A colored composition for topical application, which comprises, a hydrophilic continuous phase comprising bismuth vanadate as a coloring agent.

1. Field of the Invention
The present invention relates to cosmetic compositions containing a yellow pigment of intense, saturated color which does not generate free radicals. More particularly, the invention relates to make-up compositions for the skin both of the human face and body, the lips and superficial body growths such as the nails, the eyelashes, the eyebrows and the hair.
2. Description of the Background
Make-up compositions such as foundations, face powders, eyeshadows, lipsticks, concealers, blushers, mascaras, eyeliners, lip pencils, eye pencils and nail varnishes and make-up products for the body consist of a suitable vehicle and coloring agents of various natures, intended to impart to these compositions a certain color, before and/or after applying them to the skin, the lips and/or the superficial body growths.
These coloring agents can be lakes, inorganic or organic pigments and/or pearlescent pigments, and alternatively dyes. In the range of yellow pigments, cosmeticians have available pigments of inorganic origin such as yellow iron oxides and pigments of organic origin. Inorganic pigments, and in particular inorganic oxides, have the advantage of being relatively stable, but have the drawback of imparting rather dull, pale colors to the material being colored. Organic lakes have the advantage of imparting lively colors to the compositions, but are mostly unstable with respect to light, temperature or pH. Some of these lacquers also have the drawback of leaving unsightly marks on the skin or the nails after application, by running of the dye. As for pearlescent pigments, they allow varied, but never intense, colors to be obtained, with iridescent effects, but these are usually fairly weak.
Moreover, certain coloring agents have the drawback of generating free radicals in make-up formulations, which modify the color of the applied make-up and the stability of the compositions, and then on the skin after application, which promotes ageing of the skin such as the appearance of wrinkles, fine lines and yellowing of the skin. In particular, yellow iron oxides often promote the oxidation of polyunsaturated oils such as plant oils, which limits the range of compositions. Coloring agents which exhibit this drawback include, in particular, brown-yellow iron oxide mixtures sold under the trade name xe2x80x9cSicovit Yellow 10 E 172xe2x80x9d by BASF, for example, pigments of organic origin and the aluminium lake of tartrazine on alumina (20/80) (CI: 19140, CI:77002) sold under the trade name FD and C Yellow 5 by Warner Jenkinson.
At the present time, in order to overcome this problem, antioxidants such as ethoxyquine, for example, are used. Unfortunately, it is often difficult to find an antioxidant which is 100% effective given the multitude of ingredients present in make-up compositions. Furthermore, the antioxidants themselves often generate degradation products including the oxidation of the antioxidant which can cause interference.
Accordingly, one object of the present invention is to provide, for use in a cosmetic composition, a specific yellow pigment of intense, saturated color, which is stable and which has the advantage of generating far fewer free radicals than the conventional pigments employed in particular for imparting a yellow color to cosmetic compositions.
Briefly, this object and other objects of the present invention as hereinafter will become more readily apparent can be attained by a colored composition for topical application, which comprises a hydrophilic continuous phase comprising bismuth vanadate as a coloring agent.
Surprisingly, it has now been found that bismuth vanadate (BiVO4) limits the production of free radicals, since it has the property of generating very few free radicals, and thus permits a limitation on the amounts of antioxidants which are used in compositions. In addition, the pigment of the invention makes it possible to achieve an intense coloration of a composition containing the colorant and, in particular, a very bright, intense lemon-yellow color of very great color purity, which does not run on keratin substances and is stable with respect to light, pH and temperature. In addition, the pigment broadens the color range which can be achieved in the cosmetics field and participates in the creation of vivid greens by mixing bright oranges with blues. Furthermore, the pigment reduces the amount of pigment which needs to be incorporated in a cosmetic composition in comparison to the amounts of conventional pigment needed in conventional prior art cosmetic formulations, thus making it possible to preserve the sheen of the composition, as well as that of the film deposited, which is highly desired for nail varnishes and make-up products for the lips.
More specifically, an aspect of the present invention is a colored composition for topical application, which contains a hydrophilic continuous phase and more especially a cosmetic make-up composition containing a hydrophilic continuous phase containing bismuth vanadate (BiVO4) as coloring agent and more specifically, as a pigment. This pigment can be in a pure form or deposited on substrate. In particular, this pigment in pure form is sold by BASF under the name Sicopal Gelb L1100.
The manufacture of this pigment is, in particular, described in EP 0 551 637 and EP 0 632 110 of BASF. The pigment has a particle size of about 0.3 xcexcm.
Bismuth vanadate can crystallize in various forms and in so doing expresses different yellow tones. Thus, the monoclinic lattice form, fergusonite, is a bright yellow having a density of 6.959; the tetragonal lattice form, zircon, is pale yellow having a density of 6.127; the tetragonal lattice form, scheelite, is bright yellow having a density of 6.929 and the orthorhombic lattice form, pulcherite, is pale yellow.
The property of bismuth vanadate of not generating free radicals can be demonstrated by the ethylene test described in the article xe2x80x9cEthylene formation from methionine as a method to evaluate oxygen free radical scavenging and metal inactivation by cosmeticsxe2x80x9d by J.-B. Galey, F. Millecamps and Q.-L. Nguyen, International Journal of Cosmetic Science, 13, 65-78, 1991.
An object of the invention is to compare the behavior of the inorganic pigment of the invention with the behavior of conventional pigments in a photo-oxidation test using iron as free-radical generator.
In the ethylene test measurement procedure, the FeCl3 used to activate the production of free radicals was replaced with each of the pigments to be tested. The results are shown in the table below.
The control of FeCl3 at 0.005% is on average 9000 (arbitrary unitxe2x80x94relative measurement).
The greater the amount of ethylene, the greater the production of free radicals.
Yellow iron oxide (CI:77492) is not inert. At low dose, it activates up to a certain concentration at which the protective effect of the pigment comes into play, whereas for bismuth vanadate, the degree of ethylene produced is very low and does not change as a function of the concentration. This pigment may thus be used advantageously in make-up compositions and colored antisun compositions intended in particular for protecting the skin and/or mucous membranes such as the lips, without generating free radicals and thus limiting the degradation of the skin and/or the mucous membranes.
Compared with the yellow iron oxides commonly used in cosmetics, the pigment of the invention also has the advantage of having a higher saturation of color, i.e., more vivid and of a more intense color, which makes it possible, in particular, to use in smaller amount of pigment, for an equivalent color yield.
The calorimetric parameters of bismuth vanadate sold by BASF under the trade name Sicopal Gelb L1100 relative to those of yellow iron oxide (CI:77492) are given below.
The higher the value of c, the more saturated the color. Bismuth vanadate has a more vivid, more intense color than iron oxide, thus allowing a cosmetic composition to be strongly colored with a small amount of pigment. Thus, the rheological problems (difficulty of application, non-uniform make-up effect) associated with an excessively large amount of pigment in the compositions of the prior art are largely attenuated.
Compared with an organic lake, bismuth vanadate gives better coverage for an equal amount of pigment.
The pigment of the invention can be incorporated into a cosmetic composition containing a hydrophilic continuous phase, in particular a make-up composition, in an amount which can readily be determined by one of skill in the art on the basis of the skilled artisan""s general knowledge. The amount of pigment ranges in particular from 0.01 to 50% by weight relative to the weight of the composition, preferably an amount ranging from 0.5 to 25% by weight. Even at high concentration, the pigment of the invention does not destructure the composition.
The composition of the invention can be in the form of a product to be applied to the lips, the eyes, the skin and/or the superficial body growths of human beings. It, therefore, contains a cosmetically acceptable medium, i.e. a medium which is compatible with all keratin substances, such as the skin both of the human body and face, the nails, the hair, the eyelashes and the eyebrows.
In the present invention, the medium contains a hydrophilic continuous phase, i.e. a mixture of one or more hydrophilic substances which are at least partly miscible with or soluble in water, which can be liquid, pasty or solid at room temperature (25xc2x0 C. in general). In particular, the medium comprises or can be in the form of a suspension, dispersion or solution in water or an aqueous-alcoholic medium, which is optionally thickened, or even gelled; an oil-in-water (O/W) emulsion or a multiple (W/O/W) emulsion, in the form of a cream, a paste or even a solid; an aqueous or aqueous-alcoholic gel or a hydrophilic foam; an emulsified gel; a dispersion of vesicles, in particular of ionic or nonionic lipids; a two-phase or multiphase lotion; a spray. A person skilled in the art can select the appropriate pharmaceutical form, as well as the method for preparing it, on the basis of knowledge which the skilled artisan has, given, on the one hand, the nature of the constituents used, in particular their solubility in the support, and, on the other hand, the application envisaged for the composition.
The composition thus comprises a hydrophilic continuous phase which may contain water or a mixture of water and at least one hydrophilic organic solvent such as an alcohol and in particular a linear or branched lower monoalcohol containing from 2 to 5 carbon atoms such as ethanol or propanol, a polyol such as glycerol, diglycerol, propylene glycol, sorbitol, panthenol, pentylene glycol or polyethylene glycol. This continuous phase can represent from 0.5 to 99.99% of the total weight of the composition. In addition, it can contain hydrophilic C2-C4-aldehydes and C2 ethers.
When the composition of the invention is in the form of an emulsion, it can also optionally comprise a surfactant, preferably in an amount of from 0 to 30% and in particular from 0.01 to 30% by weight relative to the total weight of the composition.
Depending on the application envisaged, the composition can also comprise a film-forming polymer such as a polyurethane, a polyacrylic, a polyurethane and a polyacrylic hybrid, a polyester, nitrocellulose, a hydrocarbon-based resin and/or a silicone resin. This is especially the case when it is desired to prepare a composition such as a water-based nail varnish, a mascara, an eyeliner or a hair composition such as a lacquer. The polymers can be dissolved or dispersed in the cosmetically acceptable medium and optionally combined with a coalescing agent and/or plasticizer.
The composition of the invention may also comprise a fatty phase, in particular a fatty phase consisting of fatty substances which are liquid at room temperature (25xc2x0 C. in general) and/or fatty substances which are solid at room temperature, such as waxes, pasty fatty substances, gums and mixtures thereof. This fatty phase may also contain lipophilic organic solvents.
Suitable fatty substances which are liquid at room temperature, often referred to as oils, include hydrocarbon-based oils of animal origin such as perhydrosqualene; hydrocarbon-based plant oils such as liquid triglycerides of fatty acids of 4 to 10 carbon atoms, for instance, heptanoic or octanoic acid triglycerides, or alternatively sunflower oil, corn oil, soybean oil, grapeseed oil, sesame oil, apricot oil, macadamia oil, castor oil, avocado oil, caprylic/capric acid triglycerides, jojoba oil, karite butter; linear or branched hydrocarbons of mineral or synthetic origin such as liquid paraffins and derivatives thereof, petroleum jelly, polydecenes, hydrogenated polyisobutene such as parleam; synthetic esters and ethers, in particular of fatty acids such as, for example, purcellin oil, isopropyl myristate, 2-ethylhexyl palmitate, 2-octyldodecyl stearate, 2-octyldodecyl erucate, isostearyl isostearate; hydroxylated esters such as isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate, heptanoates, octanoates and decanoates of fatty alcohols; polyol esters such as propylene glycol dioctanoate, neopentyl glycol diheptanoate, diethylene glycol diisononanoate; and pentaerythritol esters; fatty alcohols containing from 12 to 26 carbon atoms such as octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol; partially hydrocarbon-based fluoro oils and/or fluorosilicone oils; silicone oils such as volatile or non-volatile, linear or cyclic polymethylsiloxanes (PDMS) which are liquid or pasty at room temperature such as cyclomethicones and dimethicones, optionally comprising a phenyl group, for instance phenyl trimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenylmethyldimethyltrisiloxanes, diphenyl dimethicones, phenyl dimethicones, polymethylphenyl siloxanes; mixtures thereof.
These oils are usually present in an amount of 0 to 90%, preferably from 0 to 85% by weight relative to the total weight of the lipophilic phase.
The lipophilic phase of the composition of the invention may also comprise one or more cosmetically acceptable organic solvents, with the term acceptable relating to the properties of tolerance, toxicology and feel. These solvents are present in an amount of 0 to 60%, preferably 0 to 30% of the total weight of the composition and can be selected from the group consisting of lipophilic organic solvents, amphiphilic organic solvents and mixtures thereof. Suitable solvents which can be used in the composition of the invention include acetic acid esters such as methyl, ethyl, butyl, amyl or 2-methoxyethyl acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, isopropyl acetate; hydrocarbons such as toluene, xylene, p-cylene, hexane or heptane; aldehydes containing from 5 to 10 carbon atoms; ethers containing at least 3 carbon atoms; and mixtures thereof.
The composition of the invention may further comprise any ingredient conventionally used in the fields under consideration, and more especially in cosmetics and dermatology. These ingredients include, in particular, preserving agents, aqueousphase thickeners (polysaccharide biopolymers, synthetic polymers) and fatty-phase thickeners, fragrances, hydrophilic and lipophilic active agents and mixtures thereof. The amounts of these various ingredients are those conventionally used in the fields under consideration, and, for example, from 0.01 to 20% of the total weight of the composition. The nature of these ingredients and their amounts must be compatible with the production of stable, thickened, glossy compositions of the invention.
The composition of the invention may also comprise an additional particulate phase which can be present in an amount of 0 to 30% of the total weight of the composition, preferably from 0.05 to 20%, and which can comprise pigments and/or pearlescent agents and/or fillers used in cosmetic compositions.
The term xe2x80x9cpigmentsxe2x80x9d should be understood as meaning white or colored, inorganic or organic particles which are insoluble in the liquid hydrophilic phase and which are intended to color and/or opacity the composition. The term xe2x80x9cfillersxe2x80x9d should be understood as meaning colorless or white, inorganic or synthetic, lamellar or non-lamellar particles. The term xe2x80x9cpearlescent agentsxe2x80x9d should be understood as meaning iridescent particles, in particular produced by certain molluscs in their shell or synthesized pearlescent particles. These fillers and pearlescent agents serve in particular to modify the texture of the composition.
Pigments other than bismuth vanadate can be present in the composition in an amount of 0 to 25% of the weight of the final composition, and preferably in an amount of 2 to 15%. Suitable inorganic pigments include titanium oxide, zirconium oxide and cerium oxide, as well as zinc oxide, iron oxide, chromium oxide and ferric blue. Suitable organic pigments which can be used include carbon black and barium, strontium, calcium or aluminium lakes or alternatively the diketopyrrolopyrroles (DPP) described in EP 0 542 669, EP 0 787 730, EP 0 787 731 and WO 96/08537.
The pearlescent agents can be present in the composition in an amount of 0 to 20% of the total weight of the composition, preferably an amount ranging from 1 to 15%. Suitable pearlescent agents include mica coated with titanium oxide, with iron oxide, with natural pigment or with bismuth oxychloride, such as colored titanium mica.
The filler component is normally present in an amount of 0 to 30% of the total weight of the composition, preferably 0.5 to 15%. Suitable fillers include talc, zinc stearate, mica, kaolin, Nylon (in particular orgasol) powder, polyethylene powder, Teflon, starch, boron nitride, copolymer microspheres such as Expancel (Nobel Industrie), Polytrap (Dow Coming) and silicone resin microbeads (Tospearl from Toshiba, for example).
The composition of the invention advantageously comprises a solid or pasty fatty phase containing one or more gums and/or one or more waxes. The waxes include hydrocarbon-based waxes, fluoro waxes and/or silicone waxes and can be of plant, mineral, animal and/or synthetic origin. In particular, the waxes have a melting point of greater than 25xc2x0 C., preferably greater than 45xc2x0 C.
Suitable waxes include beeswax, camauba wax or candelilla wax, paraffin, microcrystalline waxes, ceresin or ozokerite; synthetic waxes such as polyethylene waxes and Fischer-Tropsch waxes, silicone waxes such as alkyl- or alkoxydimethicones containing from 16 to 45 carbon atoms.
The gums are generally high molecular weight PDMSs or cellulose gums or polysaccharides and the pasty substances are generally hydrocarbon-based compounds such as lanolins and derivatives thereof or alternatively PDMSS.
The nature and amount of the solid substances depend on the desired mechanical properties and textures. As a guide, the composition can contain from 0 to 50% by weight of waxes relative to the total weight of the composition, preferably from 1 to 30%.
This composition can have the appearance of a cream, salve, fluid lotion, soft paste with a dynamic viscosity at 25xc2x0 C. ranging from 1 to 40 Pa.s, ointment or a solid which is poured or cast and in particular as a stick or a dish.
The composition of the invention can be used advantageously for making-up the skin and/or the lips and/or the superficial body growths depending on the nature of the constituents used. In particular, this composition can be a tube of lipstick or a lip lacquer, a lip gloss which can be used just as it is or for application to a film of lipstick in particular to increase its gloss and/or its color (known as a topcoat). It can also be a solid foundation, a concealer product or a product for the contours of the eyes, an eyeliner, a mascara, an eyeshadow, a blusher or a nail varnish. These compositions can also contain cosmetic or dermatological active agents, in particular in order to give the composition a care or treating appearance. Thus, the composition can contain vitamins and other lipophilic active agents such as lanolin or a UVA screening agent or a hydrophilic active agent such as a hydrating agent such as glycerol.
An aspect of the invention is the use of the above composition as a cosmetic to care for and/or make-up and/or protect the skin and/or the lips and/or the superficial body growths of human beings, as well as the use of this composition for the preparation of an ointment intended to treat and/or protect the skin and/or the lips and/or the superficial body growths. Another aspect of the invention is a cosmetic treatment process for the skin and/or the lips and/or the superficial body growths, which consists in applying the composition defined above to the skin and/or the lips and/or the superficial body growths.
In particular, a preferred aspect of the invention is a lip product, a foundation or a nail varnish.
The composition of the invention can be obtained by a process of preparation conventionally used in cosmetics or dermatology.
A further aspect of the invention is the use, in a colored cosmetic composition or for the manufacture of a colored dermatological composition, of a coloring agent as described above, in order to protect the skin and/or the lips and/or the superficial body growths against the harmful effects of free radicals and/or to combat the signs of ageing, in particular photo-induced ageing, of the skin. These signs of ageing are, in particular, wrinkles, fine lines and flaccid and/or yellowed skin.
Still a further aspect of the invention is a process for the cosmetic protection of the skin and/or the lips and/or the superficial body growths against the harmful effects of free radicals and/or for combating the signs of photo-induced ageing of the skin, which consists in applying the composition as defined above to the skin and/or the lips and/or the superficial body growths,

Cosmetic composition containing a hydrophilic continuous phase containing bismuth vanadate


Method and apparatus for integrating distributed shared services system which integrates web based applications with each other and with other centralized application to provide a single sign-on approach for authentication and authorization services for distributed web sites requiring no access time back to the authentication/authorization server is provided.

1. Field of the Invention
The present invention relates to method and apparatus for integrating distributed shared services system. In particular, the present invention relates to method and apparatus for integrating web based applications with each other and with other centralized application which provides a single sign-on approach for authentication and authorization services for distributed web sites and which requires no access time back to the authentication/authorization server.
2. Description of the Related Art
The rising use of the world wide web (the web) for access and distribution of information has prompted many service providers and retailers alike to adopt the internet as a principal information portal for customers and clients. For example, traditional brick and mortar companies are creating and providing their web sites to interface and interact with their customers. This approach is beneficial to both parties alike for many reasons. Some of these reasons include the speed at which the sought information can be transferred to the intended recipient, the cost effective manner in which to provide information compared to, for example, traditional postal systems. In the case of banks, customers can easily log onto the bank's web site and after a login procedure, can access their account information with little or no wait time. Moreover, depending on the speed at which the banks can update the account information, the customers can also retrieve up-to-date account activity information. At the other end, the banks can obtain substantial savings by providing and maintaining their web site for interaction with their customers as opposed to having dedicated customer support personnel properly trained and made available around the clock.
Recognizing the web site and the internet as a principal medium for businesses to interact with their clients and customers, in addition to providing information specific to the client and customer vis a vis the business, the businesses are also expanding their web sites to provide information and access to related businesses or links (for example, by providing hypertext links within their web site linked to a Uniform Resource Locator (URL) of another related business or information provider).
In the case of brokerage firms and investment banks, in addition to the ability to retrieve account information, the customers are likely to be interested in information related to various financial instruments and activities. For example, for a brokerage account holder who has a margin account with approval to trade in option contracts, the account holder is likely to be interested in information related to trading in options such as call and put options, as well as detailed information on how option contracts are created, bought, sold, traded, and the impact of each of such activity. By way of another example, a relatively new brokerage account holder who recently opened a cash account and a 401K account with the brokerage firm may be interested in obtaining information related to the various different types of IRA accounts, basic trading information and relative risks for the various trading techniques, and so on.
While some brokerage firms and investment banks may have the capability to provide such information, with a growing pool of account holders, many firms find it more expedient to initially outsource to outside vendors who already have established practice of providing information and/or service. In this manner, the firms can better attempt to meet the customers' demand for the rapidly increasing and varied types of related information and/or services.
One disadvantage to the outsourcing approach, however, is that in many cases, the users are required to provide login information each time the user logs onto a third party vendor web site. For example, an account holder with C. Schwab & Co., the assignee of the present application, may wish to enroll in an online interactive education courses that are offered through Schwab.com web site but provided by a third party vendor. After initially logging onto schwab.com's web site, the account holder clicks on a hypertext link in schwab.com's web site, and the account holder's web browser is directed to the web site of the third party vendor providing the online interactive education courses. Here, the Schwab account holder must log in once again to register or to resume the course from where it was left of during the last session.
While still within schwab.com's server domain, the account holder is nevertheless required to separately log onto the third party vendor's site. Such user authentication or validation is necessary each time the account holder clicks on a hypertext link to be redirected to another information source. Moreover, once the account holder provides the log-in information to the third party vendor, the third party vendor must access back to the central server at schwab.com to verify the account holder's log-in information or to retrieve any other information related to the account holder that may be relevant to the account holder vis a vis the third party vendor. For example, in the case where the account holder is returning to a previous online interactive education course, once the account holder logs onto the third party vendor site, the server at the third party vendor accesses the central server at schwab.com to confirm that the account holder is indeed a Schwab account holder, and furthermore, to determine where in the interactive course the account holder left off during the last session.
Additionally, the third party vendor may want to retrieve additional information related to the account holder to better tailor the account holder's interactive course. For example, assuming that the online interactive education course provides information on options trading, the third party vendor would find it useful to have the account holder's trading history to determine whether the account holder has traded in option contracts at all, and if so, how often and so on. This type of information is especially useful to effectively design such interactive education course to be suited for each account holder.
As discussed above, irrespective of the type of third party vendors and the application or information provided, a user or an account holder is required to provide login information each time the user wishes to access the third party vendor application from a central server domain such as schwab.com.

This patent is subject to a terminal disclaimer.


A three-dimensional display system provides a projection screen having a predetermined angularly-responsive reflective surface function. Three-dimensional images are respectively modulated in coordination with the predetermined angularly-responsive reflective surface function to define a programmable mirror with a programmable deflection angle.

Modern three-dimensional ("3D") display technologies are increasingly popular and practical not only in computer graphics, but in other diverse environments and technologies as well. Growing examples include medical diagnostics, flight simulation, air traffic control, battlefield simulation, weather diagnostics, entertainment, advertising, education, animation, virtual reality, robotics, biomechanical studies, scientific visualization, and so forth.
The increasing interest and popularity are due to many factors. In our daily lives, we are surrounded by synthetic computer graphic images both in print and on television. People can nowadays even generate similar images on personal computers at home. We also regularly see holograms on credit cards and lenticular displays on cereal boxes.
The interest in 3D viewing is not new, of course. The public has embraced this experience since at least the days of stereoscopes, at the turn of the last century. New excitement, interest, and enthusiasm then came with the 3D movie craze in the middle of the last century, followed by the fascinations of holography, and most recently the advent of virtual reality.
Recent developments in computers and computer graphics have made spatial 3D images more practical and accessible. The computational power now exists, for example, for desktop workstations to generate stereoscopic image pairs quickly enough for interactive display. At the high end of the computational power spectrum, the same technological advances that permit intricate object databases to be interactively manipulated and animated now permit large amounts of image data to be rendered for high quality 3D displays.
There is also a growing appreciation that two-dimensional projections of 3D scenes, traditionally referred to as "3D computer graphics", can be insufficient for inspection, navigation, and comprehension of some types of multivariate data. Without the benefit of 3D rendering, even high quality images that have excellent perspective depictions still appear unrealistic and flat. For such application environments, the human depth cues of stereopsis, motion parallax, and (perhaps to a lesser extent) ocular accommodation are increasingly recognized as significant and important for facilitating image understanding and realism.
In other aspects of 3D display technologies, such as the hardware needed for viewing, the broad field of virtual reality has driven the computer and optics industries to produce better stereoscopic helmet-mounted and boom-mounted displays, as well as the associated hardware and software to render scenes at rates and qualities needed to produce the illusion of reality. However, most voyages into virtual reality are currently solitary and encumbered ones: users often wear helmets, special glasses, or other devices that present the 3D world only to each of them individually.
A common form of such stereoscopic displays uses shuttered or passively polarized eyewear, in which the observer wears eyewear that blocks one of two displayed images, exclusively one each for each eye. Examples include passively polarized glasses, and rapidly alternating shuttered glasses.
While these approaches have been generally successful, they have not met with widespread acceptance because observers generally do not like to wear equipment over their eyes. In addition, such approaches are impractical, and essentially unworkable, for projecting a 3D image to one or more casual passersby, to a group of collaborators, or to an entire audience such as when individuated projections are desired. Even when identical projections are presented, such situations have required different and relatively underdeveloped technologies, such as conventional autostereoscopic displays.
The consideration of freedom from headgear has thus motivated developments in autostereoscopic displays that automatically render a stereoscopic viewing experience for the observer without requiring the observer to use or wear special accommodations or devices. Autostereoscopic displays attempt to present a spatial image to a viewer without the use of glasses, goggles, or other personally-worn physical viewing aids. Autostereoscopic displays are appealing because they hold the prospect of offering the best experiential approximation to the optical characteristics of a real object.
Numerous autostereoscopic schemes for displaying images that actually appear three-dimensional have been proposed. Current physically realizable autostereoscopic displays can be classified generally into three broad categories: re-imaging displays, volumetric displays, and parallax displays.
Re-imaging displays typically capture and re-radiate the light from a three-dimensional object to a new location in space. Volumetric displays span a volume of space and illuminate individual parts of that space. Parallax displays are surfaces that radiate light of directionally varying intensity. Displays of each type have been used in commercial display systems, and each has inherent strengths and weaknesses.
The more common display approaches tend to fall into the two main categories of volumetric and parallax.
Autostereoscopic displays of the volumetric type produce 3D imagery by generating a collection of points within a volume that operate as light sources that emit, or appear to emit, light. If these points emit light isotropically, which is often the case, the resulting images appear ghosted or transparent. As a result, a typical volumetric display does not create a true 3D light field because the volume elements that are aligned depth-wise are not perceived to block one another. That is, the images do not display occlusion.
Autostereoscopic displays of the parallax type perform stereo separation of images internally, so that an observer is not required to use additional eyewear. A number of display systems of this type have been developed that present a different image to each eye as long as the observer remains in a fixed position in space. Most of these are variations on the parallax barrier method, in which a fine vertical grating or lenticular lens array is placed in front of a display screen. When the observer's eyes remain fixed at a certain location in space, each eye can only view one set of display pixels (even or odd) through the grating or lens array, and not the other set. This geometry can then ensure that each eye sees only its own respective image, corresponding to the set of pixels that display that distinct view of the image. The two image views, seen individually by the respective right and left eyes of the viewer, are configured so that the human visual system interprets the separately viewed images concurrently as a single 3D image. This occurs without the observer having to wear or use any personal assistive devices. However, the parallax barrier method typically requires the observer to remain stationary in one location. Further, in many cases, such displays generate a two-dimensional light field that provides horizontal but not vertical parallax.
A more recent and potentially much more realistic form of autostereoscopic display is the hologram. Holographic and pseudo-holographic displays output a partial light field that presents many different views simultaneously by effectively re-creating or simulating for the viewer the original light wavefront. The resulting imagery can be quite photorealistic, exhibiting occlusion and other viewpoint-dependent effects (e.g., reflection), as well as being independent of the viewer's physical position. In fact, the viewer can move around to observe different aspects of the image. The holographic image also has the potential to allow many observers to see the same image simultaneously.
Although much more realistic, a dynamically presented holographic image also requires far greater computational ability and bandwidth than is generally required for a two-view stereo display. Effective means are also noticeably wanting for dynamically recreating the original wavefront, or an acceptable facsimile thereof, in real time and at commercially acceptable costs.
Thus, a need still remains for highly effective, practical, efficient, uncomplicated, and inexpensive autostereoscopic 3D displays that allow the observer complete and unencumbered freedom of movement. Additionally, a need continues to exist for practical autostereoscopic 3D displays that provide a true parallax experience in both the vertical as well as the horizontal movement directions.
A concurrent continuing need is for such practical autostereoscopic 3D displays that can also accommodate multiple viewers independently and simultaneously. A particular advantage would be afforded if the need could be fulfilled to provide such simultaneous viewing in which each viewer could be presented with a uniquely customized autostereoscopic 3D image that could be entirely different from that being viewed simultaneously by any of the other viewers present, all within the same viewing environment, and all with complete freedom of movement therein.
Still further, due to the special user appeal but the daunting unsolved technical challenges, a distinctive need particularly continues for practical autostereoscopic 3D displays that provide a realistic holographic experience. Even more extraordinary would be a solution to the need for a holographic or pseudo-holographic viewing system that enables multiple simultaneous and individuated viewing as described above.
Yet another urgent need is for an unobtrusive 3D viewing device that combines feedback for optimizing the viewing experience in combination with provisions for 3D user input, thus enabling viewing and manipulation of virtual 3D objects in 3D space without the need for special viewing goggles or headgear.
In view of the ever-increasing commercial competitive pressures, increasing consumer expectations, and diminishing opportunities for meaningful product differentiation in the marketplace, it is increasingly critical that answers be found to these problems. Moreover, the ever-increasing need to save costs, improve efficiencies, improve performance, and meet such competitive pressures adds even greater urgency to the critical necessity that answers be found to these problems.
Solutions to these problems have been long sought but prior developments have not taught or suggested any solutions and, thus, solutions to these problems have long eluded those skilled in the art.


Described is a composition for a hair-treatment preparation which is preferably in the form of an optically clear, transparent or translucent product that can be used as an aerosol foam and contains (A) at least one nonionic, amphiphilic associative thickener in an appropriate cosmetic carrier and (B) at least one propellant. The preparation can be used as a leave-in hair treatment or as a hair rinse which condition the hair and confers to it luster and volume.

The object of the invention is a composition for a hair treatment preparation which preferably is in the form of an optically clear, transparent or translucent product and is used as an aerosol foam. In particular, the preparation can be a hair-care preparation usable as a leave-in hair treatment or as a hair rinse. The composition contains certain associative thickeners and propellants and optionally cationic hair-care agents and hydrophilic silicones.
As a rule, common hair-conditioning preparations, such as rinse-off treatments or leave-on treatments, are formulated on the basis of aqueous emulsions. Essential ingredients are cationic substances, for example cationic surfactants, hydrophobic substances, for example fatty alcohols, and other oil components, emulsifiers and other specific active ingredients and perfumes. The most important ingredients are the cationic surfactants, fatty alcohols and emulsifiers. A review of the general make-up of rinsing treatments and hair treatments can be found in Schrader, xe2x80x9cGrundlagen und Rezepturen der Kosmetikaxe2x80x9d [Fundamentals and Formulations of Cosmetics], 2nd edition, 1989, pages 728 to 737. The main function of conditioners is to improve the stylability, combability, luster and feel of the treated hair. The treated hair often feels somewhat heavier and more burdened which is not always desirable. Moreover, the conventional oil-in-water [O/W] hair care emulsions are normally milky-white and opaque. Desirable are products which are in an visually attractive form and clear, transparent or at least translucent. Various forms of clear hair care preparations are known and are described, for example, in E. Flick, xe2x80x9cCosmetic and Toiletry Formulationsxe2x80x9d, second edition, volume 2, pages 373 ff. The preparation of these clear hair care formulations is based on the use of thickening-type polymers, such as, for example, cellulose derivatives (tradenames Natrosol(copyright), Methocel(copyright)), high-molecular-weight chitosan derivatives (tradename Kytamer(copyright) PC), complex polysaccharides (commercial names karaya gum, tragacanth, Jaguar(copyright) brands, Keltrol(copyright) brands) and acrylic acid polymers. The major drawback of all these described clear hair care preparations is that their care effect is so weak that it does not come anywhere near the effect of conventional hair care preparations based on mixtures of fatty alcohols and quaternary surfactants. For this reason, in the marketplace these prior-art clear hair care preparations definitely do not sell as well as the standard treatments.
It has been found that it is possible, by use of nonionic, amphiphilic associative thickeners, to produce preparations which meet the typical requirements placed on hair conditioners in terms of hair conditioning and which, at the same time, can be in a visually attractive form and confer to the hair a less heavy, less burdened feel than that resulting from treatment with a conventional hair care preparation. It has been found, however, that such preparations are not yet entirely satisfactory in terms of emulsification while they are being worked into the hair. The product does not feel sufficiently substantial, namely the amount of emulsion is too small.
We have now found that these drawbacks can be eliminated by use of a hair treatment composition based on a combination of associative thickeners and propellants commonly used with aerosol foams. The object of the invention is therefore a composition for a hair treatment preparation containing
(A) at least one nonionic, amphiphilic associative thickener in an appropriate cosmetic carrier and
(B) at least one propellant.
The composition of the invention preferably contains additionally at least one hair-care substance (C) containing at least one cationic group and/or at least one hair-care silicone compound (D) with at least one hydrophilic group. The combination of the invention was found to have outstanding foaming properties even without an added surfactant, making the combination particularly well suited for preparing aerosol foam products.
The associative thickener (A) is preferably contained in the composition of the invention in an amount from 0.1 to 5 wt. % and particularly from 0.1 to 2 wt. %. The propellant is preferably present in an amount from 0.05 to 40 wt. % and particularly from 0.2 to 10 wt. %. The cationic substance (C) is preferably contained in the composition of the invention in an amount from 0.01 to 10 wt. % and particularly from 0.1 to 5 wt. %, and the silicone compound (D) preferably in an amount from 0.01 to 10 wt. % and particularly from 0.1 to 5 wt. %.
A hair treatment preparation made with the composition of the invention meets the requirements placed on hair conditioners in terms of the conditioning effect in the best manner and shows improved emulsification during use. After the treatment, the hair, in both the moist and the dry state, is noticeably smoother, and the wet combability is noticeably improved. Surprisingly, we have now found that the thickener makes it possible to incorporate the cationic substances and the said silicone compound without bringing about the negative side effects of the thickener. The technical properties of the preparation of the invention even exceed those of a conventional hair treatment based on an aqueous emulsion of fatty alcohols and quaternary surfactants. Comparative beauty salon tests performed side by side on the same scalp confirmed the better combability and more natural feel of hair treated with the preparation of the invention. The negative, dull feel of hair treated with fatty alcohol/cationic surfactant mixtures is practically eliminated when the preparation of the invention is used. The hair feels lighter and less burdened. Moreover, the combination of the invention in the form of an aerosol foam makes it possible to package the preparation in the form of a visually attractive, clear formulation which in turn permits advantageous packaging in a transparent container, for example one of glass or transparent plastic, for example polyethylene, polypropylene or polyethylene terephthalate. The aerosol foam application form is particularly advantageous for hair treatment. While being worked into the hair, the preparation packaged without the propellant feels less substantive and does not contain sufficient emulsion. Tests run by trained hair dressers have shown that the aerosol foam application form is clearly preferred.
The nonionic, amphiphilic associative thickener (A) is a polymer containing both hydrophilic and hydrophobic groups. Associative thickeners are water-soluble polymers containing surfactant-like hydrophobic constituents which in a hydrophilic and particularly in an aqueous medium are capable of associating, namely interacting, with themselves as wall as with other hydrophobic substances. The resulting associative network causes the medium to thicken or gel. Typically, associative thickeners are prepared by polymerization of polyethylene oxide propolymers and at least difunctional, polycondensable substances, for example isocyanates, whereby monohydric alcohols or diols with large aryl, alkyl or aryl/alkyl groups are incorporated so as to produce the hydrophobic modification. Hence, hydrophobically modified polyalkylene glycols are the preferred associative thickeners. The hydrophilic moiety is thus formed of polyoxyalkylene units, preferably of polyoxyethylene but also polyoxypropylene units or of a mixture thereof. The hydrophobic moiety is preferably formed of hydrocarbon groups, for example long-chain alkyl groups, alkylaryl or arylalkyl groups.
Particularly preferred associative thickeners are hydrophobically modified aminoplastxe2x80x94polyether copolymers. Regarding their structure and preparation, the reader is referred to WO 96/40815. In WO 96/40815 are described water-dispersible or water-soluble copolymers formed as products of an acid-catalyzed polycondensation of an at least difunctional aminoplast monomer, an at least difunctional alkylene polyether and a monofunctional compound with hydrophobic groups. Suitable aminoplasts are shown in FIG. 1 of WO 96/40815. Particularly preferred are the glycoluril derivatives of formula X in WO 96/40815. Suitable alkylene polyethers are the polyethylene oxide diols. These can have a degree of ethoxylation from 20 to 500, preferably from 60 to 350 and particularly from 100 to 250. Suitable monofunctional compounds with hydrophobic groups are those of formula XIV in WO 96/40815.
According to the invention, suitable associative thickeners are selected from among polymers of general formula (I)
wherein Amp denotes an aminoplast monomer or the radical of an aminoplast oligomer or polymer, AO denotes an alkylene oxida group, R denotes hydrogen, C1-C4-alkyl or C1-C4-acyl and x and y denote numerals greater than 1.
Particularly preferred are the reaction products formed by acid-catalyzed polycondensation of (a) a glycoluril of general formula (II)
wherein R stands for H or preferably for OMe, (b) a polyethylene oxide diol with a degree of ethoxylation from 20 to 500, preferably from 50 to 350 and particularly from 100 to 250, and (c) an optionally ethoxylated hydrophobic alcohol, alkylphenol, thiol, carboxamide, carbamate or hydrophobic carboxylic acid such as those described on pages 17 to 19 of WO 96140815. The particularly preferred glycoluril is 1,3,4,6-tetramethoxymethylglycoluril.
Suitable associative thickeners are those with an INCI name of polyether 1, PEG 180/octoxynol-40/TMMG copolymer and PEG 180/laureth 50/TMMG copolymer sold by Sxc3xcd-Chemie under the tradenames Pure-Thix(copyright) HH, L and M.
Usable propellants (B) are, for example, the lower alkanes, for example n-butane, i-butane and propane or a mixture thereof, as well as dimethyl ether or a fluorohydrocarbon such as F 152a (1,1-difluoroethane) or F 134 (tetrafluoroethane), furthermore propellants which at the pressures involved are gaseous, for example N2, N2O and CO2, as well as mixtures of the aforesaid propellants. n-Butane, i-butane and propane, particularly propane/butane mixtures, and dimethyl ether, and mixtures thereof are preferred.
The cationic material (C) is a substance which because it contains cationic or cationizable groups, particularly primary, secondary, tertiary or quaternary amino groups, exhibits substantivity for human hair. Suitable cationic materials are selected from among cationic surfactants, betaine surfactants, amphoteric surfactants, cationic polymers with cationic or cationizable groups, cationically derivatized proteins, cationically derivatized protein hydrolyzates and betaine.
Suitable cationic surfactants are those containing a quaternary ammonium group. They include cationic or amphoteric betaine surfactants. Particularly preferred cationic materials (C) are cationic surfactants. Suitable cationic surfactants contain amino groups or quatemized hydrophilic ammonium groups which in solution bear a positive charge and are represented by general formula (III)
xe2x80x83N(+)R1R2R3R4 X(xe2x88x92)xe2x80x83xe2x80x83(III)
wherein R1 to R4 independently of each other denote aliphatic groups, aromatic groups, alkoxy groups, polyoxyalkylene groups, alkylamido groups, hydroxyalkyl groups, aryl groups or alkaryl groups with 1 to 22 carbon atoms, and X(xe2x88x92) denotes an anion, for example a halogen, acetate, phosphate, nitrate or alkylsulfate, and preferably chloride. Besides the carbon atoms and hydrogen atoms, the aliphatic groups can contain linking groups or other groups, for example hydroxyl groups, or other amino groups.
Examples of suitable cationic surfactants are alkyldimethylbenzylammonium chlorides or bromides, the alkyltrimethylammonium salts, for example cetyltrimethylammonium chloride or bromide, tetradecyltrimethylammonium chloride or bromide, alkyldimethylhydroxyethylammonium chlorides or bromides, the dialkyldimethylammonium chlorides or bromides, the alkylpyridinium salts, for example lauryl-pyridinium or cetylpyridinium chloride, the alkylamiddothyltrimethylammonium ether sulfates as well as compounds with a cationic character, such as amine oxides, for example alkylmethylamine oxides or alkylaminoethyldiethylamine oxides. Particularly preferred is cetyltrimethylammonium chloride which, for example in the form of a 26% aqueous solution, is sold by Henkel KGaA, D{umlaut over (s)}seldorf, Germany, under the tradename Dehyquart(copyright) A and by Hoechst A G, Frankfurt, Germany, under the tradename Genamin(copyright) CTAC, and in the form of a 50% solution in isopropanol by Akzo Chemicals GmbH, D{overscore (u)}ren, Germany, under the tradename Arquad(copyright) 16-50.
Other suitable cationic surfactants are those known as esterquats. By esterquats are meant, in general, quaternized fatty acid triethanolamine ester salts. Esterquats are known, for example, from WO 91/01295. Suitable esterquats are those of general formula (VIII)
R1COxe2x80x94(OCH2CH2)xxe2x80x94N(4)R3R4xe2x80x94(CH2CH2)yxe2x80x94R2 X(xe2x88x92)xe2x80x83xe2x80x83(VIII)
wherein R1CO denotes an, optionally hydroxy-substituted, C6-C22-acyl group, R2 denotes hydrogen or an R1CO group, R3 denotes a C1-C4-alkyl group or the (CH2CH2O)2xe2x80x94H group, R4 denotes a C1-C4-alkyl-group or the (CH2CH2O)4xe2x80x94R2 group, X[+] is a suitable anion, for example halogen, alkylsulfate or alkylphosphate, and x, y, z and q stand for a numeral from 1 to 12. Particularly preferred are ester-quats wherein R1CO denotes a C12-C20-acyl group, R2 denotes an R1CO group, R3 denotes CH2CH2OH, R4 denotes methyl, X(xe2x88x92) denotes methylsulfate and x and y stand for the numeral 1. Such compounds are available commercially under the tradenames Dehyquart(copyright) L, Dehyquart(copyright) F, Schercoquat(copyright) and Tetranyl(copyright).
Suitable amphoteric surfactants are the derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds of formula (IV)
wherein R5 denotes a straight-chain or branched alkyl, alkenyl or hydroxyalkyl group with 8 to 18 carbon atoms and from 0 to about 10 ethylene oxide units and from 0 to about 1 glycerol unit, Y denotes an N-, P- or S-containing group, R6 denotes an alkyl or monohydroxyalkyl group with 1 to 3 carbon atoms, x equals 1 when Y is a sulfur atom and x equals 2 when Y is a nitrogen atom or a phosphorus atom, R7 denotes an alkylene or hydroxyalkylene group with 1 to 4 carbon atoms and Z(xe2x88x92) denotes a carboxylate, sulfate, phosphonate or phosphate group.
Other amphoteric surfactants such as the betaines are also suitable for the hair-treatment preparations of the invention. Examples of betaines include C8-C18-alkylbetaines, such as cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryldimethyl-alpha-carboxyethylbetaine, cetyldimethylcarboxymethylbetaine, oleyldimethyl-gamma-carboxypropylbetaine and lauryl-2-bis(2-hydroxypropyl) -alpha-carboxyethylbetaines, C8-C18-sulfobetaines, such as cocodimethylsulfopropylbetaine, stearyldimethylsulfopropylbetaine, lauryldimethylsulfoethylbetaine, lauryl-bis(2-hydroxyethyl)sulfopropylbetaine, the carboxyl derivatives of imidazole, the C8-C18-alkyldimethylammonium acetates, the C8-C18-alkyldimethylcarbonylmethylammonium salts, the C8-C18 fatty acid alkylamidobstaines, for example, coco fatty acid amidopropylbetaine, sold, for example in the form of a 30% aqueous solution, by Goldschmidt AG under the tradename Tego(copyright) Betaine L7, and the N-coco fatty acid amidoethyl-N-[2-(carboxymethoxy)ethyl]glycerol (CTFA1 name: cocoamphocarboxyglycinate), sold, for example in the form of a 50% aqueous solution, by Miranol Chemical Co. under the tradename Miranol(copyright) C2M.
The suitable cationic polymers are preferably hair-strengthening or hair-conditioning polymers. Suitable polymers of component (C) preferably contain quaternary amino groups. The cationic polymers can be homopolymers or copolymers, with the quaternary nitrogen contained either in the polymer chain or preferably as a substituent in one or more monomers. The ammonium groups-containing monomers can be copolymerized with non-cationic monomers. Suitable cationic monomers are unsaturated compounds capable of undergoing free radical-initiated polymerization and bearing at least one cationic group, particularly ammonium-substituted vinyl-monomers, for example trialkylmethacryloxyalkylammonium, trialkylacryloxyalkylammonium, dialkyldiallylammonium and quaternary vinylarnmonium monomers with cyclic, cationic nitrogen-containing groups, such as pyridinium, imidazolium or quaternary pyrrolidones, for example alkylvinylimidazolium, alkylvinylpyridinium or alkylvinylpyrrolidone salts. The alkyl groups of these monomers are preferably lower alkyl groups such as, for example, C1-C7-alkyl groups and preferably C1-C3-alkyl groups.
The ammonium group-containing monomers can be copolymerized with non-cationic monomers. Suitable comonomers are, for example, acrylamide, methacrylamide, alkylacrylamide, dialkylacrylamide, alkyl methacrylamide and dialkyl methacrylamide, alkyl acrylate, alkyl methacrylate, vinylcaprolactone, vinylcaprolactam, vinylpyrrolidone, vinyl esters, for example vinyl acetate, vinyl alcohol, propylene glycol or ethylene glycol, the alkyl groups of these monomers preferably being C1-C7-alkyl groups and particularly C1-C3-alkyl groups.
Suitable polymers with quaternary amino groups are, for example, the polymers described in the CTFA Cosmetic Ingredient Dictionary under the name polyquaternium, such as methylvinylimidazolium chloride/vinylpyrrolidone copolymer (polyquaternium 16), or (quaternized vinylpyrrolidone/dimethylaminoethyl methacrylate copolymer (polyquaternium 11).
A suitable cationic polymer that can be contained in the composition of the invention is, for example, vinylpyrrolidone/dimethylaminoethyl methacrylate methosulfate copolymer, sold by Gaf Co., USA, under the tradenames Gafquat 755 N and Gafquat(copyright) 734, of which Gafquat(copyright) 734 is particularly preferred. Other cationic polymers are, for example, the copolymer of polyvinylpyrrolidone and imidazolimine methochloride, sold by BASF, Germany, under the tradename LUVIQUAT(copyright) HM 550, the terpolymer of dimethyldiallylammonium chloride, sodium acrylate and acrylamide, sold by Calgon, USA, under the tradename Merquat(copyright) Plus 3300, the terpolymer of vinylpyrrolidone, dimethylaminoethyl methacrylate and vinylcaprolactam sold by ISP, USA, under the tradename Gaffix(copyright) VC 713, and the vinylpyrrolidone/methacrylamidopropyltrimethylammonium chloride copolymer sold by Gaf under the tradename Gafquat(copyright) HS 100.
Suitable cationic polymers derived from natural polymers are the catlonic derivatives of polysaccharides, for example the cationic derivatives of cellulose, starch or guar. Also suitable are chitosan and chitosan derivatives. The cationic polysaccharides have general formula (V)
Gxe2x80x94Oxe2x80x94Bxe2x80x94N+RaRbRc Xxe2x88x92xe2x80x83xe2x80x83(V)
wherein
G denotes an anhydroglucose radical, for example starch anhydroglucose or cellulose anhydroglucose, B denotes a divalent linking group, for example alkylene, oxyalkylene, polyoxyalkylene or hydroxyalkylene, Ra, Rb and Rc independently of each other denote alkyl, aryl, alkaryl, arylakyl, alkoxyalkyl or alkoxyaryl, each with up to 18 carbon atoms, the total number of carbon atoms in Ra, Rb and Rc preferably being at the most 20;
X(+) denotes a common counterion with the same meaning as in formula (I) and preferably chloride. A cationic cellulose is sold by Amerchol under the name Polymer JR and has the INCI name polyquaternium 10. Another catinric cellulose has the INCI name polyquaternium 24 and is sold by Amerchol under the tradename Polymer LM-200. A suitable cationic guar derivative is sold under the tradename Jaguar(copyright) R and has the INCI name guar hydroxypropyltrimonium chloride.
Particularly preferred cationic substances are chitosan, chitosan salts and chitosan derivatives. The chitosans used according to the invention are completely or partially deacetylated chitins. Chitosan is preferably prepared from the chitin contained in crustacean shell wastes, an inexpensive and natural starting material available in large quantities. The molecular weight of chitosan is distributed over a wide range, for example from 20,000 to about 5 million g/mol. Suitable is, for example, a low-molecular-weight chitosan with a molecular weight of 30,000 to 70,000 g/mol. Preferably, however, the molecular weight is higher than 100,000 g/mol and particularly between 200,000 and 700,000 g/mol. The degree of deacetylation is preferably 10 to 99% and particularly 60 to 99%.
A suitable chitosan is, for example, the one sold by Kyowa Oil and Fat, Japan, under the tradename Flonac(copyright). It has a molecular weight of 300,000 to 700,000 g/mol and is 70 to 80% deacetylated. A preferred chitosan salt is chitosoniumpyrrolidonecarboxylate sold, for example, by Amerchol, USA, under the name Kytamer PC. The chitosan contained therein has a molecular weight of about 200,000 to 300,000 g/mol and is 70 to 85% deacetylated. Suitable chitosan derivatives are the quaternized, alkylated or hydroxyalkylated derivatives, for example hydroxyethylchitosan or hydroxybutylchitosan.
The chitosans and chitosan derivatives are preferably in neutralized or partly neutralized form. The degree of neutralization of chitosan or of the chitosan derivative is preferably at least 50% and particularly between 70 and 100%, based on the number of free basic groups. Suitable as neutralization agents are. In principle, all cosmetically tolerated inorganic or organic acids. for example formic, tartaric, malic, lactic, citric, pyrrolidonecarboxylic and hydrochloric acid etc, among which pyrrolidonecarboxylic acid is particularly preferred.
Other suitable cationic hair-care compounds are the cationically modified protein derivatives or cationically modified protein hydrolyzates known, for example, under the INCI names lauryldimonium hydroxypropyl hydrolyzed wheat protein, lauryldimonium hydroxypropyl hydrolyzed casein, lauryldimonium hydroxypropyl hydrolyzed collagen, lauryldimonium hydroxypropyl hydrolyzed keratin, lauryldimonium hydroxypropyl hydrolyzed silk, lauryldimonium hydroxypropyl hydrolyzed soy protein or hydroxypropyltrimonium hydrolyzed wheat, hydroxypropyltrimonium hydrolyzed casein, hydroxypropyltrimonium trimonium hydrolyzed collagen, hydroxypropyltrimonium hydrolyzed keratin, hydroxypropyltrimonium hydrolyzed rice bran protein, hydroxypropyltrimonium hydrolyzed silk, hydroxypropyltrimonium hydrolyzed soy protein and hydroxypropyltrimonium hydrolyzed vegetable protein.
Suitable cationically derivatized protein hydrolyzates are mixtures of substances obtained, for example, by reaction of alkaline, acid or enzymatically hydrolyzed proteins and glycidyltrialkylammonium salts or 3-halo-2-hydroxypropyltrialkylammonium salts. Proteins of vegetable as well as animal origin can be used as starting materials for the protein hydrolyzates. Common starting materials are, for example, keratin, collagen, elastin, soy protein, rice protein, milk protein, wheat protein, silk protein or almond protein. Hydrolysis produces mixtures of substances with a molecular weight ranging from about 100 to about 50,000. The average molecular weights are usually in the range from about 500 to about 1000. Advantageously, the cationically derivatized protein hydrolyzates contain one or two long C8-C22-alkyl chains and correspondingly two or one short C1-C4-alkyl chain. Compounds containing one long alkyl chain are preferred.
The hydrophilic group of the hair-care silicone compounds (D) used according to the invention are preferably selected from among hydroxyl groups, primary, secondary or tertiary amino groups, quaternary ammonium groups, alkylene oxide groups, betaine groups or thiosulfate groups.
Suitable and particularly preferred are cationic silicone compounds. These compounds are substituted with cationic or cationizable groups. Suitable cationic silicone compounds have at least one amino group or at least one ammonium group. Suitable silicone polymers with amino groups are known under the INCI name of amodimethicones. These are polydimethylsiloxanes with aminoalkyl groups. The aminoalkyl groups can be lateral or terminal. Suitable aminosilicones are those of general formula (VI)
R8R9R10Sixe2x80x94(OSiR11R12)xxe2x80x94(OSiR13Q)yxe2x80x94OSiR14R15R16xe2x80x83xe2x80x83(VI)
wherein
R8, R9, R14 and R16 independently of each other are equal or different and denote C1-C10-alkyl, phenyl, hydroxyl, hydrogen, C1-C10-alkoxy or acetoxy, preferably C1-C4-alkyl, and particularly methyl, R10 and R16 independently of each other are equal or different and denote xe2x80x94(CH2)axe2x80x94NH2 where a equals 1 to 6, C1-C10-alkyl, phenyl, hydroxyl, hydrogen, C1-C10-alkoxy or acetoxy, preferably C1-C4-alkyl and particularly methyl;
R11, R12 and R13 independently of each other are equal or different and denote hydrogen, a C1-C20 hydrocarbon possibly containing O atoms and N atoms, preferably C1-C10-alkyl or phenyl, more preferably C1-C4-alkyl and particularly methyl;
O denotes xe2x80x94Axe2x80x94NR17R18 or Axe2x80x94N+R17R18R19, wherein A denotes a divalent C1-C20-alkylene linking group possibly containing O atoms or N atoms or OH groups, and R17, R18 and R19 independently of each other are equal or different and denote hydrogen, C1-C22 hydrocarbon, preferably C1-C4-alkyl or phenyl. Preferred radicals for O are xe2x80x94(CH2)3xe2x80x94NH2, xe2x80x94(CH2)3NHCH2CH2NH2, xe2x80x94(CH2)3OCH2CHOHCH2NH2, xe2x80x94(CH2)3N(CH2CH2OH)2, xe2x80x94(CH2)3NH3+ and xe2x80x94(CH2)3OCH2CHOHCH2N+(CH3)2R20, wherein R20 denotes a C1-C22 alkyl group possibly also containing OH groups; x denotes a numeral between 1 and 10,000 and preferably between 1 and 1000, and y denotes a numeral between 1 and 500 and preferably between 1 and 50.
The molecular weight of the aminosilicones is preferably between 500 and 100,000. The amine content (meq/g) is preferably in the range from 0.05 to 2.3 and particularly from 0.1 to 0.5.
Suitable silicone polymers with two terminal quaternary ammonium groups are known under the INCI name quaterium 80. These are dimethylsiloxanes with two terminal aminoalkyl groups. Suitable quaternary aminosilicones are those of general formula (VII)
R21R22R23N+xe2x80x94Axe2x80x94SiR8R9xe2x80x94(OSiR11R12)nxe2x80x94OSiR8R9xe2x80x94Axe2x80x94N+R21R22R23 2Xxe2x88x92xe2x80x83xe2x80x83(VII)
A has the same meaning as in formula (VI) hereinabove and is preferably xe2x80x94(CH2)3OCH2CHOHCH2N+(CH3)2R20, wherein R20 denotes a C1-C22-alkyl radical possibly also containing OH groups,
R8, R9, R11 and R12 have the same meaning as in formula (VI) hereinabove and preferably denote methyl;
R21, R22 and R23 independently of each other denote C1-C22-alkyl radicals possibly also containing hydroxyl groups, with preferably at least one of the radicals having at least 10 carbon atoms and the other radicals having from 1 to 4 carbon atoms;
n is a numeral from 0 to 200 and preferably from 10 to 100. Such diquaternary polydimethylsiloxanes are sold by Goldschmidt, Germany, under the tradenames Abil(copyright) Quat 3270, 3272 and 3274.
Suitable silicones with alkylene oxide groups are polydimethylsiluxanes with polyoxyalkylated substituents, particularly silicones modified with polypropylene oxide, polyethylene oxide or a mixture thereof. The alkylene oxide groups can be lateral or terminal, and the compounds can be polydimethylsiloxane/polyalkylene oxide block copolymers. The siloxanes modified with alkylene oxides are also referred to as dimethylsiloxane-glycol copolymers or dimethicone copolyols. Suitable silicones with hydroxyl groups are the dimethiconols. These are polydimethylsiloxanes with hydroxyl end groups. Suitable silicones with thiosulfate groups are known under the INCI name dimethicone/sodium PG propyidimethicone thiosulfate copolymer.
The composition of the invention is preferably prepared in an aqueous or aqueous alcoholic medium and is characterized particularly by clarity and transparency, For this reason, the composition is advantageously placed into visually attractive packaging made of transparent or translucent print-resistant material. Suitable packaging materials are, in particular, glas and transparent or translucent plastics such as, for example, polyethylene terephthalate. The composition can contain as the alcohol, in particular, a lower alcohol with 1 to 4 carbon atoms usually employed for cosmetic purposes, for example ethanol and isopropanol. The water content is preferably from 40 to 95 wt.% and particularly from 60 to 90 wt. %. The alcohol content is preferably from 1 to 30 wt.% and particularly from 5 to 20 wt. %. Other, particularly preferred water-soluble solvents or moisturizers are the polyhydric alcohols, particularly those with 2 to 4 carbon atoms, for example glycerol, ethylene glycol or propylene glycol, in an amount from 0.1 to 10 wt. % and preferably from 0.5 to 5 wt. %. Purely aqueous formulations are particularly preferred.
In a preferred embodiment, the composition of the invention also contains at least one nonionic surfactant. Suitable nonionic surfactants are, for example, the nonionic emulsifiers listed in the xe2x80x9cInternational Cosmetic Ingredient Dictionary and Handbookxe2x80x9d, 7th edition, volume 2, in the section on xe2x80x9cSurfactants-Emulsifying Agentsxe2x80x9d. Suitable nonionic surfactants are preferably those selected from among the ethoxylated fatty acids with 10 to 26 carbon atoms, ethoxylated monohydric or polyhydric alcohols with 1 to 6 carbon atoms, ethoxylated fatty alcohols with 10 to 26 carbon atoms, ethoxylated hydrogenated or non-hydrogenated castor oil, alkyl polyglucosides, glyceride alkoxylates, fatty acid glyceride polyalkylene glycol ethers or fatty acid partial glyceride polyalkylene glycol ethers, each with less than 30 alkylene glycol units, for example polyethylene glycol-(7)-glyceryl cocoate, polyglycolamides, fatty acid sugar esters, ethoxylated fatty acid sugar esters and partial glycerides. The degree of ethoxylation of the ethoxylated surfactants is usually from 1 to 400, preferably from 2 to 200 and particularly from 3 to 25.
In a preferred embodiment, the composition of the invention contains only water-soluble surfactants and emulsifiers, i.e., surfactants which at a 1 wt. % water content are clear and soluble at 20xc2x0 C.
Preferred nonionic surfactants are, in particular, fatty alcohol ethoxylates. Suitable area, for example, alcohols with 10 to 18, and preferably 10 to 16 carbon atoms, and a degree of ethoxylation of, preferably, 2 to 200 and particularly 3 to 25. The additional nonionic surfactants are preferably used in an amount from 0.01 to 5 wt. %.
In another preferred embodiment, the composition of the invention contains at least one film-forming, hair-strengthening synthetic or natural polymer. This additional polymer can be nonionic, anionic or amphoteric and is preferably used in an amount from 0.5 to 10 wt. %. By film-forming, hair-strengthening polymers are meant polymers which when used in a 0.1 to 5% aqueous, alcoholic or aqueous-alcoholic solution are capable of depositing a polymer film on the hair thus strengthening the hair.
Moreover, the composition of the invention can additionally contain additive ingredients commonly used in hair-treatment compositions, for example non-strengthening nonionic polymers, non-strengthening anionic polymers and non-strenghtening natural polymers or a combination thereof, preferably in an amount from 0.01 to 10 wt. %; perfume oils, preferably in an amount from 0.01 to 5 wt. %; wetting agents or emulsifiers from the classes of anionic, cationic, amphoteric or nonionic surface-active substances, preferably in an amount from 0.01 to 10 wt. %; moisturizers; preservative: bactericidal and fungicidal materials, for example 2,4,4-trichloro-2-hydroxydiphenyl ether, parabens or methylchloroisothiazolinone, in an amount from 0.01 to 1.0 wt. %; buffering agents, for example sodiumn citrate or sodium phosphate, in an amount from 0.1 to 1.0 wt. %; tinting agents, for example fluorescein sodium salt, in an amount from about 0.1 to 1.0 wt. %; hair-care agents, for example vegetable and herb extracts, protein hydrolyzates, silk hydrolyzates or lanolin derivatives in an amount from 0.1 to 5 wt. %; light-protective agents, antioxidants, free radical scavengers, antidandruff agents, fatty alcohols, luster-imparting agents, vitamins and regreasing agents, in an amount from 0.01 to 10 wt. %.
The composition of the invention can have a pH from 2.0 to 9.5. Particularly preferred are weakly acidic pH values between 4.5 and less than 7, especially 5.5 to 6.5. When the composition of the invention is in the acidic range, it can contain an organic or inorganic acid, for example formic, tartaric, malic, maleic, fumaric, glyoxylic, pyrrolidonecarboxylic, citric, lactic, sulfuric, acetic, hydrochloric or phosphoric acid atc.
To use the composition of the invention, an amount thereof sufficient for the desired conditioning effect is distributed in or on dry hair or, after the hair has been washed, in or on the wet or moist hair. The amount to be used depends on the hair fullness and typically is between 1 and 25 g. In the preferred use as a rinse product, the hair is rinsed after a sufficient exposure time of, for example, 1 to 15 minutes. It is then optionally combed, or styled into a hair-do and then dried. In the use as a leave-in product, the hair is not rinsed after the application of the composition.
The following examples will explain the object of the invention in greater detail.

Composition for a hair treatment preparation in the form of an aerosol foam