Advancements in polymers used in hair care a review

Abstract

Polymeric materials gained rapid significance in professional cosmetics formulation due to their large variety of functions. They are critically important for the creation of modern cosmetics and personal-care products. Polymers used in hair care represents promising means as film formers in hair fixatives, emulsifiers in hair-colorants, conditioning agents for hair, thickeners, rheology modifiers and sun protection agents. In the present paper different polymers which are used in hair care are classified on the basis of their application, along with their examples and mechanism of action.

Full text

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International Journal of Research in Cosmetic Science 2016; 6(1): 6-16
ISSN 2277–7172
Original Article
Advancements in polymers used in hair care: a review
Apoorva Mahajan (B.Pharm, MBA)
Rayat & Bahra Institute of Pharmacy, Mohali, Punjab, India
Address for correspondence
Apoorva Mahajan
Rayat & Bahra Institute of Pharmacy,
Sahauran, Kharar, Distt. Mohali, (Punjab)-140104
E mail: apoorva_mahajan6@yahoo.com
Contact No. +91-7838743471
Fax No. +91-1605009680
Received 19 February 2016; accepted 29 February 2016
Abstract
Polymeric materials gained rapid significance in professional cosmetics formulation due to their large variety of functions.
They are critically important for the creation of modern cosmetics and personal-care products. Polymers used in hair care
represents promising means as film formers in hair fixatives, emulsifiers in hair-colorants, conditioning agents for hair,
thickeners, rheology modifiers and sun protection agents. In the present paper different polymers which are used in hair care
are classified on the basis of their application, along with their examples and mechanism of action.
© 2016 Universal Research Publications. All rights reserved
Key words: Polymers, Fixative, Styling, Conditioning, Thickening, Coloring polymers.
Introduction [1-8]
Polymers have become increasingly important components of
cosmetic over the past few decades. The term "polymer"
derives from the ancient Greek word πολύς (polus, meaning
"many, much") and μέρος (meros, meaning "parts"), and
refers to a molecule whose structure is composed of multiple
repeating units, from which originates a characteristic of high
relative molecular mass and attendant properties. Most of the
polymers are organic compounds that are chemically based
on carbon, hydrogen, and other non metallic elements; they
have very large molecular structures. Some polymers are
obtained from natural resources and are then chemically
modified for various applications, while others are chemically
synthesized and used. Polymers, both natural and synthetic,
are created via polymerization of many small molecules,
known as monomers. Their consequently large molecular
mass relative to small molecule compounds produces unique
physical properties. The polymers used in hair care typically
have low densities and are largely used as film formers,
coloring agents, conditioning agents, thickeners and sun
protection agents. In this paper, the polymers have been
classified on the basis of their applications along with their
examples.
Hair Styling and Fixative Polymers [9-14] do exactly what
their name implies: they fix the hair in place. Traditionally,
hair fixative polymers have been applied to the hair as sprays,
lotions, gels and mousses. Polyquaternium-69 is a type of
advancement in Styling and Fixative Polymer.
Polyquaternium-69 has been designed by polymerization of
vinyl pryrrolidone, vinyl caprolactam, DMAPMA, and the
alkylated quaternary DMAPMA+- C12H25CL. It is a
hydrophobic polymer, yet water soluble and predominately
non-ionic with a weakly cationic nature providing a broad
range of compatibility with cosmetic ingredients including
anionic gellants.
Thickening and Rheology Modifier Polymers [15-18] are
long, branched or unbranched molecules which provide
thickening effects simply by entanglement, cross-linking or
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International Journal of Research in Cosmetic Science
Universal Research Publications. All rights reserved

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International Journal of Research in Cosmetic Science 2016; 6(1): 6-16
cluster formation. They all are extensively used in gels, oils,
emulsions and nanoemulsions to increase the viscosity and
thickness of the particular product by giving it more richness
and a smooth and creamy performance. Carbopol Ulterez 10
Polymer is a type of advancement in Thickening and
Rheology Modifier Polymer. Carbopol Ultrez 10 is a cross-
linked polyacrylic acid polymer that provides efficient
rheology modification with enhanced self-wetting for ease of
use. Carbopol. The self wetting properties eliminate the need
for mechanical dispersers and have the outstanding ability to
suspend and stabilize formulations.
Hair Coloring and Highlighting Polymers [19-25] act as
thickeners for oxidation dyes, conditioners and hair-
protectors. The thickeners used in hair care are classified as
associative thickeners, hydrophobically modified ethoxylated
urethanes (HEUR), alkylmethicones and aminosilicones and
nonassociative thickeners. Acrylates/Steareth-20
Methacrylate Copolymer is a type of advancement in Hair
Coloring and Highlighting Polymer. Acrylates/steareth-20
methacrylate copolymer is a Hydrophobically-modified
Alkali Soluble Emulsion (HASE). It provides synergistic
interaction with surfactants, particulates and hydrophobic raw
materials as well as enhanced stabilization.
Conditioning and Cleansing Polymers [26-28] are effective
hair modifiers designed to deposit, adhere and adsorb to
proteins of the hair. They improve the hair manageability and
make the hair softer and smoother. They are classified as
cationic conditioning polymers, nonionic conditioning
polymers and silicone polymers. Polyquaternium-74 is a type
of advancement in Conditioning and Cleansing Polymer.
Polyquaternium-74 is an amphoteric polymer used to deliver
high conditioning and delivery performance in rinse- off
personal care applications. It gives light hair feel and has
strong affinity with dimethicone to boost deposition.
UV and Sun protection Polymers [29-30] are designed to
provide substantive, broad-spectrum UV-A and UV-B
protection to hair; they protect the hair fiber structure (both
inside and out) against damage caused by the sun exposure.
They maintain the tensile strength of the hair after UV
exposure, and have an excellent toxicity profile. Polysilicone-
19 is a type of advancement in UV and Sun Protection
Polymer. Polysilicone-19 is a silicone copolymer with
methoxycinnamic acid, cocos alkyl and cationic groups.
Classification of Polymers Used In Hair Care On The
Basis Of Their Application
1. Styling and Fixative Polymers
2. Thickening and Rheology Modifier Polymers
3. Coloring and Highlighting Polymers
4. Conditioning and Cleansing Polymers
5. UV and Sun Protection Polymers
1. Styling And Fixative Polymers [9-14]
Hair fixative polymers do exactly what their name implies:
they fix the hair in place. Different film polymers have
different humidity resistance properties, which determine
both the holding power and the lack of tack in humid
climates. The higher the humidity resistance of fixative
polymers the higher is its curl retention (CR). Styling
polymers are often used as source of “hold” in styling
products. These polymers generally function by forming
films that spot-weld and seam-weld the hair in the desired
style. These tiny welds suffer enormous stress due to the
natural movement of the hair. Hair style fixation should be
achieved with a tiny amount of styling and fixative polymer
applied from “Hair Sprays, Setting/Styling Gels and Lotions,
and Mousses.”The hair styling and fixative polymers must
not phase-separate. The mechanical properties like body,
bounce, increased hair volume; non-clumping, lack of
extreme stiffness, non-hygroscopic nature and less cohesion
of the polymer film should be maintained. Examples of most
commonly used hair fixatives are: polyquaternium-11,
polyquaternium-4, polyquaternium-46, polyquaternium-16,
polyquaternium-39, polyquaternium-2, polyquaternium-28,
VP/methylacylamide/vinyl imidazole copolymers, PVP,
PVP-VA, acrylates type copolymers, butyl or ethyl esters of
PVM/MA copolymers, and guar derivatives like
guarhydroxypropyltrimonium chloride.
1.1 Mechanism of Action (MOA)[9-14] includes the
following steps:

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International Journal of Research in Cosmetic Science 2016; 6(1): 6-16
1.2 Classification of Polymers used as Styling and
Fixative Polymers:[9-14]
 Homopolymers: Polymers that contain only a single
type of repeat unit are known as Homopolymers. They
consist of long molecular chains in which each link is an
identical monomer. Polymer nomenclature is generally based
upon the type of monomer residues comprising the polymer.
 Random copolymers consist of long molecular
chains which comprises of two different monomers which are
arranged randomly along the chain. They have a solubility
parameter that is intermediate between homopolymers made
from the same monomers.
 Block copolymers are the monomers of
homopolymer blocks joined together. In block copolymers
the molecular blocks are covalently linked, but the
segregation is limited to micro domain or nano domain
dimensions. This limited segregation leads to polymer alloys
in which glassy micro domains confer mechanical rigidity,
and rubbery micro domains confer shock-absorbing
properties. These materials are thermoplastic elastomers that
can display enhanced mechanical properties when compared
to the homopolymers. Amphipathic block copolymers contain
polar blocks that confer the desirable attribute of facile
removal of the polymer from hair by shampooing. The
cosmetic and styling properties can be enhanced by the
inclusion of a non-thickening amphiphilic block copolymer in
a fixative formulation based on a conventional hair fixative
polymer.
 Graft copolymers are branches consisting of one
type of monomer which are “hung” from a main chain
consisting of another type of monomer. For graft copolymers
the technique of free-radical polymerization by reaction with
a nitroxide and the RAFT (reversible addition-fragmentation
chain transfer) polymerization technique can be applied
1.3 Applications of Styling and Fixative Polymers:[9-
14]
 Hair Sprays: Hair sprays meet the requirement for a
quick- dry preparation which imparts just sufficient rigidity to
the set to keep them in place and control loose ends during
the day, while not detracting from the natural sheen of the
hair. The objective of a hair spray is to deposit onto the dry
hair an invisible film to protect it against all external agents
that are likely to change its desirable features. Most of the
hair spray consists of more than one polymer. All
components must be considered and these comprise fixative
polymers, solvent, propellant, adjuvant and the value system
of the aerosol. Thestyling and fixative polymer sprays should
be a compromise between adhesion &elimination, and
tightness & lightness. The film should not be sticky or tacky
to the touch and should hold the hair, but at the same time
leave it free to move. The spray should be very fine and also
the force of the spray should be gentle, it should not be wet,
which means that the characteristics of the spray should allow
it to be of a fineness not to wet the hair but also not to dry
before reaching the hair. Styling and fixative spray should be
spread over a wide area in a short period and dry quickly. The
film should be relatively flexible to follow the movement of
the hair without breaking. The film should be substantive to
the hair but should be soluble enough to be shampooed off
easily. Formulation for styling and fixative polymer sprays
generally consist of an amphoteric polymer constituting
either of (a)a hydroxyl-containing ethylenically unsaturated
monomer (which provides hydroxyl functionality to the
polymer) or(b) an acid-containing ethylenically unsaturated
monomer (which provides carboxy functionality to the
polymer) or(c) an amine-containing ethylenically unsaturated
monomer (which provides amine functionality to the
polymer) or(d) an ethylenically unsaturated monomer devoid
of acid, amine and hydroxyl content. As this polymer
composition is insoluble in water, acid neutralizing agent is
added for the process of solubilization.
 Setting/Styling Gels and Lotions: Styling gels and
lotions are pseudo plastic in nature to enable easy removal
from the jar and ensure smooth application on the hair.
Setting lotions are intended to strengthen and maintain for an
extended period a temporary deformation imparted by
waving. The solution of a polymeric material is deposited on
the shampooed hair which after setting and drying leaves a
flexible film that ensures the cohesiveness and hold of the
hair style and also protects it from the effects of humidity.
The lotion is based on the synthetic polymers which are
soluble in hydro alcoholic solutions. A hair fixative gel is a
cosmetic product which is widely used to create and maintain
a variety of hairstyles. Two important properties desired in
hair gel products are stiffness and hold, which are controlled
by the fixative polymer in the formulation. When a gel is
applied to the hair, a polymer–fiber composite is created that
is morphologically similar to high performance fiber
composites used in load-bearing applications. Formulation
for styling and fixative polymer setting/styling gel and lotion
mostly consist of (a) hydro alcoholic solution, (b) film-
forming polymers (which are usually cationic), (c)
plasticizers (which are used for increasing the flexibility of
the film and providing resilience to extensive handling), (d)
additives(which is used for enhancing sheen, softness and
disentangling), (e) perfumes, and (f) colorants.
 Mousses: Hair mousse is a toiletry added to hair for
extra shine and volume without any clumps or buildup. It
often comes either in spray or cream form. Mostly, hair
mousse is purple inside the can, but when released
the isobutylene makes it an off-shade white in color.
Depending upon the nature of fixative, hair styling mousses
provides a strong, flexible hold to the hair with a natural look.
Mousses are commonly applied to wet hair before blow
drying and are combed through without rinsing, to distribute

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International Journal of Research in Cosmetic Science 2016; 6(1): 6-16
the product through the hair. The hair is then styled and dried.
Mousses are packaged either in aerosol form or as a non-
aerosol pump and they typically dispense thick, creamy white
foam. Mousses can improve wet hair manageability by
lowering combing forces. They reduce flyaway and minimize
static. Fixative mousses claim to add body while providing
conditioning benefits. Styling mousses enhance body and
style retention. Formulation for Styling and Fixative Polymer
Mousse consist of (a)resins (which are generally cationic,
cationic and neutral, cationic and anionic, or amphoteric),(b)
water (which provides the medium for the formula), (c)
alcohol (which helps to reduce tack and acts as a VOC), (d)
hydrocarbons which are the most commonly used as a
propellant that dispenses the product out of the can), (e) non-
ionic emulsifier/surfactant (which helps in generating the
foam), and surfactants (which is used for lowering the surface
tension to help spread the polymer film over the hair surface
and to support the foam character of the product).
1.4 Type of Advancement in Styling and Fixative
Polymer:Polyquaternium-69 [9-14]
Polyquaternium-69 is a water-soluble, quaternary polymer
composed of (a) vinyl caprolactam (VCL)(which increases
the hydrophobicity and provides increased film flexibility and
durability of hold), (b) vinyl pyrrolidone (VP) (which
provides initial stiffness on hair after drying), (c)
dimethylaminopropylmethacrylamide (DMAPMA) (which
imparts conditioning and provides smoothness of the film and
flexibility of hold), (d) and methacryloylaminopropyllauryl
-dimonium chloride (MAPLDAC) (a hydrophobically
modified quaternary monomer which provides durability,
substantivity and the associative behavior of the polymer with
hydrophobically modified gellants). Together, these
monomers combine to provide the enhanced styling benefits
of polyquaternium-69. Polyquaternium-69 is a hydrophobic
polymer, yet water soluble and predominately non-ionic with
a weakly cationic nature providing a broad range of
compatibility with cosmetic ingredients including anionic
gellants. It is also synergistic with hydrophobic gellants and
has extremely low flaking and broad raw material
compatibility. It provides improved humidity resistance and
excellent high humidity curl retention. It provides enhanced
frizz control and mechanical properties without
compromising basic attributes such as gel clarity, stability,
mousse foam properties, and low VOC requirements. It is
more durable, has elastic hold, and increases shine and
luster.Polyquaternium-69 can be easily incorporated into
various styling products such as clear and cream gels, aerosol
and non-aerosol mousses, styling lotions, and sprays.
Advanced formulation of polyquaternium-69 comprise of (a)
polyquaternium-69 (which is used in combination with
another styling polymer, copolymer 845
(VP/Dimethylaminoethyl Methacrylate Copolymer)). This
combination increases the conditioned feel of hair both in the
wet and dry state. (b) Palmitamidopropyltrimonium Chloride
(PATC)(which is added primarily to raise the cloud point of
the concentrate to enhance stability, but its auxiliary benefits
are evident in increasing the quality of the foam and
conditioning aspects to hair, both in the wet and dry state).
The formula is made to be 6% VOC. This particular
formulation has increased curl formation and style memory.
Utility: Low VOC regulations have driven the researchers to
create fixatives that can be delivered from aqueous solutions.
In this context Polyquaternium-69 provides hydrophilic-
hydrophobic balance which leads to an excellent high
humidity curl retention, increased durability of hold, anti-
frizz effects under high humidity and high utility in meeting
low VOC requirements.
2. Thickening And Rheology Modifier Polymers [15-18]
Polymers comprising of long, branched or unbranched
molecules provides thickening effects. The mechanism of
action of thickening polymers can be attained by
entanglement, cross-linking or cluster formation. They are
extensively used in gels, oils, emulsions and nanoemulsions
to increase the viscosity and thickness of the particular
product by giving the product more richness, smooth and
creamy performance.
2.1 Mechanism of Action (MOA) of Thickening and
Rheology Modifier Polymers is: [15-18]
 Entanglement (like cooked spaghetti): In the
procedure for polymeric thickening, polymer chains are
dissolved in a solvent, which entangles much the same way
soft, cooked spaghetti noodles wrap around each other.
Solution viscosity increases as the polymer concentration
increases simply because more and more chains are trying to
occupy a limited space. As the polymer concentration
increases, it becomes more difficult to separate individual
polymer chains by the application of force over a given area.
 Cross-linking (bind to each other to form large
netlike structures): Cross-linking polymers (that is, hooking
two polymer chains together by periodic insertion of a
difunctional monomer that can react with both chains)
radically alters their properties. An optimum level of cross-
linking is required to maximize the polymer’s viscosity
performance i.e. solution polymers must be able to extend
and uncoil in solution so that chain entanglement can occur.
Cross-linking assures and enhances the ability of polymers to
overlap. At the same time, it effectively increases the
molecular weight of the polymers.
 Cluster formation (sit together forming micro
lumps): In the procedure for cluster formation grafting the
hydrophobe along the length of the hydrophilic backbone of
the polymer is achieved. The hydrophobic domains of the
polymeric thickeners behave like surfactant hydrophobes and
find themselves forced together by their unfavorable
interactions with water. As the polymer concentration
increases, the hydrophobic interactions evolve from

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International Journal of Research in Cosmetic Science 2016; 6(1): 6-16
intramolecular to intermolecular. These interpolymeric
associations create transient, noncovalent and interpolymeric
cross-links further leading into formation of cluster or micro
lumps.
2.2 Classification of Thickening and Rheology
Modifier Polymers:[15-18]
 Polyethylene Glycols (PEGs): Polyethylene glycol is
synthesized by the interaction of ethylene oxide with water,
ethylene glycol, or ethylene glycol oligomers. The starting
materials used for synthesis of PEG polymers with low
polydispersity index (narrow molecular weight distribution)
are ethylene glycol and its oligomers. PEG polymers thicken
by surrounding themselves with a sheet of water (cluster
effect).In most of the cases they are water-soluble at all use
levels. PEG shows a high solubility in organic solvents and,
therefore, end-group modifications are relatively easy. They
provide emulsifying properties which helps to stabilize
emulsions. Examples of widely used PEG-thickeners are
PEG-150 distearate, PEG- 7 glycerylcocoate, and PEG-200
hydrogenated glyceryl palmate and PEG-120 methyl glucose
dioleate.
 Carbopol Polymers: Carbopol polymers have greater
ability to thicken, suspend and stabilize aqueous
formulations. They have been the standard in the personal
care industry for forty years in a wide variety of applications
such as gels, creams, lotions and suntan products.
 Acrylate Copolymers/Carbomers: A carbomer is a
homopolymer of acrylic acid with a high molecular weight,
which is cross-linked with several polyalcohol allyl ethers.
It's the polyalcohol portion that confers a carbomer with its
high water solubility, unusual in polymers of this size.
Carbomers crosslink each other by forming a net, due to
which carbomers can help to greatly stabilize emulsions,
thereby allowing the formulator to decrease the amount of
primary emulsifiers but still hold the emulsion together.
Hence, carbomers are excellent agents to form stable, high-
viscosity creams and lotions. Another important feature of
carbomers is their ability to suspend hard-to-dissolve agents
like pigments, particles, antidandruff agents or other
polymers. Carbomer is an excellent thickening agent and is
consistent from batch to batch. It does not support bacterial
growth, and is hypo-allergenic. It also has a particularly nice
"skin feel," producing solutions and gels that feel rich and
luxurious to the touch. Examples of Acrylate
Copolymers/Carbomers are Carboxymethylene polymer,
Carboxyvinyl polymer, Acrylates/C10-30 alkyl acrylate
crosspolymeretc
2.3 Applications of Thickening and Rheology
Modifier Polymers: [15-18]
 Hair Styling Gels: Hair Styling Gels are aqueous
compositions that are usually thickened with cross linked
poly (acrylic acid); namely the carbomers. Carbomers confer
yield stress and shear thinning characteristics on aqueous
systems. In order to develop water- soluble fixatives nonionic
derivatized starches, poly-N-vinylacetamide, amphoteric
urethanes, and dehydroxanthan gum have been introduced.
Copolymers containing up to 10 weight percent of 2-
acrylamido-2-methy 1-1 -propane sulfonic acid or its salts in
combination with anionic or nonionic monomers provide a
better balance between conflicting requirements of good curl
retention at high humidity but they can be removed from hair
by merely rinsing with water. An extension of this class of
polymers has been introduced in the form of fluorine
modified comb polymers based on acryloyldimethyltaurine
acid.
 Nanoemulsions: Oil-in-water nanoemulsions are
liquid/liquid dispersions in which the droplet size is less than
100 nm. These small droplet size emulsions are transparent
and the droplets can be stabilized by a shell of emulsifiers,
which are structured as lamellar phase that completely wraps
each droplet. Nanoemulsions, are similar to regular emulsions
by virtue of the fact that they are thermodynamically unstable
and the small droplet size is achieved by subjecting the
system to enormous shear energies using homogenizers or
dispersers. Nanoemulsions often need to be thickened to be
acceptable to consumer expectations. Two conventional ways
to thicken a nanoemulsion is (a) by increasing the
concentration of the dispersed oil phase (which is usually not
an option for the cosmetic formulator because it usually leads
to compositions with an undesirable oily or greasy feel), and
(b) by adding conventional polyionic thickeners, but these
thickeners usually cause flocculation and/or coalescence of
the nanoemulsion and destroy the transparency for which the
nanoemulsion was made in the first place.
 Oils: Useful compositions have been thickened by
particulates such as clays or fumed silica; structuring waxes,
triglyceride gellants such as glyceryltribehenate, and silicone
elastomers. Block copolymers such as hydrogenated
styrene/isoprene block copolymers are useful as gellants.
Silicones thickened by elastomers tend to have unacceptably
high viscosities.
2.4 Type of Advancement in Thickening and
Rheology Modifier Polymer: CarbopolUlterez 10 Polymer
[15-18]
CarbopolUltrez 10 Polymer is a cross-linked polyacrylic acid
polymer that provides efficient rheology modification with
enhanced self-wetting properties which eliminates the need
for mechanical dispersers.This new polymer is unique
because it is exceptionally easy to disperse and requires no
mixing. CarbopolUltrez 10 will self-wet in minutes after the
polymer is put on the surface of water. In addition,
carbopolultrez 10 is a universal polymer, offering a wide
range of performance properties valuable in many personal
care applications and, are suitable for general thickening for
gels, creams and lotions. Since the dispersion viscosity of
carbopolultrez 10 is extremely low, adding additional

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International Journal of Research in Cosmetic Science 2016; 6(1): 6-16
ingredients when making a formula is easy, reducing
processing time in a formula. This polymer is highly efficient
for cost effectiveness, and has improved aesthetic properties
(i.e. less tacky feel than traditional carbomer polymers,
providing excellent gloss, clarity and smoothness desired in
gel products). CarbopolUltrez 10 polymer has outstanding
ability to suspend and stabilize formulations. It can be
polymerized in toxicologically preferred solvent system,
cyclohexane and ethyl acetate. Advanced formulation of
carbopolultrez 10 polymer mainly uses the liposome formula
which demonstrates the use of carbopolultrez 10 as an
additional thickener. This formula does not use soap or
surfactant based emulsifiers which could damage the
liposome structure, but is instead emulsified with
acrylates/c10-30 alkyl acrylate cross polymer, which is a
primary emulsifier and can emulsify very high amounts of
oils at low usage levels. Both polymers are added using the
indirect addition technique, whereby the polymers are
dispersed in the oil phase.
Utility: Cross-linked polyacrylic acid polymers have been
developed as polymeric emulsifiers for efficient rheology
modification with enhanced self-wetting for ease of use.
CarbopolUltrez 10 polymer is a unique, multi-purpose
carbopol polymer that is the easiest to disperse, has a low
dispersion viscosity, requires no mixing to disperse, and
makes processing easier, less time consuming, more cost
efficient, provides high efficient thickening, excellent clarity,
and a non-tacky elegant feel in gels, cream, and lotions.
3. Coloring And Highlighting Polymers [19-25]
Hair Coloring and Highlighting Polymers act as thickeners
for oxidation dyes, conditioners and hair-protectors. The
thickeners used in hair care are classified into associative
thickeners, hydrophobically modified ethoxylated urethanes
(HEUR), alkylmethicones & aminosilicones and
nonassociative thickeners. The formulations for thickened
oxidation dye compositions must be stable and should be
readily rinse-able from the hair with water. The compositions
must have desired rheological properties, and the dye mixture
should allow rapid diffusion of the dye precursors. The
mixture should contain conditioning agents and should have
comparable viscosities.
3.1 Mechanism of Action (MOA) of Thickened
Oxidation Dye Compositions: [19-25]: Polymeric oxidation
dyes are made up of dye precursors, which are colorless
compounds that can penetrate the hair fiber. Traditional Hair
Coloring Systems usually contains oxidative ‘permanent’
dyes which comprises of 2-part kits : Dye precursor alkaline
solution and Oxidizer
3.2 Classification of Thickeners used as Hair
Coloring and Highlighting Polymers: [19-25]
 Associative Thickeners: These thickeners consider
the structure of the thickeners with their reported
performance in oxidation dyeing. They can be further
classified as anionic, cationic, amphoteric, nonionic, and
hydrophobically modified alkali swellable.
 Hydrophobically modified Ethoxylated Urethanes
(HEUR): This class enhances color intensity from thickened
oxidation dyes. Once the hair has been dyed with either a
direct dye or an oxidative dye, the color must be maintained.
Examples for this class are: PEG-180/octoxynol-40/TMMG
copolymer, PEG-180/laureth-50/TMMG copolymer, and
polyether-1.
 Alkylmethicones & Aminosilicones: They play a
significant role in color retention. They provide more uniform
dyeing along the length of the fiber, improve hair softness
and pliability and have good shampoo fastness properties.
Examples for this class are amodimethicone and
trimethylsiloxyamadimethicone
 Nonassociative Thickeners: They are highly suitable
for hair lightening. Examples for this class are cross linked
acrylic acid homopolymers, nonionic guar gums, and
dimethylaminoethyl methacrylate homopolymers and
copolymers quaternized with methyl chloride.
3.3 Type of Advancement in Hair Coloring and
Highlighting Polymer: Acrylates/ Steareth-20
Methacrylate Copolymer[19-25]
Acrylates/Steareth-20 Methacrylate Copolymer is a
Hydrophobically-modified Alkali Soluble Emulsion (HASE).
HASE polymers are synthesized from an acid/acrylate
copolymer backbone and a monomer that connects the
hydrophobic groups as side chains. The polymer is made
through emulsion polymerization and is synthesized from
acrylic acid, acrylate esters and a steareth-20 methacrylate
ester. Mechanism of Actioncomprises of two mechanistic
components that work jointly to produce the observed
thickening. The first component is polyion swelling, which
occurs when the polymer is neutralized with base and
becomes a polyelectrolyte; the resulting polyion swells as a
result of mutual ionic repulsion of the carboxylate ions that
are covalently attached to the polymer chain. In the second
mechanistic component, swollen thickener molecules are
hydrophobically associated to form an overall network
structure. The hydrophobic associations between the
macromolecules are easily disrupted by shear and are
reformed into a new conformation when the shear force is
ceased. A characteristic feature of acrylates/steareth-20
methacrylate copolymer is its highly associative andpseudo
plastic nature. This polymer has broad pH range stability, and
is also used as an emulsion and foam stabilizer. The polymer
is salt & shear tolerant, has instant neutralization/thickening
property and has high yield value. Advantage of
acrylates/steareth-20 methacrylate copolymer includes it’s
easy to handle and non-hygroscopic nature. The polymer has
increased manufacturing efficiency. The polymer is able to
formulate clear products and can be used with electrolytes. It
has synergistic interaction with surfactants, particulates and

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International Journal of Research in Cosmetic Science 2016; 6(1): 6-16
hydrophobic raw materials and provides enhanced
stabilization. The polymer is compatible with nonionic,
anionic, zwitterionic and some cationic surfactants and has
the ability to stabilize suspensions. It thickens and stabilizes
hydrogen peroxide and does not promote or support
contamination, unlike natural thickeners. The polymer has
flexibility in choice of preservative system and is supported
by comprehensive environmental, health and safety data.
Advanced Formulation of Acrylates/Steareth-20 Methacrylate
Copolymer comprise of: [19-25]
Utility: Hydrophobically-modified Alkali Soluble Emulsions
are being extensively used in hair-coloring products to gel the
product on the substrate, but to simultaneously allow good
color development. Acrylates/Steareth-20 Methacrylate
Copolymer a rheology modifier is an anionic hydrophobically
modified alkali-soluble acrylic polymer emulsion (HASE)
with unusually high aqueous thickening and stabilizing
efficiency. This polymer is a liquid, cold-processable product
that instantaneously thickens upon neutralization providing
ease of handling and increased manufacturing efficiency.
4. Conditioning And Cleansing Polymers [26-28]
The Conditioning and Cleansing Polymers are effective hair
modifiers designed to deposit, adhere, or adsorb to proteins of
the hair. They improve the hair manageability and make the
hair softer and smoother. These are classified as cationic
conditioning polymers, nonionic conditioning polymers and
silicone polymers. Cationic polymers are preferred as they
are hold by the negatively charged hair proteins by
electrostatic forces, whereas nonionic polymers are easily
washed off by surfactants. Silicone polymers are a diverse
family of synthetic inorganic polymers based upon
polydimethylsiloxane.
4.1 Mechanism of Action (MOA) of Conditioning
and Cleansing Polymers is:[26-28]:
A conditioner improves the quality of the surface to which it
is applied particularly improvement involves the correction or
prevention of certain aspects associated with surface damage.
Conditioning of the hair must be a continuous process, as
both substrates are in a constant cycle of shedding and
renewal. Hair damage results from both mechanical and
chemical treatments that alter the physical structures of the
hair. Conditioning agents cannot enhance repair, but can
temporarily increase the cosmetic value and function of the
hair shaft until removal of the conditioner occurs with
cleansing. Several mechanisms by which conditioners can
improve the cosmetic value of the weathered hair shaft are (a)
by increasing shine, (b) by decreasing static electricity, (c) by
improving hair strength and (d) by protecting against
ultraviolet radiation. Conditioning the hair can mitigate this
hair damage by improving sheen, decreasing brittleness,
decreasing porosity, and increasing strength.
Polymeric conditioners help hair look and feel better by
improving the physical condition of these surfaces. Hair
conditioners are intended primarily to make wet hair easier to
detangle and comb and to make dry hair smoother, shinier,
and more manageable. Cationic polymers are very efficacious
conditioning agents because of their substantivity to the
respective substrate, which is directly attributable to
electrostatic interactions between oppositely charged sites on
the hair shaft and on the polymer backbone. Conditioners
typically remain on the fiber surface, reducing combing
forces & flyaway, and in some systems, providing
enhancement of volume, curl retention, body and
manageability.
4.2 Classification of Conditioning and Cleansing
Polymers:[26-28]
 Cationic Conditioning and Cleansing Polymers:
Cationic polymers (positively charged) are preferred as they
are hold by the negatively charged skin/hair proteins by
electrostatic forces, as all cationic polymers carry a
quaternary ammonium compound they are called
polyquaternium-X, where X is simply sequentially chosen.
Examples include polyquaternium-6, polyquaternium-7,
polyquaternium-11, etc.
 Nonionic Conditioning and Cleansing Polymers:
Nonionic polymers when present in a dried state are very
hydrophobic, but when hydrated, are quite hydrophilic. This
dual functionality is characteristic which allow them to
spread quickly over the surface of hair, driven primarily by
their low surface tension on these protein substrates. They are
easily removed by surfactants (unlike mineral oil and other
oily conditioners) and hence are easily washed off during
shampooing and rinsing.
 Silicone Polymers: Silicone polymers are a diverse
family of synthetic inorganic polymers based upon
polydimethylsiloxane that can be prepared and modified in
numerous ways in order to produce materials suitable for a
wide range of applications. Silicones used in hair care
products are typically long, flexible molecules with a
backbone comprised of thousands of repeating units of some

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International Journal of Research in Cosmetic Science 2016; 6(1): 6-16
variation of – (O-Si-O) - linkages with differing organic
(carbon-containing) pendant groups attached to the central
silicone atom. These are typically liquid at room temperature
and are oily in their consistency. They are most often
insoluble in water, but are sometimes modified with ethylene
glycol groups or other atoms to render them as water-soluble.
The physical properties of silicones cause them to adsorb
onto the surface of hair and to spread out, forming a smooth
film, which increases slip along and between hair strands and
decreases combing forces. This renders them as superior
conditioner agents and detanglers. Additionally, they provide
thermal protection, which reduces structural damage incurred
from the use of heated styling tools. They have also been
found to increase the longevity of color in dyed hair. Silicone
polymers have a high refractive index, which allows them to
impart an extraordinary level of gloss to the hair, which gives
the appearance of shiny, glamorous tresses.
Most commonly used silicone polymers are (a)
cyclomethicones (which are used to provide transient shine
with no buildup and prevention against clogging or
windowing of pumps), (b) dimethicones (which are used to
provide shine, improved feel and softness. It is also used as
resin plasticizer, helps reducing static electricity and
resistance against humidity), (c) dimethiconecopolyols
(which are used as resin plasticizer, emulsifier, and foam
stabilizer. It also helps in reduction of irritation to the hair),
(d) alkyl-modified silicones (decyldimethicone,
stearylmethicone, andcetylmethicone) (which are used to
improve volume/body, and combing properties), silicone
resins (silsequinoxanes, siloxysilicates) (which are used to
provide improved volume/body and humidity resistance), and
silica (which is used as antifoamer, thickener and suspending
agent).
4.3 Applications of Conditioning and Cleansing
Polymers:[26-28]
 Shampoo: Shampoo is defined as suitable detergents
for the washing of hair, packaged in a form which is
convenient for use. Raw materials used in the formulation of
a shampoo are (a) surfactants (which can be classified as
primary/principle surfactants and secondary/auxiliary
surfactants), (b) foam boosters, (c) conditioning agents, (d)
additives, (e) preservatives, (f) sequestering agents, (g)
viscosity modifiers (which are used as thickening or thinning
agents), (h) opacifying or clarifying agents, (i) fragrance, (j)
color, (k) stabilizers (which are used as suspending agents),
(l) antioxidants and (m) UV absorbers. Primary/Principle
surfactants (lauryl sulfate and sodium or ammonium laureth
sulfate) are used to provide detergency and foam. Primary
surfactant has fine ability to clean sebaceous soil, while
providing excellent lather and viscosity building properties.
Secondary/Auxiliary surfactants (amides such as
cocamonoethanolamide (cocamide MEA), betaines) are used
to improve detergency, foam, and hair condition. A
characteristic consideration of shampoo is that they should
have ease of spreading and ease of rinsing. They should
possess abundant lathering power and efficient soil removal
efficiency. They should comprise of ease of combing and
setting wet as well as dry hair. They should provide lustre of
hair, efficient speed of drying and safety.
 Conditioners: Conventional conditioner
formulations are based upon lamellar gels or emulsions using
either ceto-stearyltrimethylammonium chloride or
distearyldimethylammonium chloride as cationic surfactants
and ceto-stearyl alcohol as co-surfactant. These products
form a gel matrix that confers conditioning benefits from
rinse-off products. Polymeric conditioners can improve wet
combability and ameliorate electrostatic charging of the hair.
Conditioners must provide ease of wet and dry combing and
should minimize porosity. They should smooth, seal and
realign damaged areas of the hair shaft. Conditioners should
impart sheen and a silken feel to the hair and should possess
the property to moisturize. They should provide some
protection against thermal and mechanical damage and
should add volume/body to the hair. Polyquaternium-10
(cationic hydroxyethylcellulose), polyquaternium-6
(polydiallyldimethylammonium chloride homopolymer) and
polyquaternium-7 (which is a copolymer of diallyldimethyl -
-ammonium chloride and acrylamide), are found in
conditioner formulations.
 Conditioning Shampoos: Conditioning shampoos are
intended primarily to cleanse and secondarily to improve
manageability and promote desired feel & appearance they
confer the wet hair attributes (i.e. hair softness and ease of
wet-combing), and the dry hair attributes (i.e. good cleansing
efficacy, long-lasting moisturized feel, and manageability
with no greasy feel). The mechanism of action of
conditioning shampoos introduced the concept of polymer-
surfactant complex coacervates that phase-separate and
deposit on the hair during rinsing. 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 and this 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 bind, hydrophobic interaction between the
hydrophobic surfactant tails causes the polymer-surfactant
complex to phase separate. If the surfactant concentration is
sufficiently high to form micelles or hemi-micelles along the
polyion chain, then the polyion is resolubilized. Conditioning
shampoos are formulated within the range of surfactant
concentrations that correspond to this solubilized regime. If

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International Journal of Research in Cosmetic Science 2016; 6(1): 6-16
this solubilized complex (shampoo) is diluted to a
concentration in the vicinity of the critical micelle
concentration, then the complex coacervate phase separates.
The separated phase is deposited on the hair during rinsing.
4.4 Type of advancement in Conditioning and
Cleansing Polymers: Polyquaternium-74 [26-28]
Polyquaternium -74 (molecular weight: ~1.2 M) is
amphoteric copolymer, i.e. bearing both cationic and anionic
charges. Cationic charge density of polyquaternium -74
varies from 0 meq/g to 1 meq/g as a function of pH. It is used
to deliver high conditioning and delivery performance in
rinse- off personal care applications. It gives light hair feel
and has strong affinity with dimethicone to boost deposition.
Mechanism of Action (MOA)
Polyquaternium -74 must have the ability to improve wet
combability and should be anti-static. It must restore
disrupted cuticle and should provide aid of active delivery
(flocculation during rinsing). It should neutralize the negative
charges of most shampoos and hair proteins and help hair lie
flat. It should ionically bond itself to hair and possess
antimicrobial properties.Polyquaternium -74 has(a) volume
enhancing properties (i.e. they re-firm hair from root and
thicken hair shaft), (b) anti-dandruff properties (i.e. they
eliminate fungus), (c) repairing properties (i.e. they restore
damaged keratin fiber), (d) moisturizing properties (i.e. they
nourish hair from inside), (e) shine providing properties (i.e.
they smoothen the hair surface), and (f) color protecting
properties (i.e. they lock and revive the color). Advanced
formulation of polyquaternium -74 polymer comprise of (a)
water, (b) dimethicone (which is used to boost deposition),
(c) polyquaternium-74 polymer, (d) laureth-7, sodium
benzoate and (e) phenoxyethanol, (which acts as a
preservative).
Utility: Amphoteric polymers are highly used to deliver high
conditioning and delivery performance in rinse- off personal
care applications. Polyquaternium-74 is a synthetic high
performance conditioning polymer whose flocculation and
deposition characteristics enable it to match or outperform
traditional conditioning polymers in detangling, overall hair
conditioning, shine enhancement and buildup reduction when
combined, as shown here, with a submicron dimethicone
emulsion.
5. UV And Sun Protection Polymers [29-30]
UV and Sun Protection Polymers are the breakthrough in hair
care technology for the effective broad spectrum UV-
protection of hair. UV and Sun protection polymers are
multifunctional UV-absorbing polymers for use in both
leave-in and rinse-off hair care products, including shampoos,
conditioners and non-aerosol hair styling products. They are
designed to provide substantive, broad-spectrum UV-A and
UV-B protection to hair. They protect the hair fiber structure,
both inside and out, against damage caused by sun exposure,
and maintains the tensile strength of hair after UV exposure.
It works well in formulations over a broad pH range, from 4
to 10. They have excellent toxicity profile, which is fully
water soluble, and is also compatible with a variety of
surfactants and in formulations containing up to 95 percent
alcohol.
Exposure to ultraviolet radiation depletes the protective lipids
found on the surface of the cuticle. This increases combing
forces necessary to detangle hair, which generally results in
formation of split ends and breakage. UV-B radiation (280-
320 nm) cleaves disulfide bonds (S-S) in the cuticle which
depletes cystine in the structure, and thus damages the protein
structure of the protective cover of the hair strand. This
process increases surface roughness and porosity, which
results in frizz, tangling, and ultimately, breakage. The
surface of human hair is highly hydrophobic, which helps to
seal moisture into the hair shaft, protect it from the
environment and mitigate effects from fluctuations in
humidity that can cause structural damage. UV-B breaks
down tryptophan found in the protein structure of the hair and
create a more highly negatively charged surface, which
becomes more hydrophilic and less capable of moisture
retention and more susceptible to ill effects of the
environment. Ultraviolet radiation also penetrates into the
cortex of the hair where it breaks down protein structures
within the hair strand, compromising the mechanical integrity
of the hair. This results in a lower tensile strength which
ultimately enhances easy breakage of hair. UV-A radiation in
the cortex reacts with both natural melanin pigments and
chemical dye molecules, causing photo bleaching and
yellowing, both definitely undesirable effects. UV and sun
protection polymers have greater charge density which
enhances its substantivity to the surface of hair. Also, as a
lighter weight, water-soluble polymer, it has no greasy tactile
sensation. The novel twist to the polymer structure is the
inclusion of groups capable of absorbing UV radiation at the
ends of the pendant groups. These portions of the molecule
transform the harmful, high energy UV radiation into a lower
energy form (infrared) that is emitted as heat. This sun
protection quality is perhaps the most valuable contribution
UV and sun protection polymers makes to any personal care
product formula.
5.1 Type of Advancement in Heat Repair and Sun
Protection Polymer: POLYSILICONE-19 [29-30]
Polysilicone-19 is a silicone copolymer with methoxy-
- cinnamic acid, cocos alkyl and cationic groups.
Polysilicone-19 provides efficient protection against UV-

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International Journal of Research in Cosmetic Science 2016; 6(1): 6-16
damage. It is a photo protective polymer, which is
specifically designed for protection of hair against UVB and
UVA. As polysilicone-19 is cationic, it is substantive to the
hair keratin, forming a thin protective layer which absorbs
damaging UV irradiation. Polysilicone-19 protects hair color
against fading in the sun light and fiber integrity against
damage by UV irradiation. They have high substantivity to
hair surface from rinse-off applications. Polysilicone-19 is
compatible with anionic surfactants. It can be used in anionic
post treatments for colorants with or without polycationic
ingredients.In the advanced formulation of polysilicone-19
polymer, polysilicone-19 is applied into the oily phase of an
emulsion like formulation e.g. conditioner, balm or hair
mask. In shampoo formulations polysilicone-19 is mixed with
a concentrated surfactant (anionic nonionic or amphoteric)
before further dilution with aqueous ingredients.
Utility: Silicone copolymers with methoxycinnamic acid,
cocos alkyl and cationic groups are significantly used as UV-
absorbing polymers providing heat repair and sun protection.
Polysilicone-19 provides efficient protection of the hair fiber
against UV-damage. It is a photoprotective polymer, which is
specifically designed for UVB and UVA protection of hair
Conclusion [1-8]
Polymeric materials are critically important to the creation of
modern cosmetics and personal-care products. Low VOC
regulations have driven the researchers to create fixatives that
can be delivered from aqueous solutions. In this context
Polyquaternium-69 provides hydrophilic-hydrophobic
balance which leads to an excellent high humidity curl
retention, increased durability of hold, anti-frizz effects under
high humidity and high utility in meeting low VOC
requirements.
Cross-linked polyacrylic acid polymers have been developed
as polymeric emulsifiers for efficient rheology modification
with enhanced self-wetting for ease of use. Carbopol Ultrez
10 polymer is a unique, multi-purpose carbopol polymer that
is the easiest to disperse, has a low dispersion viscosity,
requires no mixing to disperse, and makes processing easier,
less time consuming, more cost efficient, provides high
efficient thickening, excellent clarity, and a non-tacky elegant
feel in gels, cream, and lotions. Hydrophobically-modified
Alkali Soluble Emulsions are being extensively used in hair-
coloring products to gel the product on the substrate, but to
simultaneously allow good color development.
Acrylates/Steareth-20 Methacrylate Copolymer a rheology
modifier is an anionic hydrophobically modified alkali-
soluble acrylic polymer emulsion (HASE) with unusually
high aqueous thickening and stabilizing efficiency. This
polymer is a liquid, cold-processable product that
instantaneously thickens upon neutralization providing ease
of handling and increased manufacturing efficiency.
Amphoteric polymers are highly used to deliver high
conditioning and delivery performance in rinse- off personal
care applications. Polyquaternium-74 is a synthetic high
performance conditioning polymer whose flocculation and
deposition characteristics enable it to match or outperform
traditional conditioning polymers in detangling, overall hair
conditioning, shine enhancement and buildup reduction when
combined, as shown here, with a submicron dimethicone
emulsion.
Silicone copolymers with methoxycinnamic acid, cocos alkyl
and cationic groups are significantly used as UV-absorbing
polymers providing heat repair and sun protection.
Polysilicone-19 provides efficient protection of the hair fiber
against UV-damage. It is a photoprotective polymer, which is
specifically designed for UVB and UVA protection of hair
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Source of support: Nil; Conflict of interest: None declared