KR20020087984A - Nanoscopic Hair Care Products - Google Patents

Abstract

The present invention relates to hair treatment formulations comprising a payload that is reactive with hair or is closely related to polymeric nanostructures that can be immobilized on or within the hair. The nano-characteristics of the objects have three distinctive features. First, the properties imparted can be nearly permanent or semi-permanent, depending on the chemical state involved in the attachment. In the semi-permanent case, the desired effect can be removed while controlling by removal of the nano-structure by simple chemical or physical means. Second, the nanoscopic objects are small invisible. The presence of them does not impair hair feel or the like. The influence of the nano-like objects or structures can be felt to be soft and flexible. Third, the nano-technology approach is infinitely flexible and adaptable. It can be used with a large number of existing dyes, colorants, UV absorbers, fragrances and emollients for hair treatment. Also included in the present invention are methods for treating hair using the hair treatment formulations of the invention.

Description

Nanoscopic Hair Care Products

Human hair includes a proteinaceous spiral known as keratin, such as animal hair, horns, claws, skin and feathers. Proteins of this structure degrade as they are continuously exposed to sunlight, harsh chemicals (such as dyes and bleaches) and airborne contaminants. As it ages, hair follicles also stop producing essential melanin, so the hair turns gray. In order to maintain a young appearance or for fashion purposes, the beauty industry is developing hair conditioners and dyes. In addition, fragrances and UV blockers are added to the shampoo and conditioner to impart the desired properties. However, technical approaches that have been conventionally adopted to achieve these objectives have been developed by way of ad hoc.

Today's hair dyes and dyeing systems apply dye precursors to hair and then use coarse chemicals (such as oxidants) to convert these dye precursors into chromoma. In this basic approach, precursors must penetrate deep into the hair shaft and then an oxidative conversion reaction takes place. Similarly, where bright colors or shades are preferred, bleaching agents must penetrate deep into the hair to destroy the inherent melanin deposits. Repeated dyeing or bleaching with harsh chemicals tends to damage the hair considerably. Sensitive people can also cause allergic reactions when the scalp is exposed to these chemicals.

The present invention relates to the field of hair protection products.

Summary of the Invention

The present invention provides a systematic nanoscopic platform that enables a comprehensive list of hair protection products. In one embodiment, the present invention provides a technological platform for developing dyed products that do not require oxidizing agents or bleaching agents. Nano-technology scaffolding is based on a completely different premise for dyeing. The present invention provides a conditioning effect, UV blocking ability and sustained fragrance release ability in a similar manner. Nano-technology scaffolding offers advantages that cannot be achieved by other means to date.

More specifically, the present invention relates to hair treatments comprising dyes or other payloads that are closely related to the polymer nanostructures, wherein the nanostructures comprise hair-reactive functional groups or other properties (e.g., To covalently bind to hair or to be immobilized on or in the hair). The present invention describes a systematic approach, wherein a nanoscopic object or structure is formed into small spheres or particles (herein referred to as "nanospheres" or "nanoparticles") to which hair can be attached, or hair It is formed in the form of an invisible, small molecular mesh (herein referred to as a "nano macromolecular network" or "nano polymer network").

Nanospheres and nanoscopic networks are made from polymeric materials, which can be obtained or synthesized naturally. Natural species can be improved or derived using well established organic chemistry techniques. Synthetic species can be specifically designed to exhibit custom properties.

The geometry is just one example of the full spectrum of nano-technology that can be applied to the hair products industry. Various variations of the two basic ways are conceivable and are encompassed by the present invention. For example, a mixture of networks and spheres can be developed to impart one or more properties per treatment. In addition, the networks are fully crosslinked (chemically or physically) or partially crosslinked. They may be entangled networks rather than crosslinked networks. The network may further be attached to the hair, or polymer species deposited on the hair surface at scattered points, such that the molecular network resembles a collection of nanocrystalline whiskers. The spheres can be formed into microcells, where a group of surfactant molecules captures the payload, and the resulting microcrystals are deposited onto the hair or deposited onto the hair using a mordant or polymer electrolyte. Upon crosslinking.

Regardless of the geometrical feature, the nano-like feature of the developed article has three distinct characteristics. First, the properties imparted can be nearly permanent or semi-permanent, depending on the chemical state involved in the attachment. In the semi-permanent case, the desired effect can be removed while controlling by the removal of the nano-structure by simple chemical or physical means. Second, the nanoscopic objects are small invisible. The presence of them does not impair hair feel or the like. The influence of the nano-like objects or structures can be felt to be soft and flexible. Third, the nano-technology approach is infinitely flexible and adaptable. It can be used with a large number of existing dyes, colorants, UV absorbers, fragrances and emollients for hair treatment.

The invention further provides a step of applying a hair treatment formulation to the hair, wherein the hair treatment formulation comprises a payload as an intimate relationship with the polymer nanostructures, wherein the polymer nanostructures are reactive with the hair or have a hair surface. Or may be fixed therein); And changing the state so that the payload and the nanostructures are attached to the hair.

Brief description of the drawings

1 shows one embodiment of the nanoparticles of the invention and a process for the preparation of the sequestration of the payloads of dyes, fragrances, emollients, drugs, monomers and the like into the microcrystals by polymerizable surfactants, wherein The polymerizable surfactant is polymerized to form nanoparticles with specific interiors.

Detailed description of the invention

Hair treatment formulations of the invention include formulations or payloads that are permanently or semi-permanently intimately associated with the polymer nanostructures, wherein the polymer nanostructures are reactive with the hair (eg, by covalent bonds) or have a hair surface or It can be fixed inside. In one embodiment, the polymer nanostructures may comprise hair-reactive functional groups for binding or attachment of the nanostructures to the hair to be treated.

"Intimate relationship" means that the payload is surrounded, contained, chemically attached or in a permanent or semi-permanent relationship by the polymer nanostructures.

"Hair-reactive" means that the payload-containing nanostructures form covalent bonds with the hair.

As used herein, the terms “payload” and “payload formulation” collectively refer to any substance or agent that is desirable for permanent or semi-permanent attachment to human or animal hair, or for the treatment of human or animal hair. will be. It may improve the properties of the hair or impart new desirable properties to the hair. The payload is referred to herein as a pendant group. The payload may be, but is not limited to, a dye or a colorant, a pigment, an opaque agent, an aromatic, a drug, a softener, an insect repellent, an antimicrobial agent, and an antimicrobial agent. While the following disclosure is directed to certain exemplary formulations, it should be understood that other materials having desirable functions or suitable properties for hair treatment may also be included in the polymer nanostructures according to the teachings herein, which is within the scope of the present invention. do.

"Dye" means a molecule capable of absorbing wavelengths in the visible or ultraviolet region of the electromagnetic spectrum.

Nano-technology is an emerging research area where objects / structures are nano-dimensional. "Nano" means one billionth. Thus, objects of 1 nanometer to 1 micron (1 micrometer or 1000 nanometers) fall within the nano-technology range.

Nano-technology based coloring system

The ability of nano-technology is confirmed by the ability of designed products to divide engineering requirements into different parts of the system. Without the need for the colorant or precursor thereof to penetrate deep into the hair axis, the nano-objects can simply deposit onto the surface of the hair or only partially penetrate inside. Durability or reflectivity may be the result of, for example, how the nanostructured structure adheres to the hair or crosslinks between neighboring objects or through crosslinking agents. In the latter two cases, the nanoscopic objects do not need to directly bond with the hair. In all cases, nanoparticles or nanoscopic networks are only carriers for the active ingredient (eg dye). They do not necessarily have to be colored. Their primary function is twofold. First, they must provide a means of fixing themselves to the surface or shallow interior of the hair. Second, they must encapsulate an appropriate dose of dye component (for nanospheres or nanoparticles) or allow the dye component to be connected to a carrier (for nano network). Nanoparticles can take on shapes other than spherical but can perform the same function in parallel.

In direct attachment or indirect annealing, the nano-technological approach does not rely on high temperature or extreme pH or harsh chemicals, since its use would defeat the purpose of the present invention. Examples of deposition / deposition are given below. Those skilled in the art of polymer precipitation and complex formation will undoubtedly consider additional means of immobilizing nanospheres based on the teachings herein. These are included within the spirit and scope of the present invention.

The above concepts are illustrated by the following examples. First, with respect to nanospheres or nanoparticles, the payloads, for example dye molecules or aggregates thereof (collectively referred to herein as dyestuffs) are captured, ie polymer shells. Or surrounded by or contained in a matrix. The nanoparticles of the present invention may comprise a polymer shell surrounding the payload or may comprise a three dimensional polymer network enclosing the payload, both of which are referred to as "polymer shells". Alternatively, for hair dyes, some or most of the particles will comprise a blocking agent, such as a colloidal white pigment (eg titanium oxide or zinc oxide) when lighter colors / shades are preferred. Nanoparticles comprising dye materials are mixed with these bleaches or opacifiers. Once the mixed particles are deposited on the hair, the entire system exhibits the desired color / shade.

Nanospheres can be made from nontoxic, allergic polymers. Many polymers have been approved by the FDA for topical use. Among many others, silicon (silicon) and cellulose are prominent examples. Synthetic hydrocarbon-based polymer systems are equally suitable alternatives. Protein or synthetic peptides can also be used for this purpose. There is a well-established encapsulation technique for incorporating an appropriate amount of dye into the particles of controlled size distribution. There is a great deal of literature on methods and materials to achieve this goal.

However, the present invention includes a functional group for attaching to the hair or a functional group for attaching to the hair to the surface of the nanoparticles in order to permanently or semi-permanently attach the payload to the hair. Alternatively, the surface of the nanoparticles includes functional groups capable of binding to a linker molecule that binds or attaches the particles to hair. In both cases these functional groups are referred to herein as "hair-reactive functional groups".

Chemical linkage on the surface of the nanoparticles does not include molecules of the payload. The payload formulations are physically entrapped in the nanoparticles, so no chemical modification of the payload molecules is necessary. The resulting encapsulated payload formulations or nanoparticles have improved retention time inside or on the hair surface without changing the inherent properties of the payload formulation.

The payload-containing nanoparticles can be prepared according to one of known encapsulation methods (eg, interfacial polymerization, microemulsification polymerization, precipitation polymerization and diffusion). The process of preparing a multicomponent mixture and then atomizing / spraying into a drying chamber is another method. Reactive functional groups on the polymer shell provide a means for attaching the hair treating nanoparticles to human hair.

Nanoparticles of the present invention are prepared by contacting a payload with a set of monomers, oligomers, or polymers (herein referred to as "polymerizable sets"). The monomers, oligomers or polymers gather around the payload and then polymerize in the presence or absence of a crosslinking reaction to form a polymer network or polymer shell surrounding the payload. The polymerizable set of one embodiment includes at least some components that provide reactive functional groups on the surface of the final polymerizable beads that are bound to the hair to be treated.

Alternatively, the nanoparticles, optionally having a hair-reactive functional group on its surface, may polymerize the polymerizable set and then subject the payloads to suitable conditions to provide hair-reactive payload nanoparticles. Under conditions that are absorbed and captured in a polymer network or shell).

Certain monomers, oligomers or polymers useful in the preparation of the nanoparticles of the present invention include those comprising polymers in combination with amine, hydroxyl or sulfhydryl monomers or amine-, hydroxyl-, or sulfhydryl-reactive monomers or polymers. to be.

When the ionic strength or surfactant content of the medium is changed by rinsing under mild conditions, the hair-reactive functional groups capable of electrostatically interacting with complementary groups on the surface of the hair are nanospheres. It can be introduced along the main chain of the polymer constituting. Examples of interactions include charge-charge, dipolar, hydrogen bonding, hydrophobic or dehydration interactions. The nanospheres can be made of a polymer electrolyte, wherein the isoelectric point is in the alkaline pH range. These particles can be effectively precipitated or aggregated using other polymer electrolytes (linear or branched polymer binders) having acidic isoelectric points. When the hair is first exposed to the nanospheres and then again to the second polymer electrolyte fixative, the complex is formed in situ, which coats the treated hair.

Another method is to deliver the payload-containing nanoparticles in the form of microdispersions to the hair surface using a powerful surfactant formulation. Once in place, the surfactant is rinsed away, wherein the nanoparticles are strongly attached to the treated hair. One example is silicon-based nanoparticles. Such particles can easily be dispersed in a block or graft copolymer of poly (dimethylsiloxane-ethylene glycol) liquid. The latter medium can be rinsed with water since the components are water soluble, leaving insoluble nanoparticles in the form of sticky precipitates. Functionalized siloxanes can also use complex formation to further refine this precipitation principle. For example, siloxanes with carboxylate groups can be precipitated by the dual effect of removing surfactants and adding polyamines (eg, polyethyleneimine in aqueous rinse solutions). Conversely, amino-substituted siloxanes can form a crosslinked network with the nanoparticles present therein in the field by the addition of polyacids such as polyacrylic acid or polymaleic acid or copolymers thereof. .

Complex formation can be induced by the addition of polyvalent cations or anions that are reactive towards complementary charged surface groups, respectively.

The principles of thermodynamic-induced precipitation / deposition and complex formation-induced precipitation / deposition on the hair surface can equally be applied to other synthetic or natural nanostructures. For example, the payload may first be chemically bound onto a protein carrier. This protein-payload complex is dispersed in the medium and then applied to the hair. The change in thermodynamic equilibrium of this medium causes the complex to deposit on the hair surface. Thus hair is treated. Since the bonding is performed chemically outside of the hair, conventional chemical means can be used without worrying about hair damage or skin sensitivity. Protein deposition can then be achieved by a simpler, more gentle fixation reaction.

We repeatedly delegate different engineering requirements to different parts of the system. The color comes from the dye material contained in the nanoparticles. However, a controlled degree of persistence comes from the attachment methodology. The precipitation / complex formation approach can be difficult or easy to reverse react. It can be manipulated so that reversibility occurs only in the presence of certain agents. Thus, ordinary hair colds or shampoos do not desire color. For example, functionalized silicones are difficult to wash away unless certain siloxane-containing surfactants are used (eg, blocks or graft copolymers of siloxane-polyethylene glycol). Equivalently, complex or precipitate dissolution may or may not occur under similarly manipulated rinse conditions. Thus, the artificially formed hair color may continue to be preserved and, if necessary, returned.

The derived cellulosic materials can be made to function in a similar manner. Synthetic polypeptides can also be used for dye encapsulation. These cellulosic or proteinaceous surfaces can be modified to reveal various isoelectric points, and these properties can be used to control their sedimentation / aggregation / complex formation properties.

Nanospheres are only one geometric form as possible dyes or other payload carriers. Dye molecules can be attached to linear, branched or lightly crosslinked polymer carriers, and they also remain soluble or dispersible in a suitable and chemically mild liquid (aqueous or mixed aqueous). Securing the dye onto the hair is carried out via a reaction / precipitation / complex formation process on the surface of the hair via any of the methods disclosed above and numerous other methods. An example is a polymer with a dye having a tree-like structure. As long as the residual functional groups are present after the dye has been deposited on the tree, the whole can be deposited on the surface of the hair in subsequent operations (removal of surfactants, addition of precipitants, aggregation or introduction of complexing agents, etc.). have. Even after initial dye attachment, although there are no identifiable functional groups at all, the carrier can have great utility due to its ability to adhere firmly to the hair as a result of changes in the thermodynamic environment of the medium.

One group of polymers useful as the nanostructures of the present invention are dendrimers and other highly branched polymers. Dendrimers also have a high degree of symmetry. Because these polymers are branched, they are compact and good permeability (and therefore permanent) into the hair is expected. One or more different types of functional groups can be designed on dendrimers and highly branched polymers. Such functional groups can be used to attach dye molecules, alkyl or siloxane chains for softening, or other molecules of interest to the dendrimer to be a compact carrier.

Payloads comprising linear, branched or lightly crosslinked polymer carriers may be attached to the hair using either an adhesive or a cationic fixative.

Complexes using carboxyl-, phosphate-, phosphonate-, sulfate-, and sulfonate-containing polymers with alkaline earth metals with very low toxicity (eg Mg ²⁺ , Ca ²⁺ and Sr ²⁺ ) Can be mad. Thus, for example, soluble polymers containing carboxyl groups and one or more payloads (such as dye molecules or compounds that increase softening) are applied to the hair. In the next step, soluble calcium or magnesium salts are added to the hair to precipitate the polymer on and inside the hair.

In summary, the nanoscopic carrier approach provides a flexible and invisible system for dyeing hair. Unlike conventional chemical attack, the system is gentle to the hair, the color can be long lasting or can be reacted back by custom-tailored means.

Nano-technology based softeners, fragrances and UV protection treatments for hair

In a manner similar to the dyeing method described above, the nanoscopic carriers of the present invention can also be used to deposit fragrances, UV absorbers / blockers and other preferred agents onto the hair. The carriers may be in the form of particles and may simply be polymers of any structure. It is part of the present invention to use the fixing method enabled by the carriers.

Silicones and polyolefins give the hair a soft hand. They may simply be deposited on the hair as the carrier itself in the context of the present invention. Therefore, the fixing step is part of the improvement. For example, cationic silicone is used in the first rinse. This coating is then fixed in place through subsequent rinsing containing anionic silicone, resulting in a composite that forms a silicone network on the surface of the hair. In this example silicone may be replaced with charged polyolefins.

In certain cases, for example when the payload is a fragrance or a medicament, it is preferred that the payload is released slowly from the nanostructures on or inside the hair. Nanoparticles can be designed such that the payload formulation is embedded or entrapped in the polymer shell or matrix of the nanoparticles, but is also released from the nanoparticles in a long or controllable manner. The release profile is programmed using the chemical properties of the polymer network of the nanoparticles. The nanoparticles can be formulated to have almost infinite designed properties due to structural properties such as crosslink density, hydrophilic-hydrophobic balance of copolymer repeat units and stiffness / elasticity of polymer networks (eg glass transition temperature). have. In addition, abrasive nanoparticles or other nanostructures can be developed to controllably release the payload.

Furthermore, the polymer matrix may include components that respond to environmental stimuli that cause increased / reduced content release. A “smart polymer” is a polymer that can be induced to undergo a unique thermodynamic transition process by adjusting any one of numerous environmental parameters (eg, pH, temperature, ionic strength, cosolvent composition, pressure, electric field, etc.). Smart polymers, for example based on lower critical solution temperature (LCST) transitions, can stop their release when exposed to warm or hot water during cleaning. When cooled back to room temperature, sustained release resumes. Smart polymers include N-isopropyl acrylamide and acrylamide; Polyethylene glycol, di-acrylate and hydroxyethyl methacrylate; Octyl / decyl acrylate; Acrylate aromatic and urethane oligomers; Vinylsilicone and silicone acrylates; Polypropylene glycol, polyvinylmethyl ether; Polyvinylethyl 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-gelling-temperature agarose; And copolymers thereof, but is not limited thereto. If crosslinking is desired between the polymers, multifunctional compounds such as bis-acrylamide and ethoxylated trimethyl propane triacrylate and sulfonate styrene can be used. In a preferred embodiment, the smart polymer comprises polyacrylamide, substituted polyacrylamide, polyvinylmethyl ether and modified cellulose.

If it is desired that the payload is visible (e.g. the payload is a dye or UV protectant), the nanoparticles are made of an optically transparent or translucent material such that light comes into contact with the payload and then is reflected , Refracted or absorbed.

The polymerizable set can be selected to provide hydrophobic or lipophilic nanoparticles, where a wide range of bioactive compounds or drugs can be readily entrapped therein. If the particles are hydrophilic, they are readily dispersed in a stable aqueous suspension or emulsion by a surfactant, which can subsequently be easily washed off without affecting the performance of the payload formulations therein. The inherent thermodynamic compatibility of the formulations and the polymer shell or matrix material can increase the loading level per particle.

The following examples are intended to illustrate some but not all of the concepts disclosed herein and are by no means limiting thereof. Those skilled in the art will appreciate that other ideas of different examples or different ideas of the above description can be combined to form other possible hair treatment methods.

Example 1

Using known methods, one or more identical or different dye molecules are covalently bonded to an amine-containing polymer or oligomer, such as poly (ethyleneimine), poly (allylamine hydrochloride), or poly (lysine). (Oligomers or polymers of arginine will show similar behavior). The hair is moistened with a solution containing the polymer or oligomer and dye molecules (polymeric or oligomeric dye) attached thereto. In some cases it may be necessary to rinse out excess material. To set or cure the amine-containing polymer, the hair is then exposed to a polymer containing carboxyl, sulfate, sulfonate, phosphate or phosphonate residues. Examples of such polymers include DNA, poly (acrylic acid), poly (itaconic acid), poly (maleic anhydride), copolymers containing maleic anhydride units, polymers with -C ₆ H ₅ COOH groups, poly (methacrylic acid ), Or poly (styrene sulfonate, sodium salt). The excess material is then rinsed off. The electrostatic interaction causes the two polymers to stick together, resulting in a very low solubility of the composite.

This formulation and all other formulations of the present invention additionally include fragrances, wetting agents, oxidizing agents, antioxidants, opacifying agents, thickeners, reducing agents, antifoaming agents, surfactants (anionic, cationic, nonionic, amphoteric, amphoteric surfactants). Or mixtures thereof), binders, drugs, dispersants, conditioners, limited amounts of organic solvents, antibacterial agents, preservatives, and the like, and mixtures thereof.

Example 2

One or more dye molecules may be selected from the group consisting of carboxyl-containing polymers or oligomers, for example poly (acrylic acid), poly (itaconic acid), poly (maleic anhydride), copolymers containing maleic anhydride units, -C ₆ H ₅ COOH Covalently bonded to the polymer having a group, poly (methacrylic acid). The hair is moistened with a solution containing the polymer or oligomeric dye. Rinse out excess material. In order to set up this polymer, the hair is treated with a poly cation (polymer or oligomer), for example poly (ethyleneimine), poly (allylamine hydrochloride), poly (lysine), poly (arginine), or poly (diallyldimethyl). Ammonium chloride).

Example 3

The hair is exposed to a solution containing a polymeric or oligomeric dye (poly cation) as described in Example 1. It may be necessary to rinse the hair after the first treatment. The hair is then exposed to a solution comprising at least one polymeric or oligomeric dye (poly anion) as disclosed in Example 2 and rinsed off.

Example 4

Alkyl chains defined herein as linear or branched molecules comprising predominantly C, CH, CH ₂ and CH ₃ units include amine-containing polymers or oligomers such as poly (ethyleneimine), poly (allylamine hydrochloride) or To poly (lysine). Linear or branched siloxane chains may also be attached to the amine-containing polymer or oligomer. One or more identical or different dye molecules may also be added to the polymer by known methods. The hair can then be exposed to this poly cation and the excess reactant can be rinsed off. The hair is then exposed to poly anions, which may have alkyl chains, siloxane chains or dyes bound thereto. One possible polyanion, which may act as a softener, is a vinyl ether of maleic anhydride and CH ₂ = CHO (CH ₂ ) _n CH ₃ , where n is at least 2 and preferably is greater than 4. Of copolymers.

Example 5

The amine-containing dye is reacted with benzoquinone, naphthoquinone, anthraquinone or derivatives thereof to form a polymeric or oligomeric dye. Three of many possible additions are disclosed below.

Example 6

The amine-containing dye may be prepared by one or more reactive groups such as acid chloride (-C (O) Cl), sulfonyl chloride (-SO ₂ Cl), vinyl sulfone (-SO ₂ CH = CH ₂ ), or cyanuric acid Active derivatives of chlorides]. Examples of each of these four possible linking species for dyes and polymers are disclosed below. Other amine-reactive functional groups (eg epoxides or acid anhydrides) that may appear on the reactive dye molecules may also be used.

Example 7

Polymer electrolytes having pendant groups that improve the properties of the hair or impart new and desirable properties are deposited on the hair. An oppositely charged polymer electrolyte (which may also have one or more pendant groups that improves the properties of the hair or imparts new and desirable properties) is added to the hair, where it is condensed and fixed with the first polymer.

Example 8

Polymers or oligomers having one or more pendant groups, which improve one or more properties of the hair or impart one or more new and desirable properties, are deposited on the hair. Excess reactant may be rinsed away from the hair. The pressure sensitive adhesive we defined as the species containing the metal atom of 2 or more oxidation numbers is added to the deposited polymer, and the polymer is fixed in this way.

Example 9

The adhesive is deposited on the hair. Excess reactant may be rinsed away from the hair. Excess reactant may be rinsed away from the hair. A polymer or oligomer comprising at least one pendant group that improves one or more properties of the hair or imparts one or more new and desirable properties is deposited on the hair. The pressure-sensitive adhesive forms a complex with the polymer to fix the polymer.

Example 10

One or more dye molecules are covalently bonded to a polymer or oligomer of ethyleneimine (eg triethylenetetraamine) (see Scheme 1). In addition to ethyleneimine, any polymer with free amine groups can be used, for example poly (allylamine hydrochloride) and poly (lysine). Additional starting materials include small molecules with multiple amines (eg ethylenediamine) and macropolymers of ethyleneimine (branched or linear). It is known that amines react with numerous dyes. For example, US Pat. No. 6,203,578 discloses the reaction of amines with benzoquinones, naphthoquinones and anthraquinones and some derivatives thereof, and also with dyes having amine-reactive groups. Other amine-reactive groups found on commercially available reactive dyes include vinyl sulfone and cyanuric chloride based residues.

After the dye is introduced into the polymer, a group capable of chelation of the metal is introduced. One of the possible ways to do this is by reaction of the amines remaining on the molecule with esters of α-chloro, α-bromo, or α-iodoacetic acid. The ester is removed after addition of the molecule to the polymer as a protecting group. Thus, the triethylenetetraamine-dye adduct is reacted with esters of α-haloacetic acid [ClCH ₂ C (O) OR, BrCH ₂ C (O) OR, ICH ₂ C (O) OR] (Scheme 1 Reference). The ester group is then removed by known methods (deprotection) to obtain a metal-chelated polymeric dye. Introduction of protected metal chelators and methods of deprotection thereof are known (see US Pat. No. 6,080,785). In a preferred embodiment, the ester of α-haloacetic acid is a methyl ester. ClCH ₂ C (O) OCH _3, for example, is a cheap chemical that is available in large quantities. It should be noted that the carboxymethyl group can be introduced by reaction of formaldehyde with hydrogen cyanide and amine. Addition of these two reactants to ethylenediamine (Strecker synthesis) yields ethylenediaminetetraacetic acid (EDTA) (see Beyer and Walter in Handbook of Organic Chemistry, Prentice Hall, 1996). It should also be noted that the chelated polymeric dyes shown in Scheme 1 are close analogs of EDTA and nitrilotriacetic acid [N (CH ₂ COOH) ₃ ], which are effective metal chelating agents.

Example 11

This example (see Scheme 2) discloses two important features of the chemical reactions disclosed herein. First is the ability to fix the polymeric dye using an adhesive using groups capable of chelating metals. The second is to extract metal atoms from the polymer using EDTA or NTA (they reverse the initial dyeing process). The exact geometry of the metal-polymer composite will vary depending on the metal. Intramolecular (initiated in Scheme 2) and intermolecular crosslinks between polymeric or oligomeric dye molecules are envisaged. As with all the methods disclosed herein, it is possible to control the penetration depth of the dye into the fiber in part by the molecular size. One or more surfactants or other additives may also be present in this formulation or other formulations (see Example 1).

Example 12

In this example (see Scheme 3), a polymeric dye is prepared first, and then a softener is added to the oligomeric dye or polymeric dye and a chelating group is introduced. Although siloxanes and alkyl chains are expected to act as softeners, another important property of these long chains is to reduce the solubility of the polymeric or oligomeric dyes. Thus, when rinsing and removing the surfactant in the formulation, the polymeric dye may be deposited on the hair. The addition of metal (Scheme 4) will increase durability. As in Example 11, the addition process of the metal is reversible using EDTA and NTA (see Scheme 5). Scheme 3 shows the introduction of alkyl or siloxane chains with epoxide groups. Although epoxide chemistry is the preferred embodiment of the spirit of this example, other possible reactive groups that can be used to introduce long chain alkyl or siloxane groups by known means include anhydrides, acid chlorides, carboxylic acids, sulfonyl chlorides (sulfones). To prepare an amide), and the like.

Example 13

Various molecules that impart desirable properties to the hair or the formulation can be included in the reactive monomers, for example in the reaction between amines and acid chlorides (see Schemes 6 and 7). It will later be possible to polymerize these monomers into polymers with the desired properties, where the level or concentration of certain groups is carefully controlled.

Example 14

N-isopropylacrylamide (NIPA) (see Scheme 7b) will be a thermally sensitive polymer. In other words, polymers having NIPA (or similar monomers) have higher water solubility at low temperatures than at high temperatures. Thus, it is possible to design polymers that settle out when rinsing hair in warm or hot water.

Example 15

In this embodiment (see FIG. 1), a set of molecules (which may be dyes, fragrances, emollients, drugs, monomers or other molecules that improve hair properties or impart new desirable properties) is emulsified with a polymerizable surfactant. Let's do it. The resulting microcrystals are then polymerized to form nanoparticles, which are applicable to the hair and then have an adhesive or polymer having a charge opposite to that of the surfactant's head group, depending on the surfactant's head group. Set using electrolyte. The surfactant can be designed to be an analog of EDTA or NTA, in particular to be effective in chelation of metal ions.

Example 16

Derivatives of itaconic anhydride and maleic anhydride can be used as polymerizable surfactants (see Scheme 8). To prepare these surfactants, a fatty alcohol (or amine: not disclosed) can be reacted with the anhydride to produce a surfactant. Carboxyl groups are head groups. In the deprotonation state it imparts a high degree of solubility to the alkyl chain of the surfactant. This hair group can be precipitated using an appropriate adhesive. In certain cases, it may be desirable to add ethylene oxide units to the carboxyl groups of the polymerizable surfactants to produce anionic surfactants (the lower four structures of Scheme 8). It is not intended that the present invention be limited to the polymerizable surfactants disclosed herein. Numerous other polymerizable surfactants have been developed and may be applicable to the situations disclosed herein. Several documents demonstrating the synthesis processes, uses and properties of these materials are described in Stahler, et al., Langmuir 1998, 14, 4765-4775; Stahler, et al., Langmuir 1999, 15, 7565-7576; Kline, Langmuir 1999, 15, 2726-2732; Soula and Guyot, Langmuir 1999, 15,7956-7962; Shen, et al., Langmuir 2000, 16, 9907-9911; Viitala, et al., Langmuir 2000, 16, 4953-4961; Jung, et al., Langmuir 2000, 16, 4185-4195; Gargallo, et al., Langmuir 1998, 14, 5314-5316; Liu, et al., Langmuir 1997, 13, 4988-4994; Xu, et al., Langmuir 1999, 15, 4812-4819.

Example 17

A surfactant is prepared by reacting two or more amine groups (these amines may be pendant, or the spacing between the amines may be three or more carbons, but in a preferred embodiment is two) with one or more alkyl or siloxane chains. (See Scheme 9). The amines are then derivatized with carboxymethyl groups to prepare surfactants capable of chelating metals. Thus, a set of dyes, fragrances, emollients, drugs, or other small molecules or polymers can be introduced into the solution together with the surfactant and the resulting microcrystals can be precipitated onto the hair using a suitable tackifier. . A particularly useful embodiment of the present invention is the reaction of ethylenediamine with an oxirane ring (epoxide) on an alkyl or siloxane chain. The carboxymethyl group is then introduced into the resulting molecule. One or more of the carboxyl or hydroxyl groups can be functionalized with ethylene oxide units, which is generally done for nonionic surfactants.

Example 18

Numerous molecules are added to the poly (acryloyl chloride), which acts as a scaffold, which imparts desirable properties to the polymer. See Scheme 10 for examples of some of the many possible species (amines and alcohols in the preferred embodiments). The species can react with poly (acryloyl chloride) to form functionalized polymers with tailoring properties.

Example 19

Numerous molecules are added to the poly (acrylic acid anhydride), which acts as a scaffold, which imparts desirable properties to the polymer. See Scheme 11 for examples of some of the many possible species (amines and alcohols in the preferred embodiments). The species can react with poly (acrylic acid anhydride) to form functionalized polymers with tailoring properties. Copolymers of maleic anhydride are expected to react similarly to the polymers disclosed in Scheme 11.

Example 20

Branched alkyl chains are also possible, but fatty amines of the general formula CH ₃ (CH ₂ ) _n NH ₂ are derivatized using carboxymethyl groups according to the methods disclosed herein to form CH ₃ (CH ₂ ) _n N (CH ₂ COOH A surfactant of ₂ ) is obtained. One or two carboxyl groups of this surfactant can be deprotonated. These surfactants can be used to make small sets of molecules soluble (they can include dyes, fragrances, emollients, drugs, monomers, and the like). The resulting microcrystals are then precipitated on the hair using an adhesive. Since these surfactants can be made insoluble by chelating with a suitable metal, they can generally be useful in all cases where it is desirable to remove the surfactants from the formulation. As is the case with nonionic surfactants, some ethylene oxide units can be added to this surfactant. It is expected that tackifiers that crosslink with chelating surfactants will have an intermediate effect in limiting the release of small molecules trapped inside the microcrystals by these surfactants. Thus, the capture and immobilization of small molecules by this method can provide an effective means to time-relaease certain small molecules (eg, fragrances and drugs). Surfactants with different chelating ability (see examples of Example 17 and Scheme 9) can be combined to finely control the properties of the timely release formulation.

Example 21

One or more sets of surfactants are used to introduce one or more insoluble or highly insoluble species (including polymers and oligomers) into the aqueous solution. After rinsing off the material, insoluble or nearly insoluble species are deposited on the hair.

Example 22

Known dye molecules (including but not limited to acid dyes, direct dyes, reactive dyes, tackifier dyes, sulfur dyes, and vat dyes) are reacted with the polymers and the polymers are subjected to any of the methods described herein. One method is used to deposit onto the hair.

Example 23

The tackifier dye is bound to a polymer or oligomer and the material is deposited on the hair. Addition of a tackifier causes crosslinking of the polymer molecules via tackifier dye pendant groups.

Example 24

Dye molecules, emollients, polymer electrolyte chains, carboxymethyl groups or other species that can impart desirable properties to hair are used to derivatize proteins that function as scaffolds. The resulting protein complexes are then precipitated on the hair and immobilized to some extent using the methods described herein (eg, polymer electrolytes or tackifiers).

Claims (18)

A hair treatment formulation comprising a payload that is reactive with hair or is closely related to polymeric nanostructures that can be immobilized on or within the hair. The hair treatment formulation of claim 1 wherein said polymeric nanostructure is a nanoparticle comprising said payload entrapped in a polymer shell. The hair treatment formulation of claim 1 wherein the polymeric nanostructure is a nanoscopic network. The hair treatment formulation of claim 3 wherein said nanoscopic network is selected from the group consisting of linear polymers, branched polymers, and highly branched polymers. 5. The hair treatment formulation of claim 1, wherein the polymeric nanostructure further comprises hair-reactive functional groups. 5. The hair treatment formulation of claim 1, wherein the polymeric nanostructure further comprises functional groups that react with a mordant. 5. The hair treatment formulation of claim 1, wherein the polymeric nanostructure further comprises functional groups that react with a cationic fixing agent. 5. The hair treatment formulation of claim 1 wherein the polymeric nanostructure further comprises functional groups that react with the anionic binder. 5. The hair treatment formulation of claim 1, wherein the polymeric nanostructure further comprises functional groups that react with a fixing agent that depends on hydrophobic interaction or hydrogen bonding. Applying to the hair a hair treatment formulation comprising a payload that is reactive with the hair or is closely related to the polymeric nanostructures that can be immobilized on or within the hair, and Varying conditions such that the payload and nanostructures adhere to the hair. The method of claim 10, wherein the nanostructure further comprises hair-reactive functional groups that covalently bond to the hair in varying conditions. The method of claim 10, wherein the nanostructure further comprises functional groups that electrostatically interact with complementary groups on the surface of the hair when the ionic strength or surfactant content is changed by rinsing in a changed condition. Way. The method of claim 12, wherein the electrostatic interaction is selected from the group consisting of charge-charge, dipolar, hydrogen bonding, hydrophobic or dehydration interactions. The method of claim 10, wherein the nanostructure is a polymer electrolyte and the change in conditions exposes the nanostructure to a polymer electrolyte having opposite isoelectric points to form a composite coating the treated hair. The method of claim 10, wherein the hair treatment formulation further comprises a surfactant, the nanostructures are in a microdispersion state, and wherein the change in conditions rinses off the surfactant and deposits the nanostructures on the treated hair. Attaching. The method of claim 10, wherein the nanostructure is a crosslinkable surfactant comprising functional groups reactive with the adhesive, wherein a change in the conditions is applied to the hair to form a composite coating the treated hair. How to do. The method of claim 10, wherein the nanostructures are dispersed in a medium and the change in condition is a change in thermodynamic equilibrium of the medium that causes the nanostructures to deposit on the surface of the treated hair. The method of claim 10, wherein the nanostructure comprises functional groups that are reactive with the pressure sensitive adhesive, and wherein the change in the condition applies an adhesive to the hair to form a composite that coats the treated hair.