CA2195857C - Deposition of materials to surfaces using zwitterionic carrier particles - Google Patents

Abstract

Compositions to deposit an active substance on a target surface (i.e. skin, hair). The active substance remains on the surface after the product is rinsed off the surface. The preferred deposition is from compositions-containing an anionic or nonionic active in the co-presence of an anionic surfactant. The compositions contain carrier particles having a zwittetionic or cationic surface and a plurality of outwardly protruding filaments containing charged organocarbyl groups. The active substance is contained within the carrier particles.

Description

pCT/EP95/02711 prraOSrmrOh OF hLAmERTAT ~ m0 ~L1RFACES LrSTNC ZWTT'~'ERTONIC
aRr .g PARTr r. .~ ...._ The invention relates to compositions for depositing an active substance onto a target surface, methods of preparing the compositions, and methods of using the compositions.
-sa~karound of the Tm~ent~on, _ _ _ _":_,_.
Many household products and personal products contain active ingredients which need to be delivered to and deposited onto a target surface, i.e., fabric, skin, hair, or teeth. The product must leave the active ingredient (e.g., a perfume, an antimicrobial agent) on the target surface after the product is washed and rinsed off the surface-. Since these surfaces are negatively charged, the usual approach for deposition from "leave on" products is to use cationic actives for-deposition. Deposition of anionic actives from aqueous solutions onto anionic surfaces can be also achieved by using cationic polymers as deposition aids. For example, cationic polymers can be used to promote the adsorption of anionic surfactants such as sodium dodeeyl sulfate onto anionic silica particles. Similarly, cationic polymers may also be used to deposit silica particles onto glass.
Deposition of anionic or nonionic activesontoanionic surfaces fromcompositions containing anionic surfactants is much more difficul t Unfortunately, a great number-of _ household and personal products (e. g., shampoos, toothpaste, soap bar, and skin cleansing compositions) contain anionic surfactants. Anionic surfactants interfere with deposition by adsorbing onall surfaces-as well_as-forming complexes!

~: \ ~ . ~ ', precipitates with cationic deposition aids. -Even if deposition occurs, the formulatiDns may exhibit poor-stability due to ~locculation-arid precipitation,'particularly' at high concentration of an anionic active and/or-at a.high concentration of an anionic surfactant: SiIiconeoil droplets disperse$ in shampoo cad-be deposited onto hair using a commercially available cationic pplymer, Jaguar~
available ~rom Rhone-POUlenc (see e.g., European'Patent Application 093-6013. 'However; 'the higher the concentration of anionic surfactant, the harder it is to attain deposition of actives-. Thus, it is desirable to improve the deposition of actives onto a negatively charged target surface in the presence of an anionic surfactant. -, There is a need for coiqpositionsand methods for-effective delivery and deposition of active substances onto negatively charged surfaces, particularly when compositions also contain anionic surfactants.
The use of nonionic "hairy" structures for steric stabilization of particles in different media has been -described in °NOnaqueous Silica Dispersions Stabilized by Terminally-Grafted Polystyrene Chains", Journal of Colloid and Interface Science, Vol: 68, No. 1, (January 1979), pp.
190-195. .This document, however, does not address the problem of deposition at all. There have been attempts also to use functionalized materials for deposition onto surfaces.
(See e.g., U.S. Patent 5,171,264]. ThesQ-documents, however, do not address the problem of deposition in the presenceof anionic surfactants.

o The present invention accordingly provides-a composition for -depositing an active substance onto a target surface, the composition containing (i) from about 0.1~ to about 50~wt-of carrier particles selected from the group consisting of:
(a) particles with a zwitterionis surface,-the surface having a plurality of outwardly protruding filaments containing positively charged organocarbyl groups and a plurality of outwardly protruding filaments containing negatively charged organdcarbyl groups; and (b) particles with a cationic-surface, the surface having a plurality of outiJardly protruding filaments containing positively charged organocarbyl groups;
(ii) from about 0.01 to about 50~wt of an active substance-within said particle.
Tn a preferred-embodiment of the invention, the composition further includes a cationic or an amphoteric polymer deposition aid.
The term °zwitterionic~~ as used herezn_means a mixture of cationic and anionic (not-necessarily neutral); thus the surface of the zwitterionic particle must have both cationic and anionic groups (i.e:, positively charged and negatively charged organocarbyl groups).
-W0 96103972 219 5 ~ ~ ~ PCT/EP95102711 The term "a plurality of outwardly protruding filaments" as used herein means that a plurality of chemical chains protrude outwardly from the surface-of .the particles, iri essence forming a filamentous, hairy-like surface. The term "organocarbyl groups" means chemical groups or moieties -comprised of at least carbon-and-hydrogen, and optionally of heteroatoms, such as oxygen, nitrogen, phosphorus, and sulphur. Suitable examples of negatively charged organocarbyl groups include, but are not limited to, sulfate, sulfonate,-carboxylate, phosphate groups, and mixtures thereof. Suitable ~camples of. positively charged organocarbyl groups include, but.are not-limited to, primary amine, secondary amine, tertiary amine, quaternary ammonium salts, amidines, pyridinium salts and mixtures thereof. -The term "particles" includes solid and semi-solid particles, -as well as emulsion droplets.
The zwitterionic or-cationic particles employed in the present invention serve as carrier particles for an active material which is entrapped in or distributed throughout the carrier particles. In use, when the compositions according to the invention are applied to a target surface, the active material is deliverQd to and deposited onto a target surface by virtue of the deposition-of the carrier particles.
The present invention is based, atleast in part,-on the finding that particles having a filamentous zwitterionic-or cationic surface deposit onto negatively charged &urfaces-to a substantially greater extent than the particles with filamentous anionic surface. Unhike-the anionic particles, the zwitterionic or cationic particles remain on the target surface even after the target surface is washed.--In a preferred embodiment of the invention, zw3tterionic rather than cationic particles are employed in order to minimize-or eliminate the_foYmation of flocs upon standing in an anionic surfactant system. Thedeposition ofthe particles employed in the present invention is substantially enhanced by the presence of adeposition aid, which- is selected-from cationic t 5 or amphoteric polymers.
The compositions according to the invention are especially useful when-it is desired to deposit-an anionic active substance onto a negatively charged target surface from a composition which also contains an anionic-surfactant, particularly when the concentration of an anionic surfactant is high,albeit the compositions may be employed for depositing any active substances present in any household or personal product composition. Thus, the compositions are most useful when it is desired to deposit an active substance, particularly an anionic-active substance, from a laundry detergent, a dishwashing composition, a soap bar, a liquid skin cleansing composition, a shampoo, a toothpaste or a mouthwash.
-The present invention also includesmethods of preparing and using the compositions according to the invention.
The inventive compositions contain, as a first essential ingredient, a particle which serves as a carrier for an active material. Suitable--carrier particles must be insoluble in a final formulation in order to.preserve the .
structural integrity of the particles during storage. Since consumer products are,-for the most part, aqueous based, the carrier particles included ;=n the compositions of-the invention are water-insoluble. However, the carrier particles must be water-dispersible.so that uniform stable suspensions or emulsions can be formed. The carrier i particles employed in the present invention have either a ~ilamentous zwitterianic surfaceor a filamentous cationic surface: When zwitterionic carrier particles are-employed in the invention, preferably some filaments'on the surface-pf the particles carry positively-charged organocarbyl groups or J
moieties and others carry negatively charged organocarbyl groups or moieties i.e_ the positively and negatively charge groups are-located on different filaments. When cationic carrier-particles are employed in the present-invention;- all filaments on the surface o~--the particlescarry positively charged organocarbyl groups: Carrier-particles having a filamentous zwitterionic ordationic surface deposit onto negatively charged surfaces to-a substantially greater eactent than the particles with filamentous_anionic surfaces. Unlike the anionic particles, the zwitterionic or cationic particles remain on the target surface=even after the targe.t.surface has been washed off. Although the zwitterionic particles used in the present invention may and preferably do have a net negative charge udder neutral pFI (i.e., "a net zeta 2Q potential°-), they still deposit substantially better than anionic particles with the same net negative charge. Sec!eral factors may contribute to the higher deposition o~
zwitterionic particles over homoionic particle having the same net zeta potential. Although not wishing to be bound by this theory, it is believed that changes in dynamic local potentials because of configurational changes of the filamenEous structure as--the ziaitteriohic-surface-approaches an anionic substrat-a surface may-be. playing a key-role during deposition.
The filamentous zwitterionic or-cationic surface of the carrier particles employed herein may be fo~ecl in sever2.I
ways. For example, a water-insoluble material may be coated (e.g., coating by adsorption) with a polymer which has pendant negatively and positively charged side chains, the WO 96/03972 PGT/EP95/02711, polymer thus forming a filamentous zwitterionic surface.
When this approach is taken, suitable solid materials ' include, but are not limited to, porous silica, zeolite, latex particles. Suitable polymers are polyampholytes which have a neutral backbone and pendant anionic and pendant cationic group, e.g., acrylate/betaine copolymers, as described in U.S. Patent 4,985,487, crosslinked anionic polymer/betaine polymer, as described in U.S. Patent No.

5,098,699, zwitterionic gafquat-like materials, as described in U.S. Patent No. 5,045,617, cationic/anionic/amphoteric combinations as described in U.S. Patent 4,591,610, carboxylate/ammonium zwitterionic polymers as described in U.S. Patent 3,836,537, detergent/zw itterionic polymer mixture as described in U.S.
Patent 4,075,131, crosslinked amphoteric polymer as described in U.S. Patent 4,534,892, DMDAAC/acrylic acid copolymers as described in EP 269 243 and in EP 266 1111.
When cationic carrier particles are desired, suitable polymers include but are not limited to the polymers described in U.S. Patents 3,761,418; 4,673,525; 4,820,447;
5, 064, 555; and 4, 871, 536.
The preferred polymers are Polyquaternium (CTFA name) polymers e.g., Polyquaternium-1, Polyquaternium-2, Polyquaternium-4, Polyquaternium-5, Polyquaternium-6, (also known as Merquat 100~ available from Calgon).
Polyquaternium-7 (also known as Merquat 550° available from Calgon), Polyquaternium-8, Polyquaternium-9, Polyquaternium-10 (also known as Polymer JR 400~), Polyquaternium-11, Polyquaternium-12, Polyquaternium-13, polyquaternium-14, Polyquaternium-15, Polyquaternium-16, Polyquaternium-17, Polyquaternium-18, Polyquaterriium-19, Polyquaternium-20, Polyquaternium-24, Polyquaternium-27, Polyquaternium-28, Polyquaternium-29 -Ialso known as Kytamer KC~ available from Amerchol), Polyquaternivm-30, Polyquaternium-31,- Polyquaternium-32;-Polyquaternium-33, Polyquaternium-34, Polyquaternium-35,-Polyquaternium-36, Polyquaternium-37, Polyquaternium-39.-Another way to obtain a carrier particle with a filamentous surface suitable for use in tie-present invention-is toform an emulsion of molten wax at a temperature higher than room temperature and to obtain emulsion droplets of net positive or negative charge by adding a-combination of anionic and cationic surfactants at appropriate ratios The emulsion droplets-form water-insoluble filamentous -iwitterionic particles upon cooling.
Suitable waxes include, but are not limited-to, the hydrocarbon waxes such as paraffin wax and microcrystallized waxes, waxes deriued from natural materials such as beeswax, carnuba wax, triglycerides and other animal and vegetable waxes_ The wax may also contain various plasticizers that are used to manipulate their Theological properties and melting point. When cationic carrier particles are desired, a cationic surfactant alone is employed, rather than a mixture of-cationic and anionic surfactants. The wax emulsion method of forming filainentous carrier particles~is preferred due to ease-of manufacture. Typically, the ratio of anionic surfactants to cationic surfactants is in the.
range of from 9:1 to 0.01:1, preferably in_ the range of from 2:1 to 0_5:1. The ratio of-tbtal surfactant to wax is from about 1:100 to about 1:30.
Suitable anionic surfactants are-water-soluble alkali metal salts of organic sulfates ahd-sulfonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include.the alkyl portion of higher aryl radicals_ Examples, of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulfates, especially those obtained by sulphating higher tCe-Cls) alcohols produced for examples from tallow or-coconut oil, sodium and potassium alkyl (C9-C2p) benzene sulfonates.
particularly sodium linear secondary alkyl (C,o-C15) benzene sulfonates; sodium alkyl glyceryl ether sulfates, especially those ethers of ahe higher alcohols derived from tallow or coconut oil and-synthetic alcohols derived -from petroleum;
sodium coconut oil fatty monoglyceride.sulfatesand sulpphonates; sodiurlLand potassium salts of sulphuric acid esters -of higher (Ce-C,e) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction ,products of fatty acids such as co.coriut.fatty acids esterified with isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane monosulfonates such as those derived by reacting alpha-olefins (Ce-C2o) with sodium bisuTphite and those derived from reacting paraffins with 502 and C1~ and then hydrolyzing with a base to produce a random sulfonate;
and olefin-sulfonates, which term is-used to describe the material made by reacting olefins,,particularly Clo-CZo alpha-olefins, with S03 and then neutralizing and hydrolyzing the reaction product. Further examples are described in "Surface Active Agents and Detergents" (VOl. R .and II) by Schwartz, Perry and Berch. Any suitable anionic maybe used and the examples are not. intended to be-limiting in any way.
Suitable cationic surfactants include, but are not, limited to, quaternary ammonium compounds (such as alkyldimethyl-ammonium halogenides), alkyl andethoxylated alkyl amines (primary, secondary and tertiary), alkyl pyridinium salts and amidines.

Another suitable way to obtain carrier particles.for.us~in the present invention is to select solid-materials with T
surface reactive groups such -as ~ydroxide,carbonate, sulfate, phosphate, oxide, silicate, (e.g., silica or 5 zeolite), calcium carbonate, titanium dioxide and clays and hydrotalcites, and to react (nr engraft) these materials_with one or more polymers which contain di-functional oxganocarbyl groups: one-of the groups serves to attach the polymer to the solid material's surface_and-the second group serves as a 10 functionalgroup on thefilament- The second group is, for example, a carboxy group to create a-negatively charged_ filament or an amine to create a positively charged filaknent.
Alternatively, the solid material with the reactive sur ace group tas described above) may be reacted with polyalkyl glycol, and subseguentiy modified (e. g., with car~oxylamine).
Latex particles with engrafted-cationic or zwitterionic-surfaces constitute another source of water-insoluble carrier particles for use in the present invention. Suitable latex particles may be obtained commercially from Snterfacial Dynamics Corp., Portland, Oregon-, telephone: (503) 684-$008.
These latex particles have short filaments terminated with functional groups and hydrophobic regions_ In a preferred embodiment of the present invention, zwitterionic particles which have a net negative charge, i.e., particles containing m4Ye fiegatively charged filaments than positively charged filament , are-employed iii-ordeY to maximize deposition and to minimize formation of flocs.,_.
The carrier particles are present in the inventive , composition in an amount of from about-0.1$ =Lo,about 50~, preferably from about 0.1$to about 20~k._..
, The secondessential ingredient included in the compositions of the invention is an active substance-which, according to the present invention, is delivered along with a carrier particle to-a target surface. inn active may be a solid or a liquid. -ACdorziing to the present invention,.the active is entrapped in, distributed throughout, absorbed or adsorbed by the carrier particles. -The identity of the active depends on the particular composition and the particular surface targeted.-When the desired target, surface.i ~.eeth,,or-an oral epithelial surface, the active material is generally selected from the group consisting of an anticaries-compound, an antimicrobial compound, an antiplaque compound, a flavorant, and mixtures thereof. Suitable--flavorants include, but are not limited to, wintergreen oil,- oregano oil, bay leaf oil, peppermint oil, clove oil, sage oil, sassafras oil, lemon oil, orange oil, anise oil, benzaladehyde, bitter almond oil, camphor, cedar leaf oil, marjoram oil, citronella oil, lavendaroil, mustard oil, pine oil, pine needle oil, rosemary oil, thyme oil, cinnamon leaf oil, and mixtures thereof_ Suitable antimicrobial compounds include, but are not limited to, thymol, menthol, triclosan, 4-hexylresorcinol,phenol, eucalyptol, benzoic acid, benzoyl ~ peroxide, butyl paraben, salicylamides, and mixtures thereof_ Suitable anti-caries compounds include, but are not limited to, pharmaceutically acceptable fluoride Compounds and zinc salts_ Typical pharmaceutically acceptablefluoride compounds that are suitable for use-in the compositions of this inyention'include sodium fluoride, potassium fluoride, lithium Fluoride, aluminum fluoride, zinc fluoride, stannous fluoride, sodiuiii mondfluoro-phosphate, acidulated phosphate fluoride,-ammonium fluoride, ammoniuiiobifluoride and amine fluoride. Zinc salts that are suitable for use in the compositions of this invention include zinc chloride, zinc sulfate, zinc acetate, zinc lactate, zinc salicylate, zinc thiocyanate and, more generally, any pharmaceutically acceptable zinc salts. , The compositions of the invention are preferably applied to target surfaces selected from mammalian skin, hair, and nails, in which case suitable active materials are cosmetic actives which include, but are not limited to, skin anti-aging compounds, skin conditioning compounds, vitamins, perfumes, antimicrobials, UV-absorbing materials, anti-acne agents, anti-cellulite compounds and mixtures thereof.
Suitable anti-aging and conditioning compounds include, but are not limited to, retinoids, Oc-hydroxy acids, salts, and esters thereof, fat-soluble vitamins, ascorbyl palmitate, ceramides, pseudoceramides (e. g., pseudoceramides described in U.S. Patents 5,198,210; 4,778,823; 4,985,547;
5,175,321), phospholipids (e. g., distearoyl lecithin phospholipid), fatty acids, fatty alcohols, cholesterol, plant sterols, and mixtures thereof. Preferred fatty acids or alcohols are those that have straight or branched alkyl chains containing 12-20 carbon atoms. A particularly preferred fatty acid is linoleic acid since linoleic acid assists in the absorption of ultraviolet light and furthermore is a vital component of the natural skin lipids. The term "retinoid" as used herein includes all natural and/or synthetic analogues of vitamin A or retinol-like compounds which possess the biological activity of vitamin A in the skin as well as the geometric isomers and stereoisomers of these compounds such as all-trans retinoid acid.

R'O 96103972 ~ i ~ ~ ~ ~ ~ PGTIEP95/02711 Suitable vitamins include, but are not limited to, vitamin A
and vitamin A derivatives, vitamin B" pantothenic acid, vitamin D, vitamin E.
Suitable skin conditioning agents, include but are not liiaited to, long-chain fatty acids, liquid water-soluble polyols, glycerin, propylene glycol, sorbitol, polyethylene glycol, ethoxylated/propoxylated ethera_of methyl glucose (e. g., methyl gluceth-20) and ethoxylatedlpropoxylated ethers of lanolin alcohol (e. g., Solulan-'75J.
Suitable W-absorbing materials include, but are not limited to, PABA and PARA amino benzoate derivatives, salicylates, cinnamates, anthranilates, dibenzoyl urethanes, 'camphor derivatives and mixtures thereof. Specific examples include, but are not limited to, benzophenone-3, benzophenone-8, ethyldihydroxypropyl-PABA, glycexyl PABA, ocGyldumethyl PABA, Parsol 1789~ (i.e., butyl methoxy debenzoyl methane), homosalate, menthyl anthranilate, octocrylene, octylmethoxy cinnamate, TEA salicylate, octyl salicylate, and mixtures thereof. -Suitable anti-cellulite agents include, but are not limited to, isobutylmethylxanthine, caffeine theophylline, yohimbine, and mixtures thereof.
Suitable anti-acne agents include, but are not limited to, resorcinol, resorcinol acetate, benzoyl peroxide, salicylic acid, azaleic acid, long chain dicarboxylic acids, various natural agents such as-those derived from green tree, and mixtures thereof..
When the desired surface is fabric; suitable active agents include, but are-not limited to, perfumes, whitening agents, brightening agents, fabric softeners.

W096103972 ~ PCTIEP95102711 Of course other active ingredients, not listed inthe specific lists -ar catego_ries above,_are suitable.for inclusion in the compositions of the invention as long as they can be incorporated in the carrier particles It should be noted-that some actiue materials may perform more than one function..-_FOr.ixistance,- menthol may perfdi:m both an antimicrobial and flavoring function; fat-soluble vitamins are nutrients for skin, and also serve as conditioning and anti-wrinkle actives.--, The active ingredient isdepasited on the target ~urface_ along with the carrier particles.and the activeis subsequently gradually released.- The release of the active is accomplished by sheer (egg., rubbing of. the paYticles-,onto the skin), temperature (e.g., melting of the particles at body temperature), diffusion-and'combination thereof. The compositions of the invention are especially useful for-depositing anionic actives.
The active material is present in the compositions according to the invention in an amount effective to deliver the desired benefit. The particular-amount of the active material depends on the identity-of the active; the desired benefit, and the nature of the composition. In general, the amount of the active is from about 0.01$ to-about- 50~, preferably from about 0.1$ to about 2Q~, most pre~erab2y from about 0.Q5~ to about 2~, by weight of the composition.
An optional but highly preferred ingredient to b2 included in the compositions according to the invention is a cationic or amphoteric polymer deposition aid. Suitable-amphoteric polymer deposition aids-include,-but are-n'oF--limited to,==
Merquat 28Q~ is copolymer of dimethyl/diallyl ammpnium -_ chloride and acrylic acid available from Calgon). Suitable cationic polymer deposition aids include but are not limited to the polymers described in U.S. Patents 3,761,418;
. 4,673,525; 4,820,447; 5,064,555; and 4,871,536.

The preferred cationic deposition aids are Polyquaternium (CTFA name) polymers, e.g. Polyquaternium-1, Polyquaternium-2, Polyquaternium-4, Polyquaternium-S, Polyquaternium-6, (also known as Merquat 100~ available from Calgon), 10 Polyquaternium-7 (also known as Merquat 550 available from Calgon), Polyquaternium-8, Polyquaternium-9, Polyquaternium-10 (also known as Polymer JR 400'), Polyquaternium-11, Polyquaternium-12, Polyquaternium-13, Polyquaternium-14, Polyquaternium-15, Polyquaternium-16, Polyquaternium-17, 15 Polyquaternium-18, Polyquaternium-19, Polyquaternium-20, Polyquaternium-24, Polyquaternium-27, Polyquaternium-28, Polyquaternium-29 (also known as Kytamer KC'' available from Amerchol), Polyquaternium-30, Polyquaternium-31, Polyquaternium-32, Polyquaternium-33, Polyquaternium-34, Polyquaternium-35, Polyquaternium-36, Polyquaternium-37, Polyquaternium-39.
The most preferred cationic polymer aids in order to attain maximum deposition are Merquat 100', Merquat 550~~, Polymer JR
40.0~, and Jaguar C13S~ (cationic guar gum).
The amount of the polymeric deposition aid in the compositions according to the invention is in the range of from about 0.001 to about 50, preferably from about O.OOlo to about 2$.
Although the compositions according to the invention may be used in any household or personal care product, their use in . products containing anionic surfactants is particularly advantageous. Consequently in a preferred embodiment of the :t~~°.~~'1~ i R'O 96!03972 r~~' PCTlEP95l02711 invention, the compositions further contain an anionic-surfactant. The anionic surfactants are usually-water-soluble alkali metal salts.of organic:sulf~tes arid sul~flnates _ having alkyl radicals containing.fram.-about 8 toabout .__ 22 carbon atoms, the term alkyl being used to include the alkyl portion of-higher acyl radicals.- Examples of suitable -synthetic anionic detergent compounds.are sodium and _.
potassium alkyl sulfates,--especially those obtained by sulphating higher (C8-C,e) alcohols produced for examples from tallow or coconut oil, sodium-and potassium alkyl-(C9-Cue) benzene sulfonates, particularly sodium linear secondary=
alkyl (C,o-C15) benzene sulfonates; sodium alkyl glyceryl ether sulfates, especially those ethers of the higher slcohols derived from tallow or coconut oil and-synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulfates and -sulfonates; soditim andpotassium salts of sulphuric-acid esters of higher-jC8-Cle) fatty -alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified-with isethionic acid and -neutralized with sodium hydroxide; sodium-and potassium-salts of fatty acid amides of methyl taurine; alkane monosulfQnates such as those derived by reacting alpha-olefins (Ce-Czo) -with sodium bisulphite and those derived from reacting-paraff-ins with SOz and C1~ and then hydrolyzing with a base--to prozluce a random sulfonate: and olefin sulfonates,-which term is used to describe the material made by react,ing,ol_efins~- _.
particularly Clo-C2o alpha-olefins, with SO= and then neutralizing and hydrolyzing the-reacti_o~_product: Another preferred surfactant is an aryl isethionate-having the formula:
P
R-C-O-CH2-CH2-S03M "

2 ~ 9 5 8 5 7 p~.,~5102,~, in which R denotes a linear or branched alkyl group and M
denotes an-alkali metal or alkaline earth metal or an amine.
_ Further examples-are described in ~~Surface Active Agents and Detergents" (VOl. I and II) by Schwartz; Perry and Berch.
Any suitable anionic-may be usedandthe examples are not intended to ~e limiting in any way. , The amount of anionic surfactant inthe compositions of the invention is generally in the-range of from about 1~ to about 99$ by weight of the composition, preferably in the range of from about 1'~ to about 65~. The particular benefit of the compositions according to the invention is their ability to deposit anionic actives ~rom compositions containing relatively high concentrations of anionic surfactants.
It has been found as part of the present invention that the pH of the compositions according to the invention affects the degree of deposition of the zwitterionic particles (and the active entrapped therein). Preferably, in order to improve the deposition from the inventive compositions, the pH of the compositions does not exceed about 1p.
The present invention further includes a method of preparing the inventive composition. The method includes the steps of incorporating an active substance into a carrier particle, the carrier--particle having been prepared by any of the methods described-above. Sn a preferred embodiment of the invention, the resulting particle is mixed with a cationic or an amphoteric deposition aid. When the core of the filamentous carrier, particle is a solid. material (e. g., zeolite or latex) the active is equilibrated into the solid by diffusion, infusion, absorption or adsorption. When the carrier particle is foizned from molten ~.iax emulsion-, the active is added to the emulsion so that when the carrier a particles with-a wax core solidify, the active isentrapped WO 96103972 PCf/EP9510271I
therein. It has been -found that. when thecompositions according to the invention further contain an anionic surfactant, improved (i.e., maximum and uniform) deposition , is obtained if the water-insoluble zwitterionic particle is pretreated (i.e., premixed or engrafted with with the deposition aid, prior to the addition a~-=the ~niflnic-surfactant. It was found that in the preparation of the compositions according to the invention mixing fob short durations of a few seconds was preferableat least-within the range tested. Longer mixing resulted in agglomeration leading to_formation of curds, strings and large.~locs,..=
Depending on the nature of thecomposition, i.e.,-a skin cleanser, a shampoo, a soap-bar, etc., the compositions may contain other ingredients suitable for-inclusion into such co~ositions and known to one of ordinary skill in the art.
For skin cleansing compositions,-both liquid and bar form examples-of optional ingredients include_opacifieYS;
preservations such as para-hydroxy benzoate esters;
antimicrobials; antioxidants such as butyl t~ydroxy toluene;
bactericides; humectants such as glycerol and sorbitol; plant extracts such as Aloe Vera, witch hazel elderflower; and colourants.
The following specific examples further illustrate the invention, but the invention is not limited thereto. e-xo ;m n ai Proc dare- . .._. ___ .-Anionic, cationic and zwitterion3c polystyrene latex particles were obtained from.Interfacial Dynamics:

WO 96!03972 PCTIEP95I027I I
19 .
Corporation. Sodium dodecyl sulfate (SDS) iaas purchased from BDH while Merquat~ (poly dimethyldiallylammonium chloride) _ polymers were obtained from Calgon Corp. Polymer JR~ and Kytamerm polymers were obtained from Union Carbide Corp.
Jaguar Ci3S~ was a product of Rhone-POUlenc Corp. Glass slides, were biomicroscopic slides-purchased from Fisher Scientific Co. -AlI-the solutions were prepared using deionized water ~th~.d~
Microscope glass-slides were cleaned by dipping in -concentrated nitric acid fox a mihute'and washed thoroughly with deionized water to-remove all the acid.
ITesired microliters of sodium dodecyl sulfate solution were.
mixed with desired microliters of the polymer and one drop of the latex particles in a cup. The concentrations of polymers and surfactants given in each example refer to the initial ones. The exact proportions of surfactant:polymer: latex for a given test are indicated in the Tables below. About 3 drops of the resulting mixture were transferred onto the glass slide.and.particle~ allowed Lo-sediment for 10 minutes.
The slide was washed under a stream of water, allowed to dry and then examined under the optical microscope for the extent of coverage and-photographed.- Extent of coverage was a relative number. based on a visual evaluation of deposition upon comparison of the obtained photographs. All results are accurate within t 5~.

.. ~.;;~ 4. . ,1 W O 96103972 ~ ~ ~ ~ 1~ ,~ ~ PCTIEP95103711 Zeta potential, a measure of the particle aurface--potential and hence surface charge; was determined by measuring the velocity of particles-in an electric potential gradient. The latex particles.were mixed with the solution of polymer and surfactant for a given time at 1~ solid concentration and diluted with polymer-surfactant solution or :distil.led vrazer-as indicated to 0_02 solid concentration-and the zeta potential was measured immediately thereafter.
Deposition of r_,atex Particles in-the absence of the oolvmer and the surfactant Preliminary deposi~iori studies o~.late7c particles-onto bare glass surfaces;undex natural pH conditions (pH = 6.4) were conducted. The results that were obtained are summarized in Table I.
hATEX SURFACE EXTENT OF COVERAGE Z%) Anionic < 5 Cationic 90 Zwitterionic 25 As expected, best deposition on bare glass slide tnegatively charged under the testcondi~ion~) wasobtai~ed with the_ cationic latex particles, while practically ho deposition was obtained with the anionic sulfate latex. Interes-tingly, the zwitterionic latex..having a net_negative zeta potential of -40 mV, identical to that.of the anionic latex, coated the negatively charged glass to a signif~a~t.=extent. This higher deposition of zwitterionic particles was unexpected. One possibility is that the zwitterionicpartiales have patches of=anionic or cationic groups and the latteris-responsible for the adhesion onto glass surfaces:- This can however, be discounted because the presence-of patches would have resulted in instability and flocculation of the zwitterionic particles, and the stable nature of'.these suspensions prove the contrary tn be true.
D ~osi ion on oolvm r Dr r a d c~_rfa ( wo s n slenosition) Deposition studies were further conducted on-glass slides pretreated with the polymeric deposition-aid. Deposition of latex particles-was evaluated after immersing the glass slide in cationic Merquat 550~ (0.1$) and anionic Carbopol~ polymer solutions (0.1$) for 3 minutes and rinsing-to remove the f-ree polymer. The results that were obtained are given in Table a.

WO 96103972 ~ PCTIEP95I02711 EXT ENT OF COVERAGE (9s7 Glass Anionic Cationic zwitterionic Pretreated Latex Latex Latex with Cationic 70 < 6 > 85 polymer Anionic 5 30 50 polymer Deposition om the cationic polymer coated surface_.was, as expected, highest with the anionic latexs- Z~aitte_rionic_lateac particles, however, deposited ve3y well on the-cationic-polymer coated and quite,well on the anionic polymer coated surfaces. This Example demonstratesthat both cationic-and zwitterionic particles may be used as carrier particles,~or deposition on negatively charged-target_surfaces.,. °°
Denos;t~on on bare surfaces from Po~vmer+-surfactant solutions (one step denositidnl - - .
Latex particles were conditioned in premixed surfactant.+
polymer solutions and deposited on bare glass slides for_a given time and then rinsed under-a stream-of water to remove unattached particles. Deposition of anionic, cationic, and zwitterionic latex particles'froin 20'in'NI ((5.687 and-250 mNi (7~) sodium dodecyl-sulfate solutipns=__we~Q te~tedwxtl~the ~_ cationic Merquat 550&', Polymer JFt 400, Polymer JR 30Ni' is _ polymer which is similar to Polymer JR 400", a substantially _ higher molecular weight), Celquat SC240"-Lalso-known as Polyquaternium-4), and Kytamer&,-anionic Carbopol° and the amphoteric Merquat 2$0~ polymers. fihe results thatwere_ obtained for deposition from 0.5~ sodium dodecyl sulfate solutions and from 7~ solutions are summarized in Tables 3A
and 3B. respectively.
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FCTlEP95/02711 The resultsin--Tables 3A and 3B indicate that practically no deposition occurred from the-anionic Carbopol° solutions;
some depositiori tp9k place from the_cationic,and.amphoteric _ polymer solutions. From 0.6$,SDS solutioris good deposition was obtained in the presenceof~.he:cationic Merquat 550~, v Kytamer~, JR400~ and-JR30M~ solutions. From the 7$ SDS
solution (SDS:POlymer: Zwitterionic =_3:1:1)-deposition was obtained in the order shown below:
Merquat 55D~ # JR3011~. # Kytamerm 5 Merguat-280p > Carbopolg' The results indicate better deposition of--the zwitLeriflnic latex particles than the anionic or the cationic latexes under most conditiohs especially under higher (7$) surfactant (SDS) concentrations. For example, deposition o~ the zwitterionic latex particles-obtained from 0.6$ sulfate solution (Table 3A1-with Merqua~ 550m and Polymer JR 400M~ was higher in comparison-to depositions of the other-latex particles. Even more importantly, from 7$ sulfate solutions (Table 3B) the deposition of_thezwitterionic particles-obtained with Polymers Merquat 280, Merquat 550m,, Polymer JR
30D1~, Kytamer~, Merquat 100~, and Celquat~ was better in-comparison to depositions of-other later particles.
EXAMPLE 4 _ _ _ _ _ - _ _ _ fiests were conducted,to=evaluaLe_~he_~ffect of the pH of the composition on the depositioh of zwitteuonic latex particles on glass surfaces from 250.mM (7$) SDS solution also- _ containing either an amphoteric-tMerquat-280°')- or a cationic (Merquat 550~) polymer. Polymer-concentration was 0.08 and the ratio--SDS:polymer:latexwas 3:llf _fihe results that-were obtained are-summarized in Table 5. _ _ R'O 96103972 ~ ~ ~ ~ ~ ~ ~ PCTIEP95102711 pH Catioaic pH Amphoteric Polymer Polymer 2.3 8 2 3 4.2 8 4 10 6.0 5 6.6 15 8.1 8 9.4 5 10.3 0 12.3 0 12.0 0 The results in Table 4 indicate significantly lower deposition in the alkaline pH range above 10.
20 The effect of different orders) of addition of the components in the compositions according to the invention deposition was-investigated. Order of miicing tests consisted of mixing first two of the three components (zwitterionic latex, surfactant and polymer) for 10-seconds. This was followed by either mixing with the third component for another ten seconds and then transfer of the mixture onto the slide or transfer onto the slide placed on a horizontal mixer and then mixing -with the third component -for ten seconds:
The results obtained for the order of mixing effects for SDSIPolymer JR400~ system are given in Table 6. SDS
concentration was 0.075; Polymer JR400" concentration was 0.075$; the ratio SDS:POlymer:Latex was 4:4:1.

W096103972 ~ ~ PCTIEP951~2711 Order of Addition Extent of Coverage (~) ' (Polymer + Latex) + SDS > 100 (MUltilayeX) (Polymer + SDS) + latex < 5 The results-in Table 5 indicate that the order of addition had a dramatic effect ou=the-extent of coxerage, with-coverage varying anywhere from a few percent for the order (polymer+surfactant-l-+ latex to.,more thap-lOD$ for the order (polymer+latex) + surfactant. It is to be noted that many multilayer patches were obtained_in the latter case. Thus, zwitterionic particles pretreated with the polymer deposition aid or with polymer chains appropriately grafted-on their might deposit best from concentrated surfactant solutions.
Mixing time effect was studied for only the order (polymer+latex) + surfactant. Polymer JB400~ concentration was 0.075. SDS concentration vJas 0.07. The ratio SDS:polymer:latex was 2:2:1. The results that were obtained are summarized in Table 7.

WO 96!03972 PCTIEP95I02711 Mixiaff Time Extent of Coverage (%) seconds 50 5 30 seconds 30 3 minutes 15 It was found that mixing for short durations of a few seconds 10 was preferable at least within the range tested. Longer mixing led to agglomeration resulting in formation of curds, strings and large flocs.

DeDOS ; on from ~ a an so> > ; on Las ho : o> > r A~ d Deposition of latex particles with various surface charge from 0.6$ SDS and 7~ SDS solutions onto bare glass surface _ was measured in the absence of polymeric deposition aid. The SDS:latex ratio. was 4:1.
The results that were obtained are summarized in Table 7:

Extent of Coverage (%) ~EX SURFACE 0.6% SDS 7% SDS

Anionic 0 0 Cationic 10 8 Zwitterionic 10 12 W096103972 ~ PCTIEP95/02711 The amount of antimicrobial DP30D deposited from liquid-skin cleansing formulation was compared to DP300 deposited from cationic and zwitterionic wax particles---The wax particles were prepared by emulsifying melted wax mixtures in 190.mL of 0.0025 N HC1 at 80 °C fQr -30 ni3.ii: yfter cooling to rood, temperature, stable wax particles of 1-5 um were obtained.
The composition of the zwitterionic wax mixture was as '.
1D follows:
wax (Baler 1397) 6.5 g dihardened tallow dimethylammonium chloride- 0.75g polyoxyethylene stearylether 1.0 g . stearic-acid 0.75 g _ . _._ _ . __. ,r _ Triclosan DP300 texCiba-Ge_igy) l.O g (10~ by weight of wax particle) The ratio of cationic urfactant and anionic surfactant can be adjusted to obtain wax particles with various-charges.
For cationic wax particles, 1.5g of dihardened tallow _ dimethylammonium chloride and no stearic acid was used.-ThepH of the wax particle s9lutions _was,adjusted to 5.5 before addition to the liquid cleansing formulation, The liquid cleanser and the wax particles weremixed=-in a 1:1 ratio. The liquid cleansing,foYmulation contained 0.1~-of Polymer JR 400~ and sodium laureth sulfate, Sodium cocoyl 3D isethionate, 12.75 of anionio surfactant t6~ sodium laurethsulfate and 6:75 cocoylisethipnate)-. SOU1 of a tested formulation_was rubbed on human stratum ccarneum(1 cm-) for 30 sec. and rinsed with water. The amount of DP300 deposited on stratum corneum-was determined by HPLC.

The results that were obtained are as-follows:
deposition of DP300 withbut wax particles: 0.8 ug/cma deposition from cationic wax particles: 2.5 ug/cma deposition-iwitterionic wax particles: 1.5 ug/cm2 This example demonstrates the criticality of the inclusion of carrier particles into compositions according to the invention a substantial increase in -deposition of the active was obtained when the active-was incorporated into cationic or awitterionic carrier particles.
A suitable liquid soap cleansing formulation within the scope of the invention is as follows:
INGREDIENT % BY WEIGHT

Sodium Laureth Sulfate 6.8 Sodium Lauryl Sulfate 5.0 Lauramide DEA 2.2 Sodium Sulfate 2.6 Cocamidopropyl Betaine 1.8 Sodium Chloride- 0.6 Styrene/ACrylate Copolymer 0.8 Triclosan containing Wax 0.5 PartlCleS* -Water to 100 * wax particles with Zwitterionic surface described in Example 8.

R'O 96103972 ~ PCT/EP95/02711 EKAMpT.E 1 O
Another suitable liquid-cleansing-formulation within the scope of the invention is as-follows: _. a y INGREDIENT 'k BY SVEIGHT

Sodium Laurel Sulfate 4.5 Sodium Chloride 2.0 Quaternium - 15 1.7 Potassium Cohydrolyzed 1.7 Collagen Lauryl Polyglucose 1.6 Cocoamide MEA 0.4 Wax * 0.5 Particles Carrying Vitamins **

water to 10D~

* wax tionic_surface"described particles in EXample with a ca 8.

** Vitamin A and/or Vitamin E t40$
by weight of the wax particles) Another suitable liquid soap cleansing formulation is as follows:
INGREDIENT . . $ BY WEIGHT

Acyl Isethionate 1-15$

Anionic other than 1-15$
Acyllsethionates (SLES)*

Amphoteric Surfactant** 5-15$

Wax particles containing 1-5$
perfume***

I5 Sequestrant (EDTA or EHDP) 0.01-0.7$

Cationic Polymer (Jaguar C13-S~) 0.05-3.0$

Standard additives (e.g., dyes, 0-10$
perfumes) I I Water - balance * Sodium lauryl ethersulfate ** Cocamidopropyl betaine *** Wax particles with zwitterionic- surface prepared in Example 8.

WO 96103972 . . . P~~p95102711 F:XFLT~PLE ~2 _.. .._.. . . ... .. . . ._.. __. . ._.. _ _.-The following Example illustrates a sta~dard_toothpaste-- _ composition according to the present invention:
INGREDIENT 'k, WEIGHT

Alumina trihydrate 50.00 Sorbitol syrup (70g 27.00 solutionl Sodium lauz7rl sulfate 1.50_-Sandoperol PLA 1.50-Sodium carboxymethyl 0.85 cellulose Sodium monofluorophosphate 0.76 -Sodium saccharin 0.20 Titanium dioxide 0.50 Porous Alumina Particles 1.00 Carrying * Flavor Water (demineralizedl Balance to 100 * Flavor by-weight of the particles concentration,is 50$

WO 96/03972 PCTlEP95/02711 A typical soap bar composition within the scope of the invention is asfollows:-INGREDIENT
%, BY WEIGHT

Sodium Cocoyl Isethionate about,50~
(DEFI) -Free Fatty Acid about 20~

10 Anhydrous Soap about 10~

Sodium Stearate about-5~

Sodium Isethionate about 5~

Sodium Alkylbenzene- about 2~
sulfonate 15 Miscellaneous (water, about 6~k colorants, etc_) Zwitterionic wax particles about 2g carrying perfume Total 100 * 30$ perfume by weight of the particle.-

Claims (16)

1. A composition for depositing active substances onto a target surface, the composition comprising (i) from 0.1% to 50%wt of dispersible carrier particles that are insoluble in the composition, the particles being selected from:
(a) particles with a zwitterionic surface, the surface having a plurality of outwardly protruding filaments containing positively charged organcarbyl groups and a plurality of outwardly protruding filaments containing negatively charged organocarbyl groups; and (b) particles with a cationic surface, the surface having a plurality of outwardly protruding filaments containing positively charged organocarbyl groups;
(ii) from 0.01% to 50wt% of an active substance within said particle.

2. A composition according to claim 1 wherein the carrier particle has a zwitterionic surface.

3. A composition according to claim 2, wherein the zwitterionic particle has a net negative charge.

4. A composition according to claim 1 wherein the composition further comprises an anionic surfactant.

5. A composition according to claim 4 wherein the surfactant is present in an amount up to 99%wt of the composition.

6. A composition according to claim 1 wherein the composition further comprises a cationic or an amphoteric polymer deposition aid.

7. A composition according to claim 1 wherein the positively and negatively charged organocarbyl groups are located at the terminal unattached end of the filaments.

8. A composition according to claim 1 wherein particles with a zwitterionic surface are formed from an emulsion comprising molten wax, anionic surfactant and cationic surfactant.

9. A composition according to claim 1 wherein the particles with a cationic surface are formed from an emulsion comprising molten wax and a cationic surfactant.

10. A composition according to claim 1 wherein particles with a zwitterionic surface are zwitterionic latex particles.

11. A composition according to claim 1, being for depositing an active substance onto a negatively charged surface.

12. A composition according to claim 1 wherein the pH of the composition is less than 10.

13. A composition according to claim 1 wherein the active substance is a cosmetic active.

14. A cosmetic method comprising applying to the target surface a composition according to any one of claims 1 to 13.

15. A method according to claim 14 wherein the target surface is selected from mammalian skin, hair, nails and teeth.

16. A method according to claim 14 further comprising rinsing the composition off the target surface.