Aqueous carrier systems for water-insoluble materials

A composition containing at least one organic phospholipid capable of forming bilayers in aqueous solution;at least one amphoteric surfactant; and at least one nonionic surfactant present in an amount by weight equal to or greater than the amount of the phospholipid. The invention also relates to a delivery system for water-insoluble ingredients containing the above components, at least one water-insoluble ingredient, and an aqueous phase, wherein the organic phospholipid, amphoteric surfactant, and nonionic surfactant are present in a combined amount sufficient to allow the water-insoluble ingredient to be incorporated into the system. A method of treating keratinous susbstances is also disclosed.

TECHNICAL FIELD
 The present invention relates to novel carrier systems based on organic
 phospholipids capable of forming bilayers in aqueous solution, nonionic
 surfactants, and amphoteric surfactants, wherein these carrier systems
 allow water-insoluble materials such as lipophilic materials and
 water-insoluble polymers, resins, or latexes to be incorporated into
 aqueous solutions.
 BACKGROUND ART
 Organic phospholipids play an important role in the cosmetics and
 pharmaceutical industries because of their outstanding physiological
 properties, such as, for example, emulsifying, softening, and anti-oxidant
 effects. When hydrolyzed, organic phospholipids yield phosphoric acid, an
 alcohol, a fatty acid, and a nitrogenous base. Most phospholipids are
 amphipathic, i.e., have polar "heads" and non-polar "tails." As a result,
 most phospholipids tend to arrange spontaneously into a bilayer when
 suspended in an aqueous environment, with the polar heads contacting the
 water and the non-polar tails contacting each other. Most naturally
 occurring phospholipids prefer to form vesicular bilayers in water
 solutions. In such a bilayer vesicle, no non-polar part of the
 phospholipid has any contact with the water solution.
 Because of their non-polar portions, phospholipids typically are
 water-insoluble and incompatible with many water soluble anionic
 compounds, such as anionic surfactants. While they can be solubilized in
 water at low levels by a range of surfactants, this is often not easily
 accomplished.
 Instead, solubilization has been accomplished conventionally using specific
 solubilizing agents in aqueous alcoholic solutions. For example, U.S. Pat.
 No. 4,874,553 to Hager et al. discusses methods of rendering phospholipid
 mixtures water-soluble or water-dispersible by using certain amine
 compounds as solubilizing agents. U.S. Pat. No. 4,174,296 to Kass
 describes a method of improving the solubility of phospholipid compounds
 in water, in particular lecithin compounds, by mixing lecithin with
 specific single solubilizing agents, including amphoteric and anionic
 surfactants. These methods utilize alcohol for cosolubilization. Alcohol
 solutions can have the drawback of disrupting any bilayer formation by
 altering the solution such that the alcohol functions as a secondary
 solvent.
 Lecithins and other phospholipids have been used in the pharmaceutical
 industry to formulate carriers for water-insoluble drugs. For instance, in
 U.S. Pat. No. 5,173,303 to Lau et al., water-insoluble material is
 encapsulated by vesicles composed of phospholipids such as lecithin.
 Ribosa et al., in "Physico-chemical modifications of liposome structures
 through interaction with surfactants," Int'l Journal of Cosmetic Science
 14:131-149 (1992), also discuss solubilization of phospholipids via the
 interaction of liposomes with surfactants. Lau and Ribosa, however,
 investigated only dilute solutions of pure liposomes.
 Despite difficulties in solubilization, certain organic phospholipids, such
 as lecithin, can advantageously give hair and skin a soft, moisturized
 feel because they have a strong affinity for the hydrophobic surface of
 the hair and skin. In addition, these phospholipids are toxicologically
 safe. It would thus be desirable for cosmetic and pharmaceutical
 applications to provide delivery systems that include such organic
 phospholipids as a carrier for other lipophilic ingredients, without the
 need for alcohols and other similar solvents.
 In addition to solubilizing lipophilic ingredients such as oils, vitamins,
 and ceramides in aqueous systems, it would be desirable to solubilize
 other water-insoluble ingredients, specifically unneutralized or partially
 neutralized polymers, resins, or latexes, in aqueous delivery systems.
 U.S. Pat. No. 5,391,368 to Gerstein teaches solubilization of a
 hair-styling polymer in a composition comprising an anionic surfactant and
 an amphoteric surfactant. According to Gerstein, it is the amphoteric
 surfactant which dissolves the water-insoluble styling polymer because the
 polymer is not soluble in the anionic surfactant alone.
 Gerstein presents some problems, however. Many hair care and hair setting
 products are formulated at acidic pH because of a desire for such products
 to be compatible with the pH of the scalp and hair surface. Gerstein does
 not disclose a pH at which its system is formulated, but if the Gerstein
 system is acidified, the polymer will precipitate out of solution. In
 addition, the Gerstein system does not carry and there is no suggestion
 that it could carry any additional lipophilic ingredients in its mixture
 of anionic surfactant, amphoteric surfactant, and styling polymer.
 Further, Gerstein does not describe the incorporation of its styling
 polymer into any products other than the disclosed styling shampoo, nor
 does Gerstein suggest that such incorporation would be possible.
 Thus, there remains a need for an aqueous delivery system that can
 solubilize water-insoluble materials, in particular, lipophilic materials,
 unneutralized or partially neutralized polymers, resins, or latexes, where
 these water-insoluble materials will not precipitate out of solution upon
 acidification, where the amount of deposition of water-insoluble material
 can be controlled, and where the system could carry other ingredients in
 addition to the water-insoluble ingredient. For example, it would be
 beneficial to have a system which incorporates water-insoluble materials
 into compositions containing other ingredients, such as dyeing and
 permanent wave compositions. The present invention provides such a
 delivery system.
 DISCLOSURE OF THE INVENTION
 In order to achieve these and other advantages, the present invention is
 drawn to a composition made up of at least one organic phospholipid
 capable of forming bilayers in aqueous solution, at least one amphoteric
 surfactant, and at least one nonionic surfactant. The nonionic surfactant
 is present in an amount equal to or greater than the amount of the organic
 phospholipid.
 In another embodiment, the present invention relates to an aqueous delivery
 system for water-insoluble materials. The delivery system (or "carrier")
 includes the above-described composition in addition to at least one
 water-insoluble ingredient, and an aqueous phase. The nonionic surfactant
 is present in an amount equal to or greater than the amount of the organic
 phospholipid. The organic phospholipid, the amphoteric surfactant, and the
 nonionic surfactant are present in a combined amount sufficient to allow
 the water-insoluble ingredient to be incorporated into or solubilized by
 the delivery system. The present invention is also drawn to a process for
 the preparation of an aqueous system comprising: (a) combining at least
 one organic phospholipid capable of forming bilayers in aqueous solution,
 at least one nonionic surfactant, and at least one amphoteric surfactant
 to form a mixture, (b) heating the mixture obtained in step (a), (c)
 adding an aqueous solution to form a diluted mixture, and (d) cooling the
 diluted mixture. Water-insoluble ingredients can be incorporated in step
 (a).
 Finally, in yet another embodiment, the present invention is drawn to a
 method for treating keratinous substances. First an aqueous solution is
 prepared containing at least one organic phospholipid capable of forming
 bilayers in aqueous solution; at least one amphoteric surfactant; at least
 one nonionic surfactant present in an amount by weight equal to or greater
 than the amount of the phospholipid; and at least one water-insoluble
 ingredient. The phospholipid, amphoteric surfactant, and nonionic
 surfactant are present in a combined amount sufficient to allow the
 water-insoluble ingredient to be incorporated into the aqueous solution.
 The aqueous solution is then applied to the keratinous substances.
 Reference will now be made in detail to the present preferred embodiment(s)
 of the invention.
 BEST MODE FOR CARING OUT THE INVENTION
 Advantageously, the present invention allows water-insoluble materials or
 ingredients to be solubilized in an aqueous solution. No alcohol is
 required for cosolubilization, and there is no need for liposome
 preparation. Further, when the water evaporates, the residue left behind
 includes the water-insoluble material and/or the phospholipid.
 The composition of the invention is also easy to formulate and is gentle on
 the hair, skin, or eyelashes because the surfactants used are generally
 mild. Unlike the attempted solubilization of phospholipids in the prior
 art, the present invention requires the presence of at least one nonionic
 surfactant and at least one amphoteric surfactant in the concentrated
 solutions of phospholipid.
 The compositions and delivery systems of the present invention readily
 deposit the organic phospholipid/water-insoluble substances on the hair,
 skin, and eyelashes, and, because of their inherent insolubility, resist
 being washed off with water. Accordingly, these compositions and delivery
 systems can be used in hair shampoos, conditioners, hair dyeing
 compositions, including oxidative dyes and bleaches, permanent waving
 compositions, curl relaxing compositions, hair setting compositions, bath
 and body products, sunscreens, or cosmetics such as mascaras and
 foundations.
 These systems can also be used to deliver active water-insoluble
 pharmaceutical ingredients, particularly in topical applications. Such
 systems could further help protect against oxidation and rancidity by
 protecting sensitive ingredients in pharmaceuticals or foods.
 Additionally, the "load" carried by these systems can be quite high, a
 benefit that inures both to the user and to the manufacturer in an
 economic sense. Load is defined as the weight of added hydrophobe
 (water-insoluble material) divided by the weight of the phospholipid
 expressed as a percentage. Thus, 1 g of hydrophobe in a composition with 5
 g phospholipid is a 1/5 or 20% load. In the art, 50% is considered a high
 load and can be achieved with certain hydrophobes and surfactant
 combinations.
 Without being bound to a particular theory, the inventors believe that in
 the composition of the present invention, an organized structure, likely a
 laminar gel, is formed between the organic phospholipid and the nonionic
 surfactant and is solubilized by the amphoteric surfactant. The organized
 structure can incorporate other water-insoluble materials or hydrophobes.
 In aqueous systems, the structure remains organized, as evidenced by the
 clarity of the solution, exhibiting a slight Tyndall light scattering
 effect, and, when concentrated, showing lamellar anisotropic structures
 under polarized light.
 In one embodiment, therefore, the invention is drawn to a composition
 comprising at least one organic phospholipid capable of forming bilayers
 in aqueous solution, at least one amphoteric surfactant, and at least one
 nonionic surfactant, where the nonionic surfactant is present in an amount
 by weight equal to or greater than the amount of the phospholipid. Neither
 the amphoteric nor the nonionic surfactant alone will give a satisfactory
 solution with the organic phospholipids. When dissolved in either an
 amphoteric or a nonionic surfactant, solubility for the phospholipid was
 poor compared to solubility in the mixture of surfactants of the present
 invention.
 With respect to the ingredients of the inventive composition, the preferred
 organic phospholipids capable of forming bilayers in aqueous solution are
 lecithins. Lecithins are mixtures of phospholipids, i.e., of diglycerides
 of fatty acids linked to an ester of phosphoric acid. Preferably,
 lecithins are diglycerides of stearic, palmitic, and oleic acids linked to
 the choline ester of phosphoric acid. Lecithin is usually defined either
 as pure phosphatidyl cholines or as crude mixtures of phospholipids which
 include phosphatidyl choline, phosphatidyl serine, phosphatidyl
 ethanolamine, phosphatidyl inositol, other phospholipids, and a variety of
 other compounds such as fatty acids, triglycerides, sterols,
 carbohydrates, and glycolipids.
 The lecithin used in the present invention may be present in the form of a
 liquid, powder, or granules. Lecithins useful in the invention include,
 but are not limited to, soy lecithin and hydroxylated lecithin. For
 example, ALCOLEC S is a fluid soy lecithin, ALCOLEC F 100 is a powder soy
 lecithin, and ALCOLEC Z3 is a hydroxylated lecithin, all of which are
 available from the American Lecithin Company.
 In the present invention, lecithin is preferably used in an amount greater
 than 0 to about 5% by weight of the composition as a whole. Since lecithin
 itself is not a pure raw material and may have free glycerides, glycerin,
 fatty acids, and soaps, adjustments in this ratio may need to be made,
 i.e., one source of lecithin may require different ratios of nonionic and
 amphoteric surfactants than another to achieve maximum clarity of
 solution. Preferably, the composition of the invention forms a clear
 solution, though the purpose of the invention is achieved just as
 effectively with a slightly cloudy solution.
 Other than lecithins, another group of phospholipids which may be useful in
 the present invention are multifunctional biomimetic phospholipids. For
 example, the following multifunctional biomimetic phospholipids
 manufactured by Mona Industries may be useful: PHOSPHOLIPID PTC,
 PHOSPHOLIPID CDM, PHOSPHOLIPID SV, PHOSPHOLIPID GLA, and PHOSPHOLIPID EFA.
 The amphoteric surfactants useful in the present invention include, but are
 not limited to, betaines, sultaines, hydroxysultaines, alkyl
 amphodiacetates, alkyl amphodipropionates, and imidazolines, or salts
 thereof. It is recognized that other fatty acid condensates such as those
 formed with amino acids, proteins, and the like are suitable. Amphoteric
 surfactants are typically available for commercial sale in solution form
 with the active surfactant accounting for approximately 40% of the total
 solution weight. Cocoamphodipropionate is particularly preferred, for
 example, MIRANOL C2M-SF Conc. (disodium cocoamphodipropionate), in its
 salt-free form, available from Rhone-Poulenc. MIRANOL is sold in solution
 form with amphoteric surfactants composing approximately 40% of the total
 solution weight; for example, 10 g of MIRANOL contain about 4 g of
 amphoteric surfactant. Also preferred is CROSULTAINE C-50 (cocamidopropyl
 hydroxysultaine), available from Croda. CROSULTAINE is also sold in
 solution form with the amphoteric surfactant composing approximately 50%
 of the total solution weight. The amphoteric surfactants are preferably
 present in the composition in an amount ranging from about 2 to 25% by
 weight of the composition as a whole when 5% of the organic phospholipid,
 preferably lecithin, is used. When the phospholipid/amphoteric/nonionic
 system is employed as a carrier for a water-insoluble polymer or resin,
 the amphoteric surfactants are preferably present in the composition in an
 amount ranging from about 6 to 25% by weight. When the
 phospholipid/amphoteric/nonionic system is employed as a carrier for a
 lipophilic material, the the amphoteric surfactants are preferably present
 in the composition in an amount ranging from about 4 to 20% by weight.
 Other amphoteric surfactants useful in the present invention include
 disodium wheatgermimido PEG-2 sulfosuccinate, available under the trade
 name MACKANATE WGD from McIntyre Group Ltd., which is a solution with
 amphoteric surfactants composing approximately 39% of the total solution
 weight, and disodium soyamphodiacetate, available under the trade name
 MACKAM 2S from McIntyre Group Ltd., which is a solution with amphoteric
 surfactants composing approximately 34.5% of the total solution weight.
 The nonionic surfactants useful in the present invention are preferably
 formed from a fatty alcohol, a fatty acid, or a glyceride with a C.sub.8
 to C.sub.24 carbon chain, preferably a C.sub.12 to C.sub.18 carbon chain,
 more preferably a C.sub.16 to C.sub.18 carbon chain, derivatized to yield
 a Hydrophilic-Lipophilic Balance (HLB) of at least 10. HLB is understood
 to mean the balance between the size and strength of the hydrophilic group
 and the size and strength of the lipophilic group of the surfactant. Such
 derivatives can be polymers such as ethoxylates, propoxylates,
 polyglucosides, polyglycerins, polylactates, polyglycolates, polysorbates,
 and others that would be apparent to one of ordinary skill in the art.
 Such derivatives may also be mixed polymers of the above, such as
 ethoxylate/propoxylate species, where the total HLB is preferably greater
 than or equal to 10. Preferably the nonionic surfactants contain
 ethoxylate in a molar content of from 10-25, more preferably from 10-20
 moles.
 Nonionic surfactants may be selected from, but are not limited to, the
 following:

# of Cs Name Trade Name
 C-12 Laureth-23 BRIJ 35, available from ICI Surfactants
 C-16 Ceteth-10 BRIJ 56, available from ICI Surfactants
 C-16 Ceteth-20 BRIJ 58, available from ICI Surfactants
 C-16 IsoCeteth-20 Arlasolve 200, available from ICI Surfactants
 C-18 Steareth-10 Volpo S-10, available from Croda Chemicals Ltd.
 C-18 Steareth-16 Solulan-16, available from Amerchol Corp.
 C-18 Steareth-20 BRIJ 78, available from ICI Surfactants
 C-18 Steareth-25 Solulan-25, available from Amerchol Corp.
 C-18.dbd. Oleth-10 BRIJ 97, available from ICI Surfactants
 C-18.dbd. Oleth-20 Volpo-20, available from Croda Chemicals Ltd.
 Alkyl polyglucose surfactants sold under the name PLANTAREN, available from
 Henkel, may also be used. The nonionic surfactant is preferably present in
 an amount of about 5 to 20% by weight relative to the weight of the whole
 composition when 5% lecithin is used. More preferably, the nonionic
 surfactant is present in an amount of about 10 to 20% by weight.
 In one preferred embodiment of the composition of the present invention,
 the organic phospholipid capable of forming bilayers in aqueous solution,
 the amphoteric surfactant, and the nonionic surfactant are present in the
 composition such that the nonionic surfactant and the amphoteric
 surfactant are each present in an amount by weight greater than the amount
 of phospholipid. In a more preferred embodiment, the amount of
 phospholipid in the composition is kept fixed while the amounts of the
 amphoteric and nonionic surfactants are increased. In a still more
 preferred embodiment, calculating the phospholipid as present at a value
 of 1, the phospholipid, amphoteric surfactant and nonionic surfactant are
 preferably present in the composition in a ratio ranging from about
 1:0.8:2 and above by weight relative to the whole composition, i.e., where
 the amounts of the surfactants can be increased independently of each
 other but the amount of phospholipid stays fixed. The ratio is considered
 to be "above" 1:0.8:2 when the amount of either of the surfactants
 increases. When the phospholipid/amphoteric/nonionic system is employed as
 a carrier for a lipophilic material, the ratio preferably ranges from
 about 1:1.2:2 and above. When the phospholipid/amphoteric/nonionic system
 is employed as a carrier for a water-insoluble polymer or resin, the ratio
 is preferably about 1:1.2:3 and above, and more preferably above about
 1:1.2:4. The loading capability for hydrophobes carried by the delivery
 system of the present invention is maximized if the ratio of nonionic
 surfactant to phospholipid is minimized, with the bilayers still being
 solubilized, because an excess of nonionic surfactant may disrupt the
 organized structure.
 In one preferred embodiment, the composition of the present invention
 comprises ALCOLEC S (soy lecithin), MIRANOL C2M-SF Conc. (disodium
 cocoamphodipropionate, an amphoteric surfactant), ARLASOLVE 200
 (IsoCeteth-20, a nonionic surfactant) in a ratio of 5:15:10 (which is a
 LAN ratio of 1:1.2:2) when a lipophilic water-insoluble ingredient is
 employed, and 5:15:20 (which is a LAN ratio of 1:1.2:4) when a
 water-insoluble polymer, resin, or latex is employed, wherein the ratios
 are calculated by weight relative to the whole composition. In general,
 the preferred compositions of the invention are known as the "LAN" because
 they contain a lecithin (L), an amphoteric surfactant (A), and a nonionic
 surfactant (N). Although lecithin is particularly preferred, the
 amphoteric and nonionic surfactants may vary.
 When used as an ingredient in further formulations, the LAN is compatible
 and generally gives clear solutions with anionic surfactants such as alkyl
 sulfates and ethoxylated alkyl sulfates. Other anionic surfactants such as
 sulfosuccinates may also be used. Typically, LAN compositions can resist
 storage at 45.degree. C. for three months or more, which would predict
 that they have a shelf life at room temperature of at least three years.
 In another aspect, the present invention relates to an aqueous delivery or
 carrier system comprising: at least one organic phospholipid capable of
 forming bilayers in aqueous solution, at least one nonionic surfactant
 preferably present in an amount greater than or equal to the amount of the
 phospholipid, at least one amphoteric surfactant, at least one
 water-insoluble ingredient, and an aqueous phase. The lecithin, nonionic
 surfactant, and amphoteric surfactant are present in a combined amount
 sufficient to allow the at least one water-insoluble ingredient to be
 incorporated into or solubilized by the aqueous system. The amount
 sufficient for solubilization may vary depending on the type of
 composition; for example, shampoo and mascara formulations require a lower
 concentration of LAN than do conditioner, deep treatment, bleach,
 permanent wave, dye, and relaxant compositions.
 Water-insoluble materials or ingredients include, but are not limited to
 the following:
 (1) Lipophilic "ingredients" or "materials" such as silicones, oil-soluble
 vitamins such as Vitamin E and Vitamin A, sunscreens, ceramides and
 natural oils: The lipophilic ingredients may be in the form of sunscreens,
 bacteriostats, moisturizers, colors, topical pharmaceuticals and the like.
 Preferred lipophilic ingredients include: Vitamin E, Vitamin E Acetate,
 Vitamin A Palmitate, olive oil, mineral oil,
 2-oleamido-1,3-octadecanediol, octylmethoxy cinnamate, octyl salicylate,
 and silicones such as dimethicone, cyclomethicone, phenyl trimethicone,
 dimethiconol, dimethicone copolyol, and laurylmethicone copolyol. The
 lipophilic ingredients will, for example, moisturize or condition the
 skin, hair, and/or eyelashes and leave behind no oily feel.
 (2) Water-insoluble polymers, resins, and latexes which are unneutralized
 or partially neutralized, wherein the polymers and resins include but are
 not limited to those containing carboxyl moieties, such as acrylates and
 other carboxy polymers. Typically, water-insoluble polymers and resins
 have to be neutralized to about 90% of their carboxyl moieties to make
 them water soluble for the purpose of formulating products in aqueous
 solution and for the purpose of making products which have good
 non-build-up properties, i.e., can be easily washed off the hair after
 use. However, when used with the compositions of the present invention,
 little or no neutralization is needed to dissolve these polymers/resins.
 In part, an unneutralized or partially neutralized water-insoluble polymer
 or resin is solubilized because it is neutralized by the amphoteric
 surfactant contained in the presently claimed delivery system, but the
 amphoteric surfactant acting alone will not solubilize the polymer or
 resin in water and allow the pH to be acidic. As discussed with reference
 to the Gerstein patent above, if the polymer or resin is neutralized by
 the amphoteric surfactant alone, when one attempts to acidify the solution
 to prepare a hair care composition with acidic pH, as is desirable, the
 carboxyl moieties of the polymer or resin becomes unneutralized and
 precipitation occurs. It is the combination of the organic phospholipid,
 the nonionic surfactant, and the amphoteric surfactant of the present
 invention which achieves the solubility of the water-insoluble polymers or
 resins.
 As for latexes, they generally have been used in cosmetics in an
 unneutralized form since they are used for their milky (insoluble)
 appearance. In the context of the present invention, however,
 water-insoluble latexes are neutralized to an alkaline pH and dissolve,
 producing a clear solution. To the best of the inventors' knowledge,
 neutralized latexes have not previously been used in cosmetic
 compositions.
 In the case of the non-neutralized or partially-neutralized polymers or
 resins, where such substances are applied to the hair or skin from an
 alcoholic or aqueous/alcoholic system, their washability from the hair
 leaves a great deal to be desired. In contrast, where such polymers or
 resins are applied in a delivery system comprising at least one organic
 phospholipid; at least one amphoteric surfactant; and at least one
 nonionic surfactant, wherein the nonionic surfactant is present in an
 amount equal to or greater than the amount of the organic phospholipid,
 the polymers or resins can easily be rinsed off from the hair (no
 build-up) while providing strong hold for curls, if curls are what is
 desired.
 The following are examples of polymers that can be incorporated into the
 delivery system of the present invention. The list is not intended to be
 limiting:
 AMPHOMER LV-71 from National Starch
 (octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer),
 OMNIREZ-2000 from ISP (PVM/MA half ethyl ester copolymer),
 RESYN 28-2930 from National Starch (Vinyl acetate/crotonates/vinyl
 neodecanoate copolymer),
 LUVIMER 100P from BASF (t-butyl acrylate/ethyl acrylate/methacrylic acid),
 and
 ULTRAHOLD STRONG from BASF (acrylic acid/ethyl acrylatelt-butyl
 acrylamide).
 Unneutralized or partially neutralized water-insoluble latexes have been
 used as film-formers in various applications. The following are latexes
 that can be incorporated into the delivery system of the present
 invention:
 AMERHOLD DR-25 from Amerchol (acrylic acidimethacrylic acid/acrylates/meth
 acrylates),
 LUVIMER 36D from BASF (ethyl acrylatelt-butyl acrylatelmethacrylic acid),
 and
 ACUDYNE 258 from Rohm & Haas (acrylic acid/methacrylic
 acid/acrylates/methacrylates/hydroxy ester acrylates).
 Up to 60% by weight of each of these polymers/resins/latexes were dissolved
 in 35% phospholipid/amphoteric surfactant/nonionic surfactant solutions
 where the phospholipid was lecithin and the ratio of
 lecithin:amphoteric:nonionic was 1:1.2:4. All the solutions were clear,
 indefinitely dilutable with water without precipitation and stable after 2
 months on the shelf.
 The aqueous phase of the inventive delivery system can contain additional
 ingredients such as anionic surfactants, organic salts, inorganic salts,
 proteins, hair dyes, water-soluble polymers, quatematy ammonium compounds,
 complex and simple carbohydrates, amino acids, preservatives and
 fragrances.
 If the inventive system is to be used in concentrated form, i.e., with
 about 5% by weight of the organic phospholipid and 1% of added
 water-insoluble ingredient, the composition preferably has a pH ranging
 from 4-12 for maximum stability and clarity. The more concentrated the
 solution, the better the delivery.
 If this blend is diluted with water or the blend is used as an ingredient
 in another composition, then the pH has a broader range, i.e., preferably
 ranges from 2-12, and a wider variety of additives can be included in the
 solution. When water is added to a concentrated LAN, it may appear to form
 a cloudy solution at first if a large amount of water is added at once.
 The LAN will eventually go into solution, however, and become clear or at
 least clearer. The time to clear decreases as the LAN ratio increases.
 Once the organized structure of the LAN forms, the addition of more water
 does not affect clarity. These dilute blends are still very effective in
 delivering water-insoluble ingredients. The blends can be freeze-dried to
 hygroscopic solids that redissolve into water. Encapsulation of such
 solids so that they do not pick up and retain excess moisture is also
 contemplated. Such encapsulated solids can have desirable storage
 properties and would be easy to dissolve into water at various dilutions.
 Understandably, the need for dilution varies depending on the
 water-insoluble material to be employed.
 Another embodiment of the present invention is drawn to a process for
 preparing the aqueous system of the present invention. This process
 comprises: (a) combining the following ingredients to obtain a mixture: at
 least one organic phospholipid capable of forming bilayers in aqueous
 solution, at least one nonionic surfactant, and at least one amphoteric
 surfactant, where the nonionic surfactant is present in an amount by
 weight equal to or greater than the amount of the organic phospholipid,
 (b) heating the mixture obtained in step (a), and (c) adding an aqueous
 solution to the heated mixture to obtain the desired carrier system.
 Water-insoluble ingredients may be added in step (a). Preferably the
 carrier system obtained can cany a high load (i.e., 50% is considered a
 high load) of the organic phospholipid/water-insoluble ingredient. The
 mixture is preferably heated at a temperature of 65.degree. C. to
 85.degree. C., depending on the melting points of the solid surfactants.
 More specifically, the preparation of the carrier system of the present
 invention may be carried out as follows. Lecithin (L) is dispersed in
 water. The water-insoluble material is combined with nonionic
 surfactant(s) (N) at appropriate ratios and added to the lecithin/water
 dispersion. An amnphoteric surfactant (A) is added and the mixture is
 heated, preferably to a temperature of from 75.degree. C. to 85.degree. C.
 The combination of these ingredients results in a solution which is clear
 to slightly hazy and is referred to as the "LAN," which can then be used
 as a "raw material" to make finished products.
 Alternatively, lecithin, amphoteric surfactant(s) and nonionic
 surfactant(s) can be weighed to appropriate ratios and heated to
 70.degree. C. with stirring. Water is then added q.s. at the same
 temperature. Another alternative method of preparation comprises adding
 the water-insoluble ingredient with mixing after solutions have cooled.
 This last alternative method helps protect heat-sensitive water-insoluble
 ingredients.
 The resulting compositions may vary from clear to slightly hazy and are
 infinitely dilutable with water. The slight haze can be overcome by
 adjusting the ratio of lecithin to the surfactants, adjusting pH, or
 reducing concentrations of water-insoluble ingredients.
 In another embodiment, the present invention is drawn to a method for
 treating keratinous substances such as, but not limited to, hair, skin, or
 eyelashes. First an aqueous solution is prepared containing at least one
 organic phospholipid capable of forming bilayers in aqueous solution; at
 least one amphoteric surfactant; at least one nonionic surfactant present
 in an amount by weight equal to or greater than the amount of the
 phospholipid; and at least one water-insoluble ingredient. The
 phospholipid, amphoteric surfactant, and nonionic surfactant are present
 in a combined amount sufficient to allow the water-insoluble ingredient to
 be incorporated into the aqueous solution. The aqueous solution is then
 applied to the keratinous substances. The term treating in the context of
 this invention includes, but is not limited to, shampooing, conditioning,
 dyeing, bleaching, permanent waving, relaxing, setting, moisturizing, and
 making-up, for example, applying mascara or foundation.
 As mentioned previously, the composition and carrier system of the present
 invention can be used as an ingredient itself in, for example, shampoos,
 conditioners (rinse-off and leave-in), deep treatments for hair, body
 washes, bath gels, hair dyeing compositions, permanent wave formulations,
 relaxers, make-up preparations, particularly mascara and foundation, and
 skin creams or lotions.
 With respect to hair products, the carrier system of the present invention
 can be used to formulate hair products, e.g., for normal hair,
 color-treated hair, dry hair, fine hair, and damaged hair. For each type
 of hair, the LAN can be used to create a regimen comprising shampoo,
 conditioner, and deep treatment, (i.e., deep conditioner). LAN
 compositions used for these products preferably contain lecithin (L), at
 least one amphoteric surfactant (A), such as disodium
 cocoamphodipropionate, and at least one nonionic surfactant (N), e.g., a
 blend of Oleth-10 and PPG-5-Ceteth-20. Additional nonionic, amphoteric,
 and also anionic surfactants can be added. The LAN compositions may
 further contain at least one water-insoluble ingredient (also referred to
 as a bydrophobe) such as olive, mineral, or other oils, octyl salicylate,
 Vitamin E (Tocopherol), octyl methoxycinnamate, and ceramides including
 2-oleamido-1,3-octadecanediol.
 In general, the concentration of the LAN is increased within each regimen
 from shampoo to conditioner to deep treatment. Thus, the deep treatment
 formulations have the most concentrated hydrophobe-carrying LAN.
 The LAN systems of the invention can be further associated, in the hair
 products described above, with proteins including hydrolyzed soy protein,
 lauryldimonium hydrolyzed soy protein (cationic Soya protein) and wheat
 amino acids. The proteins could also include corn, wheat, milk, or silk
 proteins, collagens, keratins, or others. Furthermore, taurine and
 arginine hydrochloride may be associated therein to maximize protein
 binding to the hair. Cationic proteins or proteins in general may be
 stabilizers for the LAN and enhance its delivery by changing the charge on
 the surface of the LAN structure. The skin and the hair attract cationic
 ingredients, and proteins are generally substantive to these tissues.
 In conditioning emulsions, nonionic emulsifiers such as glyceryl stearate
 and PEG-100 stearate can be used, and the LAN is treated as a
 water-insoluble, particularly a lipophilic, ingredient itself.
 Other ingredients in the LAN hair care compositions may include cationic
 polymers, such as polyquaternium 4, polyquaternium 6, polyquaternium 7,
 polyquaternium 10, polyquaternium 11, polyquatemium 16, polyquaternium 22,
 and polyquaternium 32, cationic conditioners, such as quaternium 27,
 behenamidopropyl PG-dimonium chloride, hydroxyethyl tallowdimonium
 chloride, hexadimethrine chloride, stearalkonium chloride, and cetrimonium
 chloride, isoparaffms, sodium chloride, propylene glycol, preservatives
 such as phenoxyethanol, methylparaben, ethylparaben, and propylparaben, pH
 adjusters such as phosphoric acid, humectants such as trehalose, and
 emollients such as octyldodecanol. Many other examples of materials from
 the classes listed above would be readily known to one of ordinary skill
 in the art.
 Further, shampoos, conditioners, and deep treatments within the scope of
 the present invention may be used on hair which has been treated, e.g.,
 with color (dye or bleach) or chemicals (permanent wave or straightening),
 or which is dry or fine and show significant substantivity for the hair.

The invention will be fiurther clarified by the following examples, which
 are intended to be illustrative of the invention, but not limiting
 thereof.
 EXAMPLES
 Example 1
 Determining Solubility Parameters in Mixture of Surfactants
 5 g lecithin was dissolved in mixtures of MIRANOL C2M-SF Conc. (amphoteric
 surfactant) and ARLASOLVE 200 (Iso-Ceteth-20, nonionic surfactant). The
 water-insoluble (lipophilic) ingredient was olive oil. The results are
 shown in Tables 1 and 2 below.
 TABLE 1
 Optimizing Ratios of LAN Containing Olive Oil
 Olive Oil/Lecithin Ratio (LOAD)
 0.2 0.3 0.4 0.5 0.6 1
 1:1.2:2 LAN clear hazy cloudy cloudy cloudy cloudy
 1:1.2:3 LAN clear cloudy cloudy cloudy cloudy cloudy
 1:1.6:4 LAN clear clear clear clear clear cloudy
 1:2.0:5 LAN clear clear clear clear clear cloudy
 In Table 1, lecithin was fixed at 5 g, and various ratios of the LAN were
 studied as a function of load from 20 to 100%. (Load equals weight of
 added lipophile divided by weight of lecithin). At the lowest ratios of
 surfactants to lecithin, only a 20% load was achieved. In other words, for
 the ratio 1:1.2:2, the LAN solution was clear only at 0.2 or 20% load. As
 the ratio of surfactants to lecithin increased, however, the organized
 structure broke down. Thus, even though the LANs with bigger ratios of
 surfactants to lecithin theoretically can carry more lipophile, optimum
 results are achieved with a maximum of lecithin to a minimum of
 surfactant. The results show that a ratio of 1:1.2:2 gave a clear,
 dilutable mixture with olive oil.
 TABLE 2
 Optimizing the Amount of Nonionic and Amphoteric Surfactants
 ALCOLEC MIRANOL ARLASOLVE
 F100 C2M-SF Conc. 200
 (LECITHIN) (AMPHOTERIC) (NONIONIC) CLARITY RATIO
 5 g 10 g 10 g cloudy 1:0.8:2
 5 g 10 g 8 g cloudy 1:0.8:1.6
 5 g 15 g 15 g clear 1:1.2:3
 S g 15 g 10 g clear 1:1.2:2 *
 5 g 15 g 5 g cloudy 1:1.2:1
 5 g 15 g 3 g cloudy 1:1.2:0.6
 5 g 15 g 8 g cloudy 1:1.2:1.6
 5 g 12 g 10 g cloudy 1:0.96:2
 5 g 12 g 8 g cloudy 1:0.96:1.6
 5 g 13 g 9 g cloudy 1:1.04:1.8
 * optimum ratio
 Table 2 does not consider lipophilic load. The amounts of amphoteric and
 nonionic surfactants thus varied over a wider range of concentrations
 around the pair of points that are clear at 20% load in Table 1 (1:1.2:2)
 and (1:1.2:3). The table shows that the LAN ratio made a difference in the
 clarity of the solution. When the amount of the nonionic surfactant was
 increased, the solutions remained clear, but when the amount was
 decreased, the solutions became cloudy. The ratio of amphoteric to
 nonionic surfactant is maintained at a certain level for optimum results
 to be obtained but the total concentration of surfactants plays a role as
 well. For instance, when the ratio of amphoteric surfactant to nonionic
 surfactant was maintained at 1.2:2 and the total surfactant concentration
 was decreased relative to lecithin (i.e., from 1:1.2:2 to 1:0.96:1.6,
 which is the same ratio but different relative concentrations), the result
 was a cloudy solution. In this case, increasing the nonionic to 2.0, for
 example, did not clarify the mixture at this weight of lecithin.
 The dilutability of solutions above the ratio of 1:0.8:2 (5 g:10 g:10 g)
 was infinite, though at that ratio the solutions were not quite clear. At
 a LAN ratio of 1:1.2:2, the solution was generally both clear and
 infinitely dilutable.
 Example 2
 Study of Solubility of Lipophilic Ingredients
 The solubility of 2-oleamido-1,3-octadecanediol (a ceramide) and olive oil,
 lipophilic ingredients often used in hair care products, was evaluated in
 a mixture comprising 5 g lecithin and varying amounts of MSRANOL C2M-SF
 Conc. and ARLASOLVE 200. Both 2-oleamido-1,3-octadecanediol and olive oil,
 at the 1% level, formed a clear, stable lecithin solution with 15% (15 g)
 MIRANOL and 10% (10 g) ARLASOLVE. Thus, the lipophiles were solubilized
 best with a LAN ratio of 1:1.2:2.
 Example 3
 Study of HLB Values
 Using different ratios of the nonionic surfactants BRIJ 72 (HLB 4.9) and
 BRIJ 700 (HLB 18.8), an HLB range from 5 to 18 was obtained. Only the even
 HLB values were studied. The formulations tested contained 5% ALCOLEC S,
 15% MIRANOL C2M-SF Conc, and 15% nonionics (LAN ratio 1:1.2:3) with
 different HLB's. Surprisingly, none of the HLB values investigated
 provided clear solutions. In each case, thick gels were formed instead of
 solutions. See Table 3.
 TABLE 3
 HLB Systems (q.s. to 100 g water)
 MIRANOL
 ALCOLEC C2M-SF Conc.
 F100 (AMPHOTERIC OTHER
 (LECITHIN) SURFACTANT) NONIONIC SURFACTANT INGRED
 CLARITY STABILITY
 5 g 15 g 13.82 g BRIJ 72 + 1.18 g BRIJ 700 (HLB 6) --
 very cloudy --
 5 g 15 g 11.66 g BRIJ 72 + 3.34 g BRIJ 700 (HLB 8) --
 verycloudy --
 5 g 15 g 9.5 g BRIJ 72 + 5.5 g BRIJ 700 (HLB 10) --
 very cloudy --
 5 g 15 g 7.34 g BRIJ 72 + 7.66 g BRIJ 700 (HLB 12) --
 very cloudy --
 5 g 15 g 5.18 g BRIJ 72 + 9.82 g BRIJ 700 (HLB 14) --
 very cloudy --
 5 g 15 g 3.02 g BRIJ 72 + 11.98 g BRIJ 700 (HLB 16) --
 very cloudy --
 5 g 15 g 0.86 g BRIJ 72 + 14.14 g BRIJ 700 (HLB 18) --
 very cloudy --
 * BRIJ 72 = Steareth-2 HLB 4.9
 * BRIJ 700 = Steareth-100 HLB 18.8
 Example 4
 Study of Solubility and Effectiveness of Dyes in the LAN
 Solubility and effectiveness of dyes used in combination with the LAN were
 studied. The LAN provides three novel and surprising aspects to hair
 coloring/dyeing preparations in particular: (1) The LAN obviates the need
 for classical cosolvents typically included in hair coloring compositions
 such as ethanol, alkyl polyols, or propylene glycol, which serve to help
 solubilize dyestuffs into the color base; (2) No quaternized arnine
 compounds are needed to effect conditioning of the hair when the LAN is
 used; and (3) No nitrogen blanketing of the hair color composition is
 necessary during the compounding or storage of these compositions.

In a treatment base of:
 SEPIGEL 305 (polyacrylamide/C.sub.13 --C.sub.14 isoparaffin/laureth 7,
 2.000%
 available from SEPPIC)
 xanthan gum 1.000%
 behenamidopropyl PG-dimonium chloride (cationic 3.000%
 conditioner)
 cetrimonium chloride (cationic conditioner) 3.000%
 cyclomethicone and dimethicone 3.000%
 octyl methoxycinnamate (sunscreen) 0.100%
 propylene glycol
 fragrance 0.500%
 preservatives selected from phenoxyethanol, methylparaben, 0.800%
 ethylparaben, and disodium EDTA
 proteins and amino acids selected from taurine, arginine 1.210%
 hydrochloride, lauryldimonium hydroxypropyl hydrolyzed soy
 protein, and hydrolyzed soy protein with wheat amino acid
 phosphoric acid 85% (pH adjuster) 0.060%
 trehalose (humectant) 0.001%
 water q.s. to 100
 Example 10
 Color Retention Effects of Color Treatment Products Against Chlorine Water
 and Shampooing
 Dyed brown hair was treated with 5 ppm chlorine water during a regime of
 deep treatment, shampoo and conditioner formulated as described above for
 color-treated hair for 1 week (1 deep treatment, 4 shampoos and 4
 conditioners). To obtain significant experimental data, an experiment was
 carried out in which 72 brown hair swatches were colored, followed by:
 24 swatches treated with:
 Treatment (10 minutes/room temperature (RT), rinse)
 Shampoo (5 minutes/RT, rinse)
 Conditioner (10 minutes/RT, rinse)
 The shampoo and conditioner treatment was repeated 3 more times,
 representing one week of product use, and the chlorine treatments (5 ppm
 chlorine water for 30 minutes at room temperature/rinse) were done after
 the 1st and the 4th cycle:
 24 swatches treated with chlorine water during the regimen for
 color-treated hair as described above but without Arginine, Taurine,
 Proteins, LAN, Vitamin E, sunscreens in the products
 24 swatches treated with chlorine water during the regimen for
 color-treated hair as described above but with water instead of the
 described hair products
 The table below shows that frequent use of the products for color-treated
 hair protects the color from fading against chlorine water and shampoos. L
 indicates how much the color has faded. The higher the L value, the
 lighter the color, i.e., the more fading has occurred. The effects of the
 LAN and additional ingredients such as the proteins are also apparent.
 TABLE 5
 MEAN L VALUES
 After 1 week
 of shampooing/
 chlorine water Change % change
 Control treatment in L in L
 water only 24.61 28.09 3.48 14.14%
 regimen of invention 23.96 25.61 1.65 6.89%
 regimen w/o LAN, 24.74 27.46 2.72 10.89%
 proteins, amino acids,
 vitamin E, or sunscreens
 It is clear that the smallest change in L, i.e, the least fading, occurred
 when the LAN containing regimen of the invention was used.
 Example 11
 Solubility of AMPHOMER LV-71 in LAN v. Non-LAN Solutions
 The following four solutions were prepared according to Table 6 below.
 Solution A: A 1:1.2:5 aqueous LAN solution containing the water-insoluble
 polymer AMPHOMER LV 71.
 Solution B: A 1:1.2:5 aqueous LAN solution containing AMPHOMER LV 71 and
 sodium lauryl ether sulfate (SLES), an anionic surfactant.
 Solution C: An aqueous solution of AMPHOMER LV 71 in an amphoteric
 surfactant and an anionic surfactant. No lecithin and no nonionic
 surfactant were present. This solution was prepared according to Example 1
 of U.S. Pat. No. 5,391,368 to Gerstein.
 Solution D: An aqueous solution of AMPHOMER LV 71 in an amphoteric
 surfactant only. No lecithin or nonionic surfactant were present.
 TABLE 6
 Solution Solution Solution Solution
 A B C D
 ALCOLEC F100 (Lecithin) 2.67 2.67 -- --
 MIRANOL C2M-SFConc. 8 8 8 8
 (Amphoteric)
 ARLASOLVE 200 (Nonionic) 13.35 13.35 -- --
 AMPHOMER LV 71 (Polymer) 3 3 3 3
 SLES (Anionic) -- 50 50 --
 WATER 72.98 22.98 39 89
 The solutions A-D were acidified with 10% hydrochloric acid down to pH 3.
 The pH and the appearance of each solution after acidification to various
 pH levels are shown below:
 TABLE 7
 Initial Appearance after acidification to pH:
 Solution pH Appearance 7 6 5 4 3
 A 6.9 clear clear clear clear clear clear
 B 7.05 clear clear clear clear clear clear
 C 7.4 clear clear clear cloudy cloudy cloudy
 D 7.2 clear clear hazy cloudy cloudy cloudy
 It is evident from the results shown in Table 7 that solubilization of a
 water-insoluble polymer in an aqueous LAN solution (solutions A and B) is
 far superior to solubilization of the same polymer in a non-LAN solution
 (solutions C and D). Solutions A and B stayed clear from pH 7 down to pH
 3, whereas solution C was cloudy from pH 5 down and solution D began to
 get hazy at pH 6. In other words, the water-insoluble polymer precipi
 tates out of solution at acidic pH in the non-LAN systems.
 Example 12
 Solubility of other Water-insolubles in LAN v. Non-LAN Solutions
 The same tests as in Example 11 were carried out with ULTRAHOLD STRONG,
 another water-insoluble polymer, and LUVIMER 36D, a water-insoluble latex.
 The components of Solutions 1-6 are set forth in Table 8 below.
 TABLE 8
 Solution Solution Solution Solution Solution Solution
 1 2 3 4 5 6
 ALCOLEC -- -- 2.67 -- -- 2.67
 F100
 MIRANOL 8 8 8 8 8 8
 C2M-SF
 CONC
 ARLASOLVE -- -- 13.35 -- -- 13.35
 200
 SLES 50 -- -- 50 -- --
 LUVIMER 8.12 8.12 8.12 -- -- --
 36D
 ULTRAHOLD -- -- -- 3 3 3
 STRONG
 WATER 33.88 83.88 67.86 39 89 72.98
 Solutions 3 and 6 were LAN solutions, with LAN ratio 1:1.2:5. Solutions 1
 and 4 contained an amphoteric and an anionic polymer, and Solutions 2 and
 5 contained only an amphoteric polymer. The solutions were acidified with
 10% hydrochloric acid down to pH 3. The pH and the appearance of each
 solution after acidification to various pH levels are shown below in Table
 9.
 TABLE 9
 Initial
 Appear- Appearance after acidification to pH:
 Solution pH ance 7 6 5 4 3
 1 7.40 clear clear cloudy cloudy cloudy cloudy
 2 7.32 clear cloudy cloudy cloudy cloudy cloudy
 3 7.12 clear clear clear clear clear clear
 4 8.42 cloudy cloudy cloudy cloudy cloudy cloudy
 5 7.62 cloudy cloudy cloudy cloudy cloudy cloudy
 6 7.35 clear clear clear clear clear clear
 These results demonstrate, as in Example 11, that solubilization of a
 water-insoluble polymer or latex in an aqueous LAN solution is far
 superior to solubilization of the same polymer or latex in a non-LAN
 solution. LAN solutions 3 and 6 remained clear all the way down to pH 3,
 whereas solutions 4 and 5 were initially cloudy even before acidification,
 solution 1 was cloudy from pH 6 and solution 2 from pH 7.
 Example 13
 Determination of Load of Polymer/Latex that LAN Solution can Carry
 LAN solutions containing a water-insoluble polymer or latex were prepared
 as set forth in Table 10. Solution E had a LAN ratio of 1:1.2:4 and
 contained 10% by weight of AMPHOMER. Solution F had a LAN ratio of 1:2:5
 and contained 15% by weight of AMPHOMER. Solution G had a LAN ratio of
 1:1.2:4 and contained 60% by weight of AMERHOLD DR-25 (latex).
 TABLE 10
 Solution E Solution F
 Solution G
 ALCOLEC F100 5 5 5
 MIRANOL C2M-SF CONC 15 25 15
 ARLASOLVE 200 20 25 20
 WATER-INSOLUBLE AMPHOMER LV-71 AMPHOMER LV-71
 AMERHOLD DR-25
 POLYMER OR LATEX 10 15 60
 WATER 50 30 --
 Each of solutions E, F, and & were clear solutions. At amounts of polymer
 or latex over 60% by weight, the polymer or latex could still be dissolved
 in the LAN system but the solution became very viscous.
 Example 14
 Determination of Additional Load LAN/polmer System can Carry
 LAN solutions containing 3% of AMPHOMER (water-insoluble polymer) as well
 as a silicone ingredient were prepared as set forth in Table 11. Solution
 H had a LAN ratio of 1:1.2:4 and contained 1% by weight of
 phenyltrimethicone. Solution I had a LAN ratio of 1:1.2:4 and contained 1%
 by weight of dimethicone.
 TABLE 11
 Solution H Solution I
 ALCOLEC F100 5 5
 MIRANOL C2M-SF 15 15
 CONC
 ARLASOLVE 200 20 20
 SILICONE Phenyltrimethicone Dimethicone
 COMPOUND 1 1
 WATER-INSOLUBLE AMPHOMER LV-71 AMPHOMER LV-71
 POLYMER 3 3
 WATER 56 30
 Both solutions H and I were clear solutions. This demonstrates that the LAN
 system is effective in carrying water-insoluble ingredients as well as
 simultaneously carrying other ingredients. For example, LAN/polymer
 systems can also contain ceramides, sunscreens, oil, vitamins.
 Example 15
 Performance of LAN Solutions Containing Non-neutralized Polmers
 A LAN carrier solution was prepared having the following ingredients:

%
 ALCOLEC MIRANOL ARLASOLVE AMPHOMER RESYN AMP
 WATER NEUTR
 Solution 0.15 0.45 0.6 2 2 0.386
 99.08 60%
 1
 Solution 0.10 0.30 0.4 2 2 0.386
 97.24 60%
 2
 The performance of the above solutions in hair setting is shown in FIG. 2,
 which illustrates the exceptional curl retention of hair treated with the
 above solutions of LAN/partially neutralized polymer/resin at 95% after 4
 hours.
 Example 17
 Effect of Degree of Neutralization on Hair Setting Performance
 Four 0.8% LAN (1:1.2:4) solutions were prepared, each containing 1% of
 AMPHOMER LV-71 and being 20%, 40%, 60% and 80%, respectively, neutralized
 by AMP (aminomethylpropanol).
 TABLE 14
 ALCOLEC MIRANOL ARLASOLVE AMPHOMER AMP WATER
 % NEUTRALIZ
 Solution 0.1 0.3 0.4 1 0.043 98.157
 20%
 A
 Solution 0.1 0.3 0.4 1 0.087 98.113
 40%
 B
 Solution 0.1 0.3 0.4 1 0.131 98.069
 60%
 C
 Solution 0.1 0.3 0.4 1 0.174 98.026
 80%
 D
 The curl retention of the above solutions A-D are shown in FIG. 3. The
 figure illustrates that the efficiency of LAN solutions containing
 partially neutralized polymers or resins is dependent on the degree of
 neutralization, i.e., the hair setting performance increased as the degree
 of neutralization decreased. In other words, the aqueous LAN systems are
 able to successfully incorporate water-insoluble high performance
 polymers/resins whereas previously such polymers/resins could be
 incorporated only into non-aqueous systems based on organic solvents.
 Example 18
 Performance of LAN Solutions Containing Partially Neutralized Polymers and
 Increasing Amounts of Polymer/resin: Curl Efficiency
 Five LAN carrier solutions were prepared. Each contained 0.8% LAN (ALCOLEC
 F100, MIRANOL C2M-SF Conc., and ARLASOLVE 200) and 0% to 4%, respectively,
 of a 60% neutralized water-insoluble polymer, AMPHOMER LV-7 1. See Table
 15:
 TABLE 15
 ALCO- MIRA- ARLA- AMPHO-
 LEC NOL SOLVE MER AMP WATER
 LAN 0.1 0.3 0.4 0 0 99.2
 Solution 0.1 0.3 0.4 1 0.131 98.07
 A
 Solution 0.1 0.3 0.4 2 0.262 96.94
 B
 Solution 0.1 0.3 0.4 3 0.393 95.81
 C
 Solution 0.1 0.3 0.4 4 0.524 94.68
 D
 The compositions were compared for percent curl efficiency over a period of
 4 hours. See FIG. 4, which shows that as the amount of styling polymer in
 the LAN solution increased from 0% to 4%, so did the curl retention, i.e.,
 efficiency.
 Example 19
 Performance of LAN Solutions Containing Martially Neutralized Polymers and
 Increasing Amounts of Polymer/resin
 Five solutions were prepared. Solution 1 contained 4% LUVISKOL VA64, which
 is a water-soluble polyvinylpyrrolidone/vinyl acetate co-polymer from
 BASF, and 96% water. Solutions 2-5 were LAN/AMPHOMER solutions in which
 the LUVISKOL was gradually replaced with AMP as the amount of AMPHOMER
 increased. See Table 16:
 TABLE 16
 ALCOLEC MIRANOL ARLASOLVE AMPHOMER AMP
 LUVISKOL WATER
 Solution 1 -- -- -- -- -- 4 96.00
 Solution 2 0.1 0.3 0.4 1 0.131 3
 95.07
 Solution 3 0.1 0.3 0.4 2 0.262 2
 94.93
 Solution 4 0.1 0.3 0.4 3 0.393 1
 94.81
 Solution 5 0.1 0.3 0.4 4 0.524 --
 94.68
 The compositions were compared for percent curl efficiency over a period of
 4 hours. See FIG. 5, which shows that as the LAN/polymer solution replaced
 the conventional water soluble polymers/resins, the performance increased,
 i.e., the curl retention was excellent for Solutions 4 and 5, wherein
 there was little or no LlVISKOL.
 Example 20
 Improvement of Permanent Waving Efficieny
 Three sets of 6 hair swatches (12 hair fibers, 13.8 cm each, per swatch)
 were wrapped around permanent waving rods, then saturated with the
 following solutions:
 TABLE 17
 SOLUTION SOLUTION SOLUTION
 1 2 3
 (control) (LAN 1:1.2:4) (LAN + polymer)
 Ammonium 11.67 11.67 11.67
 Thioglycolate (60%)
 (permanent wave
 lotion)
 ALCOLEC F100 -- 0.0625 0.0625
 (Lecithin)
 MIRANOL C2M-SF -- 0.1875 0.1875
 Conc. (Amphoteric)
 ARLASOLVE 200 -- 0.25 0.25
 (Nonionic)
 AMPHOMER LV-71 -- -- 1
 Aminomethylpropanol -- -- 0.13
 (AMP)
 Water 88.33 87.83 86.7
 Ammonium Hydroxide q.s. to pH 9.2
 After 30 minutes at room temperature, the hair swatches (still on the rods)
 were thoroughly rinsed with water and blotted dry. They were then treated
 with a 2% hydrogen peroxide solution for 5 minutes at room temperature,
 rinsed thoroughly with water and blotted dry. The hair swatched were
 removed from the rods and their length measured. The following results
 were obtained:
 TABLE 18
 Average Curl Length (cm)
 Hair Treated with Solution 1 7.0 .+-. 0.62
 Hair Treated with Solution 2 7.4 .+-. 0.38
 Hair Treated with Solution 3 6.2 .+-. 0.45
 As can be seen in Table 18, the hair treated with the reducing solution
 containing LAN/AMPHOMER displayed a better curl efficiency. The
 improvement is statistically significant at a 95% confidence level.
 Example 21
 Preparation of Clear Transparent Hydrogen Peroxide Gel
 A series of clear taansparent gels made up of LAN/Polymer that contained
 3%, 6%, 9%, and 12% hydrogen peroxide at pH 3-4 were obtained. The polymer
 used in the gels was VISCOPHOBE DB-1000, an acryic acid latex from Union
 Carbide. A typical clear hydrogen peroxide/LAN/VISCOPHOBE gel has the
 following formula:

ALCOLEC F100 1
 MIRANOL C2M-SF CONC 10
 ARLASOLVE 200 15
 VISCOPHOBE DB-1000 12
 Hydrogen Peroxide 24
 Water 38
 Phosphoric Acid q.s. to pH 3
 The viscosity of the gels can be adjusted by the amount of the VISCOPHOBE
 used in the formula. As shown below in Table 19, the hydrogen
 peroxide/LAN/VISCOPHOBE gels are efficient color developers when compared
 with PRO-OXIDE, a commercially available developer from REDKEN.
 TABLE 19
 Developer L a b
 Hair Color 1
 20 vol. PRO-OXIDE 29.65 20.93 13.35
 20 vol. H.sub.2 O.sub.2 /1:4:16 LAN/12 VISCOPHOBE 30.83 18.43 13.05
 20 vol. H.sub.2 O.sub.2 /1:4:15 LAN/15 VISCOPHOBE 33.32 19.31 15.12
 20 vol. H.sub.2 O.sub.2 /1:4:25 LAN/15 VISCOPHOBE 31.11 17.95 13.10
 Hair Color 2
 20 vol. PRO-OXIDE 24.25 6.12 5.29
 20 vol. H.sub.2 O.sub.2 /1:4:16 LAN/12 VISCOPHOBE 24.07 5.38 5.25
 As shown in Table 19, the L value, which indicates the lightness or
 darkness of the color, increased for Hair Color 1 as compared to the
 PRO-OXIDE L value and decreased for Hair Color 2. In other words, this
 Table shows that hydrogen peroxide/LAN/VISCOPHOBE gel works as well or
 better than the known developer PRO-OXIDE. It is advantageous to use a gel
 as a developer since it is easier to control its application due to the
 reduced flow as compared to a liquid developer.
 The hydrogen peroxide/LAN/VISCOPHOBE gels can also be used with a liquid
 aqueous color system to yield aqueous no-solvent color gels. When a clear
 hydrogen peroxide/LAN/VISCOPHOBE gel at pH 34 is mixed with an aqueous
 color system at pH 8 or higher in a 1:1 ratio, a thick color gel is
 obtained that can efficiently color the hair. As for the bleaching effects
 on hair, the hydrogen peroxide/LAN/VISCCOPHOBE gels can be used to lift
 natural hair color at room temperature and show increased efficiency at
 higher temperatures.
 Example 22
 Mascara Formulation
 A mascara composition is formulated from the following ingredients,
 including the LAN, which is present in a ratio of approximately 1:1.2:4
 and in an amount of less than

1%:
 (A)
 Water 39.250
 PVP-K-30 (PVP/VA copolymer, GAF/BASF) 1.000
 Butylene glycol 2.000
 Hydroxyethylcellulose 0.350
 Methyl paraben 0.400
 Triethanolamine 1.500
 Simethicone (MIRASIL SM from Rhodia Chimie) 0.100
 KAMA KM 13 (Polysaccharide resin from Kama Int'l) 4.000
 Iron oxide 8.000
 Polymethyl methacrylate isopropyl titanium triisostearate 2.000
 (B)
 Beeswax 4.300
 Glyceryl stearate 4.000
 Paraffin 2.500
 Carnauba wax 3.100
 Stearic acid 3.000
 Butylparaben 0.050
 PVP/eicosene copolymer (GANEX V220, from ISP) 1.500
 PERFORMA V103 Polymer (synthetic wax from New Phase) 1.000
 (C)
 Cyclopentasiloxane (DC 245 from Dow Corning) 2.000
 Cyclopentasiloxane/Dimethiconol (DC 2-9071 from 3.000
 Dow Corning)
 Silica 1.000
 Polyethylene (MICROPOLY 524 from Presperse) 2.000
 (D)
 Lecithin (ALCOLEC F100) (L) 0.133
 Disodium Cocoamphodipropionate (MIRANOL) (A) 0.400
 Isoceteth-20 (ARLASOLVE 200) (N) 0.530
 Octylacrylamide/acrylates/butylaminoethyl 0.160
 methacrylate copolymer (AMPHOMER LV-71)
 Methylparaben 0.005
 Ethylparaben 0.003
 Disodium EDTA 0.003
 Phenoxyethanol 0.013
 Water 1.403
 (E)
 AVALURE UR450 (resin solution from B. F. Goodrich) 10.000
 (F)
 Imidazolidinyl urea 0.300
 Water 1.000
 The procedure used to make the mascara composition was as follows, using a
 total of 100 g of material:
 (A) 39.250 g water was heated to 60.degree. C. and 1.000 g of PVP/VA
 copolymer was added. When the copolymer was dispersed, 2.000 g of butylene
 glycol and 0.350 g of hydroxyethylcellulose, which were pre-mixed, were
 added and the entire mixture dispersed using a Homomixer. When dispersed,
 0.400 g methyl paraben, 1.500 g triethanolamine, 0.100 g MIRASIL SM
 (simethicone), and 4.000 g KAMA KM 13 (Polysaccharide resin) were added.
 Next iron oxide and polymethyl methacrylate isopropyl titanium
 triisostearate were added, one at a time and put in the Homomixer until
 dispersed, about 30-45 minutes at a temperature of about 85.degree. C. to
 90.degree. C.
 (B) All the ingredients in sequence B were weighed and heated to 85 to
 90.degree. C. The resulting composition was emulsified with a paddle
 mixer, adding the product of sequence B to the product of sequence A
 above, for 15 minutes. The resulting combination was cooled to 60.degree.
 C.
 (C) All the ingredients in sequence (C) were added to the combination of A
 and B at 600.degree. C.
 (D) All the ingredients in sequence (D) were added to the A-B-C combination
 at 55.degree. C.
 (E) All the ingredients in sequence (E) were added to the A-B-C-D
 combination at 45.degree. C.
 (F) All the ingredients in sequence (F) were added to the A-B-C-D-E
 combination at 45.degree. C.
 The A-B-C-D-E-F combination composition was cooled to 30-35.degree. C. The
 mascara composition formed had a creamy texture, glossy appearance, and
 when applied to eyelashes, provided a deep, rich color, enhanced the
 eyelashes so they appeared thicker and longer, and applied comfortably,
 with no clumping or stickiness.
 It will be apparent to those skilled in the art that various modifications
 and variations can be made in the delivery system, composition and methods
 of the invention without departing from the spirit or scope of the
 invention. Thus, it is intended that the present invention cover the
 modifications and variations of this invention provided that they come
 within the scope of the appended claims and their equivalents.