HAIR CARE COMPOSITION
The present invention relates to new polymers and their use for protecting the hair
fibre and other keratineous materials from damaging treatment.
Damage to the hair typically manifests itself in cuticle and protein loss from the
hair fibre, hair fibre dryness, hair fibre brittleness, hair breakage and frayed or split
ends.
Many every day activities damage the hair. For example, environmental sources
of hair damage include exposure to UV and chlorine. Chemical sources of hair
damage include treatments such as bleaching, perming and straightening, and
overly frequent washing with harsh surfactant-based cleansing shampoo
compositions. Mechanical sources of hair damage include excessive brushing and
combing and prolonged use of heated appliances for drying and styling the hair.
WO2008/058989 describes a permanent way of preventing damage to the hair by
covalently bonding to the hair a polymeric compound comprising polyethylene
glycol.
The present invention addresses the problem of hair damage prevention, but has
the additional advantage that it describes ways of repairing damaged hair. The
polymers used in this process are also relatively easy to produce.
Summary of the Invention
The present invention relates to a hair care composition comprising a polymeric
compound comprising allyl methacryate and at least one polymeric segment of
polyethylene glycol covalently attached to a central backbone.
The invention also provides the use of the polymeric compound described above
for derivatising hair.
A further aspect of the invention is a hair fibre covalently bonded the above
described polymeric compound.
Also claimed are polymers of poly[poly(ethylene glycol) methyl ether
methacrylate-co-allyl methacrylate.
Detailed description
The present invention relates to a method of protecting hair by covalently bonding
to the hair a polymeric compound allyl methacryate and at least one ethylene
glycol segment. Modification of proteins with polyethyleneglycol is commonly
known as PEGylation.
It is preferred if the polymeric compound comprises at least one polymeric
segment of ethylene glycol covalently attached to a central backbone, preferably
the central backbone comprises a acrylate, methacrylate group or mixtures
thereof. Thus one way of describing a preferred polymeric compound comprising
polyethylene glycol, is of a central backbone with a cluster of PEG polymers or
PEG segments.
It is preferred if the molecular weight Mw of the polymer is from 1,000 to 100,000
more preferably from 5,000 to 60,000, most preferably from 10,000 to 50,000.
It is also preferable if the number of acrylate, methacrylate groups within the
central back bone is from 1 to 20, preferably from 2 to 10 .
In addition to the above the polymeric compound comprising polyethylene glycol
may comprise other polymeric units.
A preferred polymer type is poly[poly(ethylene glycol) methyl ether methacrylateco-
allyl methacrylate]alternatively known as u>vinyl-poly[Poly(ethylene glycol)
methyl ether methacrylate-co-allyl methacrylate].
Such polymers are usually prepared by catalytic chain transfer polymerisation
(CCTP) and are thus known as CCTP polymers.
The level of polymeric compound comprising polyethylene glycol is preferably
from 0.01 to 15 wt.% of the total composition, more preferably from 0.1 to 10
wt.%.
Product Form
The final product form of hair treatment compositions according to the invention
may suitably be, for example, shampoos, conditioners, sprays, mousses, gels,
waxes or lotions.
The product may be a leave on product (left on the hair for at least 30 minutes) or
a wash off product, in particular a shampoo or post-wash conditioner.
The pH of the formulations of the invention are in the range from pH 3 to pH 11,
more preferably used at a pH from 3 to 8 .
Hair Treatment Composition Base Formulation
The composition of the invention may be a shampoo formulation. Shampoo
compositions preferably comprise one or more cleansing surfactants, which are
cosmetically acceptable and suitable for topical application to the hair. Further
surfactants may be present as emulsifiers.
Suitable cleansing surfactants, are selected from anionic, amphoteric and
zwitterionic surfactants, and mixtures thereof. The cleansing surfactant may be the
same surfactant as the emulsifier, or may be different.
Anionic Cleansing Surfactant
Shampoo compositions according to the invention will typically comprise one or
more anionic cleansing surfactants which are cosmetically acceptable and suitable
for topical application to the hair.
Examples of suitable anionic cleansing surfactants are the alkyl sulphates, alkyl
ether sulphates, alkaryl sulphonates, alkanoyl isethionates, alkyl succinates, alkyl
sulphosuccinates, N-alkyl sarcosinates, alkyl phosphates, alkyl ether phosphates,
alkyl ether carboxylates, and alpha-olefin sulphonates, especially their sodium,
magnesium, ammonium and mono-, di- and triethanolamine salts. The alkyl and
acyl groups generally contain from 8 to 18 carbon atoms and may be unsaturated.
The alkyl ether sulphates, alkyl ether phosphates and alkyl ether carboxylates may
contain from 1 to 10 ethylene oxide or propylene oxide units per molecule.
Typical anionic cleansing surfactants for use in shampoo compositions of the
invention include sodium oleyl sulpho succinate, ammonium lauryl sulphosuccinate,
ammonium lauryl sulphate, sodium cocoyi isethionate, sodium lauryl isethionate and
sodium N-lauryl sarcosinate. The most preferred anionic surfactants are sodium
lauryl sulphate, sodium lauryl ether sulphate(n)EO, (where n ranges from 1
to 3), ammonium lauryl sulphate and ammonium lauryl ether sulphate(n)EO, (where
n ranges from 1 to 3).
The total amount of anionic cleansing surfactant in shampoo compositions of the
invention is generally from 5 to 30, preferably from 6 to 20, more preferably from 8
to 16 wt% of the total composition.
Co-surfactant
The shampoo composition can optionally include co-surfactants, preferably an
amphoteric or zwitterionic surfactant, which can be included in an amount ranging
from 0 to about 8, preferably from 1 to 4 wt%.
Examples of amphoteric and zwitterionic surfactants include, alkyi betaines, alkyi
amidopropyl betaines, alkyi sulphobetaines (sultaines), alkyi glycinates, alkyi
carboxyglycinates, alkyi amphopropionates, alkylamphoglycinates, alkyi amidopropyl
hydroxysultaines, acyl taurates and acyl glutamates, wherein the alkyi and acyl
groups have from 8 to 19 carbon atoms. Typical amphoteric and zwitterionic
surfactants for use in shampoos of the invention include lauryl amine oxide,
cocodimethyl sulphopropyl betaine and preferably lauryl betaine, cocamidopropyl
betaine and sodium cocamphopropionate.
Another preferred co-surfactant is a nonionic surfactant, which can be included in an
amount ranging from 0 to 8 wt%, preferably from 2 to 5 wt% of the total
composition.
For example, representative nonionic surfactants that can be included in shampoo
compositions of the invention include condensation products of aliphatic (Cs - Cis)
primary or secondary linear or branched chain alcohols or phenols with alkylene
oxides, usually ethylene oxide and generally having from 6 to 30 ethylene oxide
groups.
Further nonionic surfactants which can be included in shampoo compositions of the
invention are the alkyl polyglycosides (APGs). Typically, the APG is one which
comprises an alkyl group connected (optionally via a bridging group) to a block of
one or more glycosyl groups. Preferred APGs are defined by the following formula:
wherein R is a branched or straight chain C5 to C20 alkyl or alkenyl group, G is a
saccharide group and n is from 1 to 10.
The shampoo composition can also optionally include one or more cationic cosurfactants
included in an amount ranging from 0.01 to 10, more preferably from
0.05 to 5, most preferably from 0.05 to 2 wt% of the total composition. Useful
cationic surfactants are described herein in relation to conditioner compositions.
The total amount of surfactant (including any co-surfactant, and/or any emulsifier)
in shampoo compositions of the invention is generally from 5 to 50, preferably
from 5 to 30, more preferably from 10 to 25 wt%.
Cationic Deposition Polymer
A cationic polymer is a preferred ingredient, especially in shampoo compositions
of the invention.
The cationic polymer may be a homopolymer or be formed from two or more types
of monomers. The molecular weight of the polymer will generally be between 5 000
and 10 000 000 Dalton, typically at least 10 000 and preferably from 100 000 to 2
000 000. The polymers will have cationic nitrogen containing groups such as
quaternary ammonium or protonated amino groups, or a mixture thereof.
The cationic nitrogen-containing group will generally be present as a substituent on
a fraction of the total monomer units of the cationic polymer. Thus when the polymer
is not a homopolymer it can contain spacer non-cationic monomer units. Such
polymers are described in the CTFA Cosmetic Ingredient Directory, 3rd edition. The
ratio of the cationic to non-cationic monomer units is selected to give a polymer
having a cationic charge density in the required range.
The cationic deposition polymer will generally be present in compositions of the
invention at levels of from 0.01 to 5, preferably from 0.02 to 1, more preferably from
0.04 to 0.5 percent by weight of the composition.
Conditioning Surfactant
Conditioner compositions usually comprise one or more conditioning surfactants
which are cosmetically acceptable and suitable for topical application to the hair.
Suitable conditioning surfactants are selected from cationic surfactants, used singly
or in a mixture.
Cationic surfactants useful in compositions of the invention contain amino or
quaternary ammonium hydrophilic moieties which are positively charged when
dissolved in the aqueous composition of the present invention.
Examples of suitable cationic surfactants are those corresponding to the general
formula:
[N(Ri)(R2)(R3)(R4)]+ (X)-
in which Ri, R2, R3, and R4 are independently selected from (a) an aliphatic group of
from 1 to 22 carbon atoms, or (b) an aromatic, alkoxy, polyoxyalkylene, alkylamido,
hydroxyalkyl, aryl or alkylaryl group having up to 22 carbon atoms; and X is a saltforming
anion such as those selected from halogen, (e.g. chloride, bromide),
acetate, citrate, lactate, glycolate, phosphate nitrate, sulphate, and alkylsulphate
radicals.
Fatty Materials
Conditioner compositions of the invention preferably additionally comprise fatty
materials. The combined use of fatty materials and cationic surfactants in
conditioning compositions is believed to be especially advantageous, because this
leads to the formation of a structured phase, in which the cationic surfactant is
dispersed.
By "fatty material" is meant a fatty alcohol, an alkoxylated fatty alcohol, a fatty acid or
a mixture thereof.
Preferably, the alkyl chain of the fatty material is fully saturated.
Representative fatty materials comprise from 8 to 22 carbon atoms, more preferably
16 to 22. Examples of suitable fatty alcohols include cetyl alcohol, stearyl alcohol
and mixtures thereof. The use of these materials is also advantageous in that they
contribute to the overall conditioning properties of compositions of the invention.
Alkoxylated, (e.g. ethoxylated or propoxylated) fatty alcohols having from about 12
to about 18 carbon atoms in the alkyl chain can be used in place of, or in addition
to, the fatty alcohols themselves. Suitable examples include ethylene glycol cetyl
ether, polyoxyethylene (2) stearyl ether, polyoxyethylene (4) cetyl ether, and
mixtures thereof.
The level of fatty alcohol material in conditioners of the invention is suitably from
0.01 to 15 wt%, preferably from 0.1 to 10 wt% of the total composition. The weight
ratio of cationic surfactant to fatty alcohol is suitably from 10:1 to 1:10, preferably
from 4:1 to 1:8, optimally from 1:1 to :7.
Suspending Agents
In a preferred embodiment, the shampoo compositions of this invention further
comprises from 0.1 to 5 wt% of a suspending agent for the coated particles.
Suitable suspending agents are selected from polyacrylic acids, cross-linked
polymers of acrylic acid, copolymers of acrylic acid with a hydrophobic monomer,
copolymers of carboxylic acid-containing monomers and acrylic esters, crosslinked
copolymers of acrylic acid and acrylate esters, heteropolysaccharide gums
and crystalline long chain acyl derivatives. The long chain acyl derivative is
desirably selected from ethylene glycol stearate, alkanolamides of fatty acids
having from 16 to 22 carbon atoms and mixtures thereof. Ethylene glycol
distearate and polyethylene glycol 3 distearate are preferred long chain acyl
derivatives. Polyacrylic acid is available commercially as Carbopol 420, Carbopol
488 or Carbopol 493. Polymers of acrylic acid cross-linked with a polyfunctional
agent may also be used, they are available commercially as Carbopol 9 10,
Carbopol 934, Carbopol 940, Carbopol 941 and Carbopol 980. An example of a
suitable copolymer of a carboxylic acid containing a monomer and acrylic acid
esters is Carbopol 1342. All Carbopol (trade mark) materials are available from
Goodrich.
Suitable cross-linked polymers of acrylic acid and acrylate esters are Pemulen
TR1 or Pemulen TR2. A suitable heteropolysaccharide gum is xanthan gum, for
example that available as Kelzan mu.
The suspending agent is preferably a polymeric suspending agent.
Styling polymers
If the composition is a styling product it is preferred if a styling polymer is present
The hair styling polymer if present is preferably present in the compositions of the
invention in an amount of from 0.001 % to 10% by weight, more preferably from
0.1 % to 10% by weight, such as from 1% to 8% by weight.
Hair styling polymers are well known. Suitable hair styling polymers include
commercially available polymers that contain moieties that render the polymers
cationic, anionic, amphoteric or nonionic in nature. Suitable hair styling polymers
include, for example, block and graft copolymers. The polymers may be synthetic
or naturally derived.
The amount of the polymer may range from 0.5 to 10%, preferably 0.75 to 6% by
weight based on total weight of the composition.
Adjuvants
The compositions of the present invention may also contain adjuvants suitable for
hair care. Generally such ingredients are included individually at a level of up to
2, preferably up to 1 wt% of the total composition.
Suitable hair care adjuvants, include amino acids and ceramides.
The invention will now be illustrated by the following non-limiting Examples.
Example of the invention are illustrated by a number, comparative Examples are
illustrated by a letter.
Polymers of the invention were prepared by CCTP as described in figure 1.
Examples:
Preparation of CCTP co-polymer PEG-AMA (Mw 3800)
Methanol (38ml_) and demineralised water (38ml_) were placed into a round
bottomed flask with a magnetic stirrer bar, sealed with a suba-seal, para-film and
purged with nitrogen for 2hrs prior to the experiment starting. Di(ethylene glycol)
methyl ether methacrylate (DEGMEMA) monomer (29.41 ml_, 0.1 6 Mol, 188.22
g.mol 1) was placed into a round bottom flask, along with allyl methacrylate (AMA)
monomer ( 1 .07ml_, 0.008 Mol, 126 g.mol 1) sealed with a suba-seal, para-film and
purged with nitrogen for 2hrs. Initiator 4,4'-azobis(4-cyano-valeric acid) (CVA)
(0.28g, 8.21 x 10 4 Mol, 280.28 g.mol 1) was placed into a round bottom flask with a
magnetic stirrer bar, sealed with a suba-seal, para-film and purged with nitrogen
for 2hrs. Bis(boron difluorodimethylglyoximate) cobalt (II) (CoBF, chain transfer
agent) (3.06mg, 7.97x1 0 6 Mol, 503 g . mol 1) was placed into a round bottom flask
with a magnetic stirrer bar, sealed with a suba-seal, para-film and purged with
nitrogen for 2hrs.
The MeOH and H2O mixture was cannulated into the round bottom flask
containing CVA and the solution was heated to 80°C in an oil bath with a fuzzylogic
temperature controller. The DEGMEMA/AMA monomer mixture was
cannulated into the round bottom flask containing CoBF and 3.2ml_ of this solution
was transferred into the solvent/initiator round bottom flask using a degassed
syringe. A feed pump was used to supply the remaining monomer/CoBF mixture
into the solvent/CVA mixture at a rate of 0.43mL/min (feed completed after 60
minutes) and samples for analysis were taken periodically using a degassed
syringe. After five hours the reaction was removed from the oil bath and air was
bubbled through the reaction solution.
Purification
The remaining monomer and solvent in the reaction were removed using a
vacuum pump with the collection flask cooled in liquid nitrogen. The sample flask
was heated to 30°C to stop the solution from freezing.
Preparation of PEGylated polymers
Comparative PEGylated polymers were prepared as in WO2008/058989.
DSC Studies
Sample preparation
European hair fibres were bleached two times with L'Oreal platifiz precision
powder and Oxydant creme ( 1 :1 .5) for 30min, rinsed completely with running
water from the tap, and naturally dried overnight before the next application.
These hair fibres were immersed in 1% active solution and water (as a control) at
pH 5.5 for 1 h respectively, rinsed with distilled water for 30 sec and naturally
dried overnight. And then they were cut into approximate! 2mm length with
scissors.
DSC method
About 6 mg of sample was weighted into a pressure resistant (25 bar), stainless
steel, large volume pan (60 capacity). 50 of water was added and the pan
was sealed. Samples were then mixed using a rotary mixer and left overnight to
allow the water to equilibrate throughout the sample. Samples were run through a
temperature programme of 120-1 80°C at a rate of 5°C/ min in 30ml/min nitrogen
atmosphere. The helix transition temperature was collected and analyzed with
one-way ANOVA. Each sample was carried out at least four times.
DSC Data
The DSC data of bleached hair fibre as well as bleached and PEGylated hair
fibres is given in Table 1 below. A high denaturation temperature (Td) indicates
that the hair is not denatured.
Table 1 - Comparison of the Denaturation data of with CCTP Co-Polymer
PEG-AMA & PEGylated hair
The Example of the invention shows a 10°C enhancement compared to the
damaged hair.
Connparative Examples (Examples A and B) in which the hair is merely pegylated
preventing hair damage to a lesser extent.

CLAIMS
1. A hair care composition comprising a polymeric compound comprising allyl
methacryate and at least one polymeric segment of polyethylene glycol
covalently attached to a central backbone.
2.. A hair care composition according to any preceding claim in which the
central backbone comprises a acrylate, methacrylate group or mixtures
thereof.
3 . A hair care composition according to any preceding claim in which the
molecular weight Mw of the polymer is from 5,000 to 60,000.
4 . A hair care composition according to any preceding claim in which the
number of acrylate, methacrylate groups within the central back bone is
from 2 to 10 .
5 . A method of protecting hair by applying to the hair a polymeric compound
as described in any preceding claim.
6 . A hair fibre covalently bonded to a polymeric compound as described in
any preceding claim.
7 . A polymeric compound of poly[Poly(ethylene glycol) methyl ether
methacrylate-co-allyl methacrylate.