrophobes are segregated within the core of the aggregate
and the hydrophilic groups are located on the surface where they
interact strongly with water.
9
For a given system, micelles initially
form at the precise concentration at which the driving force for
surface adsorption becomes equal to the driving force for aggregate
formation. Tis driving force is the chemical potential of the
surfactant species. Te lowest concentration at which micelles form
is named the critical micelle concentration (CMC). Te aggregates are
large; for example, micelles of sodium dodecyl sulfate at the CMC
contain about 100 molecules and the thickness of the head group
layer is about 0.4 nm.
10

Surfactant micelles have liquid centers. Tey efectively solubilize
hydrophobic substances only when the temperature of the system is
above the Kraf point. Kraf found this phenomenon in 1895, and
68 years later Shinoda explained that the Kraf point corresponds to
the melting point of the hydrated solid surfactant.
11

Micelles have diferent shapes. Te simplest shape is the
spherical micelle that was postulated by Hartley in 1936. Te
shape of a micelle can be explained on the basis of the principle
Chapter 3
79
of opposing forces (see Figure 1). Two or three amphipathic
molecules alone cannot form a stable micelle because micellization
is essentially a cooperative process that requires the participation
of many amphipathic molecules bound together by hydrophobic
interaction. However, if hydrophobic interaction accounted solely
for the formation of micelles, then the association would continue
until phase separation occurred, as in oil separating from water.
Terefore, there must be a force that opposes the hydrophobic
association and controls the size of the micelles. Tis force is the
repulsion between the head groups that could arise from ion-ion
repulsion and/or hydration of the head groups.
12
Teoretically,
the repulsive surface terms are difcult to handle from a
thermodynamic perspective but the presence of micelles has been
validated experimentally.
If micelle structure was determined solely by thermodynamics,
spherical micelles would always be favored over other shapes.
However, real micelles are not restricted to a spherical shape;
spherical structures account for only a small minority of micelles.
Te shapes of surfactant molecules and the way they can be packed
Figure 1. The shape of a surfactant micelle is determined by
the balance between the mutual repulsion between hydrophilic
groups at the micelle surface and the cohesion due to hydrophobic
interaction. This has been dubbed the principle of opposing forces.
Shampoo and Conditioner Science
80
also plays an important role in determining micelle shape. Although
thermodynamics and packing geometries are inextricably linked,
by considering the limits of possible packing arrangements we can
obtain insight into the shapes of micelles and the transformation
from one shape to another as physical and chemical conditions
are changed. In this context, the many shapes of micelles, arising
from the principle of opposing forces, can be appreciated by
considering Packing Factor Teory (Figure 2).
13
First, consider a
spherical micelle. In this instance the micelle radius, R, the volume
of the hydrophobic core, v, and the surface area of the amphipathic
molecule at the hydrophobe/water interface, a, are related by:

Eq. 1
Te radius of a micelle, R, cannot exceed the fully extended
length, l, of the hydrophobe chain of the surfactant molecule. Tis
gives the critical condition for the formation of spherical micelles:
Eq. 2
Figure 2. The packing factor of a surfactant molecule is the volume of
the tail group divided by the volume of the cylinder subtended by the
head group to the length of the tail group.
Chapter 3
81
Te fraction, v/al, is known as the packing factor (Figure 3).
When the packing factor has a value of 1/3, the surfactant molecule
can be approximated by a conical shape and the molecules pack into
a sphere (Figure 4).
When the packing factor has a value of , the micelles become
cylinders (Figure 5), and when the packing factor has a value of
1, the surfactant molecules pack as planar bilayers in a so-called
lamellar structure (Figure 6).
For ionic surfactants, the area per head group can be decreased
by adding soluble salt to the solution to lessen the ionic repulsion
between the head groups. (Salt also enhances the hydrophobic
interaction.
14
) Increase in salt and/or surfactant concentration causes
spherical micelles to transition to rods and then to long worm-like
micelles.
15
Te wormlike micelles behave like polymers in solution.
16

Figure 3. Surfactant molecules with a packing factor of 1/3 have a
shape that can be approximated by a cone.
Figure 4. These conical molecules pack naturally into a sphere.
Shampoo and Conditioner Science
82
Tese micelles also form branched as well as linear structures, and
above a certain concentration (the critical overlap concentration, C*)
they entangle just like polymer molecules
17
and display viscoelastic
rheology.
18-20
Tis behavior is depicted in Figure 7 as it was
explained by Candau in 1993.
21
An increase in salt concentration
causes spherical or elliptical micelles to transition into rods, then
to worms then to branched worms. As the surfactant concentration
increases, the micelles form entangled networks. Consumers desire
Figure 5. Surfactant molecules with a packing factor
of pack naturally into cylinders.
Figure 6. Surfactant molecules with a packing factor of 1 pack
naturally into bilayer planes.
Chapter 3
83
thicker shampoos, in part because they are easier to apply, but
also for aesthetic reasons; a thicker formula is generally perceived
as being more-luxurious. Te desired rheology is achieved from
formulations that contain worm-like micelles.
Wormlike micelles do, however, show non-polymeric behavior
at certain shear rates when the shear stress becomes independent of
the shear rate and the relaxation time becomes monodisperse.
22
Tis
behavior has been explained on the basis that the entanglements
can be broken and reformed as the rod-like micelles disassemble
and then reassemble upon passing through each other.
23-24
Systems
like these have been dubbed phantom networks by Cates to
signify that one micelle fows through another just as we imagine a
phantom would pass through a wall. Te phantom network behavior
may explain why shampoos can show viscoelasticity without the
stringiness observed in entangled polymer solutions.
At higher concentrations, the rod-like micelles mutually repel,
and this favors alignment into a nematic phase. At still higher
concentrations the aligned rods pack in a hexagonal array to form
hexagonal phase liquid crystals (Figure 8). Te hexagonal phase
has the properties of a clear ringing gel that is birefringent in
polarized light.
Figure 7. Ionic surfactant micelles change shape as a function of ionic
strength and surfactant concentration.
Shampoo and Conditioner Science
84
As the surfactant concentration is increased further and/or
dissolved salt concentration is increased, the surface of the micelles
becomes less curved until the large planar aggregates of the lamellar
phase are formed (Figure 9). Modern shampoos consist essentially
of entangled worm-like micelles and conditioners are usually in the
form of the lamellar phase.
In summary, shampoo and conditioner formulation essentially
involves the preparation of surfactant mixtures that possess the
Figure 8. Rod-like micelles can pack into hexagonal liquid crystal phase.
Figure 9. Increase in surfactant concentration causes micelles to transition from
spheres to rods to hexagonal phase to lamellar phase to inverse hexagonal
phase to inverse micelles.
Chapter 3
85
aforementioned structures, while also being esthetically pleasing.
Te hair care formulation scientist has an ever-increasing variety
of surfactants available in the formulation toolbox, and so these
structures can be obtained via a wide range of concoctions.
Nonetheless, attaining such stable structures is not a trivial task,
due to the presence and interactions of so many ingredients in
the typical formulation. Terefore, with historical knowledge
involving many established ingredients already being relatively
well-understood, it is a brave formulation chemist that opts to cut a
new pathway. Moreover, it is also probably prudent to arrive at these
structures in the most cost-efective manner. For these reasons, it
is imperative to understand how the surfactant structure, together
with interactions with other molecules alters the nature of the
aggregate structures.
Oily Soil Removal Mechanisms
Te principal function of a shampoo is to remove oily soil from
the hair. Tere are several principal detergency mechanisms for
removing oily soils: roll-up,
25
emulsifcation, penetration, and
solubilization.
In the roll-up mechanism, the detergent solution causes a steady
increase in the contact angle of the oil at the oil/fber/aqueous
interface (Figure 10).
Te oil droplet is rolled up on the surface, and when the contact
angle reaches 180

degrees, the interfacial force that is holding it to
the surface is overcome by the wetting tension of the oil and aqueous
solutions on the fber surface. Roll-up is favored by fbers that are
Figure 10. In this mechanism the oil contact angle at the oil/water/ber interface
steadily increases until it rolls up and oats off of the solid surface. This
mechanism was rst reported by N. K. Adams.
Shampoo and Conditioner Science
86
oleophobic and hydrophilic.
26
Te removal of oily soil by detergent
compositions is not necessarily predictable due to the wide variation
of the surface properties of hair that arise from prior treatments
and weathering. Moreover, the transport of the detergent solution
to the fber surface can occur by three diferent routes: (i) along the
fber surface, (ii) through a previously applied permeable surface
treatment, or (iii) through the body of the fbers (Figure 11).
Roll-up of oily drops on fbers occurs when the contact angle
exceeds a critical value and this causes the oily drop to adopt an
unstable axially asymmetric attachment on one side of the fber.
27

Te rate of roll up depends also on the viscosity of the oily soil,
and mechanical action is ofen necessary to dislodge viscous oily
soils from the fber surface. In some cases, the oil forms a viscous
emulsion when contacted by the detergent composition, and the
resulting viscous soil can be difcult to remove from the fber.
Perfect hair is covered by a covalently attached monolayer of
18-methyleicanosoic acid (18-MEA), which confers hydrophobicity
on the hair. Modern grooming techniques and weathering removes
this layer of 18-MEA.
28
Removal of the layer of 18-MEA results
in hair becoming macroscopically hydrophilic.
29
Te roll-up
mechanism, therefore, should be expected to become more
prominent on damaged rather than pristine hair.
Initially if the fber is completely coated in oil, or if the fber itself
is hydrophobic, the detersive solution cannot easily reach the oil/fber
interface, and the soil will be removed by emulsifcation (Figure 12).
Figure 11. In the roll-up mechanism, the detergent solution can be transported
to the ber/oil interface along the ber surface, through a permeable coating
on the ber, or through the ber itself.
Chapter 3
87
Emulsifcation is favored by low oil/water interfacial tension that
allows the oil surface to be expanded into an emulsion droplet.
30

In the penetration mechanism of oily soil removal, surfactant-
rich phases penetrate the oil at the interface. Tis results in an
interfacial liquid crystalline phase that swells and is broken of
to reveal a fresh soil interface, and then the process is repeated
again and again.
31
Te penetration mechanism occurs with polar
soils and/or phase separated coacervates of nonionic surfactants
above the lower critical solution temperature (LCST). Spontaneous
emulsifcation, in the absence of detersive surfactant, has been
observed for non-polar-polar soil mixtures like sebum.
32
Te
penetration mechanism can occur with anionic surfactants that
form coacervate phases in the presence of calcium salts.
33

Solubilization is the process of incorporating a water-insoluble
hydrophobic substance in the internal hydrophobic core of micelles.
Direct solubilization can occur in the presence of an excess of
surfactant micelles with respect to oily soil.
34
Te rate of exchange
of surfactant molecules between micelles is important because the
micelles must re-assemble around the soil to solubilize the soil by
encompassing it inside the micelle.
Foam/Lather
One essential attribute of a shampoo is its ability to produce
a rich lather or foam. Te important elements of a foam are
the lamellae and the Plateau border. Te micrograph in Figure
13 depicts these structural features of a foam. Te lamellae are
stabilized by surfactants adsorbed at the air-water interface.
Figure 12. Emulsication can remove the soil if the interfacial tension between the
oily soil and the surfactant solution is low.
Shampoo and Conditioner Science
88
Foams lose stability by two main mechanisms: draining of the
liquid and puncture of the lamellae. Te foam lamellae are the
junctions between two foam bubble cells and the plateau border is
situated at the triple-cell junction. Te Laplace pressure in the liquid
components of the foam is inversely proportional to the curvature
of the interface. Te higher curvature of the plateau border results
in a lower pressure in that region and this causes the liquid in the
foam to drain preferentially from the lamellae to the plateau borders.
Based upon this reasoning, it can be understood that drainage can
be hindered in two ways, namely by blockage of the lamellae or by
blockage at the plateau border. About two decades ago, Des Goddard
carefully measured the drainage from foam flms and deduced
that polyquaternium-24 adsorbed across the lamellar interface and
hindered the drainage of liquid from the foam. In addition, about
thirty years ago, Stig Friberg concluded that certain liquid crystals
blocked the plateau border region and delayed foam drainage and
conferred longer-term stability on surfactant foams. In the case of
cationic polymers, hindered drainage of the lamellar liquid could be
caused by adsorption of the cationic entities at the lamellar surface
with the nonionic and/or anionic blocks in the lamellar liquid.
Figure 13. Micrograph showing surfactant foam structure.
Chapter 3
89
Alternatively, formation of phase-separated coacervates between the
cationic polymer and the anionic surfactant could result in blockage
of the plateau border. Of course, if the interaction of the cationic
polymer was strong enough to form inverse micellar structures,
then there would be a possibility that the phase-separated particles
could cause a local reversal of the curvature in the lamellae and this
in turn would result in breakage of the lamellar flm and subsequent
foam destabilization. Tis type of foam destabilization mechanism
has been extensively reported by Peter Garrett.
Solid Foams
Cationic conditioners
that would normally be
incompatible with liquid
shampoos can be delivered
from solid foams. Solid
foams also make it possible
to have one scent for the
solid and then to allow
a diferent fragrance to
bloom when the solid is
wetted by water.
35
Te
porous solids are made by
mixing the surfactants,
glycerin as a plasticizer,
and water in the presence
of a water-soluble polymer.
Figure 14 shows a solid
foam in which poly(vinyl
alcohol) is the water-soluble
polymer. Afer a heating
and mixing cycle, the
porous solid is formed by
aeration.
Figure 14. Micrograph showing solid foam structure
(reproduced from US Patent Application 20110195098).
Shampoo and Conditioner Science
90
The Anatomy of a Shampoo Formulation
Shampoos consist essentially of water, a primary surfactant,
one or more co-surfactants, and soluble salt. Other ingredients
are added for fragrance, preservation, conditioning, and styling
attributes. Cleaning is achieved mainly by the primary surfactant,
which is ofen an anionic surfactant that would adopt a conical
shape if it was present in water alone. Te co-surfactant is usually
a nonionic or zwitterionic surfactant with a relatively small head
group surface area. Tis molecular shape allows the co-surfactant
to serve two roles: (i) it packs between the molecules of the primary
surfactant to reduce the curvature and to promote the formation
of worm-like micelles with their high viscosity and luxurious
rheology; and (ii) it packs between the primary surfactant in the
lamellae of the foam to provide good lather that is easily removed
by rinsing. Salt enhances the function of the co-surfactant by
damping down the ionic repulsion between primary surfactant
head groups and promoting the formation of wormlike micelles. If
excess salt or co-surfactant is added, shampoo compositions can
separate into phases that contain co-existing micelles and liquid
crystals. Tese phase-separated compositions ofen exhibit thin
viscosities and haziness.
The Primary Surfactant
Te lauryl sulfates have been the primary surfactant workhorses
of the shampoo industry for decades. Te sulfate head groups bear
an anionic charge when dissolved in water. Te long chain alkyl
tail group has an average length of 12 carbon atoms. It is important
to understand that this is an average chain length; commercial
lauryl sulfates have a distribution of chain length from as short as
8 carbons to as long as 18 carbons. Tis chain length distribution
changes from supplier to supplier and it also changes depending
on the source of raw materials. Formulators should be aware that
changes in the chain length distribution of the surfactants can lead
to subtle changes in the properties of the shampoo.
Chapter 3
91
During the 1970s, triethanolamine lauryl sulfate was preferred
as a primary surfactant due to its excellent cleaning properties and
luxurious fash foaming capability. However, it was replaced by
laureth sulfates for two reasons: the concern over the formation of
nitrosamines from secondary amine components and the reduced
eye irritation exhibited by the laureth sulfates.
Over the last two decades, the primary surfactants of most
shampoos have been sodium laureth sulfate, ammonium lauryl
sulfate, and sodium lauryl sulfate.
Te co-surfactantofen called the foam boosterhas most
prominently been selected from two types of materials: alkylamide
MEA and alkylamidobetaines. Modern shampoos contain primarily
betaines as co-surfactants.
Enhancing Mildness
Isethionates are surfactants noted for their mildness to skin,
and for at least three decades, they have been the basis of non-soap
detergent bars such as Dove (Unilever). Tey have been making
inroads into shampoos based upon mildness claims. Moreover,
Unilever researchers discovered that the mildness can be enhanced
even further by including mildness beneft agents that can be
focculated by cationic polymers present in the formulation and
delivered as focs upon dilution of the formulation.
36
Te preferred
beneft agent in this case is petrolatum; the cationic polymers
are well known polymers like polyquaternium-10 and guar
hydroxypropyltrimonium chloride. Tis could form the basis of
shampoos that are mild to the skin.
Certain non-cross-linked linear acrylic copolymers can lower
the irritation potential of surfactants and provide products that are
clear and highly foaming.
37
Te preferred polymers interact with the
surfactant and efectively shifing the CMC to higher concentrations,
while lowering the critical aggregation concentrationthe latter
being the concentration at which the surfactant selectively interacts
with the polymer rather than adsorbing at the liquid surface
(Figure 15). It is postulated that free surfactant molecules and
Shampoo and Conditioner Science
92
free surfactant micelles are responsible for irritation of skin and
eyes and that binding of the surfactant to the polymer efectively
reduces the concentration of free micelles. A measure of mildness
is the delta CMC, which is defned as the diference between the
CMC of the surfactant alone and the higher CMC of the surfactant
in the presence of the polymer. Larger values of delta CMC for a
particular surfactant are apparently correlated with lowering of the
irritation potential. Te delta CMC provides a measure that is useful
for selecting, comparing, and optimizing polymers that reduce the
irritation potential of selected surfactant systems. Carbomer and
acrylates copolymer have been identifed as polymers that exhibit a
satisfactory delta CMC.
Conditioning Shampoos
Todays conditioning shampoos are expected to confer wet-hair
attributes of hair sofness and ease of wet-combing, and the dry hair
attributes of good cleansing efcacy, long-lasting moisturized feel,
and manageability with no greasy feel.
Te origin of conditioning shampoos can be traced to the
balsam shampoos of the 1960s followed by the introduction of
polyquaternium-10 by Des Goddard
38,39
in the 1970s and 1980s in
which he introduced the concept of polymer-surfactant complex
coacervates that phase-separate and deposit on the hair during
Figure 15. Plot of surface tension vs. surfactant concentration for
surfactant alone and for surfactant in the presence of polymer. The
difference in the CMC induced by the presence of the polymer is
claimed to be related to the effect of the polymer in enhancing the
mildness of a shampoo.
Chapter 3
93
rinsing. Te frst two-in-one shampoos depended on a complex
coacervate being formed between anionic surfactant and the
cationic hydroxyethylcellulose, polyquaternium-10. Tis complex
was solubilized in excess surfactant and it phase-separated as a
coacervate liquid phase upon dilution during the rinsing cycle.
Later guarhydroxypropyltrimonium chloride was introduced as
an alternative cationic polymer that worked on the same principle
as polyquaternium-10. Tese two polymer types continue to
dominate the compositions of conditioning shampoos.
40
Guar is a
galactomannan and it is interesting that, in recent years, recently
a new cationic galactomannan hydrocolloid, cationic cassia,
has been claimed to confer conditioning shampoo benefts.
41,42

Polygalactomannans consist of a polymannan backbone with
galactose side groups. In guar gum, there is a pendant galactose
side group for every two mannan backbone units. Tese galactose
groups sterically hinder the substitutable C-6 hydroxyl unit,
limiting the extent of possible cationic substitution on guar gum.
In cassia, however, there is less steric hindrance of the C-6 hydroxyl
group and, consequently, higher degrees of cationic substitution
are possible with cassia (60% for cassia relative to 30% for guar).
Cationic cassia can be used as a conditioning polymer in shampoos
and conditioners to impart cleansing, wet-detangling, dry-
detangling, and manageability.
Te mechanism of conditioning shampoos depends upon the
formation of polymer/surfactant coacervates that phase-separate
during rinsing (Figure 16). Polyions in aqueous solution are
surrounded by an electrical double-layer of counterions, and the
location of the counterions with respect to the polyion is determined
by a balance between chemical potential and electrochemical
potential, called the Donnan Equilibrium. Surfactant ions contain a
large hydrophobic group that makes them intrinsically less soluble
in water than inorganic ions such as chloride or bromide. When
surfactant ions interact with an oppositely charged polyion, they
bind strongly and displace the water-soluble inorganic ions from
the polyion; that is, they ion-exchange. Once the surfactant ions
Shampoo and Conditioner Science
94
bind, hydrophobic interaction between the hydrophobic surfactant
tails causes the polymer-surfactant complex to phase separate at
concentrations below the surfactant critical micelle concentration.
Above the CMC, the surfactant concentration is sufciently high
to form micelles or hemi-micelles along the polyion chain, and the
polyion/surfactant complex is solubilized. Conditioning shampoos
are formulated within the range of surfactant concentrations that
correspond to this solubilized regime. When these shampoos are
diluted to a concentration that is in the vicinity of the CMC, then the
complex coacervate phase-separates. Te separated phase is deposited
on the hair during rinsing, and it can co-deposit other additives such
as silicone conditioning agents or anti-dandruf agents. Maximum
coacervate deposition occurs at precise ratios of cationic polymer to
anionic surfactant, but the optimum ratio for coacervation might not
coincide with the best ratios for cleaning and foaming.
Cationic guar has been a known additive for 2-in-1 shampoos
for more than three decades. However, it has now been shown that
improved post-shampoo detangling times are achieved by including
a small degree of hydrophobic substitution in the cationic guar
derivatives.
43

Figure 16. A schematic phase diagram that explains the mechanism of coacervate
formation in 2-in-1 shampoos.
Chapter 3
95
Synthetic copolymers of acrylamide and a Triquat monomer are
postulated to provide improved deposition on hair and improved
conditioning performance with respect to wet combing.
44

Silicones have become standard ingredients in many conditioning
shampoos for the smooth, silky hair feel that they confer. Silicones
were introduced to shampoos as 2-in-1 conditioning agents in
the 1980s. Te introduction of silicones needed to overcome two
substantial defciencies: (i) silicones are well known defoamers, and
(ii) silicones are incompatible with typical shampoo compositions
and they tend to separate due to their low specifc gravity. Initial
attempts to stably suspend the silicone included the use of water
miscible saccharides such as corn syrup.
45
Later products comprised
xanthan gum in the shampoo as a suspending agent and acceptable
foaming attributes were conferred on the shampoos by formulating
with relatively high levels of alkyl sulfates as the primary surfactant,
cocamide MEA as the co-surfactant, and ethylene glycol distearate
as a surfactant structuring agent.
46
In the actual application, there
is a technical contradiction involved in the deposition of silicone
conditioning components from a detersive, cleansing system;
the detersive system is designed to remove oil, grease, dirt, and
particulate material from the hair, and the conditioning agent
has to be deposited on that same hair in one process. As a result,
large excess amounts of silicone are used to ensure deposition,
and one consequence of this is that large amounts of the expensive
conditioning silicone can be rinsed away rather than deposited on
the hair. Cationic polymer/anionic surfactant coacervates enhance
the deposition of silicones on hair and, consequently, increase the
efciency of conditioning shampoos.
47,48

Volatile cyclic siloxanes confer the desired silky initial feel, but
these materials are difcult to formulate in consistent homogenous
formulations, Tey tend to spread uncontrollably over the hair and
skin.
49
Tis efect can be controlled with polymeric silicone gels
formed in volatile silicones to provide both the initial silky feel and a
high viscosity and smooth feel when dry.
50
Branched molecules with
a silicone core and hydrocarbon branches, or networks formed from
Shampoo and Conditioner Science
96
these branched units, have been disclosed as suitable for improving
sensory feel, while minimizing phase separation and conferring
good shampoo removability.
51

Shampoos containing more than one cationic conditioning
polymer and a quaternary silicone give more uniform deposition on
hair than standard shampoos based on polyquaternium-10 as the
sole conditioning polymer. Tus, a conditioning polymer cocktail
comprising poly(acrylamide-co-acrylamidopropyltrimonium)
chloride, guar hydroxypropyltrimonium chloride, and silicone
quaternium-13 give uniform deposition on hair. In this instance, the
claims are based upon multiple testing and analysis:
52

A multiple attribute consumer assessment study that measured
the attributes of cleanliness, wet-comb, dry-comb, hair sofness,
lather amount, and creaminess.
Secondary Ion Mass spectrometry to detect silicon on the hair
surface. Tis method revealed that a standard commercial
shampoo concentrated silicone on the cuticle edges of the hair,
whereas the patent application shampoo distributed silicone
more evenly.
X-ray photoelectron spectroscopy (XPS) to measure the thickness
of the silicone polymer layer on hair from Si:C:O ratios. Tis
method revealed that the commercial shampoo deposited
a signifcant amount of silicone, and the patent application
shampoo deposited only one or two molecular layers.
Instron ring compression as a measure of combability.
Complex coacervates can also be formed from mixtures of
cationic and anionic polymers. Tis could be the underlying
mechanism in shampoos that include an anionic and cationic
polymer that provide sleekness and gloss.
53

Two drawbacks of silicones are that they ofen destabilize foam
and the fnal compositions are hazy due to light scattered from
the suspended silicone droplets. Initially, silicone copolyols were
introduced to overcome the insolubility of silicones in shampoo
compositions, but this drastically reduced the amount of silicone
Chapter 3
97
deposited onto hair and compromised conditioning performance.
Clear, silicone-containing conditioning shampoos have been
formulated by adding trideceth-2 carboxamide MEA to reduce the
silicone droplet size.
54
Transparent conditioning shampoos can be
formulated by incorporating the silicone as microemulsifed droplets,
but the small microemulsion droplets tend to be rinsed away rather
than deposited during the shampooing process. Moreover, coalescence
of the droplets can lead to loss of transparency in the product during
storage. Attempts have been made to overcome these challenges by
including silicone emulsions with high internal viscosities, typically
greater than 100,000 centistokes, but the high internal phase viscosity
gives deposited silicone that is can be difcult to remove and this
causes buildup with each consecutive shampooing. Such buildup
usually reduces the volume of the desired hair style and causes
droop and fatness. Fortunately, shampoo compositions providing
superior conditioning to hair while also providing excellent storage
stability and optionally high optical transparency or translucency can
be obtained by combining low viscosity microemulsifed silicone oil
with cationic cellulose polymers and cationic guar polymers having
molecular weights of at least about 800,000 and charge densities
of at least about 0.1 meq/g.
55
Conditioning shampoo formulations
that include a silicone microemulsion in a conditioning shampoo
containing guar hydroxypropyltrimonium chloride and an anionic
detersive surfactant have also been reported to be clear.
56,57
If pre-
gelatinized starch, such as hydroxypropyl distarch phosphate, is
included with polyquaternium-10, transparent conditioning shampoos
can be obtained.
58

Another way to minimize buildup is to treat the hair with water-
in-water emulsions that can be prepared by including cationic
polymers with soluble salts in surfactant compositions.
59
Tese water-
in-water emulsions provide conditioning benefts with good spread
of the conditioning phase on the hair and less chance of buildup.
Te living free radical polymerization techniques that have
emerged in the last decade ofer the prospect of preparing precise
polymers with unprecedented accuracy in molecular structure and
Shampoo and Conditioner Science
98
variety of chemical types.
60
Tis technique has enabled synthesis of
a wide diversity of block and graf polymers that were previously
unattainable. Such polymers ofer the prospect of conferring
conficting properties within one molecule, which in turn can lead
to improved compatibilities in the same system while maintaining
stability. Tese conficting properties could possibly be achieved
by blending diferent polymers, but diferent polymers do not mix
readily at the molecular level and phase separation may result.
61

Block, graf, and gradient copolymers serve to compatibilize such
compositions and gradient polymers have been proposed for this
purpose. Block copolymers comprising polycationic blocks and
nonionic blocks for surface deposition
62
and for improved foam
retention
63
have been claimed, which are desired to deposit on
hair in order to modify the chemical properties of the surface
for protection or compatibility; to modify hairs hydrophobic or
hydrophilic surface properties; or to modify feel or mechanical
properties of the substrate from two-in-one products. Te polymers
disclosed are block copolymers of polyTMAEAMS (methylsulfate
[2-(acryloyloxy)ethyl]-trimethylammonium) g/mole) and
polyacrylamide.
Conditioning shampoos can also be formulated to function
by mechanisms other than cationic polymer-induced complex
coacervation, such as:
Conditioning can be achieved by including chain extended
silicones in an anionic surfactant-based shampoo. Specifc
examples of useful silicones include silicone emulsions
containing divinyldimethicone/dimethicone copolymer.
64

Shampoos containing polyalkylene oxide alkyl ether particles
give larger coacervate cohesive focs (20500 microns) that
resist shear and confer superior deposition efciency on hair for
good wet conditioning.
65

Conditioning shampoos containing a polyester formed from
adipic acid and pentaerythritol provides conditioning for dry
hair (possibly from reduced hair friction), with no greasy feel.
66

Chapter 3
99
Inclusion of polybutene is thought to increase the deposition
of silicone conditioners and provide improved conditioning
benefts, such as wet and dry feel and combing.
O Lenick disclosed a unique class of alkyl polyglucoside quaternary
surfactants possessing all the multifunctional attributes of cleansing,
conditioning, and self-preserving.
67
Tis could have the potential of
greatly simplifying the formulation of multifunctional shampoos.
A conditioning shampoo that contains a conditioning gel
phase in the form of vesicles is described by Unilever researchers.
68

Cationic conditioners are usually incompatible with anionic
shampoos, and consequently conditioners based upon cationic
surfactants are usually applied as separate post-shampoo products.
Te Unilever researchers prepared a conditioning gel phase by
combining a small amount of water, fatty alcohol, a long-chain
secondary anionic surfactant (sodium cetostearyl sulfate), and
a long-chain cationic surfactant (behenyltrimethylammonium
chloride), and subjecting the mixture to high shear to form a stable
vesicular gel phase. Prolonged shear causes the lamellar gel phase to
roll-up into an array of multilamellar vesicles (Figure 17). Te gel
phase was added to a dilute primary surfactant solution (sodium
laureth sulfate) to form a conditioning shampoo that conferred good
wet smoothness on hair.
Deposition of Particles on Hair to Confer Styling Benets
Whereas conditioning shampoos are formulated to reduce hair
inter-fber friction, some consumers need an increase in friction in
Figure 17. Lamellar gel subjected to high shear rolls up into vesicles of gel phase that can
be used for conditioning. (Figure reproduced from US Patent Application 20110243870).
Shampoo and Conditioner Science
100
order to achieve styling benefts. Factors that infuence hair body
and fullness include hair diameter, hair fber-to-fber interactions,
natural confguration (kinky, straight, wavy), bending stifness,
hair density, and hair length. Increases in friction can be achieved
by depositing particles such as titanium dioxide, clay, pearlescent
mica, or silica on the hair surface. Particles can be deposited for
more purposes than merely increasing inter-fber friction, e.g., for
conferring color, for slip (spherical particles are best for this), and
for conditioning (hollow silica, hollow polymer particles). Hollow
particles can be included in shampoo to increase hair volume.
69,70

Deposited hollow particles that can increase fber-fber interaction
include complexes of gas-encapsulated microspheres (such as silica
modifed ethylene/methacrylate copolymer microspheres and
talc-modifed ethylene/methacrylate copolymer microspheres);
polyesters; and inorganic hollow particles.
It has already been noted that cationic guar enhances
the deposition of conditioning agents. In a like manner, this
macromolecule enhances the deposition of particles on hair.
71

Silicones and particulates can be deposited simultaneously. Tus,
enhanced deposition of particulate actives, such as zinc pyrithione
(shown on cadaver skin treated in a Franz difusion cell), has
been reported
72
from shampoos comprising a water-soluble
silicone (such as silicone quaternium-13, cetyltriethylammonium
dimethicone copolyol phthalate, or stearalkonium dimethicone
copolyol phthalate), a cationic conditioning agent (such as
acrylamidopropyltrimonium chloride/acrylamide copolymer, or
guar hydroxypropyltrimonium chloride), a cleansing detergent,
and suspending agents (such as carbomer, hydroxyethylcellulose,
and PVM/MA decadiene cross-polymer) to insure homogeneous
distribution of the insoluble active.
Hydrophobic modifcation of cationic hydroxyethylcellulose
is claimed to endow better efcacy. Tus, polyquaternium-24,
a hydrophobically modifed cationic hydroxyethylcellulose, is
also disclosed as being a preferable thickener for zinc-depositing
compositions.
73
Chapter 3
101
It has been discovered that responsive particles, with two
contrasting polymers adsorbed to the particle core,
74
can adsorb
to the hydrophilic hair surface and render it hydrophobic, thereby
conferring conditioning attributes to the hair. For example, grafing
of aminopropyl-terminated dimethicone and polyethylenimine
on titanium dioxide particles produces responsive particles.
Tese particles form stable dispersions in water and aqueous
solutions because they are sterically stabilized by expansion of
the polyethylenimine into the aqueous medium. However, when
they are deposited on hair and dried, the polyethylenimine layer
collapses and the dimethicone layer expands to render the surface
hydrophobic. Te usefulness of these responsive particles is
demonstrated by including them in typical conditioning shampoo
and conditioner formulations. In the case of the shampoo, inclusion
of the responsive particles results in a higher water contact angle on
the treated hair and the conditioner with particles causes an increase
in the hydrophobicity of the hair. On the other hand, shampoos
containing ethoxylated alcohols have been found to enhance the
deposition of large particle silicones (52000 microns), and in this
case it is claimed that cationic polymer is not required.
75

Two-phase Systems for Visual Attributes:
Tere is esthetic appeal to products that exist as separate phases
in the bottle but which mix during application to provide added
beneft, such as moisturizing or conditioning, by interaction of the
components of the two phases. Te most obvious way to formulate
such products is to use the immiscibility of water and oil in
formulations that are shaken prior to use to produce a metastable
emulsion. However, when a surfactant is included in the system such
a visually attractive phase separation can be mixed into an emulsion
due to shear in manufacturing and packing operations. Tere are
known de-emulsifers, which are widely used in the oil industry,
but these demulsifers also tend be defoamers that compromise the
lather of shampoos. Neutralized polyacrylate can be added as a non-
emulsifying foam stabilizer to yield phase-separated compositions
Shampoo and Conditioner Science
102
that resist the production difculties to make phase-separated
shampoos that form temporary emulsions upon shaking and foam
during use.
76


A two-phase shampoo system can also be formed by
mixing polar lipophilic shampoo components with non-polar lotion
constituents such as mineral oil.
77

Under appropriate conditions, phase-separated systems can be
prepared from polymer solutions or micellar surfactant solutions. If
two distinct aqueous phases are desired in a composition, one must
take into consideration the thermodynamics of coexisting phases
and the driving force for such phase separation that comes directly
from the chemical thermodynamics of the system. Tis is especially
the case for systems that contain polymers or micelles because the
confgurational entropy is reduced as molecules are assembled
into polymers or aggregated into micelles, and mixing can become
unfavorable. If the free energy of mixing is insufcient to maintain
uniform dispersion, spontaneous phase separation will occur.
Phase separation becomes more likely as the micellar aggregates or
polymers get bigger. Te addition of salts to ionic surfactant micellar
systems causes a reduction in the surfactant intra-micellar head-
group interaction, and ofen an increase in hydrophobic interaction.
Tis can cause a pronounced increase in micelle size and consequent
phase separation into a surfactant-rich phase and a surfactant-poor
phase. Tis approach has been adopted by adding mineral salt to
induce two distinct layers,
78
and by adding the detergent builder,
sodium hexametaphosphate, to cause phase separation. In this case,
a thickener is required and the system comprises a surfactant, a
thickener, a polyalkylene glycol, and a non-chelating mineral salt.
Te system spontaneously separates into two layers.
A multiphase composition comprising surfactant, betaines,
co-surfactant (such as an alkyl ether carboxylate, an acylglutamate;
or an acylisethionate), and an appropriate concentration of salt
forms a stable multiphase system that becomes temporarily
uniformly dispensed upon agitation.
79

Multiphase cleansing products have been introduced that go
beyond mere phase separation insofar as the separate phases can be
Chapter 3
103
arranged to form visually attractive patterns inside a transparent
container.
80
Te phases comprise an aqueous cleansing phase, a
beneft phase, and a non-lathering structured phase. Te aqueous
cleansing phase must be capable of adequate lathering.
81
Te
beneft phase comprises hydrophobic component(s) or conditioning
components. Tese products are designed at the nanoscale: the
structured phase can be a lamellar-phase formed by adding sufcient
electrolytes to an appropriate surfactant. Structurants such as
starch have been used in personal cleansing formulations,
82
but the
surfactant itself can be structured. Tus, lamellar phase does exhibit
a yield stress that is sufcient to stably suspend the beneft phase.
However, the yield stress of lamellar phase can vary dramatically
with temperature, and, in order to overcome this problem, the
cleansing and beneft phases were density matched by adding
microsphere particles to reduce the specifc gravity of the cleansing
phase or high density particles to the beneft phase to increase its
specifc gravity. In this context, it is interesting that it has been
recently disclosed that controlled phase separation and deposition
could conceivably be achieved by loading the desired active phase
into hollow-sphere polymer carriers,
83
and again it has been reported
that certain cationic guar derivatives can enhance the deposition of
conditioning additives and/or solid particle beneft agents.
84

Lamellar phase, especially if it is made from unneutralized long-
chain fatty acids, usually displays poor dispersion kinetics and a
lather that is slow to build up or slow to rinse of. However, it has
surprisingly been discovered that swollen lamellar gels can exhibit
both high product viscosity and fast dispersion kinetics if they are
formed by combining C16-24 normal monoalkylsulfosuccinates
with n-alkyl fatty acids of approximately the same chain length.
85
In
this context, Guth claimed a composition that was low-irritating to
skin and eyes but synergistic in foaming by combining zwitterionic
surfactants-fatty acid complexes with sulfosuccinates,
86
and Pratley
reported synergistic foaming and mildness from compositions
with combinations of specifc long-chain surfactants with specifc
short-chain surfactants and these included fatty acids and
Shampoo and Conditioner Science
104
alkylsulfosuccinnates.
87
Amine-oxide copolymers have also been
claimed as suds-enhancers.
88

Concentrated Cleansing Compositions
Most personal care products are based on aqueous compositions
but concentrated cleansing/personal care compositions ofer
the benefts of lower transportation costs, less packaging, and
convenience for air travelers. If these products are solid, they
must possess sufcient strength to resist the forces of extrusion
during manufacture, shipping, and handling, but should disperse
rapidly in water during use. Porous solid particles that are
strengthened by hydrophilic polymers such as poly(vinyl alcohol)
or hydroxylpropylmethylcellulose have been shown to exhibit the
desired properties.
89
Control of interconnectivity of the porous
network is vital to this application and is described by a star volume,
a structure model index, or a percent open cell content.
Conditioners
Conditioning of damaged hair is commonly achieved by
treatment with aqueous formulations that contain fatty alcohols,
cationic surfactants, and (optionally) silicones. Tese components
are considered to adsorb in a hydrophilic head-down, hydrophobic
tail-up conformation that confers hydrophobicity on the damaged
hydrophilic hair surface. Te role of a conditioner is to confer sleek
lubricity and gloss on the hair. Conditioners are usually based
upon cationic surfactants, and they most ofen are in the form
of emulsions of multi-lamellar vesicles. Conditioners comprise a
primary cationic surfactant, a co-surfactant, and dissolved salt.
Conventional conditioner formulations are based upon lamellar
gels or emulsions using either ceto-stearyl trimethylammonium
chloride or distearyldimethylammonium chloride as cationic
surfactants and ceto-stearyl alcohol as co-surfactant.
As a primary surfactant, the vast majority of conventional
conditioners contain either cetyl/stearyl trimethylammonium
Chapter 3
105
chloride or distearyldimethylammonium chloride. Te secondary
surfactant is most ofen ceto-stearyl alcohol.
Cetyl/stearyl trimethylammonium chloride is a conical molecule
according to Ninhams packing factor. On the other hand, ceto-
stearyl alcohol consists of molecules with the approximate shape
of an inverted conical molecule. Te role of ceto-stearyl alcohol
in a conditioner is to pack between the cationic cones and convert
the micellar structure into a lamellar structure with just enough
curvature to form a vesicle. Distearyldimethylammonium chloride
spontaneously forms vesicles in the presence of salt, and therefore
there is usually no need to add a long-chain alcohol to conditioner
formulations based upon distearyldimonium chloride.
Tese products form a gel matrix that confers conditioning
benefts from rinse-of products. Tey have been the basis of hair
conditioners for the last half-century, and they provide excellent
detangling, wet- and dry-combing, and good anti-static properties,
but they can leave the hair feeing lank and greasy, and they give a
long-lasting slippery feel during rinsing which is perceived by some
consumers as an unclean hair feel.
Pristine hair, as it emerges from the scalp, is coated with a
covalently bound layer of 18-methyleicanosoic acid (18-MEA).
90-92

It has been shown that the layer of 18MEA confers hydrophobicity
and boundary lubrication on hair fbers.
93
Tis discovery has
infuenced researchers to seek to include 18-MEA in conditioner
formulations.
94
Pristine hair shows a measured advancing water
contact angle that is high, but a receding contact angle that is
likewise high, and the hair tends to align. However, once the
18-MEA layer is removed, the receding contact angle is low (even
approaching 0

degrees), and this corresponds to cuticle edges that
are essentially hydrophilic. Tis means that the major diferences
for such 18-MEA defcient hair would be in its drying behavior
rather than its wetting characteristics. Te low receding contact
angle would tend to pin the water to the hair. Tis would
lead to longer drying times during which the capillary forces
imparted by the water between hair fbers would tend to cause
Shampoo and Conditioner Science
106
the hair fbers to clump and entangle. Te inclusion of 18-MEA
in prototype conditioner formulations that were based upon
stearoxypropylmethylamine, dimethylaminopropylstearamide, and
stearyltrimethylammonium chloride lef the conditioner on the
hair surface, and this in turn yielded improvements in inter-fber
lubricity due to improved deposition at the hair surface.
Conditioning Polymers in Hair Straightening Applications
Te two main processes for relaxing or straightening hair are
hair treatment with a reducing agent to cleave the disulphide cystine
bridges (SS) within the hair structure, and treatment of stretched
hair with a strong alkaline agent.
Repeated relaxation treatments can cause signifcant hair damage,
to both the cuticles and the cortex. Te damage can be assessed by
measuring the porosity of the hair, and the porosity of the keratin
fbers can be measured by fxing 2-nitro-para-phenylenediamine
at 0.25% in an ethanol/bufer mixture (10:90 volume ratio) at pH
10 at 37C for 2 minutes. Cationic and amphoteric polymers, such
as polyquaternium-6, polyquaternium-7, and polyquaternium-39,
added to hair relaxer formulations, mitigate this degradation of the
hair structure. Also, the inclusion of high molecular-weight (>106
g/mole) copolymers of acrylamide and diallyldimethylammonium
chloride, acryloyloxytrimethylammoniumchloride, or
acryloyloxyethyldimethylbenzylammonium chloride in the relaxing
formula results in signifcant reduction in the hair structural
damage caused by alkaline relaxation.
Conditioning Polymers
Cationic conditioning polymers are used to enhance the
conditioning properties, especially to mitigate the efects of extreme
processing that are experienced during hair-straightening. Cationic
polymeric conditioners can improve wet combability and ameliorate
electrostatic charging of the hair (manifested by fyaway).
Many cationic polymers have been developed for the purpose
of conferring conditioning properties on hair. In fact, there are
Chapter 3
107
now more than one hundred polyquaternium ingredients listed in
the INCI dictionary, and this list is still expanding. Te primary
purpose of polyquaternium polymers is to confer good conditioning
benefts. A non-exhaustive list of conditioning polymers is shown in
Table 1.
Table 1. Examples of cationic conditioning polymers
Chitosan
Cocodimonium Hydroxypropyl Hydrolyzed Collagen
Cocodimonium Hydroxypropyl Hydrolyzed Hair Keratin
Cocodimonium Hydroxypropyl Hydrolyzed Keratin
Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein
Cocodimonium Hydroxypropyl Oxyethyl Cellulose
Steardimonium Hydroxyethyl Cellulose
Stearyldimonium Hydroxypropyl Hydrolyzed Oxyethyl Cellulose
Guar Hydroxypropyltrimonium Chloride
Starch Hydroxypropyltrimonium Chloride
Lauryldimonium Hydroxypropyl Hydrolyzed Collagen
Lauryldimonium Hydroxypropyl Hydrolyzed Wheat Protein
Stearyldimonium Hydroxypropyl Hydrolyzed Wheat Protein
Polyquaternium-4
Polyquaternium-10
Cationic hydroxyethylcellulose
Polyquaternium-24
Hydrophobically modied cationic hydroxyethylcellulose
Poly(methacryloxyethyltrimethylammonium methosulfate)
Poly(N-methylvinylpyridinium chloride)
Onamer M (Polyquaternium-1), PEI-1500 (Poly(ethylenimine)
Polyquaternium-2
Polyquaternium-5-poly(acrylamide-methacryloxyethyltrimethylammonium
ethosulfate)]
Polyquaternium-6 poly(dimethyldiallylammonium chloride)
Polyquaternium-7
poly(acrylamide-co-dimethyldiallylammonium chloride)
Shampoo and Conditioner Science
108
Polyquaternium-8
Polyquaternium-11
[poly-(N-vinyl-2-pyrrolidone-methacryloxyethyltrimethylammonium ethosulfate)]
Polyquaternium-16 [Co(vinyl pyrrolidone-vinyl methylimidazolinium chloride)
Polyquaternium-17
Polyquaternium-18
Polyquaternium-22
Poly(sodium acrylate dimethyldiallyl ammonium chloride)
Polyquaternium-27
Polyquaternium-28
Polyvinylpyrolidone-methacrylamidopropyltrimethylammonium chloride)
Polyquaternium-31
Poly(N,N-dimethylaminopropylacrylate-N-acrylamidine-acrylamide-
acrylamidine-acrylic acid-acrylonitrile) ethosulfate
Polyquaternium-39
Poly(dimethyldiallylammonium chloridesodium acrylateacrylamide)
Polyquaternium-43
Poly(acrylamide-acrylamidopropyltrimoniumchloride-2-acrylamidopropyl
sulfonate-DMAPA)
Polyquaternium-44
Poly (vinyl pyrrolidone--imidazolinium methosulfate)
Polyquaternium-46
Poly (vinylcaprolactam-vinylpyrrolidone-imidazolinium methosulfate)
Polyquaternium-47
Poly (acrylic acid-methacrylamidopropyltrimethyl ammonium chloridemethyl
acrylate)
Polyquaternium-53
Polyquaternium-55
Poly(vinylpyrrolidone-dimethylaminopropylmethacrylamide-lauryldimethylpropy
lmethacrylamido ammonium chloride)
PVP/Dimethylaminoethyl Methacrylate Copolymer
VP/DMAPA Acrylate Copolymer
PVP/Dimethylaminoethylmethacrylate Polycarbamyl
Polyglycol Ester
Table 1. Examples of Cationic Conditioning Polymers (Cont.)
Chapter 3
109
PVP/Dimethiconylacrylate/Polycarbamyl Polyglycol Ester
Quaternium-80 (Diquaternary polydimethylsiloxane)
Poly(vinylpyrrolidone--dimethylamidopropylmethacrylamide)
VP/Vinyl Caprolactam/DMAPA Acrylates Copolymer
Amodimethicone
PEG-7 Amodimethicone
Trimethylsiloxyamodimethicone
Ionenes
Poly(adipic acid-dimethylaminohydroxypropyldiethylenetriamine)
Poly (adipic acid-epoxypropyldiethylenetriamine) (Delsette 101)
Silicone Quaternium-8
Silicone Quaternium-12
Polyampholytes have been commercially available as
conditioning polymers for a considerable time. A prominent
example is polyquaternium-39, which is a copolymer of
diallyldimethylammonium chloride, acrylamide, and acrylic acid.
When this is polymerized in a single batch process, the mismatch
in reactivity ratios between these monomers results in a lack of
compositional uniformity. An improved version of this type of
terpolymer of diallyldimethylammonium chloride, acrylamide, and
acrylic acid has been made by a monomer feed method for better
control of molecular weight and composition.
95

Copolymers comprising a diallylamine (typically diallyldimethyl
ammonium chloride) and vinyllactam monomers (typically
polyvinylpyrrolidone) are useful flm-formers that confer
conditioning properties such as good wet and dry combability, feel,
volume, and handleability.
96

Silicone Conditioners
Silicone quaternaries have long been known as hair conditioning
compounds.
Table 1. Examples of Cationic Conditioning Polymers (Cont.)
Shampoo and Conditioner Science
110
A recent patent application from Evonik Goldschmidt is
directed to silicone quats that confer conditioning with longer
lasting conditioning through several shampoo cycles. Te premise
is that long-term substantivity to hair requires the conditioning
agent to contain a string of cationic charges. Tis was achieved
by Goldschmidt by polymerizing cationic monomers and
grafing them to silicone backbones. In general, water-soluble
monomers polymerized in the presence of silicones yield a
mixture of water-soluble polymers and unsubstituted silicones
because the two ingredients are incompatible and attachment
of the polymer chain to the silicone would require appropriate
coupling groups. Te Evonik researchers rose to the challenge
by polymerizing the cationic monomers in the presence of
silicone polyethers. Te ether groups are compatible with the
quat monomers, and they readily chain transfer to give graf
copolymers. Once grafed, the copolymers are quaternized to
confer permanent positive charges with enhanced substantivity
to hair. Te grafs are obtained by polymerizing the readily
available monomers, dimethylaminoethylmethacrylate, or
3-trimethylammoniopropyl-methacrylamide.
Leave-on silicone conditioners specifcally targeted to non-
shampoo applications confer enhanced and relatively durable
conditioning. Tese contain emulsifed vinyl-terminated silicones
applied in combination with a conventional cationic conditioner. A
preferred product type is a mousse. Tese silicone block copolymers
can achieve excellent conditioning at relatively high viscosities (100
KPa/s-1).
Improved conditioning that confers surprisingly reduced friction
on hair can be achieved by including an aminosilicone in which the
aminosilicone has a fairly large range of average particle sizes from
about 550 microns.
97

References
1. C Tanford, The Hydrophobic Effect: Formation of Micelles and Biological Membranes,
Ch 1, Wiley Interscience: New Jersey (1980).
Chapter 3
111
2. HS Frank and MW Evans, Free volume and entropy in condensed systems: iii. Entropy
in binary liquid mixtures; partial molal entropy in dilute solutions; structure and
thermodynamics in aqueous electrolytes, J Chem Phys, 13, 507-533 (1945).
3. JT Davies and EK Rideal, Interfacial Phenomena, Ch 1, Academic Press: Waltham, MA,
(1961).
4. J Traube, Ueber die Capillarittsconstanten organischer Stoffe in wsserigen Lsungen,
Justus Liebigs Annalen der Chemie, 265, 27-55 (1891).
5. JW Gibbs, The Collected Works of J. Willard Gibbs, Longmans: New York (1928).
6. I Langmuir, The constitution and fundamental properties of solids and liquids, II. Liquids,
J Amer Chem Soc, 39, 1848-1906 (1917).
7. KJ Mysels, Soap Films: Studies of their thinning, Pergamon Press: Oxford (1959).
8. JW McBain, Colloidal electrolytes: Soap solutions and their constitution, J Amer Chem
Soc, 42, 426-460 (1920).
9. GS Hartley, Aqueous Solutions of Parafn-chain Salts, Hermann & Cie: Paris (1936).
10. C Tanford, The Hydrophobic Effect: Formation of Micelles and Biological Membranes,
pp 85, Wiley Interscience: New Jersey (1980).
11. K Shinoda, N Yamaguchi, A Carlsson, Physical Meaning of the Krafft Point: Observation
of Melting Phenomenon of Hydrated Solid Surfactant at the Krafft Point, J Phys Chem,
93, 7216-7218 (1989).
12. C Tanford, The Hydrophobic Effect: Formation of Micelles and Biological Membranes,
pp 57, Wiley Interscience: New Jersey (1980).
13. JN Israelachvili, DJ Mitchell and BW Ninham, Theory of self-assembly of hydrocarbon
amphiphiles into micelles and bilayers, Faraday Trans. 2, J Chem Soc, 72, 1525-1568
(1976).
14. MG Cacace, EM Landau, JJ Ramsden, The Hofmeister series: salt and solvent effects on
interfacial phenomena, Quart Rev Biophys, 30, 241-177 (1997).
15. S Candau, A Khatory, F Lequeux, F Kern, Rheological behaviour of wormlike micelles:
Effect of salt content, Journal de Physique IV, 03, C1, 197-209 (1993).
16. JF Berret, J Appell, G Porte; Linear rheology of entangled wormlike micelles, Langmuir,
9 (11), 28512854 (1993).
17. E Buhler, JP Munch and SJ Candau, Dynamical properties of wormlike micelles: A light
scattering study, J Phys II France, 5, 765-787 (1995).
18. H Rehage and H Hoffmann, Rheological properties of viscoelastic surfactant systems,
J Phys Chem, 92, 47124719 (1988).
19. H Hoffmann, Viscoelastic surfactant solutions, in: Structure and Flow in Surfactant
Solutions, CA Herb and RK Prudhomme, eds, ACS Symposium Series 578, American
Chemical Society (1994).
20. PA Hassan, SJ Candau, F Kern, and C Manohar, Rheology of wormlike micelles with
varying hydrophobicity of the counterion, Langmuir, 14, 60256029 (1998).
21. F Lequeux and S J Candau, Dynamical properties of wormlike micelles, in: Structure
and Flow in Surfactant Solutions, CA Herb and RK Prudhomme, eds, ACS Symposium
Series 578, American Chemical Society (1994).
22. JF Berret, Transient rheology of wormlike micelles, Langmuir, 13, 22272234 (1997).
23. NA Spenley, ME Cates, and TCB McLeish, Nonlinear rheology of wormlike micelles, Phys
Rev Lett 71, 939942 (1993).
24. ME Cates, Theoretical modeling of viscoelastic phases, Structure and Flow in Surfactant
Solutions, CA Herb and RK Prudhomme, eds, ACS Symposium Series 578, American
Chemical Society (1994).
25. NK Adam, J Soc Dyers Colour, 53, 122 (1937).
26. E Kissa, Wetting and detergency, Pure & Appl. Chem, 53, 2255-2268 (1981).
27. BJ Carroll, Equilibrium conformations of liquid drops on thin cylinders under forces of
capillarity. A theory for the roll-up process.
Shampoo and Conditioner Science
112
28. R Molina, F Comelles, MR Julia, P Erra, Chemical modications of human hair studied by
means of contact angle determination.
29. V Dupres, D Langevin, P Guenon, A Checco, G Luengo, and F Leroy, Wetting and
electrical properties of the human hair surface: Delipidation observed at the nanoscale,
J Colloid Interface Sci, 306, 34-40 (2007).
30. CA Miller and KH Ramey, Solubilization-emulsication mechanisms of detergency,
Colloids and Surfaces A, Physicochemical and Engineering Aspects. 74, 169-215 (1993).
31. ASC Lawrence, The mechanism of detergence, Nature, 183, 1491 (1959).
32. DG Stevenson, Surface Activity and Detergency, K Durham, ed., MacMillan: London
(1961).
33. CA Miller and KH Ramey, Solubilization-emulsication mechanisms of detergency,
Colloids and Surfaces A, Physicochemical and Engineering Aspects. 74, 169-215 (1993).
34. BJ Carroll, The kinetics of solubilization of nonpolar oils by nonionic surfactant solutions,
J Colloid Interface Sci, 79, 126-135 (1981).
35. JR Glenn et al, Porous, Dissolvable Solid Substrate and Surface Resident Coating
Comprising Water Sensitive Actives, US Patent Application 20110195098, Aug 11, 2011;
US Patent Application 20110189247, Aug 4, 2011; US Patent Application 20110189246,
Aug 4, 2011; US Patent Application 20110182956, July 28, 2011.
36. LS Tsaur et al, Personal Wash Cleanser Comprising Dened Alkanoyl Compounds,
Dened Fatty Acyl Isethionate Surfactant Product and Skin or Hair Benet Agent
Delivered in Flocs Upon Dilution, US Patent Application 20110245125, Oct 6, 2011,
assignee CONOPCO, INC., D/B/A UNILEVER.
37. JJ Librizzi et al, Low-irritation compositions and methods of making the same, US Patent
Application 20100311628, Dec 9, 2010, assignee Johnson & Johnson.
38. ED Goddard, Polymersurfactant interaction: Part II Polymer and surfactant of opposite
charge, in: Interactions of Surfactants with Polymers and Proteins, ED Goddard and
KP Ananthapadmanabhan, eds, CRC Press (1993).
39. ED Goddard, Polymer/surfactant interaction in applied systems, in: Principles of Polymer
Science and Technology in Cosmetics and Personal Care, ED Goddard and JV Gruber,
eds, Marcel Dekker (1999).
40. P. Brand, et al, Cleansing formulations comprising non-cellulosic polysaccharide with
mixed cationic substituents, US Patent 8,076,279, Dec 13, 2011, assigned to Hercules
Inc.
41. F. Utz, et al, Cationic cassia derivatives and applications therefore, US Patent 7,439,214,
Oct 21, 2008, assigned to Lubrizol Advanced Materials, Inc.
42. CA Lepilleur, Cationic cassia derivatives and applications therefore, US Patent 7,704,934,
April 27, 2010; US Patent 7,923,422, April 12, 2011, assigned to Lubrizol Advanced
Materials, Inc.
43. E Baldaro, et al, Home And Personal Care Compositions, US Patent Application
20110189248, Aug 4, 2011.
44. MM Pefy, et al, Personal care compositions containing cationic synthetic copolymer
and a detersive surfactant, US Patent Application 20070207109, Sep6, 2007, assigned to
The Procter & Gamble Company.
45. M. Pader, Shampoo compositions comprising saccharides, US Patent 4,364,837,
Dec 21, 1982, assigned to Lever Brothers Company.
46. RE Bolich, Jr., and TB Williams, Shampoo compositions containing nonvolatile silicone
and xanthan gum, US Patent 4,788,006, Nov 29, 1988, assigned to the Procter &
Gamble Company.
47. J Parran, Detergent compositions containing particle deposition enhancing agents,
US Patent 3,761,418, Sept 25, 1973, assigned to the Procter & Gamble Company.
48. MJ Fair, et al, Bars comprising benet agent and cationic polymer, US Patent 6,057,275,
May 2, 2000, assigned to Unilever Home and Personal Care USA.
Chapter 3
113
49. MJ O Brien, Cosmetic compositions using polyether siloxane copolymer network
compositions, US Patent Application, 2005/0197477, Sept 8, 2005, assigned to
GEAM- Silicones.
50. TN Biggs and GE LeGrow, Lightly cross-linked poly(n-alkylmethylsiloxanes) and methods
of producing same, US Patent 5,493,041, Feb 20 1996, assigned to Dow Corning
Corporation.
51. J. A. Kilgour, et al, Branched organosilicone compound, US Patent Application
2005/0165198, July 28, 2005, assigned to GE Plastics.
52. SM Niemiec, et al, Novel detergent compositions with enhanced depositing, conditioning
and softness capabilities, US Patent Application 2003/0176303, Sept 18, 2003.
53. M Maubru, Cosmetic composition comprising at least one anionic surfactant, at least
one cationic polymer and at least one amphiphilic, branched block acrylic copolymer
and method for treating hair using such a composition, US Patent 7,498,022, March 3,
2009, assigned to LOreal S.A.
54. H Denzer, et al, Transparent aqueous compositions comprising hydrophobic silicone oils,
US Patent 6,803,050, Oct 12, 2004, assigned to Kao Chemicals Europe S.L.
55. MM Pefy and JE Hilvert, Conditioning shampoo compositions, US Patent Application
20050158266, July 21, 2005, assigned to The Procter & Gamble Company.
56. MM Pefy, et al, Clear personal care compositions containing a cationic conditioning
polymer and an anionic surfactant, US Patent Application 20040234483, Nov 25, 2004,
assigned to The Procter & Gamble Company.
57. MM Pefy, et al, Clear personal care compositions containing a cationic conditioning
polymer and an anionic surfactant, US Patent Application 20040234484, Nov 25, 2004,
assigned to The Procter & Gamble Company.
58. H Albrecht, et al, Hair shampoo containing pregelatinized, cross-linked starch derivatives,
US Patent 7,279,449, Oct 9, 2007, assigned to Beiersdorf A.G.
59. F Simonet and L Nicolas-Morgantini, Cosmetic composition of water-in-water emulsion
type based on surfactants and cationic polymers, US Patent 20070237733, Oct 11, 2007.
60. VM Coessens, K Matyjaszewski, Fundamentals of Atom Transfer Radical Polymerization,
J Chem Ed, 87, 916-919 (2010).
61. C Farcet, Gradient copolymer, composition including same and cosmetic make-up or
care method; US Patent Application 20090047308, Feb 19, 2009, assigned to LOreal.
62. N Cadena, et al, Method for depositing a polymer onto a surface by applying a
composition onto said surface, USPatent 6,906,128, June 14, 2005, assigned to Rhodia
Chemie.
63. V Bergeron, et al, US Patent 7,335,700, Feb 26, 2008; US Patent 7,915,212, March 29,
2011; and US Patent 7,939,601, May 10, 2011, assigned to Rhodia Inc.
64. Q Stella, Shampoo containing a silicone in water emulsion, US Patent Application
20030143177, July 31, 2003, assigned to the Procter & Gamble Company.
65. DR Royce and RL Wells, Shampoo containing an alkyl ether, US Patent 7,087,221,
Aug 8, 2006, assigned to the Procter & Gamble Company.
66. DR Royce and RL Wells, Shampoo containing an ester oil, US Patent application
20030138392, July 24. 2003, assigned to the Procter & Gamble Company.
67. AJ OLenick, Jr, et al, Personal care products based upon surfactants based upon alkyl
polyglucoside quaternary compounds, US Patent 6,881,710, April 19, 2005, assigned to
Colonial Chemical Inc.
68. MJ Cooke, et al, Conditioning shampoo comprising an aqeuous conditioning gel phase
in the form of vesicles, US Patent Application 20110243870, Oct 6, 2011.
69. S Midha, et al, Shampoo containing hollow particles, US Patent Application
20030086896, May 8, 2003, assigned to The Procter & Gamble Company.
70. S Midha, BD Hofrichter, Composition for improving hair volume, US Patent Application
20030091521, May 15, 2003, assigned to The Procter & Gamble Company.
Shampoo and Conditioner Science
114
71. RL Wells, ES Johnson, Shampoo containing a cationic guar derivative, US Patent
6,930,078, Aug 16, 2005, assigned to The Procter & Gamble Company.
72. SM Niemiec, et al, Detergent composition with enhanced depositing, conditioning and
softness capabilities, US Patent 6,495,498, Dec 17, 2002; US Patent 6,858,202, Feb
22, 2005; US Patent 6,908,889, June 21, 2005, assigned to The Procter & Gamble
Company.
73. MF Neibauer, et al, Personal care compositions comprising a non-binding thickener with
a metal ion, US Patent Application 20070009472, Jan 11, 2007, assigned to The Procter
& Gamble Company.
74. IC Constantinides, et al, Personal care compositions comprising responsive particles,
US Patent Application 20070196299, Aug 13, 2007, assigned to The Procter & Gamble
Company.
75. T Yeoh, et al, Conditioning shampoo compositions having improved silicone deposition,
US Patent 6,200,554; March 13, 2001, assigned to The Procter & Gamble Company.
76. DR Weimer, Liquid detergent compositions, US Patent 3,718,609, Feb 27, 1973, assigned
to Continental Oil Company.
77. Olson, Shampoo composition possessing separate lotion phase, US Patent 3,810,478,
May 14, 1974, assigned to Colgate-Palmolive Company.
78. JR Williams, et al Separating multiphase personal care composition in a transparent or
translucent package, US Patent 6,429,177, Aug 6, 2002, assigned to Unilever Home &
Personal Care USA, division of Conopco, Inc.
79. C Littau, et al, Multiphase aqueous cleaning compositions, US Patent 7,012,049, March
14, 2006, assigned to Clariant International Ltd.
80. KS Wei, et al, US Patent Application 20050100570, May 12, 2005, assigned to The
Procter & Gamble Company.
81. JA Wagner, et al, US Patent Application 20050192188, Sept 1, 2005, assigned to The
Procter & Gamble Company.
82. LS Tsaur, Personal polymer liquid cleansers stabilized with starch structuring system,
US Patent 6,903,057, June 7, 2005, assigned to Unilever Home & Personal Care USA,
division of Conopco, Inc.
83. SPJ Ugazio, Polymer carriers and process, US Patent Application 20050203215,
Sept 15, 2005, assigned to Rohm & Haas Company.
84. RL Wells and ES Johnson, Shampoo containing a cationic guar derivative, US Patent
6,930,078, Aug 16, 2005, assigned to The Procter & Gamble Company.
85. Q Qiu, et al, Ordered liquid crystal cleansing composition with C16-24 normal
monoalkylsulfosuccinates and C16-24 normal alkyl carboxylic acids, US Patent
Application 20050136026, June 23, 2005, assigned to Unilever Intellectual Property
Group.
86. JJ Guth, DL Spilatro, RJ Verdicchio, Detergent compositions, US Patent 4,435,300,
March 6, 1984, assigned to Johnson & Johnson Baby Products Company.
87. SK Pratley, Aqueous cleansing composition, US Patent 6,001,787, Dec 14, 1999,
assigned to Helene Curtis, Inc.
88. MR Sivik, et al, Compositions and method for using amine oxide monomeric unit
containing suds enhancers, US Patent 6,900,172, May 31, 2005, assigned to
the Procter & Gamble Company.
89. RW Glenn Jr., et al, Personal care compositions, especially those personal care
compositions in the form of an article that is a porous, dissolvable solid structure,
US Patent Application 20090232873, Sept 17, 2009.
90. DJ Evans, et al, Separation and analysis of the surface lipids of the wool ber, Proc. 7th
Int. Wool Text. Res. Conf., Tokyo, Japan, I, 135142 (1985).
91. PW Wertz and DT Downing, Integral lipids of human hair, Lipids, 23, 878881 (1988).
Chapter 3
115
92. PW. Wertz and DT Dowing, Integral lipids of mammalian hair, Comp Biochem Physiol,
92B, 759761 (1989).
93. U Kalkbrenner, et al, Studies on the composition of the wool cuticle, Proc. 8th Int.
Wool Text. Res. Conf., Christchurch, New Zealand, I, 398 (1990); CM Carr, et al, X-ray
photoelectron spectroscopic study of the wool ber surface, Textile Res J, 56, 457
(1986); S Breakspear, et al, Effect of the covalently linked fatty acid 18-MEA on the
nanotribology of hairs outermost surface, J Struct Biol, 149, 235242 (2005); CA Torre,
et al, Nanotribological effects of silicone type, silicone deposition level, and surfactant
type on human hair using atomic force microscopy, J Cosmet Sci, 57, 3756 (2006);
M Yasuda, J Hair Sci, 95, 712 (2004); ML Tate, et al, Quantication and prevention of hair
damage, J Soc Cosmet Chem, 44, 347371 (1993).
94. H Tanamachi, et al, Deposition of 18-MEA onto alkaline-color-treated weathered hair to
form a persistent hydrophobicity, J Cosmet Sci, 60, 3144 (2009).
95. JJ Sabelko, et al, Low molecular weight ampholytic polymers for personal care
applications, US Patent Application 20070207106, Sept 6, 2007, assigned to the Nalco
Company.
96. L Chrisstoffels, et al, Polymers comprising diallylamines, US Patent Application
20070191548, Aug 16, 2007.
97. ES Baker, et al, Conditioning composition comprising aminosilicone, US Patent
8,017,108, Sept 13, 2011, assigned to the Procter & Gamble Company.
Shampoo and Conditioner Science
116