United States Patent
`
`1191
`
`[11] Patent Number:
`
`5,543,074
`
`Hague et al.
`
`145} Date of Patent:
`
`Aug. 1;, 19915
`
`l||I||ll|||l|||||I|||lllllllllll|l||l||||l|||||||||||||ll|||l|||lll||||||||
`US005543074A
`
`[54] PERSONAL WASHING COMPOSITIONS
`
`[75]
`
`Inventors: Jonathan D. Hague, Merseyside;
`Andrew M. Murray, Cheshire, both of
`G333“ Britain
`
`[73] Assignee: Chesehrough-Pond’s USA 01., Div. of
`Conopco, Inc.’ Greenwich‘ Cont-L
`
`[21]
`
`A9131. Nos 389.334
`-
`.
`Rh‘ 16’ 1995
`[22] Wed‘
`[30]
`Foreign Application Priority Data
`Feb. 111, 1994
`[GB]
`111111411 Kingdom ................. __ 9403155
`Jul. 15, 1994
`[GB]
`United Kingdom ................. .. 9414332
`[51]
`Int. Cl.‘ ............................... .. C11D 3137; C11D 9136
`[52] US. Cl. .......................... 5101122; 5141881; 5101125;
`51111121; 51111159; 51111417; 51111425; 51111415;
`5101456
`25211110. 13, 174.15,
`[53] Field of Search
`2521173. 174.23, 174.25, 174.24. 541. S44:
`424f70.1, 70.11. 70.12, 70.16, 70.22; 514.1881
`
`[55]
`
`References Cited
`
`U-S- PATENT DOCUMENTS
`311953 G,._.,,_n_
`511971 Farrah! J1-_ _
`11111981 Harman. 1'11 eta]. .
`111991 Maksimosl-11 at a].
`
`.................. .. 4124470
`
`2’g25_551_
`3,53u_353
`4,299,817
`4,983,383
`
`5,037,818
`5,085,357
`5,160,730
`5.368.850
`
`811991 Sime .
`211992 Reid ct al. .
`IU1992 Dubief et al.
`1111994 Cauwct et £11.
`
`.
`
`5011131011 PATENT DOCUMENTS
`
`426159
`
`0319330
`
`41193"?
`
`EUIOPBEH Pal 00- -
`E'|.11'OpB3I'|. Pat.
`.
`91' 1990 European Pat. 011'.
`.
`0386398
`E
`P 1. 0131.
`.
`1111992
`5160730
`111993 E332: 13:1. our.
`.
`11524434
`111993
`European Fat. 00'. _
`0524434
`311993 European Pat. oer.
`.
`115293113
`2593054 W199?
`F7331“ v
`_
`2122214
`1.11984 United Kingdom .
`wo9211111e2
`1511992 WIPO .
`wo93r11s1s3
`511993 wrpo .
`$333:
`
`_
`,
`P311301? Ex3m={33’—G1333 533133313
`Assistant‘ Exammer—-Alexander G. Ghykat
`"’”“’"'3?- 4833*» 9" F""”—M‘“°“ '-- “N13
`ABSTRACT
`[57]
`
`Personal washing compositions which contain a cationic
`deposition polymer of charge density in the range 0.0001 to
`0.005 equivalentsfgraln and average molecular weight
`greater than 2x10“ daltons in combination with a surfactant
`to increase deposition of a benefit agent dispersed in the
`composition onto the Skin or hair.
`
`7 Claims, No Drawings
`
` P&G Exhibit 2001
`
`
`
`
`Conopco v. P&G
`|PR2014-00628
`
`

`
`1
`
`PERSONAL WASHING COMPOSITIONS
`
`5,543,074
`
`BACKGROUND OF THE INVENTION
`
`1. Field of the Invention
`
`This invention relates to personal washing compositions
`which contain a cationic deposition polymer to increase
`deposition of a benefit agent onto the skin or hair.
`2. The Related Art
`
`For many years it has been known that hair can be
`conditioned by incorporation of silicone in a shampoo
`composition. U.S. Pat. No. 2,826,551 (Gccn) is typical of an
`early disclosure of such 2 in 1 shampoos. Various attempts
`have been made to improve the efficiency of use of the
`expensive silicone component. ‘This would provide better
`conditioning and the option of reducing the level of expen-
`sive benefit agent
`in the shampoo, wit.h consequent cost
`saving.
`
`Deposition polymers with a cationic charge have been
`proposed to enhance the amount of benefit agent deposited
`from the shampoo. For example cationic guar gum has been
`described for the enhancement of the deposition of antida.n-
`druff particles in U.S. Pat. No. 5,037,818 and for the
`enhanced deposition of insoluble non-volatile silicone in
`U.S. Pat. No. 5,035,857. The use of cationic polymers in
`shower gels to enhance deposition of silicone oil
`is also
`known from EP-A-457 688 (L’0real).
`
`Deposition polymers have also been proposed to enhance
`the deposition of sunscreen materials from a shampoo
`composition. In EP 386 898 a cationic polygalaetomannan
`gum derivative is used.
`Polyacrylamides have been proposed for use in shampoos
`in EP 0 23] 997. These polymers are not charged and do not
`assist in the deposition of benefit agents.
`When washing with any of the prior art systems a con-
`siderable amount of the benefit agent will be rinsed away
`with the composition. and there is scope for substantially
`improving the deposition eliiciency.
`It is an object of the present invention to provide a more
`efficient deposition polymer than the previously described
`polygalactornannan polymers.
`
`SUMMARY OF THE H‘«WEl\'I'lON
`
`According to the present invention there is provided a
`personal washing composition comprising: a surface active
`agent selected from anionic, nonionic, r.wittet-ionic and
`cationic surfactants, soap and mixtures thereof, water, a
`non—volatile insoluble benefit agent dispersed in the com-
`position and from 0.001 to 1% by weight of a deposition
`polymer which is a cationic copolymer wherein the charge
`density of the copolyrncr is in the range 0.0001 to 0.005
`eqfg, preferably 0.0008 to 0.0025 eqfg; and the average
`molecular weight of the oopolymer is more than 2x106
`daltons.
`
`Preferably the amount of deposition polymer lies in the
`range 0.05 to 0.2% by weight. Preferably the cationic
`eopolymer is a copolymer of acrylamide and a cationic
`monomer having the formula:
`
`10
`
`25
`
`40
`
`45
`
`50
`
`where: T is —O— or
`
`_c_
`ll
`0
`
`R is H or CH3 and R’ is —NH—(CH2),,—N‘(CH._.)3 X‘ or
`—O—(CH2),,——N’” (Cl-l3]3 X‘ in which n is an integer from
`1 to 4 and X is selected from Cl, Br, I and CI~l,SO3.
`
`DETAILED DESCRIPTION OF THE
`INVENTION
`
`The composition is suitable for cleansing and condition-
`ing of the skin or hair. The term “conditioning" is intended
`to cover “moisturising” and “proteetion".
`Throughout
`this
`specification reference to average
`molecular weight (Mw) means a molecular weight calcu-
`lated as follows.
`
`The intrinsic viscosity of a polymer may be determined by
`standard capillary viscontetry. The viscosity of a series of
`low polymer concentrations in a given solvent is determined
`relative to the pure solvent. The relative viscosity N, is
`defined as:
`
`Npal)-mar :oUNratu»r
`
`The specific viscosity N”, is:
`
`N,-l
`
`If N”! , where c is the polymer concentration, is plotted
`against c. a straight line is usually obtained. The point at
`which the straight line crosses the y intercept is the intrinsic
`viscosity (No.1 This is related to the coil size of the polymer.
`The intrinsic viscosity can also be related to the molecular
`weight of the polymer if the Mark-Houwink parameters are
`known. Thus,
`NJn=K(Mw}fl
`
`Where K and a are the Ma.rk—l-Iouwink parameters.
`These have been determined for polyacrylamidc, and also
`for a number of copolymcrs of acrylamide and N,N,i\l
`trimethylaminoethyi chloride acrylate. These polymers are
`in accordance with those found useful in the present inven-
`tion. The parameters can be found in Mabire et al, Polymer
`1984 (25) 1984.
`For CPA], CPA2 and CPA5 to 10 we used the MH
`parameters for 30% cationic polymer. For CPA 3 and CPA 4
`we used Ml-I parameters for acrylamide homopolymer.
`Whichever is used.
`the Mw figure is approximately the
`same. Thus, if the MH parameters for acrylamide are used
`for CPA 1, the Mw figure becomes 5,000,000 rather than
`8,000,000.
`There is a precedent in the scientific literature where an
`estimate of Mw has been made for cationic polyaerylamides
`by using the MH parameters for acrylarnide homopolymer:
`Hubbe, M. A, Colloids and Surfaces 198'? 25 p. 325.
`
`

`
`5,543,074
`
`3
`The Ml-I parameters are generated for 1M Nacl, so, in
`accordance with normal practice for polyelcctrolytes, IM
`NaCl was used as a solvent for our measurements. Intrinsic
`viscosity of some of the polymers used is given below:
`
`Polymer
`CPA I
`CPA 2
`CPA 3
`CPA 4
`CPA 5
`CPA 6
`CPA T
`CPA S
`CPA 9
`CPA 10
`IR 400
`IR 30M
`Jaguar CISS
`Mcrquat 550
`
`Intrinsic viscosity (dug)
`1M NaCl
`11.1’
`1,1‘
`1 L8
`1.2
`12.5
`8.0
`2.8
`10.4
`6.9
`3.25
`4.8
`12.0
`9.8
`2.7
`
`"CPA" polymers are copolymers of acrylamide and MN,
`N—trimethyl aminopropylacrylamide. CPA 1, 2, 5, T, 9 and
`10 have cationic charge densities of 0.00145 eqlg. CPA 3 and
`CPA 4 have cationic charge densities of 0.0004 eqlg. CPA 6
`and CPA 8 have respective cationic charge densities 0.001 94
`and 0.0009 cqlg. All CPA copolymers werc ex Allied col-
`loids. The Intrinsic viscosities for CPA 1, 2 and 5 to 10 is
`data from Allied Colloids. The data for CPA3 and CPA4 was
`produced by the above method and corresponds closely with
`the data supplied by Allied Colloids for these materials.
`Preferred “CPA" polymers have an intrinsic viscosity of
`at least 7.
`
`25
`
`30
`
`By "benefit agent" is meant a protective andlor softening
`substance that maintains softness by retarding the decrease
`in water content from the skin (stratum corneum} or hair.
`Nomtally the benefit agent is an oil. For skin, preferred
`benefit agents include
`a) silicone oils, gums and modifications thereof such as
`linear and cyclic pol ydimethylsiloxanes; amino, allryl alky-
`la.ryl and aryl silicone oils;
`b) fats and oils including natural fats and oils such as
`jojoba and beef tallow;
`c) waxes such as beeswax and lanolin;
`cl) hydrocarbons such as petrolatum and mineral oil;
`e) higher fatty acids and higher fatty alcohols. both
`saturated and unsaturated, having a carbon chain length in
`the range C12 to C22:
`f} csters such as isopropyl myrislatc and isopropyl palmi—
`tate;
`g} essential oils such as evening primrose oil;
`h) lipids such as cholesterol, ceramides. sucrose esters and
`pseudo-cei-amides as described in European Patent Specifi-
`cation No. 556 95?;
`i) vitamins such as vitamin A and E, and vitamin alkyl
`esters, including those vitamin C alkyl esters;
`j) sunscreens such as octyl methoxyl cinnamatc (Parsol
`MCX) and butyl methoxy bcnnoylrncthane (Parsol 1789};
`and
`k) mixtures of any of the foregoing components.
`For hair. the oil may take the form of a sunscreen. a
`styling or bodying agent or a conditioning oil. Among
`suitable sunscreens and other benefit agents there may be
`mentioned: the group of branched hydrocarbon materials of
`high molecular weight referred to elsewhere as perall<[en)yl
`hydrocarbons. These may be either in an organic solvent or
`directly emulsified in the shampoo composition to give
`styling or bodying effects. Polyisobutene is a preferred
`
`45
`
`55
`
`4
`branched hydrocarbon material. Also oil soluble sunscreens -
`partitioned into emulsified oil droplets. Among the oils
`suitable for this purpose are phenyl silicones and among tl1e
`suitable sunscreens are, benzophenone compounds, diben~
`zoyl methane derivatives and camphor derivatives. A pre-
`ferred sunscreen material is a UV absorber such as 2-ethyl
`hexyl methoxy cinnamate sold under the trade name Parsol
`MCX by Givaudan.
`Silicone oil is a preferred conditioning oil for skin or hair.
`The silicone may be in the form of a low viscosity oil which
`may contain a high viscosity oil or gum in solution. Alter-
`natively thc high viscosity material may be in the form of an
`emulsion in water. The emulsion may be of high viscosity oil
`or of a solution of gum in a lower viscosity oil. The particle
`size of the oil phase may be anywhere in the range from 30
`nanometres to up to 20 microns average size.
`When the oil is a silicone it may be a polydimetl1ylsilox-
`ane with an average particle size of less than 20 microns and
`preferably less than 2 microns. Small particle size enables a
`more uniform distribution of silicone conditioning agent for
`the same concentration of silicone in the composition.
`Advantageously a silicone with a viscosity in the range 1-20
`million cst is used. The silicone can be cross-linlted.
`The personal washing composition may further comprise
`from 0.1 to 5% of a suspending agent selected from poly-
`acrylic acids, cross linked polymers of acrylic acid, eopoly-
`mers of acrylic acid with a hydrophobic monomer. copoly-
`mers of carboxylic acid- containing monomers and acrylic
`esters, cross-linked copolymcrs 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 stearates, 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. Poly-
`acrylic 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 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 materials are available from Goodrich
`and Carbopol
`is a trade mark. The suspending agent is
`particularly preferred when silicone is present.
`Suitable cross linked polymers of acrylic acid and acrylatc
`esters are Pemulcn TRI or Pemulcn TR2. A suitable het-
`cropolysaccharide gum is xanthan gum, for example that
`available as Kelzan mu.
`In skin washing compositions of the invention. the surface
`active agent can be selected from any known surfactant
`suitable for topical application to the human body. Mild
`surfactants, ie. surfactants which do not damage the stratum
`corneum. the outer layer of skin, are particularly preferred.
`One preferred anionic surfactant is fatty acyl isethionatc
`of fonnula:
`
`1tco,cH,c:H,so,M
`
`where R is an alkyl or alkenyl group of 'l' to 21 carbon
`atoms and M is a solubilising cation such as sodium.
`potassium. ammonium or substituted ammonium. Preferably
`at least three quarters of the RC0 groups have 12 to 18
`carbon atoms and may be derived from coconut, palm or a
`coconutfpalm blend.
`Another preferred anionic surfactant is alkyl ether sul-
`phatc of formula:
`
`

`
`5,543,0'}’4
`
`6
`and amide bctaines of formula:
`
`RorcH,r:H,o),so,M
`
`where R is an alkyl group of B to 22 carbon atoms. n
`ranges from 0.5 to 10 especially L5 to 8, and M is a
`solubilising cation as before.
`Other possible anionic surfactants include alkyl glyceryl
`ether sulphate, sulphosuccinates, taurates, sarcosinates, sul-
`phoacetates. allryl phosphate, alkyl phosphate esters and
`acyl lactylate, alkyl glut-arnates and mixtures thereof.
`Sulphosuccinates may be monoalkyl sulphosuccinates
`having the formula: RSOZCCI-I2CH(SO3M}CO2M; and
`arnido—MEA
`sulphosuocinates
`of
`the
`formula:
`RCONCHZCHZOZCCH2CH(S03M)CO2M; wherein
`R5
`ranges from C3-C2.) alkyl, preferably Cn—C,, alkyl and M
`is a solubilising cation.
`Sarcosinates are generally indicated by the formula:
`R5CON{CH3)CH2C02M, wherein R ranges from C3-C1,
`alkyl, preferably C,1—C,5 alkyl and M is a solubilising
`cation.
`
`formula:
`are generally identified by the
`Taurates
`R5C0NR"Cl-l,Cl-I,SO3M, wherein R5 ranges from C3—C,O
`all-tyl, preferably C,2—C,5 alkyl. R5 ranges from C1-C4
`alkyl. and M is a solubilising cation.
`Harsh surfactants such as primary alkane sulphonate or
`alkyl benzene sulphonate will generally be avoided.
`Suitable nonionic surface active agents include alkyl
`polysaccharides.
`lactobionarnides. cthyleneglycol esters,
`glycerol monoethers, polyhydroxyamides (glucarnide), pri-
`mary and secondary alcohol ethoxylates, especially the
`C34,, aliphatic alcohols ethoxylated with an average of from
`1
`to 20 moles of ethylene oxide per mole of alcohol.
`If the surface active agent comprises soap, the soap is
`preferably derived from materials with a C3 to Cu substan-
`tially saturatcd carbon chain and, preferably, is a potassium
`soap with a Cu to C13 carbon chain.
`Mixtures of any of the foregoing surface active agents
`may also be used.
`It is also preferable that the composition includes at least
`one cosurfactant agent with skin—rnildness benefits. Suitable
`materials are zwittcrionic detergents which have an alkyl or
`alkenyl group of '2' to 18 carbon atoms and comply with an
`overall structural formula
`
`i“
`it’
`R1-t—C—Ntt(C1t;._),..1_—1|~tv—x—Y
`R]
`
`where R‘ is alkyl or alkenyl of 7 to 18 carbon atoms R2
`and R3 are each independently alkyl, hydroxyalkyl or car-
`boxyalkyl of l to 3 carbon atoms
`m is 2 to 4
`rt is0 or 1
`
`X is alkylcnc of l to 3 carbon atoms optionally substituted
`with hydroxyl, and Y is —C02‘ or —SO3‘
`Zwitterionic detergents within the above general formula
`include simple bctaines of formula:
`R2
`|
`R1 — — CHzC01'
`R1
`
`5
`
`pp?
`R'—CONH(CHz)...—!l\i’—CHgOOr
`R3
`
`where rn is 2 or 3.
`
`In both formulae R1. R 2 and R3 are as defined previously.
`R1 may. in particular. be a mixture of Cu and C14 alkyl
`groups derived from coconut so that at least half. preferably
`at least three quarters of the groups R‘ have 10 to 14 carbon
`atoms. R‘ and R3 are preferably methyl.
`A further possibility is a sulphohetaine of formula:
`RI
`I
`_
`R= —tpr ——(Cl{g)3S03'
`R3
`
`25
`
`30
`
`or
`
`$2
`R1 —CD1\'}{(CH;),,,t]st' — (CH3)3SO3‘
`R3
`
`where m is 2 or 3, or variants of these in which
`—(CH,)3S03‘ is replaced by
`
`$14
`—CH;Cl-ICligS03'
`
`R‘. R2 and R3 in these formulae are as defined previously.
`The surface active agent is preferably present in amount
`of from 2 to 40% by weight. and preferably from S to 30%
`by weight. The cosurfactant. is present, is preferably present
`at a level of 0.5 to 15% by weight.
`The skin washing composition according to the invention
`may also include minor amounts of other ingredients such as
`antibacterial agents, foam boosters, pearlescers, perfumes,
`dyes, colouring agents, preservatives, thickeners. proteins,
`other polymers, phosphate esters and buffering agents.
`Shampoo compositions of the invention contain anionic
`surfactant together with optional nonionic and arnphoteric
`surfactant.
`
`Suitable anionic surfactants are the alkyl sulphates, alkyl
`ether sulphates, alkaryl sulphonalcs, allcyl succinates. alkyl
`sulphosuceinates. N—a]l(oyl sarcosinatcs. alkyl phosphates.
`alkyl ether phosphates, alkyl ether carboxylates. and alpha-
`olefin sulphonatcs, especially their sodium, magnesium,
`ammonium and mono-, di— and triethanolamine salts. The
`alkyl groups generally contains from 8 to 18 carbon atoms
`and may be unsaturated. The alkyl ether sulphates, alkyl
`ether phosphates and alkyl ether carboxylates may contain
`from one to l0 ethylene oxide or propylene oxide unites per
`molecule, and preferably contain an average of 2 to 3
`ethylene oxide units per molecule.
`Further examples of suitable anionic surfactants include
`sodium oleyl suocinate, ammonium lauryl sulphosuccinate,
`ammoniurn lauryl sulphate. sodium dodccylbenzene sulphu-
`nate. triethanolarnine dodecylbenzene sulphonate, triethano-
`lamine dodeeylbcnzcne sulphonate and sodium N—lauryl
`sarcosinate. The most preferred anionic surfactants are
`sodium lauryl sulphate,
`triethanolarnine lauryl sulphate,
`triethanolamine monolauryl phosphate. sodium lauryl ether
`sulphate IEO, 2E0 and 3E0, ammonium iauryl sulphate
`and ammonium lauryl ether sulphate 1E0, 2E0 and 3E0.
`The nonionie surfactants suitable for use in the shampoo
`compositions of the invention include condensation prod-
`
`

`
`7
`
`8
`
`5,543 ,0?4
`
`nets of aliphatic (C3—C13) primary or secondary linear or
`branched chain alcohols or phenols with alkylene oxides,
`usually ethylene oxide and generally 6-30 E0.
`Other suitable nonionics include mono or di alkyl alkano-
`lamides or alkyl polyglucosides. Examples include coco
`mono or diethanolarnide, coco mono isopropanolamide, and
`coco di glucoside.
`The amphoteric surfactants suitable for use in the com-
`position of the invention may include alkyl amine oxides,
`all-ryl betaines, alkyl amidopropyl betaincs. alkyl sulphobe-
`taines, alkyl glycinates, alkyl carb-oxyglycinates, alkyl
`amphopropionates, alkyl amidopropyl hydroxysultaines,
`acyl taurates and acyl glutameates wherein the alkyl and
`acyl groups have from 8 to 18 carbon atoms. Examples
`include lauryl amine oxide, cocodirnethyl sulphopropyl
`bctaine and preferably lauryl betaine, cocamidopropyl
`bctaine and sodium cocamphopropionate.
`The surfactants are present in the shampoo compositions
`of the invention in an amount of from 2 to 40% by weight,
`and preferably from 5 to 30% by weight.
`The shampoo may also include minor amounts of other
`ingredients such as antibacterial agents,
`foam boosters,
`pearlescers, perfumes, dyes, colouring agents, preservatives,
`thickeners. proteins, other polymers, phosphate esters and
`buffering agents.
`The invention will now be described, with reference to the
`following non-limiting examples:
`[A] Skin Washing Compositions
`
`EXAMPLES
`
`In the examples:
`Coco arnidopropyl betaine was Tergobetaine F ex Gold-
`schmidt or Amonyl BA 380 ex Seppic.
`Guar hydroxypropyl uirnoniurrt chloride was Jaguar C-13-S
`ex Meyhall.
`Silicone oil emulsion was BC 893138 ex Basildon.
`Sodium cocoyl isethionate was either Jordapon CI ex PPGI
`Mazer or I-lostapan SCI ex I-Ioechst.
`Sodium lauryl ether sulphate was Genapol ZRO ex Hoechst.
`Compositions according to the invention and comparative
`compositions were tested by the following method.
`A number of tests were carried out by human volunteers.
`The experimental procedure employed was as follows:
`The volunteers washed their forearms with a shower gel.
`The procedure involved wetting the arm and also the vol-
`unteer‘s free hand with warm water then using the free hand
`to lather the arm with 0.5 grams of the shower gel, next
`rinsing for 10 seconds while rubbing with the free hand and
`then drying the a.rrr1 with a single pass with a paper towel.
`10 minutes after drying the forearm a strip of adhesive
`tape is pressed onto the areas on the forearms keeping it in
`place for 30 seconds using a spring loaded device bearing on
`a rubber bung to press the tape onto the skin with a
`repeatable pressure of 85 g.cm“2. The adhesive tape
`employed was J-La: Superclcar {TM} tape having a width of
`25 mm. Two strips of tape are applied to each forearm in this
`way to adjacent areas of the skin.
`in this test procedure silicone which has deposited on the
`skin is transferred to the tape along with some of the outer
`layer of the volunteer‘s skin.
`The amounts of silicon and skin adhering to the tape are
`determined by means of X-ray fluorescence spectroscopy.
`The tape strips are placed in an X-ray fluorescence spec-
`trometer with the adhesive side facing the beam of this
`machine. A mask is applied over the tape to define a
`standardised area in the middle of the tape which is exposed
`
`S
`
`15
`
`20
`
`35
`
`45
`
`55
`
`55
`
`to the X—ray beam. The sample chamber of the macl1.ine is
`placed under vacuum before making measurements and the
`spectrometer is then used to measure the quantities of silicon
`and sulphur. The sulphur is representative of the amount of
`skin which has transferred to the tape. Results are presented
`in terms of the ratio of Si:S.
`
`EXAMPLE 1
`
`In this example deposition of silicone from compositions
`containing a range of polymers according to the invention
`was compared with deposition from a composition contain-
`ing a polymer which is a commercially available shower gel,
`namely, guar hydroxypropyl Lrimonium chloride (compari-
`son).
`The base formulation was:
`
`Sodium lauryl ether sulphate ISLES)
`Coco amidopropyl het.'|.irIe (CAPE)
`Silicone oil emulsion
`Sorbir: acid
`Sodium citrate dihydnate
`Sodium chloride
`Citric acid
`Water + minors
`
`‘if: wt
`
`13.00
`2.00
`5.00
`0.3’?
`0.49
`2.0
`0.01
`to 100
`
`Polymers were added to the base formulation at a level of
`0.1% wt.
`
`Each composition was prepared by forming a 1% disper-
`sion of the polymer by adding it to water at -50° C. SLES
`and CAPE were added to the excess water of the formulation
`with gentle stirring. Thereafter the silicone oil emulsion was
`added with stirring to the surfactant mixture. This was
`followed by the polymer dispersion and finally the minors.
`Deposition of silicone" was determined according to the
`procedure described above. The Si:S ratio for the compari-
`son was normalised to 1 and the values for the compositions
`according to the invention expressed relative to the com-
`parison.
`The following results were obtained:
`
`Polymer
`
`Comparison
`CPA 6
`CPA l
`CPA ‘I
`
`Si:S
`
`1
`4.19
`142
`1.90
`
`improved deposition
`the
`results demonstrate.
`The
`obtained with the compositions according to the invention.
`In a further set of experiment with the same base forrnu-
`lation but with different polymers the following results were
`obtained.
`
`Polymer
`
`Comparison
`CPA 9
`CPA 10
`CPA 5
`CPA S
`
`5i:S
`
`1
`1.83
`2.10
`2.8]
`l.'l'2
`
`These results also demonstrate the improved deposition
`obtained with the compositions according to the invention.
`EXAMPLE 2
`
`In this example the variation of silicone deposition with
`the amount of polymer added to the base formulation was
`
`

`
`9
`examined and compared with that
`containing no polymer.
`The base formulation was:
`
`from a composition
`
`‘Ki wt
`
`100
`Sodium lauryl ether sulphate
`8.00
`Coco amidopropyl belaine (CAPB)
`5.01]
`Sodium cocoyl isclhionate
`5.00
`Silicone oil entuision
`
`Water I- minors to 100
`
`It was prepared by forming a premix of the cocoyl
`isethionate (25% dispersion) by adding it to water at 45° C.
`The SLES and isethionate premix were then added to the
`excess water of the formulation with gentle stirring. fol-
`lowed by the CAPE. ‘Thereafter the silicone oil emulsion
`was added with stirring. A 1% dispersion of the polymer was
`prepared by adding it to water at -50" C. This was then
`added to the surfactanllsilicone mixture to the required level
`followed by the minors.
`Deposition of silicone was determined according to the
`procedure described above.
`The following results were obtained:
`
`
`15
`
`25
`
`Polymer
`
`Eé wt
`
`Si:S
`
`Comparison
`CPA 5
`
`0.41
`0
`1.02
`0.05
`2.43
`0.1
`3.23
`0.2
`Comparison
`0.36
`0
`CPA 6
`2.95
`0.05
`4.23
`0.1
`
`0.2 4.ll5
`
`The results demonstrate that silicone deposition increases
`as the amount of polymer present
`in the composition
`increases.
`
`[13] Shampoo Compositions
`Test of Conventional Cationic Polymers
`Many of the commercially available cationic polymers
`designed for use in cosmetics show no ability to deposit
`silicone on to hair during the course of the hair washing)‘
`rinsing cycle. Table 1 details the performance of a range of
`cationic polymers promoted by their manufacturers as suit-
`able for use in shampoo applications. The polymers were
`tested as silicone deposition and retention aids in one of the
`shampoo formulations (A.B,C or D) given below in Table 3.
`
`TABLE 1
`
`silicone
`retention
`on hair
`‘ii:
`polymer
`Eg Polymer
`shampoo
`ppm
`deposition
`Mw
`
`A C135
`C
`1280
`16
`150 000
`B C138
`A
`983
`20
`250 000
`C C15
`A
`142
`3
`<l00 000
`D Cl?-S
`D
`1828
`25
`250 000
`E
`JR400
`A
`0
`—
`400 000
`F
`JR30M
`A
`0
`——
`600 000
`G 111400
`B
`651
`14
`400 000
`H IR4-00
`C
`0
`—
`400 000
`I
`E-‘C370
`A
`0
`—
`100 000
`J Quat-
`A
`0
`—
`125 000
`Plot
`
`45
`
`55
`
`60
`
`65
`
`5,543,074
`
`10
`
`TABLE l—continued
`
`silicone
`retention
`on hair
`‘.6
`polymer
`Eg Polymer
`shampoo
`ppm
`deposition
`Mw
`
`K 550
`A
`0
`—
`'I00|.'l0ll
`L —
`A
`0
`—
`—
`M —
`C
`0
`-
`—
`
`
`A figure of zero for silicone retention indicates that the
`amount detected was negligible and could not accurately be
`measured.
`
`C133 is JAGUAR (trade mark) C138, a cationic guar
`derivative ex Meyhall
`C15 is JAGUAR C15, also a cationic guar derivative ex
`Meyhall
`JR400 is POLYMER JR400, a polysaccharirie derivative ex
`Union Carbide
`
`J R30M is POLYMER JRSOM, a polysaccharide derivative
`ex Union Carbide
`FC370 is Luviquat FC 3'?0(tradc mark}, ex BASF
`Quat-pva is a copolymer prepared by reacting g]ycidy1tn'-
`methylammonium chloride with a commercial PVA;
`Mowiol 40-88. ex 1-locschst. The molecular weight (Mw} is
`127,000 (supplier’s data). The final charge density (from
`NMR) is 1.2 meqfg.
`550 is Merquat 550 ex Croxton and Garry.
`Of these examples, only example K is polyacryiamide
`based. The value given for polymer Mw in the table is
`suppliers data for all ex amples except Example K. Accord-
`ing to Croxton+Garry, Merquat 550 has a weight average
`molecular weight of 2.8 million, however, when measured
`using our Intrinsic viscosity method a value for Mw of 700
`000 is obtained.
`
`from hair-
`retention figures were obtained direct
`All
`switehes washed twice for 305, and rinsed twice for 308, in
`running tap water. Shampoo application was at the level of
`0.12 gig hair. Silicone levels were determined from )(—Ray
`Fluorescence count rates by comparison with known stan-
`dards.
`Silicone retention efiiciency from fonrtulations containing
`these low Mw polymers does not exceed 25%.
`
`EXAMPLES 3-S HIGH MOLECULAR WEIGHT
`CATIONIC POLYACRYLAMIDES
`
`Using high molecular weight polyacrylamidcs (Mw>3,
`000,000) gives previously unattainable levels of silicone
`retention, typically far in excess of 50% efficicncy. The
`results are shown in Table 2.
`
` TABLE 2
`Silicone
`retention
`ppm
`
`Efiiciertcy
`‘it:
`
`Me] wt
`
`Ex—
`ample Polymer
`
`.'Sl1e.m-
`poo
`
`3 030 000
`>70
`‘J-5000
`D
`CPAI
`3
`3 000 (B0
`43
`2060
`A
`CPAI
`4
`400 000
`—
`0
`A
`CPA2
`5
`6 000 000
`63
`63
`C
`CPA3
`6
`220 000
`3
`130
`C
`CPA4
`‘I
`
`
`
`
`"4703 A 332500 33558 )5 000 000
`
`
`
`Thus, although most commercially available cationic
`polymers with Mw below 1,000,000 intended for use in
`cosmetic products show little or no activity as deposition
`
`

`
`5,543,074
`
`12
`All figures are an average from 5 hair samples. It can be
`seen that addition of the Polymer according to the invention
`trebles the efficiency of silicone deposition.
`We claim:
`1. An aqueous persona] washing composition comprising:
`a) 2 to 40% by weight of a surface active agent selected
`from the group consisting of anionic, nonionic, zwit-
`terionic and cationic surfactants, soap and mixtures
`thereof;
`
`b} a non-volatile insoluble benefit agent dispersed in the
`composition present in an eflective amount to condition
`hair or skin, the benefit agent being selected from the
`group consisting of silicone oils and hydrocarbons; and
`c) from 0.001 to 1% by weight of a deposition polymer
`which is a cationic copolymer wherein the charge
`density of the copolymer is in the range 0.0001 to 0.005
`equivalents/grain, the average molecular weight of the
`copolymer is more than 2Xl0° daltons and the cationic
`polymer is a copolymer of aerylamide and a cationic
`monomer having the formula:
`
`R l
`
`—(CH:—lT"5J-T
`.
`
`IR
`
`where: T is —0——or
`
`_C._
`ll
`o
`
`R is H or CH3 and R1 is -—NH——(CH2),,—N*(CH3)3X‘ or
`—O—(CH2),,—N*(CI-I3}3X‘ in which n is an integer
`from 1 to 4 and x is selected from C1, Br,l and CHBSO3.
`2. A composition according to claim 1 in which the
`amount of deposition polymer lies in the range 0.05 to 0.2%
`by weight.
`3. A composition according to claim 1 in which the charge
`density of the deposition polymer lies in the range 0.0008 to
`0.0025 eqfg.
`4. A composition according to claim 1 in which the benefit
`agent is a silicone oil.
`5. A composition according to claim 6 in which the
`composition further comprises from 0.1 to 5 ‘ii: of a sus-
`pending agent for the silicone oil selected from the group
`consisting of polyacrylic acids; cross linked polymers of
`acrylic acid; oopolymers of acrylic acid with a hydrophobic
`monomer; copolymers of carhoxylic acid- containing mono-
`mers and acrylic esters; cross-linked copolymers of acrylic
`acid and acrylate esters; heteropolysaccharide gums; crys-
`talline long chain acyl derivatives; fatty acid monoglyceridc
`polyglycol ethers; propylene glycol and propylene glycol
`oleate; and mixtures thereof.
`6. A composition according to claim I which is a shampoo
`composition and in which the surface active agent is an
`anionic surfactant.
`7. A shampoo composition according to claim 6 in which
`the anionic surfactant is selected from the group consisting
`of sodium lauryl sulphate, triethanolamine lauryl sulphate,
`triethanolamine monolattryl phosphate, sodium lauryl ether
`sulphate IEO. 2E0 and 31-30; ammonium lauryl sulphate
`and ammonium lauryl ether sulphate IEO, 2E0 and 3E0
`and mixtures thereof.
`
`11
`
`aids from conventional shampoo formulations, use of very
`high Mw (>3,000.000} cationic polyacrylarnides in shampoo
`formulations gives surprisingly increased levels of silicone
`retention.
`
`TABLE 3
`SHAMPOO A.‘
`
`SLE5 ZED
`16
`Lauryl Belaine
`2
`Ethylene glycol distearate
`2.25
`BY22-026 (50% silicone emulsion) ex Toray silicone
`4
`Deposition Polymer as specified
`0.1
`SHAMPOO B:
`
`SLES 3E0
`8
`coeoamido propylbctaine
`4
`Nacl
`1.5
`B‘t'22~026
`4
`Deposition Polymer as specified
`0.3
`SHAMPOO C:
`
`SLES ZEO
`'2
`BY22~026
`1
`Deposition Polymer as specified
`0.1
`SHAMPOO D:
`
`6
`'2
`1.5
`05
`0.25
`4.3
`0.3
`0.1
`
`SLES ZEO
`coeoamido propylbetnine
`ethylene glycol distmrale
`Potassium sorbatc
`Citric Acid
`X2-1766 (60% Silicone emulsion) ex Dow Courting
`Nacl
`Deposition Polymer as specified
`
`Comparative Examples N and 0
`
`Because we believed that the higher charge density Jaguar
`Cl’? might out perform the Jaguar C133 tested in Examples
`A, B and D, we made a comparison between C17 and other
`polymers in shampoo A as follows:
`Example N: Shampoo A with Jaguar C135 933 ppm 20%
`efliciency
`Example 0: Shampoo A with Jaguar C171 413 ppm 29%
`eflicicncy
`high molecular weight
`The polyacrylamides with
`(Examples 1,2,4 and 6) clearly outperform Jaguar Cl'I'.
`The silicone level in these shampoos was 2% by weight.
`
`EXAMPLE 9 AND COMPARATIVE EXAMPLES
`P AND 0
`
`To show that the deposition polymers according to the
`invention can give benefit when added to a commercial
`shampoo we tested “Wash and Go" Dry Sensitive, (Com-
`parative Example P believed to be without deposition poly-
`mer} and “Wash and Go" Extra