Research Report
`Secunty Class 1
`CONFIDENTIAL
`
`Unilever Research
`ISle‘Nort-l1
`r
`Laboratory k
`
`Umemnmedcmmenmiwnmn
`Research Division; no further
`Section/Section Manager Shampoos / M. W. Parslow
`dlstribution outside Research or
`Copvlng wnhout authority
`
`
`Conditioning Shampoo
`
`Pnnec11nw
`
`whore)
`
`R. Y. LOCHHEAD
`
`EXIReI:
`
`P13
`
`79 1153
`
`mtRet
`
`451U21/49
`
`ReportTitle:
`
`FORMULATION OF AN ANTIDANDRUFF
`SHAMPOO WITH IMPROVED HAIR
`
`Preject No- H01
`
`CONDITIONING ATTRIBUTES.
`
`IMISNo
`
`14 02 10 260
`
`Primary Distribution
`
`ISLEWORTH
`
`Head of Laboratory
`
`Mr. R. Clark
`Dr. F. R. M. McDonnell
`Dr. D. N. G. Dicker
`
`Mr. K. V. Curry
`Dr. w. A. Senior
`
`Mr. D. J. Alexander
`Dr. B. J. Magg
`
`Date
`
`OCTOBER 1979
`
`OTHER RESEARCH
`
`OUTSIDE RESEARCH
`
`UR SL-Denis Laboratory
`Secretary,TP RP
`
`R 80 Member,TPC
`Lever Bros.Co., Edgewater
`
`Miss B. James
`Dr. S. Black
`
`- URLCH
`- URLCH
`
`Dr. H. T. Smith
`Elida Gibbs - Leeds
`
`- URLPS
`Mr. S. A. Mitchei]
`— URLPS
`Dr. M. R. Hyde
`Mr. M. w. Pars1ow — URLPS
`Mr. I. B. Na1ton
`- URLPS
`Dr. J. Martin
`- URLPS
`Mr. R. J. Moore
`- URLPS
`
`000001
`
`
`
` _g T 'IO4C
`
`
`
`
`
`UN T141V41R *1XH
`
`
`
`
`
`
`UN LMVMR VS. PROCTOR & GAMBL_E
`_
`
`[PR2013- 00509
`
`000001
`
`UNILEVER EXHIBIT 1040
`UNILEVER VS. PROCTOR & GAMBLE
`IPR2013-00509
`
`

`

`Research News
`Security Class 1
`CONFIDENTIAL
`Unrestricted circulamn wuthln
`Research Divisionmo further
`distrlbutloncutside Research
`or copying Without authority
`
`Proiect Title
`
`SBCI'OO/SGCUOT‘ Manager:
`
`Authorisr
`
`R. Y. LOCHHEAD
`
`Tnb-
`
`FORMULATION OF AN ANTIDANDRUFF
`
`SHAMPOO WITH IMPROVED HAIR
`CONDITIONING ATTRIBUTES.
`
`Unilever Research
`ISICWOI‘th
`Laboratory
`Conditioning Shampoo
`
`Shampoos / M. H. Parslow
`
`ExtRef=
`
`NIS
`
`79 “53
`
`ReportRei:
`
`P IS 79 1153
`
`IntRef:
`
`45I UZI /49
`
`PnflectNo
`
`HOI
`
`MMSN0=
`
`I4 02 IO 260
`
`Dme=
`
`OCTOBER 1979
`
`Objective
`
`To develop a Zinc PTO containing anti-dandruff shampoo which possesses
`improved hair conditioning attributes derived from utilisation of the Jaguar/
`Briphos technology.
`
`Nature and Scope of the Study
`
`Following a company brief, an attempt was made to simultaneously incorporate
`Jaguar C-l3-S and Briphos 030, as conditioning agents,
`into a Zinc—PTO-containing
`anti—dandruff shampoo.
`In order to achieve this it was essential
`to omit the
`clay suspending agent from the existing formulation because interaction between
`the polymeric cationic conditioning agent and the clay would be likely to lead to
`instability of the shampoo with respect to separation and sedimentation of the
`Zinc PTO particles.
`
`A stable product has been formulated and possible reasons for this stability
`have been advanced.
`
`Conclusions
`
`l.
`
`2.
`
`3.
`
`A conditioning variant of anti—dandruff shampoo containing Zinc PTO has been
`developed.
`
`Laboratory prepared versions of this formulated product are stable against
`sedimentation and separation after three months storage.
`
`The formulated product is equivalent to prototype 95C and superior to “Head
`and Shoulders“, and "All Clear" dry variant for wet combing properties
`measured in vitro.
`
`000002
`
`000002
`
`

`

`4.
`
`5.
`
`6.
`
`to 95C and superior to "Head and Shou1ders”
`The product is equiva1ent
`and ”A11 C1ear” dry variant at the 5% significance 1eve1 for the
`attributes Fee1, Dry—Combing, and Static, by in vitro assessment.
`
`”A11 C1ear" dry variant, and the product
`”Head and Shouiders”, “95C”,
`described here are a11 equiva1ent, at the 5% significance 1eve1, for
`91055, by in vitro assessment.
`
`"Head and Shou1ders” is superior to the formu1ated product described
`here, at the 5% significance 1eve1, for "amount of 1ather" and
`“creaminess of 1ather” by in vitro assessment.
`
`Limitations
`
`This deve1opment has been conducted on a 1aboratory sca1e and the
`conditioning properties have on1y been estab1ished in vitro.
`
`Further work wi11 be necessary to obtain safety, conduct sa1on and
`consumer tria1s, assess deposition efficiency, anti—dandruff effectiveness
`and estab1ish techno1ogy 1imitations.
`
`000003
`
`000003
`
`

`

`INTRODUCTION
`
`A recent company brief (1) requested the development of an anti-dandruff
`shampoo having shampoo attributes comparable to New Sunsilk Dry.
`
`New Sunsilk Dry is based on the URLI conditioning shampoo 95C (2) using
`sodium lauryl ether sulphate and having the quaternised guar gum derivative,
`Jaguar C-l3-S, and the phosphate ester, Briphos 030, as conditioning additives.
`
`The current dry variant anti-dandruff shampoo, "All Clear", contains
`Briphos 030.
`Therefore the problem was reduced to finding a suitable means
`of incorporating Jaguar C-lS-S into a sodium lauryl ether sulphate-based
`shampoo with Zinc—pyridine-Z-thiol-N-oxide added as the active anti-dandruff
`ingredient.
`
`Definition of the Problem
`
`is a finely divided powder of
`Zinc pyridine-Z—thiol-N-oxide (Zinc PTO)
`specific gravity l.782 and average particle size of the order of 5 microns
`and smaller.
`The material
`is supplied as a 48 per cent slurry in water,
`with some nonionic detergent added to prevent irreversible flocculation.
`
`As a consequence of its relatively high density Zinc PTO has a tendency
`to sediment from most normal shampoo formulations.
`This sedimentation may
`be retarded by simply increasing the viscosity of the shampoo, when the
`sedimentation rate would decrease in accordance with Stokes Law.
`However,
`in order to formulate a product with acceptable stability against separation
`a Brookfield viscosity of at least 3500 cps would have to be attained (3).
`Such a product would have the consistency of a cream rather than the normal
`lotion characteristics associated with shampoos.
`
`lotion-viscosity
`Stable Zinc—PTO-containing shampoos having a more normal
`can be produced by including a suspending agent in the formulation.
`It is
`essential
`that the suspending agent in the formulation adopts a network
`structure which extends throughout the product.
`This network structure
`must break down easily when sheared in order that the product may exhibit
`liquid—like flow, but the structure must be capable of reforming reasonably
`quickly in order that minimal sedimentation of the Zinc PTO occurs following
`shearing of the product.
`Most thixotropic systems do not recover quickly
`enough to meet this requirement. Rheologically the desired behaviour is
`described as shear-thinning and in order to suspend effectively at low shear
`the product must exhibit a yield point.
`At shear stresses below the yield
`stress the product will behave as a solid and at shear stresses in excess
`of the yield stress liquid like behaviour will be observed.
`Clearly the
`ideal product yield stress will have a value higher than that exerted by
`the gravitational pull on the Zinc PTO particles, but
`lower than that
`exerted in normal pouring and filling operations.
`
`In existing anti—dandruff shampoos containing Zinc PTO modified clays,
`such as Laponite, are used as suspending agents. Modified hectorite clays
`appear to be preferred - Veegum in Procter and Gamble's “Head and Shoulders”
`and Propaloid T in our concern product ”All Clear”.
`
`000004
`
`000004
`
`

`

`The apparently obvious route to a conditioning, anti-dandruff shampoo
`is to add Jaguar C-l3-S to the existing hectorite-clay—stabilised shampoo.
`It has been reported, however, that cationic, polymeric conditioning agents
`cannot be used with Veegum or Laponite (2).
`The cationic polyelectrolytes
`probably cause extensive flocculation of the clay structure, which would
`simultaneously cause a loss of the attributes connected with the polymer
`and also with the clay structure.
`
`This problem was obviously appreciated by the Procter and Gamble Company (ll)
`for in their British Patent 1,195,l58 they show,
`in particular,
`two examples
`of formulae containing the cationic cellulose ether, Polymer JR.
`In both
`cases (Examples 1 and II in the Patent Specification) the clay has been
`omitted and the detergents themselves have been structured —
`in the first
`case by adding relatively large amounts of sodium chloride and sodium
`sulphate and in the second case by having a formula based essentially on
`l0 per cent
`lauryl sulphate and TO per cent coconut alkyl dimethyl amine
`oxide.
`This latter formula is similar to Unilever's ”Jif" suspending
`base.
`
`The Solution
`
`This
`Many polysaccharides form gels in association with water.
`behaviour may be attributed to the molecular structure of these poly—
`saccharides which consist of long chain molecules having long freely
`soluble sequences of segnents interlinked with a series of sites which are
`capable of intermolecular aggregation.
`The gel
`is formed with water by a
`network of the soluble sequences of the chains cross-linked at the aggregation
`sites (4—6).
`
`Jaguar C-lB-S is a quaternary nitrogen substituted guar gum. Guar gum
`is predominantly composed of the galactomannan polysaccharide, guaran.
`
`If Jaguar C—l3—S could be induced to form a cross—linked network through-
`the shampoo then this network could possibly be capable of suspending
`out
`Zinc PTO.
`In this way the problematic clay could be omitted from the
`formulation and the polymeric cationic conditioning agent could be included
`in the Formulation at one and the same time.
`Unquaternised Guar gum,
`however,
`is characteristically very water soluble;
`it tends to dissolve
`in water to give viscous polymeric solutions rather than gels (6, 8).
`Quaternisation would tend to make such a material even more water—soluble
`and less likely to form gels.
`
`The galactomannans, generally, consist of a B—D—(l,4) mannan backbone
`having u-D-(l,6)— linked galactose branches.
`In some galectomannans, e.g.
`locust bean gum,
`the galactose substituents are clustered predominantly in
`long blocks of around 25 residues interspersed by even longer regions of
`essentially unsubstituted mannan backbone (7) illustrated schematically in
`Figure l.
`The highly branched portions of this polysaccharide are highly
`soluble and the unsubstituted portions tend to aggregate (Fig. 2).
`Therefore,
`locust bean gives gels in water.
`
`000005
`
`000005
`
`

`

`Guar gum, on the other hand, is much more highly substituted with
`galactose and it appears that the galactose side units are distributed
`relatiVely evenly along the chain,
`leaving very few unsubstituted "runs"
`of B-D—(l,4)- mannan.
`Clearly,
`the opportunity for cross-links to form
`is severely limited by the absence of unsubstituted backbone and this,
`therefore, explains why guar gum tends to give viscous solutions rather
`than gels.
`1f cross-link sites could be introduced into guar gum,
`then
`owing to its very high intrinsic solubility, excellent gels which would
`not exhibit syneresis even at very low concentrations would be expected.
`Furthermore, if the cross—links were non—covalent then transient bonds
`which would be reformed after cleavage could result.
`Such characteristics
`would give a shear-thinning gel with the right properties to be a shampoo-
`suspending agent.
`
`The quaternised guar gum derivative, Jaguar C-lB-S, interacts strongly
`with anionic surfactants (9).
`This interaction is often depicted schematically
`as a pure ion-pair bond, although for such a hydrophilic polymer a more accurate
`picture may be entrapment of the cationic polymer within the electrical double
`layer of the micelle — with, perhaps, a consequent change in micelle size and
`shape. Whichever model
`is accepted makes little difference to the following
`argument which speculates on the possibility of networks being formed within
`shampoo systems based on anionic detergents and containing Jaguar C-l3-S.
`
`At normal neat shampoo concentrations most of the anionic surfactant
`present will be in the form of micelles.
`It is conceivable that any of
`these micelles could interact with more than one molecular chain of Jaguar
`C-l3—S.
`In such a situation the micelle itself would constitute a cross—
`link between the chains.
`In this way Jaguar C-lB-S and the micelles could
`build a network throughout the whole of the shampoo.
`The micelles have the
`additional advantageous property of existing in dynamic equilibrium with the
`free monomeric surfactant and they are, therefore, continually being broken
`down and reformed at very rapid rates of the order of fractions of a second (9).
`Thus,
`the Jaguar C-l3-S micelle interaction could lead to a dynamic network
`which would continually change at the molecular level but would maintain an
`average network integrity over distances larger than molecular sizes.
`Such
`a network would have exactly the correct shear—thinning, rapid “healing"
`properties required of a suspending agent and if this was the case the
`Jaguar C-l3-S anionic surfacant shampoo system alone might be capable of
`suspending Zinc PTO particles.
`
`All of the above is, of course, reasoned speculation and it is essential
`that this model be tested experimentally in order to assess the feasibility
`of this approach.
`
`RESULTS
`
`included in two formulations (Appendices I and II) which,
`Zinc PTO was
`apart from colour and perfume, were essentially the same as 95C* with Jaguar/
`Briphos conditioning additives.
`
`*
`
`Jaguar/Briphos Conditioning Shampoo - S.J.Sime.
`
`P IS 79 1029.
`
`000006
`
`000006
`
`

`

`Stability
`
`Samples of the shampoos were placed in storage at temperatures of 00,
`lSO, 28°, 37°, and 50°C.
`After three months' storage slight separation
`of the samples at 0°C and 50°C had occurred, but all of the other samples
`appeared to be stable against separation and sedimentation 0f the Zinc PTO.
`
`A second batch of shampoo prepared one month later showed gross
`separation at 0°C, but was essentially similar to the previous batch at all
`other temperatures.
`These results represent acceptable stability.
`
`then the system
`If the stability arises from structuring of the system,
`should exhibit a yield stress.
`The yield stress required for suspension
`of the particles can be calculated using Archimedes' Principle.
`
`Thus assuming a particle size of 5 microns and a density difference
`of 0.78 g/cc -
`
`Force downwards = L‘/3 n
`
`(5 x 10'“)3
`
`x (0.78) x 981 dynes.
`
`If it is assumed that this force is exerted on an area of ”liquid”
`corresponding to the circle having the same radius as the spherical particle,
`then:
`
`Minimum yield stress for suspension
`
`II A
`
`_
`/3 n (5x10 L*)3 x 0.78 x 981
`1! (5xio"*)2
`
`_ meg/cm:
`
`0.5l dynes cm-2
`
`The rheological characteristics were measured using a Deer Rheometer.
`No yield stress was found, but
`the value of 0.5T dynes cm_2 is below the limit
`of measurement for the Deer Rheometer.
`
`The lower limit of measurement of the instrument used was 0.9 dynes cm_?.
`Since the formulations were stable against sedimentation we,
`therefore, conclude
`that the system had yield stress below the level of measurement by our existing
`techniques but still adequate for the purpose of suspending Zinc PTO.
`
`The traditional Zinc PTO—containing anti-dandruff shampoo stabilised by
`clay (Propaloid T) also had no measureable yield stress.
`
`Shampoo Attributes
`
`The two new conditioning anti-dandruff formulations were tested ”in vitro“
`for shampoo and conditioning attributes against the existing clay—stabilised
`dry variant of ”All Clear”, Procter and Gamble's "Head and Shoulders”, and
`95C* (with Jaguar/Briphos).
`
`*
`
`Jaguar/Briphos Conditioning Shampoo — S.J.Sime. P IS 79 l029.
`
`000007
`
`000007
`
`

`

`Wet Combing
`
`The T.C T. method of wet combing was emp1oyed (12). Figures refer to
`the mean of three switches.
`
`
`System
`
`Head and Shou1ders
`
`"A11 C1ear" Dry Variant
`95C*
`
`Test Formu1ation I
`
`Test Formulation II
`
`% Remaining Re1ative to 16% MLS Base
`
`59.8
`
`90.5
`24.2
`
`19.9
`
`12.5
`
`Thus "in vitro testing indicates that the new formuIations are superior
`to the competitor's product (Head and Shou1ders),
`the existing product
`(”A11
`C1ear") and comparab1e to the action standard 95C.
`
`The remaining attributes were ana1ysed by Duncan's Mu1tip1e Range Test
`at the 5% 1eve1.
`Products connected by under1ining are not significant1y
`different at the 5% 1eve1:
`(most favourab1e product on 1eft).
`
`GLOSS
`
`FORMULATION II
`
`HEAD & SHOULDERS
`
`FORMULATION I
`
`NEN SUNSILK DRY
`
`ALL CLEAR
`
`There was no significant difference between the products for 61055
`
`FEEL
`
`FORMULATION II
`
`FORMULATION I
`
`95C
`
`HEAD & SHOULDERS
`
`ALL CLEAR
`
`DRY COMBING
`
`FORMULATION II
`
`FORMULATION I
`
`95C
`
`HEAD & SHOULDERS
`
`ALL CLEAR
`
`STATIC
`
`FORMULATION II
`
`FORMULATION I
`
`95C
`
`HEAD & SHOULDERS
`
`ALL CLEAR
`
`000008
`
`000008
`
`

`

`CREAMINESS OF LATHER
`
`HEAD & SHOULDERS
`
`
`
`FORMULATION I FORMULATION II
`
`AMOUNT OF LATH_E_R
`
`
`
`
`
` HEAD & SHOULDERS FORMULATION I FORMULATION 11
`
`CONCLUSIONS
`
`1.
`
`2.
`
`3.
`
`4.
`
`5.
`
`6.
`
`A conditioning variant of anti-dandruff shampoo containing Zinc PTO
`has been developed.
`
`This formulated product is stable against sedimentation and separation.
`
`The formulated product is superior to "95C", ”Head and Shoulders", and
`"All Clear” dry variant, for wet Combing.
`
`The product is equivalent to ”95C“ and superior to ”Head and Shoulders"
`and ”All Clear“ dry variant at the 5% significance level for the
`attributes Feel, Dry—Combing and Static.
`
`"Head and Shoulders“, 95C, “All Clear” dry variant, and the product
`described here are all equivalent, at the 5% significance level, for
`gloss.
`
`"Head and Shoulders” is superior to the formulated product described
`here, at the 5% significance level, for ”amount of lather” and
`"creaminess of lather”.
`
`ACKNOWLEDGEMENIE
`
`I would like to acknowledge the assistance of Mr. J. Britzman in
`conducting the experimental work and express my thanks to Dr.R.Donaldson
`and Dr.D.Hall of U.R.L.Port Sunlight and Dr.E.R.Morris of U.R.L.Colworth
`House for their helpful discussions.
`
`RYL/NJH
`30th October l979
`
`F'f’
`
`R.Y.Lochhead
`
`000009
`
`000009
`
`

`

`REFERENCES
`
`Internal
`
`(Isleworth) References
`
`No.
`
`Internal Ref.
`
`External Ref.
`
`
`Title
`
`453U36/125
`
`P 15 79 1029
`
`"New Shampoo Technology
`for Condition" Part X1.
`Development of a rationale
`for the functionality of a
`shampoo (95C) based on
`Jaguar C-13-S in Empicol
`XCBSJ
`(an opacified base
`containing phosphate ester.
`
`
`Author
`
`S.J.Sime
`
`12.
`
`TRM 10916
`
`‘
`
`Wet combing resistance
`measurement - a new test
`method for in vitro
`
`screening - current status.
`
`J K.Prall
`
`External References
`
`Elida Gibbs, U.K.
`
`“All Clear Shampoo Development Brief", 25.7.79.
`
`G.A.Hyde and M.M.Auerboch; Cosmetics and Toiletries, 95, 57,
`
`(1979)
`
`D.A.Rees, Chemistry and Industry,
`
`(1972), 630.
`
`D.A.Rees, Advances in Carbohydrate Chemistry and Biochemistry, g3, 267.
`
`E.R.Morris, Polysaccharide Structure and Conformation in Solutions and
`Gels, P CW 78 1122.
`
`I.C.M.Dea, E.R.Morris, E.J.welsh, H.E.Barnes, and J.Price. Conformations
`and Interactions of Bacterial Polysaccharides, Part II - Galactomannan
`Interactions.
`P CN 77 1293.
`
`"Gum Technology in the Food Industry”, Academic Press,
`M.Glicksman,
`New York and London (1969).
`
`E.D.Goddard and R.B.Hannan, J.Amer.0il Chem.Soc., 63, 561,
`
`(1977).
`
`10.
`
`11.
`
`E.A.G.Aniansson et. al., J. Phys. Chem., §Q, 905,
`
`(1976).
`
`British Patent 1,195,158 to Procter and Gamble Company.
`Published
`17th June 1970.
`
`000010
`
`000010
`
`

`

`M11
`
`FORMULATION I
`-——'——*--—
`
`.
`Percentage in product
`
`) Added as Empicol X0350
`)
`The phosphate ester
`)
`in this product is
`) Briphos 03D.
`
`Sodium Lauryl Ether Sulphate (2E0)
`Coconut diethanolamide
`Ethylene glycol monostearate
`Phosphate Ester
`Jaguar C-13—S
`Zinc-pyrithione
`Formaldehyde
`NaCl
`Zinc Sulphate heptahydrate
`
`pH + 6.5 - 7.00 with 1M NaOH
`
`Product viscosity 1800-2000
`
`cps
`
`11.4
`2.5
`2.5
`1.5
`0.3
`1.0
`0.15
`0.33
`0.1
`
`FORMULATION II
`
`Sodium Lauryl Ether Sulphate (2E0)
`Coconut diethanolamide
`Ethylene glycol monostearate
`Phosphate Ester
`
`Coconut diethanolamide (Empilan CDX/A)
`Jaguar C-13-S
`Zinc pyrithione
`Formaldehyde
`NaCl
`Zinc sulphate heptahydrate
`
`11.4
`2.5
`2.5
`1.5
`
`)
`)
`)
`)
`
`2.00
`0.3
`1.0
`0.15
`0.33
`0.1
`
`pH + 6.5 - 7.00 with 1M NaOH
`
`Product viscosity 1800-2000 cps
`
`Added as Empicol XC3SJ
`
`000011
`
`000011
`
`

`

`/
`
`.I}\v”?u)\,\:\‘/\?\/A’\/"\/’\/\1/\\\// ‘
`
`Swirl/unwiw ny'm'n'rnlrIIMIr of ‘en/nrlunmnuun
`rmrfurnmlmu
`
`l1
`
`Luh bend m [be hwkhmm represents a connc‘dnn
`hcmccn d-Ir-nunmw)Hume residues, and each
`'T-Hrnumn' rcprcwnh 1h: nlluchmcnl of an 1-1»
`g:.;?.z(top) {JHU‘C rchuc
`
`I
`
`1G. 1.
`
`Reproduced from D.A.Rees, Biochem J., {1972),12fi6, 265.
`
`aX
`
`
`fIG._2_.
`
`for the formation of a cross—linked network by
`Possible mode]
`locust bean gabctomannan.
`
`000012
`
`000012
`
`