MXPA02010134A - Nanoscopic hair care products. - Google Patents

Abstract

The present invention is directed to a hair treatment preparation comprising a payload in an intimate relationship to a polymeric nanostructure, the polymeric nanostructure being reactive to hair or capable of being immobilized onto or in hair. The nanoscopic nature of the entities being engineered ensures three distinct characteristics. First, the imparted attribute can be either nearly permanent or semi permanent, depending on the attachment chemistry. In the semi permanent version, the intended effect can be controllably erased by removal of the nanostructure by simple chemical or physical means. Second, the nanoscopic entities are invisibly small. Their presence does not deteriorate the hand or feel of the hair. Third, the nano technology approach is infinitely flexible and adaptable. It can be coupled with many existing dyes, colorants, UV absorbers, fragrances, softening agents and the like for hair treatment. Methods for treating hair with the hair treatment preparations of the invention are also encompassed.

Description

NANOSCOPIC PRODUCTS FOR HAIR CARE Field of the Invention The present invention is directed to the field of hair care products. BACKGROUND OF THE INVENTION Human hair as well as wool, horns, nails, skin and feathers of animals etc., comprise proteinaceous helices known as keratin. These structural proteins are degraded by prolonged exposure to sunlight, harsh chemicals such as dyes and bleaching agents, and airborne contaminants. Hair follicles also stop producing the melanin required as a person ages, and therefore the hair turns gray. To preserve a youthful appearance or for beauty purposes, the cosmetics industry has developed hair conditioners and coloring agents. In addition, fragrances and UV blockers have been incorporated into shampoos and conditioners to impart desirable additional attributes. However, the technical methods traditionally adopted to achieve these objectives have been developed in an ad hoc manner. Current hair dyes and dye systems comprise harsh chemicals, such as oxidizing agents, to convert the pigment precursors into colored species after said precursors are first applied to the hair. This basic method requires that precursors penetrate deeply into the hair root, where the oxidative conversion takes place in a subsequent operation. Similarly, when lighter colors or shades are desired, the bleaching agents must diffuse deep into the hair to destroy intrinsic melanin deposits. Repeated dyeing and discoloration using harsh chemicals tends to damage the hair in an important way. Scalp exposure to chemicals can also induce allergic reactions in sensitive people. Summary of the Invention The present invention provides a systematic nanoscopic platform to enable an extensive list of hair care products. In one embodiment, the present invention provides a technology platform for developing hair dyeing products that do not require oxidizing or bleaching chemicals. The nanotechnology platform is based on a completely different premise for coloration. In a similar way, conditioning effects, UV blocking capabilities, and prolonged release of fragrances can be achieved with the present invention. The na-tech platform offers advantages that could not be achieved by other means to date. More particularly, the present invention is focused on a preparation for the treatment of hair comprising a dye or other payload with an intimate relationship with a polymeric anustructure, the nanostructure having functional groups that react with the hair or other characteristics that allow be linked "YOU covalently or otherwise immobilized on or in the hair. The present invention describes a systematic method wherein the nanoscopic objects or structures are either formed in the form of spheres or minute particles that can be attached to the hair, which we refer to in the present description as "nanospheres" or "nanoparticles", such as a network of invisibly small molecular dimension that surrounds a hair. What we refer to in the present description as a "nanoscopic macromolecule network" or "a nanoscopic polymer network". The nanospheres or nanoscopic networks are constructed of polymeric materials, which may be existing in nature or synthetic. The natural type can be modified or derived from well-established organic chemistry. The synthetic type can be specially designed to exhibit custom designed properties. The above geometries are only an example of the total spectrum of nanotechnology that is applicable to the hair products industry. Many variations of the two basic schemes can be envisioned and are intended to be covered by the present invention. For example, a mixture of networks and spheres can be developed to provide more than one attribute or treatment. In addition, the networks can be completely cross-linked (either chemically or physically) or partially cross-linked. They can still be a network that has a plot but is not reticulated. The net can also be attached to hair or other polymeric species deposited on the surface of the hair at points distributed spaced, so that the molecular network looks like a collection of nanoscopic hair. Spheres can be formed in the form of micelles, wherein a group of surfactant molecules capture a useful charge, the resulting micelle being crosslinked after or at the time of placement on the hair through a mordant or a polyelectrolyte. Regardless of the geometric features, the nature of the nanoscopic entities that are being designed ensures three different characteristics. First, the imparted attribute can be almost permanent or semi-permanent, depending on the chemical adjuncts. In the semi-permanent version, the effect that is attempted can be erased in a controllable manner by removing the nanostructure by simple chemical or physical means. Second, nanoscopic entities are visibly small. Their presence does not deteriorate the hands or the sensation of the hair. The impact of nanoscopic objects or structures can at best be felt as improved smoothness. Third, the nanotechnology method is infinitely flexible and adaptable. It can be coupled with many existing dyes, colorants, UV absorbers, fragrances, and softening agents for hair treatment. The present invention is further directed to hair treatment methods which comprise the application of a hair treatment preparation, the hair treatment preparation comprising a payload in an intimate relationship with a polymer nanostructure, the nanostructure being reactive polymeric to the hair or with ability to be immobilized on or inside the hair, and changing the conditions so that the payload and the nanostructure are attached to the hair. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic representation of one embodiment of a nanoparticle of the present invention, and the method for preparing it by means of isolating a payload of dyes, fragrances, softeners, medicines (drugs), monomers and in a micelle by means of polymerizable surfactants which are polymerized to make the nanoparticle as a specified interior. Detailed Description of the Invention The hair treatment preparations of the present invention comprise an agent or filler in a permanent or semi-permanent intimate relationship with a polymeric nanostructure, the polymer nanostructure being reactive (as by means of a covalent bond), or with ability to be immobilized on or in the hair. In one embodiment, the polymeric nanostructure may include functional groups reactive with the hair for bonding or adhering the nanostructure to the hair to be treated. The term "intimate relationship" means that the payload is surrounded by, or contained within, chemically attached to or otherwise in a permanent or semi-permanent relationship with the polymeric nanostructure.

The term "hair reagent" means that the nanostructure containing the payload will form a covalent bond with the hair.

The terms "payload" and "payload agent" as used in the present description collectively refer to any material or agent that would be desirable for permanent or semi-permanent adhesion to or treatment of human or animal hair. This can modify a property of the hair or can add new and desirable new properties to the hair. We also refer to the payloads in the present description as groups as "suspended groups". The payload may be, but is not limited to coloring agents or dyes, pigments, opacifying agents, essences and fragrances, pharmaceuticals and pharmaceuticals, softeners, insect repellent, antibacterial and antimicrobial, and the like. Although the following explanations are focused on certain example agents, it is important Note that other materials having any desirable activity or charaistic suitable for hair treatments in polymeric nanostructures may also be incorporated according to the teachings of the present disclosure and which are included within the scope of the present invention. The term "dye" means a molecule that can absorb wavelengths in the visible or ultraviolet region of the electromagnetic spectrum. Nanotechnology is an emerging field of study, where the objects / structure are of nanoscopic dimension. The word "nano" means one millionth. Therefore, objects characterized by dimensions from a nanometer to a miera (1 micrometer or 1000 nanometers) are within the range of nanotechnology.

Coloring Systems Based on Nanotechnology The power of nanotechnology is evidenced by its ability to allow the designed products to separate or divide the design requirements in different parts of the system. Instead of requiring the coloring agents or their precursors to penetrate deeply into the root of the hair, the nanoscopic entities can be simply deposited on the surface of the hair thread or only partially penetrate the interior. The durability or semi-permanence may be the result of, for example, the way in which the nanoscopic structure adheres itself to the hair, or the cross-links between neighboring entities or lattices through a fixation In the last two versions, Nanoscopic entities do not have to form direct bonds with the hair itself In all versions, the nanoparticle or nanoscopic networks are only transporters for the active ingredients (for example, the hair dye) .These structures do not have to be intrinsically colored First, they must provide a means of anchoring themselves on the surface or depositing themselves inside the hair, they must surround or encapsulate the correct dosage of the dye (in the case of nanospheres). or nanoparticles), or have a dye linked to the transporter (in the case of nanoscopic networks). no particles can assume other forms that are not spherical, and can still have the same capacity to perform the same function.

In any direct link, or indirect anchoring, the nanotechnology method does not resort to high temperature or extreme pH or severe chemicals, whose use would compromise the goal of the present invention. Examples of the adhesion / anchoring are presented below. Those skilled in the art of polymer precipitation and complex processing will undoubtedly provide additional means for securing the nanospheres based on the technology of the teachings of the present invention. All these teachings are intended to be covered by the spirit and scope of this description. The above examples are illustrated by means of the following effects. First, with respect to nanospheres or nanoparticles, the payload, for example, the dye molecules or their aggregates (referred to collectively as "parts of the dye"), are trapped, that is, surrounded by or contained within a shell or polymer matrix. The nanoparticle of the present invention may comprise a polymer shell surrounding the payload, or may comprise a three-dimensional polymer network that catches the payload, and both of which we refer to in the present description as the "polymer shell". Alternatively, in the case of hair dyes, if a lighter / shadow color is desired, some or most of the particles will contain blocking agents, such as colloidal white pigments (e.g., titanium oxide or zinc oxide) . Mixed with these bleaching or opacifying agents are the dye parts contained in the nanoparticles. The general system produces that the color / shade that once the mixed particles are deposited in the hair. The nanospheres can be made from non-allergenic, non-toxic polymers. Many polymers have been tested by the FDA for topical use. Silicones and cellulosics, among many others, are examples? The same. Synthetic hydrocarbon-based polymer systems are also suitable alternatives. Protein or synthetic peptides can also be used for this purpose. There are well-established encapsulation techniques to enclose the correct amount of dye in the particles of a controlled size distribution. Literature abounds both processes and material information to achieve this goal. Nevertheless, in the present invention, the surface of the nanoparticles contains functional groups for binding or adhesion to the hair, to provide a permanent or semi-permanent bond of the payload to the hair. Alternatively, the surface of the nanoparticle includes functional groups that can be linked to a linker molecule which in turn will bind or adhere the particle to the hair. In any case, to these functional groups we refer in the present description as "reactive functional groups of the hair". The chemical bond on the surface of the nanoparticles does not include the molecules of the payload. The payload agents are physically trapped within the nanoparticle, without requiring chemical modifications of the payload molecules themselves. The resulting encapsulated payload preparations or nanoparticles they have improved retention in or on the hair structure without changing the inherent character of the payload agent. The nanoparticles containing payload can be formed by one of several encapsulation methods known in the art, such as interfacial polymerization, microemulsion polymerization, precipitation polymerization, and diffusion. The preparation of mixtures of multiple components followed by atomization / spraying inside the drying chamber is still another processing scheme. The reactive functional groups in the polymer shell provide means for adhering the treatment particles to human hair. The nanoparticles of the present invention are formed by contacting a payload with a set of monomers, oligomers, or polymers, (referred to herein as a "polymer set"). The monomers, oligomers or polymers are assembled around the payload and are then polymerized, with or without crosslinking in a polymeric network or shell surrounding the payload. The polymeric assembly in one of the embodiments includes at least some components that provide reactive functional groups on the surface of the final polymer granule, which will bind to the hair to be treated. Alternatively, a nanoparticle optionally having functional groups reactive to the hair on its surface can be prepared first by polymerizing a polymeric assembly, r and after which the payload can be exposed to the low granule. suitable conditions so that the payload is absorbed or trapped in the polymeric network or carapace, to provide the reactive payload nanoparticle to the hair. The particular monomers, oligomers or polymers useful for forming the nanoparticles of the present invention, are those which contain amine, hydroxyl, or sulfhydryl monomers or polymers, with amine, hydroxyl or sulfhydryl reactive polymers. Throughout the structure that constitutes the polymer of the nanospheres, the reactive functional groups to the hair can be introduced and can be either reactive chemically or under mild conditions or be electrostatically interactive with complementary groups on the hair surface when the Surfactant content or ionic strength of the medium is changed by means of rinsing Example interactions include charge-to-charge, dipolar, hydrogen bonding, hydrophobic, or dehydration interactions. The nanospheres can be made from a polyelectrolyte as an isoelectric point in an alkaline pH range. These particles can be precipitated or added effectively using another polyelectrolyte (straight or branched polymer fixative) that has an acid isoelectric point. When the hair is first thick to the nanospheres and subsequently exposed again to a second fixation of polyelectrolytes, a complex is formed on the site, coating the treated hair. Another route is the use of a potent formulation of surfactant to bring the nanoparticles containing the payload to the surface of the ,? hair in a finely divided dispersion. Once it is in place, the surfactant is rinsed, allowing the nanoparticles to adhere strongly to the treated hair. An example is silicone-based nanoparticles. Said particles can be easily dispersed in a block polymer or graft of liquid poly (dimethylsiloxane ethylene glycol). This latter medium can be rinsed with water, because the water-soluble component leaving the insoluble nanoparticles as an adherent precipitate. The functionalized siloxanes can further refine this precipitation principle using the elaboration of the complex as well. For example, siloxanes with carboxylate side groups can be precipitated by the double use of surfactant removal and addition of a polyamine (such as polyethylene imine in the aqueous rinse solution) to the contrary, the amino-substituted siloxanes can form a network crosslinked at the site with the nanoparticles embedded therein by the addition of polyacids (such as polyacrylic acid, polymaleic acid or copolymers thereof). The elaboration of the complex can also be induced by the addition of polyvalent cations or anions, each reactive towards the charged complementary surface groups. The principle of precipitation / anchoring induced by the elaboration of the complex and induced by thermodynamics on the hair surface can be applied equally to natural nanostructures or other synthetic nanostructures. For example, the payload can be coupled chemically first on a protein carrier. The payload-protein complex is dispersed in a medium, which is then applied to the hair. A change in the thermodynamic balance of the medium causes the deposition of the complex on the surface of the hair. Therefore the hair is treated. As the coupling is carried out chemically outside the presence of hair, traditional chemical means can be used in fear of hair degradation or skin sensitivity. The placement of the protein can then be effected by smoother and simpler binding reactions. We reiterate the delegation power of different engineering requirements to different parts of the system. The color comes from the components of the dye contained within the nanoparticles. Still, the controlled degree of permanence stems of the adhesion methodology. The above method of precipitation / complex processing can be difficult to reverse or can be easily reversible. Investment capacity can be designed to occur only in the presence of certain specific agents. Therefore, washing or applying normal shampoo to the hair does not cause color fading. For example, functionalized silicones are difficult to wash, unless specific siloxane-containing surfactants such as block copolymers or siloxane-polyethylene glycol grafts are used. In an equivalent manner, the dissolution of the complex or precipitate may or may not occur under the rinse conditions designed in a similar manner. Therefore, artificially created hair color can be either preserved in a prolonged manner or inverted when desired. Note that cellulose derivatives can be made to work in a similar way. Synthetic polypeptides can also be used for the encapsulation of the dye components. Said proteinaceous or cellulose surfaces can be modified to exhibit variable isoelectric points, which can be exploited to design their precipitation / coagulation properties, complex elaboration. Nanospheres are nothing more than a geometry such as a possible dye or other charge conveyor. The dye molecules can also be adhered to lightly crosslinked, linear or branched polymer carriers, provided they remain soluble or dispersible in a chemically smooth and suitable liquid (aqueous or mixed aqueous). The fixation of the dye on the hair is implemented through the reaction / precipitation / elaboration of complex on the surface of the hair by means of any of the previously illustrated schemes and many others. Imagine that the polymer that has the dye added has an architecture similar to a tree. To the extent that residual functional groups exist after the dye is adhered to the tree, the total assembly can be deposited on the surface of the hair in a subsequent operation (removal of the surfactant, addition of the precipitant, introduction of the coagulation agent or elaboration of the complex, etc.). Even if the functional groups, non-formersible remain after the initial addition of the dye, still the conveyor can have great utility simply because of its ability to firmly adhere to the hair as a consequence of a change in the thermodynamic environment medium. A group of polymers useful as in the nanostructures in the present invention are the dendrimers and other highly branched polymers. The dendrimers also have a high degree of symmetry. Because said polymers are branched, they are compact so that good penetration and even permanence within the hair is expected. Dendrimers and highly branched polymers can be designed to have one or more different types of functional groups in them. Using these functional groups, the dye molecules, the alkyl or siloxane chains to add softness or other molecules of interest can be adhered to the dendrimer so that it becomes a compact transporter. Lightly crosslinked, linear or branched polymer carriers containing the payload may be adhered to the hair by means of a mordant, or a cationic fixing agent. Complexes can be made with polymers containing carboxyl, phosphate, phosphonate, sulfate, and sulfonate with alkaline earth metal having very low toxicity such as Mg2 +, Ca2 + and Sr2 +. Thus, for example, a soluble polymer containing, for example, carboxyl groups and one or more fillers, such as dye molecules or compounds that add softness, are applied to the hair. In a next step, a soluble calcium or magnesium salt is added to the hair to precipitate the polymer on and into the hair.

Briefly, the nanoscopic transporter method provides a flexible and invisible system for dyeing hair. In contrast to traditional chemical assaults, the system is soft to the hair, and the color can be durable or inverted by custom-designed means. Hair Treatments Softening, Fragrance and UV Ray Blockers Based on Nanotechnology In a manner similar to the dyeing process described above, the nanoscopic transporters described in the present invention can also be used to deposit fragrances, absorbents / sunblocks. UV rays, and other desirable agents for hair. The transporters can be of particulate form or simply be a polymer of arbitrary architecture. The use of fastening methods is made possible through the conveyors as a part of the innovation. Silicones and polyolefins impart a soft touch to the hair. These should be deposited on the hair simply as a carrier itself in the context of the present invention. The fixing step is then part of the innovation. For example, a cationic silicone is applied in the first rinse. This coating is then fixed in place in a subsequent phase containing an anionic silicone, resulting in the formation of a complex that creates a silicone network on the surface of the hair. The charged polyolefins can be replaced by the silicones in the previous example. In certain cases, such as for example the payload is a fragrance or a pharmaceutical agent, it is desirable that the payload be controlled release of the nanostructure on or in the hair. The nanoparticles may be designed so that the payload agent is embedded or trapped within the shell or polymer matrix of the nanoparticle, but may also be released from the nanoparticle in a prolonged or otherwise controllable fashion. The release profile is programmed by the network chemistry of the nanoparticle polymer. The nanoparticle can be formulated with almost an infinite degree of characteristics designed by means of structural features such as the crosslink density, the hydrophilic-hydrophobic equilibrium of the copolymer repeat units, and the stiffness / elasticity of the polymer lattice (by example, the transition temperature to glass). In addition, nanoparticles that can be eroded or other nanostructures can be developed to controllably release the payload. In addition, the polymer matrix may contain components that react or respond to environmental stimuli to cause the release of the increased / decreased content. "Smart polymers" are polymers that can be induced to pass through a thermodynamic or different transition by adjusting any of a number of environmental parameters (for example, pH, temperature, ionic strength, by cosolvent position, pressure, field electrical, etc.). For example, smart polymers based on a lower temperature transition of the critical solution (LCST) can cut the release when exposed to heat, or hot water during washing. When it cools back to room temperature, it assumes the sustained release. Smart polymers can be selected from, but are not limited to, N-isopropyl acrylamide and acrylamide; polyethylene glycols, di-acrylate and hydroxyethyl methacrylate, octyl / decyl acrylate, urethane and acrylated aromatic oligomers, vinyl silicones, silicone acrylate; polypropylene glycols, polyvinylmethyl ether; polyvinyl ether; polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone polyhydroxypropyl acrylate, ethylene, acrylate and methyl methacrylate, nonyl phenol; cellulose; methyl cellulose; hydroxyethyl cellulose; hydroxypropyl methyl cellulose; hydroxypropyl cellulose; ethyl hydroxyethyl cellulose; hydrophobically modified cellulose; dextran; hydrophobically modified dextran; agarose; low temperature gelling agarose; and copolymers thereof. If crosslinking between polymers and multifunctional compounds such as bis-acrylamide and triacrylate propane of ethoxylated trimethylolol and sulfonated styrene is desired, they can be employed. In the presently preferred embodiments, the smart polymers comprise polyacrylamides, substituted polyacrylamides, polyvinylmethyl ethers and modified celluloses. In cases where it is desired that the payload be visible (when it is a dye or a UV protector for example), the nanoparticles will be constructed of an optically transparent or translucent material, allowing the light to make contact with the payload and be reflected, refracted or absorbed. The polymeric assembly can be selected to provide both hydrophobic and oleophilic nanoparticles, allowing a broader adaptation of the bioactive components or drugs for that are trapped inside them in a comfortable way. Where the particles are hydrophilic, they are easily dispersible in a stable aqueous suspension or emulsion by means of surfactants, which can be subsequently washed without affecting the performance of the payload agent therein. The inherent thermodynamic compatibility of the agents and the material of the shell or polymer matrix can increase the level of charge per particle. The following examples are intended to illustrate some, but not all, of the concepts described in this description, and in no way attempt to limit it. One skilled in the art will also see that different ideas of different examples or the above explanation could be combined to produce other possible means for hair treatment. EXAMPLES Example 1 One or more of the same or different dye molecules are covalently linked, by methods known in the art to an amine-containing polymer or oligomer such as poly (ethyleneimine), poly (allylamine hydrochloride), or poly (lysine) . (One would expect an oligomer or arginine polymer to have a similar behavior). The hair is moistened with a solution containing this polymer or oligomer with dye molecules suspended therein (a polymeric or oligomeric dye). In some cases it may be necessary to rinse the excess material. To adjust or cure the amine-containing copolymer, the hair is then exposed to a polymer containing carboxyl, sulfate, sulfonate, phosphate, phosphonate moieties. Examples of such% polymers include copolymers of DNA, poly (acrylic acid), poly (itaconic acid), poly (maleic anhydride), and polymers containing maleic anhydride units, a polymer with group -C6H5COOH, poly (methacrylic acid) , or poly (styrene sulfonate, sodium salt). The excess material is then rinsed. An electrostatic interaction keeps the two polymers together, significantly decreasing the solubility of the complex. This and all other formulations and solutions mentioned herein may additionally contain fragrances, wetting agents, oxidizing agents, antioxidants, opacifiers, thickeners, reducing agents, foaming agents, surfactants, (anionic, cationic, nonionic, amphoteric) , suteryionics or mixtures thereof) suspending agents, medicines (drugs) dispersing agents, conditioners, limited amounts of organic solvents, antibacterial agents, preservatives and the like, as well as mixtures thereof. Example 2 One or more dye molecules are covalently linked to a carboxyl-containing polymer or oligomer such as poly (acrylic acid), poly (itaconic acid), poly (maleic anhydride), a copolymer containing maleic anhydride units, a polymer with groups -C6H5COOH or poly (methacrylic acid). The hair is moistened with a solution containing this oligomeric or polymeric dye. The surplus material is rinsed later. To fix this polymer, the hair is exposed to a polycation (polymer or oligomer) such as (ethyleneimine), poly (allylamine hydrochloride), poly (lysine), poly (arginine) or poly (diallyldimethylammonium chloride). Example 3 The hair is exposed to a solution containing one or more polymeric or oligomeric dyes, as described in Example 1 (polycation). It may be necessary to rinse the hair after this treatment. The hair is then exposed to a solution containing one or more polymeric or oligomeric dyes (polyanions), as described in Example 2, and rinsed. Example 4 An alkyl chain, which is defined herein as a branched straight molecule containing mainly C, CH, CH2 and CH3 units, is attached to an amine-containing polymer or oligomer, such as poly (ethylene imine), poly (allylamine hydrochloride) or poly (lysine). It is also possible to add branched straight siloxane chains to the polypeptide or oligomer containing amine. One or more of the same or different molecules of the dye can also be added to the polymer, by methods known in the art. Then the hair is exposed to this polycation, and the excess reagent can be rinsed. The hair is subsequently exposed to a polyanion which may have alkyl chains, siloxane chains, or dyes attached thereto. A possible polyanion that can act as a softener, is a copolymer of maleic anhydride and vinyl ether of the formula CH2 = CHO (CH2) nCH3, wherein n is at least 2, and preferably greater than 4. Example 5 A dye containing amines is reacted with benzoquinone, naphthoquinone, anthroquinone or a derived therefrom to form a polymeric or oligomeric dye. The following are three possible adducts. or oligomer) or oligomer) Example 6 An amine-containing dye is reacted with a dye containing one or more reactive groups such as acid chlorides (-C (O) CI), sulfonyl chlorides (-SO2CI), vinyl sulfones (-SO2CH = CH2) or a active derivative of a cyanuric chloride. Examples of each of these four possible link chemistries for dyes and polymers are shown below. Any other reactive functional groups with amine that can appear in a reactive dye molecule, such as epoxies or acid anhydrides, could also be used. (polymer u Example 7 A polyelectrolyte containing suspended groups, which modify a hair property or which adds new desirable properties or properties, is deposited on the hair. An opposingly charged polyelectrolyte, which may also contain one or more suspended groups that modify a hair property or that add a desirable property to the hair, is added to the hair, condensing it with the first polymer to immobilize it. Example 8 A polymer or oligomer containing one or more suspended groups is deposited on the hair, which modify one or more hair properties or which add one or more desirable properties. The excess reagent can be washed from the hair. A mordant is added, which we define as a species that contains a metal atom with an oxidation number of 2 or greater, to the deposited polymer, immobilizing the polymer. Example 9 A mordant deposited on the hair. The excess reagent can be washed from the hair. A polymer or oligomer containing one or more suspended groups is deposited on the hair which modify one or more hair properties or which add one or more desirable properties to the hair. The mordant forms a complex with the polymer to immobilize the polymer.

Example 10 One or more molecules of the dye are covalently linked to a polymer or oligomer of ethyleneimine, such as triethylene tetraamine (see Reaction Scheme 1). In addition to ethyleneimine, any polymer with free amine groups, including poly (allylamine hydrochloride), and poly (lysine) can be used. Additional starting materials include small multiple amine molecules, such as ethylene diamine, and large ethylene imine polymers (branched or straight). It is well known that amines react as a variety of dyes. For example, U.S. Patent No. 6,203,578 shows amine reactions with benzoquinone, naphthoquinone, and anthraquinone and some of their derivatives as well as with dyes having amine-reactive groups. The amine-reactive groups found in commercially available reactive dyes include portions based on vinyl sulfone, and cyanuric chloride. After the introduction of the dye to the polymer, a group with chelation capacity of a metal is introduced. One of the possible means to do this is by reacting the remaining amines of the molecule with an ether of a-chloro, a-bromo or a-iodoacetic acid. The ester is an acetic protective group. The ester is a protective group that is removed after the addition of the molecule to the polymer. Therefore, this tint adduct of triethylene tetra-amine is allowed to react with an α-haloacetic acid ester (CICH2C (O) OR, BrCH2C (O) OR, ICH2C (O) OR) (see Reaction Scheme 1) . The ester group is then removed by a method known in the art (deprotection) leaving a polymeric chelating dye with metal. Methods for the introduction of the protected metal chelating group and its deprotection are known in the art; consult, The North American Patent No. 6,080,785. In a preferred embodiment, the α-haloacetic acid ether is a methyl ester. For example CICH2C (O) OCH3 is a non-expensive chemical that is available in volume quantities. Note that the carboxymethyl group can be introduced by the reaction of formaldehyde and hydrogen cyanide as an amine. The addition of these two reagents to ethylenediamine (the Strecker Synthesis) produces ethylenediaminetetraacetic acid (EDTA) (see the Beyer and Walter publication in Handbook of Organic Chemistry, Prentice Hall, 1996). It should also be noted that the polymeric chelating dye shown in Reaction Scheme 1 is a close analogue of EDTA and nitrilotriacetic acid (N (CH 2 COOH) 3), both of which are effective metal chelators.

Reaction Scheme 1: dye unprotect Example 1 1 This example (see Reaction Scheme 2) demonstrates two important characteristics of the chemistry described herein. The first is the ability to immobilize a polymeric stain with a mordant using groups that can chelate a metal. Second is the extraction of the metal atoms of the polymer with EDTA or NTA, which reverses the process of application of the initial dye. Note that the exact geometry of the polymer-metal complex will vary from metal to metal. Both the intramolecular lattices (shown in Reaction Scheme 2) and the intermolecular lattices between the polymeric or oligomeric dye molecules are expected. As is the case for all the processes shown here, the penetration depth of the dye within the fiber could be controlled, in part, by the size of the molecule. One or more surfactants or other additives may also be present in this and other formulations (see Example 1). Reaction Scheme 2: EDTA, NTA or salt thereof. 25 Example 12 In this example (see Reaction Scheme 3), a polymeric dye is first created, and then a softening agent is added to the oligomeric or polymeric dye, and a chelation group is introduced. It is expected that the siloxane and alkyl chains act as softeners, but another important characteristic of these long chains is to reduce the solubility of the polymeric or oligomeric dye. Therefore, when any surfactants in the formulation are removed by rinsing, the polymer dye can be deposited on the hair. The addition of the metal (shown in Reaction Scheme 4) would act to increase its durability. As was the case in Example 1 1, the process of adding a metal is reversible using EDTA and NTA (see Reaction Scheme 5). Reaction Scheme 3 shows the introduction of an alkyl or siloxane chain with an epoxide group. Although epoxide chemistry is a preferred embodiment of the ideas in this example, other possible reactive groups that could be used to introduce the short chain alkyl or siloxane groups by means known in the art include, but are not limited to anhydrides, acid chlorides , carboxylic acids, sulfonyl chloride (to make sulfonamines), etc. Reaction Scheme 3: Unte H3) 3, Reaction Scheme 4: unprotect Z = H +, Na +, K +, NH /, Rb + etc. 10 Reaction Scheme 5: EDTA, NTA or salt thereof.

Z = H +, Na +, K +, NH /, Rb +, etc.

Example 1 A variety of molecules imparting desirable properties to the hair or to the formulation can be incorporated into the reactive monomers such as in the reaction between an amine and an acid chloride (see Reaction Schemes 6 and 7). Subsequently it will be possible to polymerize said monomers in polymers having the properties desired, where the level or concentration of certain groups is carefully controlled. Reaction Scheme 6: Reaction Scheme 7: CH3) 3, Example 14 N-isopropylacrylamide (Ñ PA) (see Reaction Scheme 7b) will make a polymer thermally sensitive. In other words at low temperatures, a polymer that has ÑIPA (or in an analogous monomer) will have a greater water solubility than at temperatures higher Therefore, a polymer can be designed that is precipitated when the hair is washed with warm water or hot water. Example 15 In this example (see figure 1) a set of molecules, which may be dyes, fragrances, softeners, drugs (drugs) monomers or other molecules that modify a property of the hair or which add new and desirable properties, is emulsified with a surfactant that can be polymerized. The resulting micelles are then polymerized into a nanoparticle, which can be applied to the hair and subsequently, depending on the main group of surfactant, use with a mordant or a polyelectrolyte with a charge opposite to that of the main groups of surfactants. The major groups can be designed to be analogues of EDTA or NTA so that the surfactant will be particularly effective in chelating a metal ion. Example 16 Itaconic anhydride and maleic anhydride derivatives can be used as the surfactants that can be polymerized (see Reaction Scheme 8). To produce said surfactants, a fatty alcohol (or amine, which is not shown) can be reacted with an anhydride to produce a surfactant. A carboxyl group is the main group. In this deprotonated form, it will impart a high degree of solubility to the alkyl chain in the surfactant. The main group can be precipitated with an appropriate mordant. In some cases, it may be desirable to create an anionic surfactant by adding units of ethylene oxide to the carboxyl group of the polymerizable surfactant (the four bottom structures of Reaction Scheme 8). The present invention is not intended to be limited to the polymerizable surfactants described herein. A variety of other surfactants that can be polymerized are developed and may be applicable to the situations described herein. A few references showing the synthesis, use and properties of these materials include, the publication of: Stáhler et al., In Langmuir 1998, 14, pages 4765 to 4775; Stáhler et al., In Langmuir 1999, 15 pages 7965 to 7576; Kline, in Langmuir 1999, 15, pages 2726 to 2732; Soula and Guyot, in Langmuir 1999, 15, pages 7956 to 7962; Shen, et al., Langmuir 2000, 16, pages 9907-9911; Viitala, et al., In Langmuir 2000, 16, pages 4953-4961; Jung, et al., Langmuir 2000, 16, pages 4185 to 4195; Gargallo, et al., Langmuir 1998, 14, pages 5314 to 5316; Liu. Et al., In Langmuir 1997, 13, pages 4988 to 4994; Xu, et al., In Langmuir 1999, 15, pages 4812 to 4819. Reaction Scheme 8: Example 17 A polyamine which contains two or more amine groups (the amines could be suspended or the space between the amines could be three or more carbons, although in this embodiment it is preferred that it be two) is reacted as one or more alkyl or siloxane chains to produce a surfactant (see Reaction Scheme 9). The amines are then derivatized with carboxymethyl groups to form a surfactant that can chelate metals. In this way, a set of dyes, fragrances, softeners, medicines (drugs) or other small molecules or polymers with this surfactant could form a solution, and the resulting micelles could be precipitated on the hair using an appropriate mordant. A particularly useful embodiment of this idea is the reaction of ethylenediamine with an oxirane ring (epoxide) on an alkyl or siloxane chain. Then the carboxymethyl groups are introduced into the resulting molecule. One or more of the carboxyl groups or the hydroxyl group can be functionalized with ethylene oxide units, as is commonly done with nonionic surfactants. Reaction Scheme 9: H3) 3, check out (replace R with H +, Na-, K + NH /, Rb-, etc.) Example 18 A variety of molecules that add desired properties to a polymer are added to the poly (acryloyl chloride), which acts as a platform. See Reaction Scheme 10 for examples of a few of the many possible species (amines and alcohols in the preferred embodiment) that could react with poly (acryloyl chloride) to create a functionalized polymer with designed properties.

Reaction Scheme 1 0 H2O dye-OH NH, dye-NH, other amines, alcohols.

Create a polymeric dye. They created polymer with thermal response. Extinguish reactive sites.

Excess of diethylenetriamine, followed by reaction with XCH2C (O) OR, then deprotection. Creates metal chelating polymer.

Functionalized polymers with designed properties.

Example 1 9 A variety of molecules that add desired properties to a polymer are added to the poly (acrylic anhydride) which acts as a platform. See Reaction Scheme 1 1 for examples of a few of the many possible species (amines and alcohols in the preferred embodiment) that could react with poly (acrylic acid) to create functionalized polymers with designed properties. It would be expected that the maleic anhydride copolymers would react in a manner similar to the polymer shown in Reaction Scheme 1 1.

Reaction Scheme 1 1 H2O dye-OH NH3 dye ~ NH2 other amines, alcohols.

Create a polymeric dye. They created polymer with thermal response. Extinguish reactive sites.

Excess of diethylenetriamine, followed by reaction with XCH2C (O) OR, then deprotection. Creates metal chelating polymer.

Functionalized polymers with designed properties.

Example 20 It is also possible that an amine is suitable with a general formula CH3 (CH2) nNH2, although branched alkyl chains are also possible, are derivatized with carboxymethyl groups according to the methods described herein to produce a surfactant with the formula CH3 (CH2) nN (CH2COOH) 2. One or both of the carboxyl groups in this surfactant can be deprotonated. A set of small molecules, which may include dyes, fragrances, softeners, medicines (drugs), monomers, etc. , it becomes soluble with this surfactant. The resulting micelles are then precipitated on the hair and with a mordant. Because this active can be made insoluble by chelation with an appropriate metal, this surfactant could be generally useful in any situation where it is desirable to remove a surfactant from a formulation. As is the case for nonionic surfactants, some units of ethylene oxide may be a to this surfactant. It is expected that the crosslinking of the mordant with the crosslinking surfactants will be an intermediate effect to limit the release of the molecules that are captured in the micelles by these surfactants. In this way, the capture and immobilization of small ones by this method can provide an effective means to allow time release of certain small molecules such as fragrances and medicines (drugs). Surfactants with different chelation potency (observe those of Example 17 and Reaction Scheme 9) could be combined to refine the properties of time release formulations. Example 21 A set of one or more surfactants is used to bring one or more insoluble or almost insoluble species, including polymers and oligomers in an aqueous solution. After rinsing the material, the insoluble or almost insoluble species are deposited on the hair. EXAMPLE 22 A known dye molecule, including but not limited to acidic dyes, direct dyes, reactive dyes, mordant dyes, sulfur dyes or vat dyes, is reacted with a polymer and the polymer is deposited on the hair by one of the methods described in this document. Example 23 A mordant dye is coupled to a polymer or oligomer and this material is deposited on the hair. The addition of a mordant, the crosslinking of the polymer molecules through the suspended groups of the mordant dye. Example 24 A protein, which acts as a platform, is derivatized with dye molecules, softeners, a polyelectrolyte oligomer chain, carboxymethyl groups or other species that can impart a desired property to the hair. The resulting protein complex is then precipitated in the hair and immobilized to one degree or another with the methods described herein, for example, a polyelectrolyte or a mordant.

Claims (1)

1. CLAIMS 1 .- A preparation for the treatment of hair comprising a payload in an intimate relationship with a polymeric nanostructure, the polymer nanostructure being reactive to the hair or capable of being immobilized on or on the hair. 2. A hair treatment preparation as described in claim 1, wherein the polymer nanostructure is a nanoparticle comprising a payload trapped in a polymer shell. 3. A hair treatment preparation as described in claim 1, wherein the polymer nanostructure is a nanoscopic network. 4. A hair treatment preparation as described in claim 3, wherein the nanoscopic network is selected from the group consisting of a straight polymer, a branched polymer, and a highly branched polymer. 5. A hair treatment preparation as described in claims 1, 2, 3 or 4, wherein the polymeric nanostructure further comprises reactive functional groups for the hair. 6. A hair treatment preparation as described in claims 1, 2, 3 or 4, wherein the polymeric nanostructure further comprises functional groups that will react with a mordant. 7. - A hair treatment preparation as described in claims 1, 2, 3 or 4, wherein the polymeric nanostructure further comprises functional groups that will react with a cationic binding agent. 8. A hair treatment preparation as described in claims 1, 2, 3 or 4, wherein the polymer nanostructure further comprises functional groups that will react with an anionic binding agent. 9. A hair treatment preparation as described in claims 1, 2, 3 or 4, wherein the polymer nanostructure further comprises functional groups that will react with a binding agent that depends on the hydrophobic interactions or the hydrogen bond. 1 0.- A method for hair treatment which comprises: applying a hair treatment preparation, the hair treatment preparation comprising a payload in an intimate relationship with a polymer nanostructure, the polymer nanostructure being reactive to the hair or ability to be immobilized on or in the hair; and changing the conditions so that the payload and the nanostructure are attached to the hair. 1 - A method as described in claim 10, wherein the nanostructure further comprises reactive functional groups to the hair which, under the change of conditions, will be covalently bound to the hair. 12. - A method as described in claim 10, wherein the nanostructure further comprises functional groups that are electrostatically interactive with complementary groups on the surface of the hair when, under changing conditions, the ionic strength or the surfactant content It is changed by rinsing. 13. A method as described in claim 12, wherein the electrostatic interaction is selected from the group consisting of dipolar charge-charge, hydrogen bonding, hydrophobic, and dehydration interactions. 14. A method as described in claim 10, wherein the nanostructure is a polyelectrolyte, and the change in conditions is to expose the nanostructure to a polyelectrolyte from an opposite isoelectric point to form a coating complex for the treated hair 15. A method as described in claim 10, wherein the preparation of the hair treatment further comprises a surfactant and the nanostructure is in a finely divided dispersion; and the change of conditions is the rinsing of the surfactant, allowing the nanostructure to adhere to the treated hair. 16. A method as described in claim 10, wherein the nanostructure is a crosslinkable surfactant comprising functional groups that are reactive with a mordant, and changing conditions is the application of a mordant to the hair to form a coating complex on treated hair. 17. - A method as described in claim 10, wherein the nanostructure is dispersed in a medium, and the change in conditions is a change in the thermodynamic balance of the medium, causing the nanostructure to be deposited on the surface of the treated hair . 18. A method as described in claim 10, wherein the nanostructure comprises functional groups that are reactive with a mordant, and the change of conditions is the application of a mordant to the hair to form a complex that covers the hair treaty.