J3856/C
FORM-2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003


COMPLETE SPECIFICATION
(See Section 10 and Rule 13)
COMPOSTION COMPRISING BRUSH COPOLYMER FOR TREATING HAIR

HINDUSTAN UNILEVER LIMITED, a company incorporated under
the Indian Companies Act, 1913 and having its registered office
at 165/166, Backbay Reclamation, Mumbai -400 020, Maharashtra, India
The following specification particularly describes the invention and the manner in which it is to be performed


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- 1 -COMPOSITION FOR TREATING HAIR
Field of the Invention
This invention relates to compositions, copolymeric 5 materials and methods for delivering benefit agents from these compositions.
Background
Personal care compositions contain a range of agents that 10 enhance the body or hair. Benefit agents, such as perfumes, silicones, waxes, flavours, vitamins and fibre active agents are expensive and generally less effective when employed at high levels in personal care compositions, cleaning compositions. As a result, there is a desire to maximise the 15 effectiveness of such benefit agents. One method of
ochTtivirKj such object is-to improve the delivery —
efficiencies of such benefit agents. Unfortunatelyf it is difficult to improve the delivery efficiencies of benefit agents as such agents may be lost due to the agents' 20 physical or chemical characteristics, or such agents may be incompatible with other compositional components or the sites that are treated.
Accordingly, there is a need for a benefit agent containing 25 delivery particles that provide improved benefit agent delivery efficiency.
The present invention relates to a benefit agent delivery system. When employed in compositions, for example cleaning 30 (e.g. shampoo or body wash) or conditioning compositions or leave-on products for skin such as the scalp and other body
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sites, the benefit agent delivery system increases the efficiency of benefit agent delivery, thereby allowing reduced amounts of benefit agents to be employed. In addition by allowing the amount of benefit agent to be 5 reduced, the benefit agent delivery system allows a broad range of benefit agents to be employed
Description of the invention
The present invention relates to compositions comprising a 10 brush copolymer of formula 1:

15 in which M1 is a unit obtainable from ring opening metathesis polymerisation (ROMP);
R is an alkyl, ether, ester or aryl unit;
M2 and M3 are independently selected from units obtainable by reversible addition fragmentation chain transfer
20 polymerization(RAFT) ;
X is a terminal unit selected from the group consisting of dithioester, trithiocarbonate, xanthate; and m is an integer from 2 to 1 million, n is an integer from 2 to 500,000 and k is an integer from 2 to 500,000.
25
The use of the above mentioned copolymers to deliver a benefit agent to the hair is also described as is a method
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of treating the hair by application to the hair a composition the above mentioned copolymers
Detailed Description
5 The present invention relates as core-shell brush copolymers for delivering benefit agents. Preferably the brush copolymers are in the form of a nanocage structure.
Core-shell brush copolymers
10 The present invention relates to a composition comprising a brush copolymer of formula 1:


15

Formula 1
in which M1 is a unit obtainable from ring opening metathesis polymerisation (ROMP) preferably a unit obtainable from the ring opening metathesis polymerisation (ROMP) of cyclooctadiene or norbornene.

20
R is an alkyl, ether, ester or aryl unit;
M2 and M3 are independently selected from units obtainable by reversible addition fragmentation chain transfer polymerization(RAFT), preferably units obtainable by 25 reversible addition fragmentation chain transfer
polymerization(RAFT) of styrene, isoprene, methyl aerylate, tert-butyl acrylate, dimethyl acryamide, acrylic acid.
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_ 4 _
acrylonitrile, methyl methacrylate, maleic anhydride, vinyl acetate, vinyl pyridine orvinyl phenyl ketone; X is a terminal unit selected from the group consisting of dithioester, trithiocarbonate, xanthate; and 5 m is an integer from 2 to 1 million, preferably from 10 to 500,000, more preferably from 100 to 200,000,, n is an integer from 2 to 500,000, preferably from 10 to 250,000, more preferably from 20 to 100,000 and k is an integer from 2 to 500,000, preferably from 10 to 250,000, more 10 preferably from 20 to 100,000
Preferably the core shell brush copolymer has the structure of formula 2:

20

in which m is an integer from 2 to 1 million, and y is an integer from 2 to 18, x is an integer from 1 to 100, n is an integer from 2 to 500,000 and k is an integer from 2 to 500,000.

25

The invention further relates to a core-shell brush copolymer of formula 3
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Formula 3
in which m is an integer from 2 to 1 million, n is an 5 integer from 2 to 500,000 and k is an integer from 2 to 500,000.
A further aspect of the invention is a core-shell brush copolymer of formula 4


10
Formula 4
in which m is an integer from 2 to 1 million, x is a value 15 from 0 to 1, n is an integer from 2 to 500,000 and k is an integer from 2 to 500,000.
The core-she11 brush copolymers of the invention are preferably particulate in nature, having dimensions ranging 20 from 2 to 2000 nm and aspect ratios from 1 to 10000, as measured by dynamic light scattering, atomic force microscopy, transmission electron microscopy, or other standard means that are known to those in the art.
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The core-shell brush copolymer is manufactured using the step of tandem ROMP (ring opening metathesis polymerisation) and RAFT (reversible addition fragmentation chain transfer polymerization).
The preferred reaction scheme is as follows:

15

The core shell brush copolymer may be further polymerised so that it forms a nanocage. The nanocage is prepared by internal cross linking, in particulate internal cross linking. In the context of the present invention a nanocage can be defined as copolymeric polymer lined in such a manner

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that it forms a shell like structure. A highly preferable use of this shell like structure is for encapsulating material.
5 It is highly preferable if incorporated within the core-shell brush copolymer is a benefit agent.
The core shell brush copolymer is preferably present (with or without the benefit agent) the total composition in an 10 amount of from 0.01 to 50 wt%, more preferably from 0.2 to 20 wt%, most preferably from 0.5 to 10 wt%.
Benefit agents:
Benefit agents can be selected from the group consisting of 15 moisturisers, anti-wrinkle agents, skin, hair and nail
nntri pnt.s, and the like chemosensates such as coolants and
those providing a warming sensation,, fragrances, silicone oils, waxes, hydrocarbons, higher fatty acids, essential oils, lipids, skin coolants, vitamins, sunscreens, 20 glycerine, catalysts, bleach particles, silicon dioxide particles, malodour reducing agents, oral care agents, household care agents, fabric care agents, detergents, antiperspirant actives, flavourings, food additives, cationic polymers and mixtures thereof. 25
Particularly preferred benefit agents are selected from hair styling polymers, colourants, hair conditioners, hair cleansers, hair growth promoters, permanent wave compounds, hair relaxers, amino acids, vitamins, hair straighteners, 30 hair growth stimulants, hair growth retardants, hair
shedding inhibitors, antibacterial compounds, antifungal
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compounds, anti-inflammatory compounds, anti-pruritic agents, sebum suppressants, sunscreens and mixtures thereof.
Especially preferred is an antifungal compound, an 5 antibacterial compound, an anti-inflammatory compound, a sebum suppressant and an anti-pruritic agent or mixtures thereof. Of particular interest is salicylic acid.
In an alternative aspect of the invention hair growth 10 promoters are of interest as benefit agents. Examples of
substances which themselves possess the ability to stimulate or increase hair growth include benzalkonium chloride, benzethonium chloride, phenol estradiol, diphenhydramine hydrochloride, chlorpheniramine maleatef chlorophyllin 15 derivatives, cholesterol, salicylic acid, cystine, red
peppor -tincture,—benzyl nicotinate, dl-m^nthnl, peppermiJit
oil, calcium pantothenate, panthenol, castor oil, hinokitiol, prednisolone, minoxidil, saw palmetto extract, nettle root extract, capsaicin, niacin, ginko biloba, 20 horsetail extract, phospholipid, glycerol oxide esters, cyclodextrin,. ketoconazole, ursolic acid, polysorbate, 1,4,3,6-dianhydro-2,5-d-o-methyl-d-glucitol, milk thistle, methyl nicotinate, finasteride, azelaic acid, medroxyprogesterone, dutasteride, topical Hedgehog agonists, 25 adenosine, tra.ns-3, 4 ' -dimethyl-3-hydorxyf lavanone and resorcinol.
These benefit agents are incorporated into the composition preferably in an amount of 0.0001 to 5 % based on the total 30 weight of the composition.
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Product Form
Compositions of the invention are preferably personal care compositions, more preferably they are hair treatment 5 compositions.
Compositions of the invention can be rinsed off or left on the hair, typically they are "rinse-off" compositions to be applied to the hair and then rinsed away. 10
A particularly preferred product form is a shampoo composition.
Shampoo Composition
15
Shampoo compositions -of the invention are generally aqueous,
i.e. they have water or an aqueous solution or a lyotropic
liquid crystalline phase as their major component.
Suitably, the composition will comprise from 50 to 98%, 20 preferably from 60 to S0% water by weight based on the total
weight of the composition.
Anionic Cleansing Surfactant
25 Shampoo compositions as claimed in the invention will
generally comprise one or more anionic cleansing surfactants which are cosmetically acceptable and suitable for topical application to the hair.
30 Examples of suitable anionic cleansing surfactants a.re the alkyl sulphates, alkyl ether sulphates, alkaryl sulphonates,

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alkanoyl isethionates, alkyl succinates, alkyl sulphosuccinates, alkyl ether sulphosuccinates, N-alkyl sarcosinates, alkyl phosphates, alkyl ether phosphates, and alkyl ether carboxylic acids and salts thereof, especially 5 their sodium, magnesium, ammonium and mono-, di- and
triethanolamine salts. The alkyl and acyl groups generally contain from 8 to 18, preferably from 10 to 16 carbon atoms and may be unsaturated. The alkyl ether sulphates, alkyl ether sulphosuccinates, alkyl ether phosphates and alkyl 10 ether carboxylic acids and salts thereof may contain from 1 to 20 ethylene oxide or propylene oxide units per molecule.
Typical anionic cleansing surfactants for use in shampoo compositions of the invention include sodium oleyl 15 succinate, ammonium lauryl sulphosuccinate, sodium lauryl
sulphale, sodium lauryl other- sulphate, sodium 1-awyl ether
sulphosuccinate, ammonium lauryl sulphate, ammonium lauryl ether sulphate, sodium dodecylbenzene sulphonate, triethanolamine dodecylbenzene sulphonate, sodium cocoyl 20 isethionate, sodium lauryl isethionate, lauryl ether carboxylic acid and sodium N-lauryl sarcosinate.
Preferred anionic cleansing surfactants are sodium lauryl sulphate, sodium lauryl ether sulphate(n)EO, (where n is 25 from 1 to 3), sodium lauryl ether sulphosuccinate (n)EO,
(where n is from 1 to 3), ammonium lauryl sulphate, ammonium lauryl ether sulphate(n)EO, (where n is from 1 to 3), sodium cocoyl isethionate and lauryl ether carboxylic acid (n) EO (where n is from 10 to 20).
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Mixtures of any of the foregoing anionic cleansing surfactants may also be suitable.
The total amount of anionic cleansing surfactant in shampoo 5 compositions of the invention generally ranges from 0.5 to 45%, preferably from 1.5 to 35%, more preferably from 5 to 20% by total weight anionic cleansing surfactant based on the total weight of the composition.
10 Further Ingredients
Optionally, a shampoo composition of the invention may contain further ingredients as described below to enhance performance and/or consumer acceptability.
15
Co-surfactant — _ __
The composition can include co-surfactants, to help impart aesthetic, physical or cleansing properties to the 2 0 composition.
An example of a co-surfactant is a nonionic surfactant, which can be included in an amount ranging from 0.5 to 8%, preferably from 2 to 5% by weight based on the total weight 25 of the composition.
For example, representative nonionic surfactants that can be included in shampoo compositions of the invention include condensation products of aliphatic (C8 - C18)ols or phenols with
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alkylene oxides, usually ethylene oxide and generally having from 6 to 30 ethylene oxide groups.
Other representative nonionic surfactants include mono- or 5 di-alkyl alkanolamides. Examples include coco mono- or di-ethanolamide and coco mono-isopropanolamide.
Further nonionic surfactants which can be included in shampoo compositions of the invention are the alkyl 10 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:
15
wherein R is a branched or straight chain alkyl group which may be saturated or unsaturated and G is a saccharide group.
20 R may represent a mean alkyl chain length of from about C5 to about C20- Preferably R represents a mean alkyl chain length of from about C8 to about C12- Most preferably the value of R lies between about 9.5 and about 10.5. G may be selected from C5 or C8 monosaccharide residues, and is preferably a
25 glucoside. G may be selected from the group comprising
glucose, xylose, lactose, fructose, mannose and derivatives thereof. Preferably G is glucose.
The degree of polymerisation, n, may have a value of from 30 about 1 to about 10 or more. Preferably, the value of n
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lies from about 1.1 to about 2. Most preferably the value of n lies from about 1.3 to about 1.5.
Suitable alkyl polyglycosides for use in the invention are 5 commercially available and include for example those
materials identified as: Oramix NS10 ex Seppic; Plantaren 1200 and Plantaren 2000 ex Henkel.
Other sugar-derived nonionic surfactants which can be 10 included in compositions of the invention include the C10-C18 N-alkyl (C1-C6) polyhydroxy fatty acid amides, such as the C12-C18 N-methyl glucamides, as described for example in WO 92 06154 and US 5 194 639, and the N-alkoxy polyhydroxy fatty acid amides, such as C10-C18 N-(3-methoxypropyl) 15 glucamide.
A preferred example of a co-surfactant is an amphoteric or zwitterionic surfactant, which can be included in an amount ranging from 0.5 to about 8%, preferably from 1 to 4% by 20 weight based on the total weight of the composition.
Examples of amphoteric or zwitterionic surfactants include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulphobetaines (sultaines), alkyl
25 glycmates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkylamphoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, wherein the alkyl and acyl groups have from 8 to 19 carbon atoms. Typical amphoteric and zwitterionic
30 surfactants for use in shampoos of the invention include lauryl amine oxide, cocodimethyl sulphopropyl betaine,
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lauryl betaine, cocamidopropyl betaine and sodium cocoamphoacetate.
A particularly preferred amphoteric or zwitterionic 5 surfactant is cocamidopropyl betaine.
Mixtures of any of the foregoing amphoteric or zwitterionic surfactants may also be suitable. Preferred mixtures are those of cocamidopropyl betaine with further amphoteric or 10 zwitterionic surfactants as described above. A preferred further amphoteric or zwitterionic surfactant is sodium cocoamphoacetate.
The total amount of surfactant (including any co-surfactant, 15 and/or any emulsifier) in a shampoo composition of the
invention is- generally- from 1 to 50%,—preferably from ? tn _
40%, more preferably from 10 to 25% by total weight surfactant based on the total weight of the composition.
20 Cationic Polymers
Cationic polymers are preferred ingredients in a shampoo composition of the invention for enhancing conditioning performance.
25
Suitable cationic polymers may be homopolymers which are cationically substituted or may be formed from two or more types of monomers. The weight average (Mw) molecular weight of the polymers will generally be between 100 000 and 2
30 million daltons. The polymers will have cationic nitrogen containing groups such as quaternary ammonium or protonated
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amino groups, or a mixture thereof. If the molecular weight of the polymer is too low, then the conditioning effect is poor. If too high, then there may be problems of high extensional viscosity leading to stringiness of the 5 composition when it is poured.
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
10 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 polymers having a cationic charge density in the required
15 range, which is generally from 0.2 to 3.0 meq/gm. The
~— cationic charge, density of the polymer is suitably __
determined via the Kjeldahl method as described in the US Pharmacopoeia under chemical tests for nitrogen determination.
20
Suitable cationic polymers include, for example, copolymers of vinyl monomers having cationic amine or quaternary ammonium functionalities with water soluble spacer monomers such as (meth)acrylamide, alkyl and dialkyl
25 (meth)acrylamides, alkyl (meth)acrylate, vinyl caprolactone and vinyl pyrrolidine. The alkyl and dialkyl substituted monomers preferably have C1-C7 alkyl groups, more preferably C1-C3 alkyl groups. Other suitable spacers include vinyl esters, vinyl alcohol, maleic anhydride, propylene glycol
30 and ethylene glycol.
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The cationic amines can be primary, secondary or tertiary amines, depending upon the particular species and the pH of the composition. In general secondary and tertiary amines, especially tertiary, are preferred. 5
Amine substituted vinyl monomers and amines can be polymerized in the amine form and then converted to ammonium by quaternization.
10 The cationic polymers can comprise mixtures of monomer units derived from amine- and/or quaternary ammonium-substituted monomer and/or compatible spacer monomers.
Suitable cationic polymers include, for example:
15
cationie—eUra4rl7y^-q^ternary-ammQji^^ ng.
polymers including, for example, dimethyldiallylammonium chloride homopolymer and copolymers of acrylamide and dimethyldiallylammonium chloride, referred to in the 20 industry (CTFA) as Polyquaternium 6 and Polyquaternium 1, respectively;
mineral acid salts of amino-alkyl esters of homo-and co-polymers of unsaturated carboxylic acids having from 3 to 25 5 carbon atoms, (as described in U.S. Patent 4,009,256);
cationic polyacrylamides(as described in W095/22311) .
Other cationic polymers that can be used include cationic 30 polysaccharide polymers, such as cationic cellulose
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derivatives, cationic starch derivatives, and cationic guar gum derivatives.
Cationic polysaccharide polymers suitable for use in 5 compositions of the invention include monomers of the formula:

10 wherein: A is an anhydroglucose residual group, such as a starch or cellulose anhydroglucose residual. R is an alkylene, oxyalkylene, polyoxyalkylene, or hydroxyalkylene group, or combination thereof. R1 , R2 and R3 independently represent alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, or
15 alkoxyaryl groups, each group containing up to about 18
CdiLuu dloiu-g-7—The total numbe^-of—ea^bon atoms—fox—each
cationic moiety (i.e., the sum of carbon atoms in R1, R2 and R3) is preferably about 20 or less, and X is an anionic counterion.
20
Another type of cationic cellulose includes the polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium-substituted epoxide, referred to in the industry (CTFA) as Polyquaternium 24. These
25 materials are available from the Amerchol Corporation, for instance under the tradename Polymer LM-200.
Other suitable cationic polysaccharide polymers include quaternary nitrogen-containing cellulose ethers (e.g. as 30 described in U.S. Patent 3,962,418), and copolymers of

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etherified cellulose and starch (e.g. as described in U.S. Patent 3,958,581).
A particularly suitable type of cationic polysaccharide 5 polymer that can be used is a cationic guar gum derivative, such as guar hydroxypropyltrimethylammonium chloride (commercially available from Rhodia in their JAGUAR trademark series). Examples of such materials are JAGUAR C13S, JAGUAR C14, JAGUAR C15, JAGUAR C17 and JAGUAR CI 6 10 Jaguar CHT and JAGUAR C162.
Mixtures of any of the above cationic polymers may be used.
Cationic polymer will generally be present in a shampoo
15 composition of the invention at levels of from 0.01 to 5%,
preferably from—Q^-&5 to 1%, more preferably from 0 fiasco
0.5% by total weight of cationic polymer based on the total
weight of the composition.
20 Suspending Agent
Preferably an aqueous shampoo composition of the invention further comprises a suspending agent. Suitable suspending agents are selected from polyacrylic acids, cross-linked
25 polymers of acrylic acid, copolymers of acrylic acid with a hydrophobic monomer, copolymers of carboxylic acid-containing monomers and acrylic esters, cross-linked copolymers of acrylic acid and acrylate esters, heteropolysaccharide gums and crystalline long chain acyl
30 derivatives. The long chain acyl derivative is desirably selected from ethylene glycol stearate, alkanolamides of
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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, since these impart pearlescence to the composition. 5 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 910, Carbopol 934, Carbopol 941 and Carbopol 980. An example of a 10 suitable copolymer of a carboxylic acid containing monomer and acrylic acid esters is Carbopol 1342. All Carbopol (trademark) materials are available from Goodrich.
Suitable cross-linked polymers of acrylic acid and acrylate
15 esters are Pemulen TR1 or Pemulen TR2. A suitable
h-eteropolysaccharidc gum ic xanthan gum-,—for example that
available as Kelzan mu.
Mixtures of any of the above suspending agents may be used. 20 Preferred is a mixture of cross-linked polymer of acrylic acid and crystalline long chain acyl derivative.
Suspending agent will generally be present in a shampoo composition of the invention at levels of from 0.1 to 10%, 25 preferably from 0.5 to 6%, more preferably from 0.9 to 4% by total weight of suspending agent based on the total weight of the composition.
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Conditioner Compositions
Another preferred product form for compositions in accordance with the invention is a conditioner for the 5 treatment of hair (typically after shampooing) and subsequent rinsing.
Such conditioner compositions will typically comprise one or more conditioning surfactants which are cosmetically 10 acceptable and suitable for topical application to the hair.
Suitable conditioning surfactants include those selected from cationic surfactants, used singly or in admixture. Preferably, the cationic surfactants have the formula
15 N+RXRZR3R4 wherein R1, R2, R3 and R4 are independently (Ci to
&3u) alley 1 or benzyl.—Preferably,.—©n^,—two or three of R\
R2, R3 and R4 are independently (C4 to C30) alkyl and the other R1, R2, R3 and R4 group or groups are (C1-C6) alkyl or benzyl. More preferably, one or two of R1, R2, R3 and Rr are
20 independently (C6 to C30) alkyl and the other R1, R2, R3 and Re¬groups are (C1-C6) alkyl or benzyl groups. Optionally, the alkyl groups may comprise one or more ester (-OCO- or -COO-) and/or ether (-0-) linkages within the alkyl chain. Alkyl groups may optionally be substituted with one or more
25 hydroxyl groups. Alkyl groups may be straight chain or branched and, for alkyl groups having 3 or more carbon atoms, cyclic. The alkyl groups may be saturated or may contain one or more carbon-carbon double bonds (eg, oleyl). Alkyl groups are optionally ethoxylated on the alkyl chain
30 with one or more ethyleneoxy groups.
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Suitable cationic surfactants for use in conditioner compositions as claimed in the invention include cetyltrimethylammonium chloride, behenyltrimethylammonium chloride, cetylpyridinium chloride, tetramethylammonium 5 chloride, tetraethylammonium chloride,
octyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octyldimethylbenzylammonium chloride, decyldimethylbenzylammonium chloride, 10 stearyldimethylbenzylammonium chloride, didodecyldimethylammonium chloride, dioctadecyldimethylammonium chloride,
tallowtrimethylammonium chloride, dihydrogenated tallow
dimethyl ammonium chloride (eg, Arquad 2HT/75 from Akzo
15 Nobel), cocotrimethylammonium chloride, PEG-2-oleammonium
p-hlnririn nnH tho rnrrnrpnnriing hyiirnvi r^q fhprpnf. Fnrf.hpr
suitable cationic surfactants include those materials having the CTFA designations Quaternium-5, Quaternium-31 and Quaternium-18. Mixtures of any of the foregoing materials
20 may also be suitable. A particularly useful cationic surfactant for use in conditioners as claimed in the invention is cetyltrimethylammonium chloride, available commercially, for example as GENAMIN CTAC, ex Hoechst Celanese. Another particularly useful cationic surfactant
25 for use in conditioners as claimed in the invention is
behenyltrimethylammonium chloride, available commercially, for example as GENAMIN KDMP, ex Clariant.
Another example of a class of suitable cationic surfactants 30 for use in the invention, either alone or together with one
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or more other cationic surfactants, is a combination of (i) and (ii) below:
(i) an amidoamine corresponding to the general formula (I)

in which R1 is a hydrocarbyl chain having 10 or more carbon atoms,
R2 and R3 are independently selected from hydrocarbyl 10 chains of from 1 to 10 carbon atoms, and
m is an integer from 1 to about 10; and
(ii) an acid.
15 As used herein, the term hydrocarbyl chain means an alkyl or alkenyl chain.
Preferred amidoamine compounds are those corresponding to
formula (I) in which 20
R1 is a hydrocarbyl residue having from about 11 to about 24
carbon atoms,
R2 and R3 are each independently hydrocarbyl residues,
preferably alkyl groups, having from 1 to about 4 carbon 25 atoms, and
m is an integer from 1 to about 4.
Preferably, R2 and R3 are methyl or ethyl groups.


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Preferably, m is 2 or 3, i.e. an ethylene or propylene group.
Preferred amidoamines useful herein include stearamido-5 propyldimethylamine, stearamidopropyldiethylamine,
stearamidoethyldiethylamine, stearamidoethyldimethylamine, palmitamidopropyldimethylamine, palmitamidopropyl¬diethyl amine, palmitamidoethyldiethylamine, palmitamidoethyldimethylamine, behenamidopropyldimethyl-
10 amine, behenamidopropyldiethylmine, behenamidoethyldiethyl-ami ne, behenamidoethyldimethylamine, arachidamidopropyl-dimethy1amine, arachidamidopropyldiethylamine, arachid-amidoethyldiethylamine, arachidamidoethyldimethylamine, and mixtures thereof.
15
Particularly preferred amidoamines useful herein ere
stearamidopropyldimethylamine, stearamidoethyldiethylamine, and mixtures thereof.
20 Commercially available amidoamines useful herein include:
stearamidopropyldimethylamine with tradenames LEXAMINE S-13 available from Inolex (Philadelphia Pennsylvania, USA) and AMIDOAMINE MSP available from Nikko (Tokyo, Japan), stearamidoethyldiethylamine with a tradename AMIDOAMINE S
25 available from Nikko, behenamidopropyldimethylamine with a tradename INCROMINE BB available from Croda (North Humberside, England), and various amidoamines with tradenames SCHERCODINE series available from Scher (Clifton New Jersey, USA).
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Acid (ii) may be any organic or mineral acid which is capable of protonating the amidoamine in the hair treatment composition. Suitable acids useful herein include hydrochloric acid, acetic acid, tartaric acid, fumaric acid, 5 lactic acid, malic acid, succinic acid, and mixtures
thereof. Preferably, the acid is selected from the group consisting of acetic acid, tartaric acid, hydrochloric acid, fumaric acid, and mixtures thereof.
10 The primary role of the acid is to protonate the amidoamine in the hair treatment composition thus forming a tertiary amine salt (TAS) in situ in the hair treatment composition. The TAS in effect is a non-permanent quaternary ammonium or pseudo-quaternary ammonium cationic surfactant.
15
Suitably,—the acid is included in a sufficient—amount to
protonate all the amidoamine present, i.e. at a level which is at least equimolar to the amount of amidoamine present in the composition.
20
In conditioners of the invention, the level of cationic surfactant will generally range from 0.01 to 10%, more preferably 0.05 to 7.5%, most preferably 0.1 to 5% by weight of the composition.
25
Conditioners of the invention will typically also incorporate a fatty alcohol. The combined use of fatty alcohols and cationic surfactants in conditioning compositions is believed to be especially advantageous,
30 because this leads to the formation of a lamellar phase, in which the cationic surfactant is dispersed.
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Representative fatty alcohols comprise from 8 to 22 carbon atoms, more preferably 16 to 22. Fatty alcohols are typically compounds containing straight chain alkyl groups. Examples of suitable fatty alcohols include cetyl alcohol, 5 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.
10 The level of fatty alcohol in conditioners of the invention will generally range from 0.01 to 10%, preferably from 0.1 to 8%, more preferably from 0.2 to 7%, most preferably from 0.3 to 6% by weight of the composition. The weight ratio of cationic surfactant to fatty alcohol is suitably from 1:1 to
15 1:10, preferably from 1:1.5 to 1:8, optimally from 1:2 to
1:5.—If tho weight ratio of cationir qnrfar.i-^rti- to fatty
alcohol is too high, this can lead to eye irritancy from the composition. If it is too low, it can make the hair feel squeaky for some consumers.
20
Further Conditioning Agents
Compositions of the invention may comprise further conditioning agents to optimise wet and dry conditioning 25 benefits.
Particularly preferred further conditioning agents are silicone emulsions.
30 Suitable silicone emulsions include those formed from silicones such as polydiorganosiloxanes, in particular
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polydimethylsiloxanes which have the CTFA designation dimethicone, polydimethyl siloxanes having hydroxyl end groups which have the CTFA designation dimethiconol, and amino-functional polydimethyl siloxanes which have the CTFA 5 designation amodimethicone.
The emulsion droplets may typically have a Sauter mean droplet diameter (D3,2) in the composition of the invention ranging from 0.01 to 20 micrometer, more preferably from 0.2 10 to 10 micrometer.
A suitable method for measuring the Sauter mean droplet diameter (D3,2) is by laser light scattering using an instrument such as a Malvern Mastersizer.
15
Suitable silicone emulsions f nr n.q^ i n nnmpo.di ti nn.g of thp
invention are available from suppliers of silicones such as Dow Corning and GE Silicones. The use of such pre-formed silicone emulsions is preferred for ease of processing and
20 control of silicone particle size. Such pre-formed silicone emulsions will typically additionally comprise a suitable emulsifier such as an anionic or nonionic emulsifier, or mixture thereof, and may be prepared by a chemical emulsification process such as emulsion polymerisation, or
25 by mechanical emulsification using a high shear mixer. Pre¬formed silicone emulsions having a Sauter mean droplet diameter (D3,2) of less than 0.15 micrometers are generally termed microemulsions.
30 Examples of suitable pre-formed silicone emulsions include emulsions DC2-1766, DC2-1784, DC-1785, DC-1786, DC-1788 and

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microenrulsions DC2-1865 and DC2-1870, all available from Dow Corning. These are all emulsions/microemulsions of dimethiconol. Also suitable are amodimethicone emulsions such as DC939 (from Dow Corning) and SME253 (from GE 5 Silicones).
Also suitable are silicone emulsions in which certain types of surface active block copolymers of a high molecular weight have been blended with the silicone emulsion
10 droplets, as described for example in WO03/094874. In such materials, the silicone emulsion droplets are preferably formed from polydiorganosiloxanes such as those described above. One preferred form of the surface active block copolymer is as described in the following formula:
15
20 wherein the mean value of x is 4 or more and the mean value of y is 25 or more.
Another preferred form of the surface active block copolymer is as claimed in the following formula: 25
30 wherein the mean value of a is 2 or more and the mean value of b is 6 or more.
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Mixtures of any of the above described silicone emulsions may also be used.
Silicone will generally be present in a composition of the 5 invention at levels of from 0.05 to 10%, preferably 0.05 to 5%, more preferably from 0.5 to 2% by total weight of silicone based on the total weight of the composition.
Other Optional Ingredients 10
A composition of the invention may contain other ingredients for enhancing performance and/or consumer acceptability. Such ingredients include fragrance, dyes and pigments, pH adjusting agents, pearlescers or opacifiers, viscosity 15 modifiers, preservatives, and natural hair nutrients such as
botanicals,—fruit extracts.,—sugar riprivafivps and aminn
acids.
The invention will now be described with reference to the 20 following non-limiting examples. In the examples and
throughout this specification, all percentages are by weight based on total composition and based on active material unless indicated otherwise.
25 EXAMPLES
Example 1. The one-pot synthesis and loading of a core-shell brush copolymer from small molecule reactants, by tandem ROMP and RAFT copolymerisation.
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The one-pot synthesis and loading of a nanocage from small molecule reactants, by tandem ROMP and RAFT copolymerisation is shown in Scheme 2 below.
Scheme 2

10 As a critical agent for the tandem synthesis of core-shell
brush copolymer, an exo-norbornene-functionalized RAFT agent 1 was prepared in 87% yield by esterification of a norbornene-functionalized alcohol 2 with an acid-functionalized RAFT agent 3 (2.0 eq), using N,N'-
15 dicyclohexylcarbodimide {DCC; 2.1 eq), and 4-
(dimethylamino)pyridine (DMAP; 0.2 eq) in CH2CI2 at room
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J3856 (C) WO Amended 24 June 2008
- 30 -

10
15
20
25
30

temperature for 11 h.20 2H NMR analysis of 1 showed a series of characteristic resonances, including those of norbornene alkene protons a and b (at 6.03-6.16 ppm), CH2OCO protons e (at 4,07 ppm), CH2OCH2 protons c and d and SCH2 protons f (at 3.20-3.55 ppm), and CH? protons g (at,0.87 ppm). Their integration area ratios of 1.95:2.00:5.95:3.10 were in excellent agreement with the number ratio of protons of 2:2:6:3, verifying the molecular structure of 1. One-pot preparation of core-shell brush copolymer from small molecule reactants was then performed by ROMP of the exo-norbornene-functionalized RAFT agent 1, followed by using the resulting polyfunctional RAFT agent and AIBN (as initiator) for "grafting from" via RAFT copolymerization of styrene (St) and maleic anhydride (MAn). The ROMP of 1
(99.7 mg) was conducted using Grubbs' catalyst RuCl2(CHC6H5) [P(C6Hu)3]2 (0.02 eq) in CH2C12 at room temperature for 1 h. XH NMR and GPC analyses of an aliquot of the reaction mixture (19 vol%, terminated by ethyl vinyl ether) determined the successful transformation of 1 into a well-defined polyfunctional RAFT agent. Near complete conversion (>99%) of 1 was verified by essential absence of 1H NMR resonances of norbornene alkene protons of 1 at 6.03-6.16 ppm, and the formation of poly(l), i.e. 4, -was supported by a series of characteristic resonances, including those of alkene protons a' and b' of the poly(norbornene)-based main-chain (at 5.00-5.50 ppm), CH2OCO protons e' (at 4.07 ppm), CH2OCH2 protons C and d' and SCH2 protons f (at 3.20-3.55 ppm), and CH3 protons g' (at 0.87 ppm). Their integration area ratios of 1.93:2.00:5.94:3.03 agreed very well with the number ratios of protons of 2:2:6:3, indicating quantitatively one RAFT functionality

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- 31 -
per repeat unit of 4. By GPC, 4 was found to have a Mn of 40.6 kDa and a low polydisperisty index of 1.24. Relative to a calculated Mn value of 31.5 kDa, the experimental Mn value of 4 indicated an initiation efficiency of 78 %.
5 , ..
By hydrolyzing the MAn units in the poly(St-stat-MAn) blocks into hydrophilic maleic acid units, 5 could be further converted into amphophilic core-shell brush copolymer 7. Hydrolysis p'roceeded readily at room temperature under basic
10 conditions using KOH (potassium hydroxide) to promote the reaction. Subsequent.neutralization of the reaction solution gave 7. Both 2H NMR and FT-IR spectroscopic characterizations were used to compare 7 with its precursor 5. :H NMR resonances of carboxylic protons centered at 12.0
15 ppm 'were observed by lH NMR measurement p'f 7 in DMSO-dg,
verifying the presence of maleic acid units in 7. Critical differences between 7 and 5 were revealed by FT-IR. Core-shell brush copolymer 5 showed two C=0 stretching frequencies at 1857 and 1778 cm-1 for its cyclic anhydride
20 groups and an absence of an O-H stretching absorbance.
However, amphiphilic core-shell brush copolymer 7 possessed only one C=0 stretching frequency at 1714 cm"1 and a broad 0-H stretching absorption at 2500-3500 cm-1, indicating complete functional group transformation from the anhydrides
25 to carboxylic acid groups. Additionally, different
solubilities for 7 relative to 5 were found. For example, 5 was soluble in CDCI3, but 7 was insoluble in CDCI3 and could be dissolved by 1:2 CDC13-CD30D.
AMENDED SHEET . 08/07/2008:
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A nanocage prepared by crosslinking the amphiphilic core-shell brush copolymer brush 7 and loaded with 15 wt% salicylic acid, was synthesised following the above Scheme This sample, nanocage loaded with 15 wt% salicylic acid, was 5 synthesized following Scheme 1. The amphiphilic core-shell brush copolymer 7 has a polynorbornene-based backbone, polyisoprene core, and poly(acrylic acid) shell. The shell cross-linking reaction of 7 was carried out using 0.11 eq of 2,2'-(ethylenedioxy)bis(ethylamine) cross-linker and 0.22 eq 10 of 1-[3'-(dimethylamino)propyl]-3-ethylcarbodiimide
methiodide (a catalyst) relative to the acrylic acid shell units of 7. The polyisoprene core of the resulting shell cross-linked nanoparticle 8 was then degraded by ozone treatment, followed by reduction with Na2S03. The nanocage 9 15 formed was then loaded with salicylic acid (-15 wt%) by
stirring th^ ?0% f-Hjnyanp-wafpr solution over 2 days, and
then the solution was lyophilized to give dry sample.
The loading of salicylic acid into nanocage was proven by AH 20 NMR analysis (spectra attached). The nanocage sample loaded with salicylic acid also showed IR absorption at 3233 cm"1, which was absent for nanocage 9. Tapping-mode AFM measurements indicated that there is detectable but not significant size change for nanocages before and after 25 loading salicylic acid. Before loading, the nanocages have diameters ranging from 20 to 4 5 nm, with heights below 1.5 nm on mica; after loading, the nanocages have diameters ranging from 20 to 50 nm, with heights below 1.5 nm on mica. As a note, the water-solubility of nanocage sample can 30 decrease due to lyophilization.
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The following are examples of compositions ss claimed in the invention.
The materials used in the examples include the following:


10
15
25

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CLAIMS
1. A composition comprising a brush copolymer of formula 1: 5


m,
Formula 1 in which Mi is a unit obtainable from ring opening
10 metathesis polymerisation (ROMP);
R is an alkyl, ether, ester or aryl unit; M2 and tM3 are independently selected from units obtainable by reversible addition fragmentation cnain transfer polymerization(RAFT);
15 X is a terminal unit selected from the group consisting of dithioester, trithiocarbonate, xanthate; and m is an integer from 2 to 1 million, n is an integer from 2 to 500,000 and k is an integer from 2 to 500,000; in which incorporated within the core shell 20 brush copolymer is a benefit agent selected from hair styling polymers, colourants, hair conditioners, hair cleansers, hair growth promoters, permanent wave compounds, hair relaxers, ,amino acids, vitamins, hair straighteners, hair growth stimulants, antibacterial 25 compounds, antifungal compounds, anti-inflammatory compound, sunscreens and mixtures thereof.

AMENDED SHEET 08/07/2008.
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J3856 (CJ WO Amended 24 June 2008
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A composition as claimed in claim 1 in which Ml of the brush copolymer is a unit obtainable from the ring opening metathesis polymerisation (ROMP) of cyclooctadiene or norbornene.

10

A composition as claimed in claim 1 or claim 2 in which M2 and/or M3 of the brush copolymer are independently selected from units obtainable by reversible addition fragmentation chain transfer polymerization(RAFT) of styrene, isoprene, methyl acrylate, tert-butyl acrylate, dimethyl acryamide, acrylic acid, acrylonitrile, methyl methacrylate, maleic anhydride, vinyl acetate, vinyl pyridine orvinyl phenyl ketone.

15 4. A composition as claimed in any preceding claim*int
* t 1
which the core-shell brush copolymer is of formula 2:

20

Formula 2
in which m is an integer from 2 to 1 million, y is an integer form. 2 to 18, x is an integer from 1 to 100, n is an integer from 2 to 500,000 and k is an integer from 2 to 500,000.

25 5. Composition as claimed in any preceding claim, in which the composition comprises the core shell brush copolymer in an amount of from 0.01% to 50%.


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■at

- 37 -
6. Composition as claimed in claim 1 in which the benefit agent is selected from the group consisting of an antifungal compound, antibacterial compound, an anti¬inflammatory compound or mixtures thereof.
7. Composition as claimed in claim 6 in which the benefit agent is salicylic acid.

10

Composition as claimed in any preceding claim which is a rinse off product.

9. Composition as claimed in Claim 11 which is a shampoo or conditioner.
* t
» ' 15 10. Use of comprising a.core-shell brush copolymer having ,
* t * '
the structure of formula 1:


20
25

in which M1 is a unit obtainable from ring opening
metathesis polymerisation (ROMP);
R is an alkyl, ether, ester or aryl unit;
M2 and M3 are independently selected from units
obtainable by reversible addition fragmentation chain
transfer polymerization(RAFT);
X is a terminal unit selected from the group consisting
of dithioester, trithiocarbonate, xanthate; and

AMENDED SHEET
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m is an integer from 2 to 1 million, n is an integer
from 2 to 500,000 and k is an. integer from 2 to
500,000;
to deliver a benefit agent to the hair. .
11. A method of treating the hair by application to the hair a composition comprising a core-shell brush copolymer having the structure of formula 1:


10

1 , • ( in which M1 is a unit obtainable from ring opening
metathesis polymerisation (ROMP);
R is an alkyl, ether, ester or aryl unit; 15 M2 and M3 are independently selected from units
obtainable by reversible addition fragmentation chain
transfer polymerization(RAFT) ;
X is a terminal unit selected from the group consisting
of dithioester, trithiocarbonate, xanthate; and 20 m is an integer from 2 to 1 million, n is an integer
from 2 to 500,000 and -k is an integer from 2 to
500,000.
Dated this 15th day of May 2009
HINDUSTAN UNILEVER LIMITED

AMENDED SHEET
,15 MAY 2009

08/0'