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Publication numberUS3577518 A
Publication typeGrant
Publication dateMay 4, 1971
Filing dateJul 18, 1969
Priority dateJul 18, 1969
Publication numberUS 3577518 A, US 3577518A, US-A-3577518, US3577518 A, US3577518A
InventorsThomas H Shepherd, Francis E Gould
Original AssigneeNat Patent Dev Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Hydrophilic hairspray and hair setting preparations
US 3577518 A
Abstract  available in
Images(10)
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Claims  available in
Description  (OCR text may contain errors)

Patented May 4, 1971 3,577,518 HYDROPHILIC HAIRSPRAY AND HAIR SE'ITING PREPARATIONS Thomas H. Shepherd, Hopewell, and Francis E. Gould,

Princeton, NJ., assignors to National Patent Development Corporation, New York, N.Y.

No Drawing. Continuation-impart of applications Ser. No. 567,856, July 26, 1966, now Patent No. 3,520,949, Ser. No. 650,259, June 30, 1967, Ser. No. 654,044, July 5, 1967, and Ser. No. 743,626, July 10, 1968. This application July 18, 1969, Ser. No. 843,245

Int. Cl. A61k 7/10 US. Cl. 424-47 27 Claims ABSTRACT OF THE DISCLOSURE Hair spray and hair setting compositions are prepared from hydrophilic copolymers of hydroxyalkyl acrylates or methacrylates with mere hydrophobic alkyl acrylates or methacrylates or alkoxyalkyl acrylates or methacrylates. There can also be included polymerizable amino compounds or olefinic carboxylic acids.

T erpolymers of alkoxyalkyl acrylates or methacrylate with alkyl acrylates or methacrylates with olefinic carboxylic acids or unsaturated amines can also be used as can tetrapolymers of the monomers set forth.

The present application relates to novel cosmetic preparations.

The present application is a continuation-in-part of application Ser. No. 567,856 filed July 26, 1966, now Pat. 3,520,949, application Ser. No. 654,044 filed July 5, 1967 and application Ser. No. 743,626, filed July 10, 1968 and application Ser. No. 650,259, filed June 30, 1967 and now abandoned.

Cosmetic manufacturers have sought in the past to produce compositions for use on human hair and skin which may be easily applied, exhibit no detrimental effect on the skin and retain their stability for a reasonable period of time. Some progress has been made in producing products of this type. However, there remains inherent defects in prior preparations such as creams, lotions, shampoos, dressings, sticks, and the like which impairs their cosmetic effectiveness. One example of this is the well-known tendency of conventional mascara to run when wet by tears or water.

As is well known the various creams used on the body have a tendency to soil clothing, bed clothes and the like. Lipsticks and suntan creams have a tendency to be greasy and essences (e.g. perfume) and other volatile components present in lipstick, creams and lotions have a tendency to be lost on standing.

It has hitherto been proposed to employ lacquers for imparting a temporary set to the hair. However, since lacquers include a water-insoluble film-forming ingredient, it has been extremely difiicult to remove them from the hair. When it is desired to change the hair style, it sometimes becomes necessary to employ a special solvent or a powerful detergent composition, neither of which is readily available in the home. Lacquers have generally been considered unsatisfactory for application to the hair for this reason. A number of water-soluble film-forming resinous materials have also been proposed for application to the hair in order to set it. However, such watersoluble materials have not been completely satisfactory because of the tendency for the resultant film to become tacky and for the hair to lose its set when exposed to conditions of high humidity.

Furthermore, at present there is no satisfactory method for straightening kinky hair.

Accordingly, it is an object of the present invention to prepare novel cosmetic compositions.

Another object is to improve the application of cosmetic compositions to the body.

An additional object is to overcome the tendency of mascara to run when wet.

A further object is to protect the body against the drying effects of cosmetics comprising alcohol solutions.

Yet another object is to overcome the greasiness present in various cosmetic creams, sticks, and lotions.

A still further object is to reduce the staining or soiling property of cosmetic creams and lotions.

An additional object is to reduce the loss of flavors or essences from cosmetic compositions.

A corollary object is to develop cosmetic compositions which release a flavor or essence when wet.

An important object of the invention is to straighten kinky or curly hair so that it can be manipulated as desired.

A related object is to set hair of any type.

A further object is to develop a hair setting composition and method which will provide a "perrnanent set even under conditions of high humidity.

A related object is to give hair a permanent" that does not result in the treated hair developing static electrical charges under conditions of low humidity.

Another object is to apply a film having one or more of the above characteristics in relation to hair, but which can be readily removed.

A still further object is to develop novel aerosol compositions useful for application to the body.

Still further objects and the entire scope of applicability of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description and specific examples, while indicating preferred embodiment of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

It has now been found that these objects can be attained by employing certain hydrophilic acrylate and methacrylate polymers in cosmetic compositions. For liquid cosmetics the hydrophilic polymer should not have substantial cross-linking (i.e. the cross-linking should not be sufficient to render the polymer insoluble in the solvent) while for powdered or creamy compositions crosslinked copolymers can be employed.

The term cosmetic is intended to embrace all types of products which are to be applied in any manner directly to the person for the purpose of cleansing or embellishment, including altering the appearance. Toilet soap and shaving soaps and creams are intended to be included in this definition as Well as deodorants, depilatories, suntan and sunscreen preparations.

The hydrophilic monomer used to prepare the hydrophilic polymer is preferably a hydroxyalkyl monoacrylate or methacrylate such as 2-hydroxyethyl acrylate, 2- hydroxyethyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, hydroxypropyl acrylates and methacrylates, e.g. 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, S-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, tetraethylene glycol monomethacrylate, pentaethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, dipropylene glycol monoacrylate. Acrylamide, methacrylamide, diacetone acrylamide, methylolacrylamide and methylol methacrylamide also are useful hydrophilic monomers. The most preferred monomer is 2-hydroxyethyl methacrylate and the next most preferred monomer is 2-hydroxyethyl acrylate.

In preparing hydroxyalkyl acrylates and methacrylates a small amount of the diacrylate or dimethacrylate is also formed. This need not be removed as it does not cause undue cross-linking.

When it is desired to shampoo out the hydrophilic polymer there are desirably included 0.1 to 15% of an ethylenically unsaturated acid to provide free acid groups. Typical examples of such acids include acrylic acid, methacrylic acid, itaconic acid, aconitic acid, cinnamic acid, crotonic acid, citraconic acid, measaconic acid, maleic acid and fumaric acid. Less preferably there can also be used partial esters of polybasic acids such as mono 2-hydroxypropyl itaconate, mono Z-hydroxyethyl itaconate, mono-Z-hydroxyethyl citraconate, mono-Z-hydroxypropyl aconitate, mono Z-hydroxyethyl maleate, mono Z-hydroxypropyl fumarate, monomethyl itacouate, monoethyl itaconate, mono methyl Cellosolve ester of itaconic acid (methyl Cellosolve is the monomethyl ether of diethylene glycol), mono methyl Cellosolve ester of maleic acid.

The use of such acid containing groups does not result in substantial cross-linking unless the polymer is heated for a substantial time above normal operating conditions for cosmetics or unless the polymerization time is prolonged using relatively high amounts of catalysts.

When cross-linked or cross-linkable hydrophilic polymers are prepared normally the cross-linking agent is preferably present in an amount of 0.1 to 2.5%, most preferably 0.1 to 1.0%, of the total monomers, although up to 15 of cross-linking agent can be used. Typical examples of cross-linking agents include ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-butylene dimethacrylate, 1,3-butylene dimethacrylate, 1,4-butylene dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, dipropylene glycol diacrylate, divinyl benzene, divinyl toluene, diallyl tartrate, allyl pyruvate, allyl malate, divinyl tartrate, triallyl melamine, N,N-methylene-bis-acrylamide, glycerine trimethacrylate, diallyl maleate, divinyl ether, diallyl mono ethylene glycol citrate, ethylene glycol vinyl allyl citrate, allyl vinyl maleate, diallyl itaconate, ethylene glycol diester of itaconic acid, divinyl sulfone, hexahydrol,3,5-triacyltriazine, triallyl phosphite, diallyl ester of benzene phosphonic acid, polyester of maleic anhydride with triethylene glycol, polyallyl sucrose, polyallyl glucose, e.g. diallyl sucrose and triallyl glucose, sucrose diacrylate, glucose dimethacrylate, pentaerythritol diacrylate, sorbitol dimethacrylate,

The cross-linked polymers are characterized by being insoluble in the solvents. Typical examples of suitable cross-linked hydrophilic polymers are those in Wichterle Pat. 2,976,576, Wichterle Pat. 3,220,960, e.g. Examples III, V, VI, VII, and IX, Wichterle Pat. 3,361,858, Examples 1, 2, 3, 6, 8, 9, 10, and 11, as well as copolymers of 30 parts ethylene glycol with 0.1 part ethylene glycol bisrnethacrylate; 54.7 parts ethylene glycol monomethacrylate, 17.2 parts diethylene glycol monomethacrylate and 0.6 part of diethylene glycol dimethacrylate; 80 parts ethylene glycol monomethacrylate, 15 parts methacrylamide and 0.4 part of ethylene glycol bis-methacrylate; 97 parts ethylene glycol monomethacrylate, 0.25 part diethylene glycol dimethacrylate and 0.25 part ethylene glycol bis-methacrylate; 60 parts ethylene glycol monomethacrylate, 19.7 parts diethylene glycol monomethacrylate, 0.3 part ethylene glycol -bis-methacrylate, 99.6 parts ethylene glycol monomethacrylate and 0.4 part ethylene glycol bis-methacrylate, 99.5 parts ethylene glycol monomethacrylate and 0.4 part ethylene glycol bis-methacrylate, 99.7 parts ethylene glycol monomethacrylate and ethylene glycol bis-methacrylate; 98.7 parts ethylene glycol monomethacrylate and 0.3 part diethylene glycol dimethacrylate. Details for making the last 9 copolymers set forth above are given in Wichterle application Ser. No. 762,618, filed Sept. 25, 1968, entitled Anhydrous Sparingly Cross-Linked Hydrophilic Copolymers. They can also be prepared using the procedures set forth in our parent application 654,044 or the procedures employed in the specific examples below.

Unless otherwise indicated all parts and percentages are by weight.

The hydrophilic polymers of this invention possess unique properties which are capable of improving a wide range of cosmetic products. In particular, they impart to such products a wide range of unusual and desirable properties and effects on the skin and hair, such as lubricity, emolliency, softening and smoothing, resistance to and protection against the drying effects of alcohol solutions, resistance to water and/or soap or detergents and water, freedom from tactile greasiness or oiliness due to mineral and/or vegetable oils, marked solvency and coupling effects for lanolin, lanolin isolates and derivatives either alone or in the presence of mineral and vegetable oils and freedom from tackiness or greasiness in preparations containing any of the above-mentioned materials.

Considering specific applications of the hydrophilic polymers; they are useful in creams, which essentially comprise an oleaginous base, either as an addition thereto or to replace, at least in part, oily fatty and/or waxy ingredients of the creams. For example, the polymers may partly replace the almond oil, mineral oil, lanolin, beeswax, paraflin wax, oleic acid, or spermaceti, and the like, which are conventionally used in creams, whether of the cleansing, emollient, or finishing types, and including cold cream, quick-liquefying cream, liquid cleanser cream, night cream, massage cream, vanishing cream, foundation cream, and various special creams. An advantage of replacing at least part of such materials is that the soiling tendency of the creams is reduced, that is to say, the creams after being spread over the skin by the user are less apt to pick up or attract soil or foreign particles, similarly, the deposited creams transfer off the users skin less readily, as by contact with clothing, bed sheets, and the like. This last advantage is of particular importance in other creams such as deodorants, including deodorizer and anti-perspirant creams, which are used under the arms and on the palms and soles and which are quite apt to come in contact with clothing and to soil it to such an extent that the garments are frequently ruined. The lanolin, petroleum, cresin, beeswax, cocoa butter, and/ or stearic acid contents of emollient and vanishing creams, and also of cream and paste rouges, can be partly supplanted to reduce their soiling tendency, and more particularly to reduce their oily or creamy feel while yet retaining their power of free motion over the skin. Because they are lubricatious in a cream preparation without increasing its oleaginous character, cross-linked polymers are suitable for addition to creams to be applied to the oily skin.

Special creams such as protective creams can usefully incorporate the polymers of this invention. The creams can be of any suitable type, such as a mixture of fats and oils, a jelly containing a physical barrier, an emulsion, or a soap base. These creams are of particular value for protecting the hands from injury, or from soiling, in carrying out many processes and procedures in industrial plants. These creams containing physical barriers are particularly adapted to receive the hydrophilic polymers, which being available in various particle sizes, may form protective barriers on the skin of varying degrees of fineness and smoothness.

Make-up powders for the face may benefit from the presence of the polymers. These powders usually comprise an opacifying agent (clay, titania, magnesia zinc oxide, etc.), a slip material (talc, metal stearates, etc.), an adherent material (stearates, clay, etc.) and an absorbent (chalk, calcium carbonate, kaolin, etc.). The hydrophilic polymers are capable of replacing in whole or in part, metal salts and oxides like chalk, lkaolin, magnesium carbonate, talc, titania, magnesium stearate, zinc oxide, zinc stearate and the like. An advantage of such a substitution is the reduced incidence of undesirable dermatological reactions. For example, in the case of magnesium carbonate, a widely used ingredient, it is known that some persons are sensitive to the presence of trace amounts of elements like selenium, arsinic, or mercury which tend to be present in the magnesium carbonate owing to the dilficulty of purifying it. The gravity of the problem is underlined by the fact that amounts of selenium as low as one part per million may be detrimental. Other conventional ingredients, if not sufficiently fine, may give rise to mechanical irritation. In the case of ingredients like talc, by omitting it there is eliminated its characteristic earthy odor, which otherwise must be masked. Of further interest is the effectiveness of the polymers for sorbing oil, this properly being useful in face powders for combating oily skin, especially on the nose. By sorption is meant the capacity of the polymeric powder to absorb oily, fatty, greasy, waxy and aqueous materials.

In addition to the foregoing capabilities, the polymers are of benefits to loose face powder compositions by virtue of their excellent adherence to surfaces including the skin, by the degree to which their particle size may be varied, and by the extent to which their flufiiness or bulk density may be changed. Therefore, they are useful in place of the adherent agents noted. By incorporating conventional amounts of a desired color and a desired perfume, a complete, esthetically suitable face powder may be made which will inherently have a mat effect, and which may be used per se or serve as a base, with or without the color and perfume, to which only minor additions need be made to obtain desired finished powders to suit different types of skin.

In compact powders, including face powder and rouge, which are pressed after the addition of a binder like gum arabic, gum tragacanth, glycerine, sorbitol, etc., the use of the hydrophilic polymers can eliminate the need for the binder as they are inherently compressible in the dry or wet state to any desired degree.

The polymers are also useful in lipstick compositions and can replace one or more olaginous ingredients in whole or part, such as the fats and waxes, with the advantage or decreased greasinese without loss of lubricity, and improved consistency retention. Fats and waxes which are commonly used in lipstick compositions include beeswax, carnauba Wax, ceresin, lanolin, lard, mineral oil, petrolatum, etc. conventionally used lipstick flavors, usually comprising a volatile, Water-immiscible organic ester, may be better retained in the lipstick owing to the good sorptive capacity of the polymers for such compounds. The polymers form free-flowing, apparently dry mixes with flavors, and thus can facilitate lipstick manufacture by serving as a carrier for introducing these volatile compounds to the production batch and losses of the flavors may be reduced.

In mascara preparations such as mascara cake, the polymers can supplant conventional soaps like triethanolamine stearate, triethanolamine, oleate, etc., and thereby render the preparation less irritating to the eyes. The waxes frequently used in these preparations, and also in roll-on mascara and cream mascara, can be at least partly replaced with advantages similar to those described in wax substitutions. The hydrophilic polymers of this invention are also capable of imparting a cleaner effect to eyelashes, avoiding the thick, pasty, or crumbly look resulting from the use of some conventional preparations or the startling effect imparted by some enamel-like preparations. Use of the polymers permits a wider selection of colors to be employed and thus may avoid dependence on the conventional but somewhat dangerous use of silver nitrate with sodium thiosulfate. Suitable colors include natural pigments, e.g. carbon, ochers, siennas, umbers, ultramarine, etc. In similar ways, the polymers are of value to other cosmetics for use around the eye, as in eye shadow sticks, eye liner pencils, and eyebrow pencils.

The hydrophilic polymers of the invention can improve shaving creams, soaps and sticks of the lathering type by strengthening and stabilizing the lather.

In sunscreen products, including suntan products and leg paints, the hydrophilic polymers provide lubricity without greasiness, and in addition, the adherence of the product to the skin is enhanced, and its water-removability improved. As these preparations are frequently in dispersion form, a further advantage resides in the stability which is imparted to the dispersions by the presence of the polymers. Of interest in this connection are simple 2-, 3-, or 4-component sunscreen preparations made by mixing a base like petrolatum or zinc oxide or lanolin with the hydrophilic polymer and water. A sunburn preventive can be added to help block out harmful radiation, including r such agents as acetanilide, cholesterol, p-aminobenzoic and salicylic acid salts, quinine salts, and the like. These compounds form compatible mixtures. Suntan make-up, whether in loose powder form for the face and other areas, or in cake form, can be benefited in the manner described for make-up powders.

In manicure compositions, water removable nail coating compositions can be prepared comprising simply a hydrophilic polymer of this invention, a coloring agent, and solvent. The polymer provides the necessary adherence to the nails. Such compositions are of value for application to the nails for a single occasion of short duration, after which the coatings are removable by simply washing the hands in water.

The polymers of this invention are also effective in hair preparations.

The present invention overcomes the disadvantages pointed out supra of previous hair preparations. Even though the hydrophilic polymers of the invention are insoluble in water, they are easily removed, e.g. with conventional shampoo.

Hair sprays produced according to this invention comprise a soluble hydrophilic polymer such as previously described and a non-toxic organic solvent. When an aerosol is to be prepared thence propellant is also used. As the organic solvent there can be employed alcohols, particularly lower aliphatic saturated alcohols e.g. ethyl alcohol, isopropyl alcohol, propyl alcohol, glycols, e.g. ethylene glycol diethylene glycol, propylene glycol and dipropylene glycol, glycerine, ethylene glycol methyl ether, ethylene glycol ethyl ether, n-propylene glycol monomethyl ether, npropylene glycol monoethyl ether, isopropylene glycol monomethyl ether, isopropylene glycol monoethyl ether, ethyl acetate. Mixtures of these solvents with minor amounts of water, e.g. up to 30% Water, can be also em ployed. Glycols and glycerine and similar polyhydric alcohols act as plasticizers for the hydrophilic polymer.

Generally the amount of hydrophilic polymer will be about 0.5 to 10%, preferably 0.75 to 5%, by weight of the total hair spray composition.

Hair setting and hair straightening compositions are also produced according to the invention using 0.5 to 10% of the hydrophilic polymer in the solvent.

Such compositions not only provide the desired temporary set-holding characteristics and maintains the hair in the desired configuration until removed, but do so even when the hair is exposed to conditions of high humidity without the development of any appreciable surface track. In addition, the hair thus treated, despite its resistance to moisture, is remarkably free from any tendency to develop static electrical charges when combed or brushed under conditions of low humidity. Furthermore, the treated hair is capable of being reset merely by use of water-dampened comb. Finally, the film on the hair may readily be removed, despite its resistance to moisture, by a mild shampoo.

The hydrophilic polymers can be used not only in solution, but also in compositions having the form of stable gels, creams and the like without requiring the presence of an emulsifying agent. They can have the physical form of a jelly, paste, plastic mass, or the like and generally comprise the hydrophilic polymer in an amount of 2 to by weight of the total composition. Advantageously there can be included 7 to of a thixotropic agent such as Carbopol 961 (sucrose acrylate having free acid groups).

The amount of solvent is usually 10% or more of the total hair preparation. When a propellant is present the solvent is normally not over 60% and is preferably to 40% of til'ie total hair preparation by weight.

When the hydrophilic polymer is packaged in an aerosol container the propellant should be sufficient to force the composition out of the container as a spray. The propellant can vary considerably, but usually is about 25 to 85%, preferably 50 to 70%, of the total hair spray composition. As the aerosol propellants there can be used compressed gasses such as carbon dioxide, nitrous oxide and nitrogen, liquid volatile hydrocarbon such as propane, n-butane, isobutane, Z-methyl butane and fluorinated compounds including perhalogenated compounds and fluorinated hydrocarbons such as dichlorodifiuoromethane, trichlorofluoromethane, 1,2-dichlorotetrafluoroethane, octafiuorocyclobutane, chlorodifluoromethane, 1,1-difiuoroethane, l-chloro- 1 l-difluoroethane. These fiuorinated compounds are available under the name Freon and Genetron. The propellant should contain a substantial amount of volatile material boiling at not over 20 C., but there can also be present a significant amount of less volatile material boiling up to 50 C., e.g. methylene chloride can be present as a substantial part of the propellant. Of course perfumes or other essences can be included in the formulations.

As catalysts for carrying out the polymerization there is employed free radical catalyst in the range of 0.05 to 1% of the polymerizable hydroxyalkyl ester, for example, the preferred amount of catalyst is 0.1 to 0.2% of the monomer. Typical catalysts include t-butyl peroctoate, benzoyl peroxide, isopropyl percarbonate, methylethylketone peroxide, cumene hydroperoxide and dicumylperoxide. Irradiation, e.g., by ultra violet light or gamma rays, also can be employed to catalyze the polymerization. Polymerization can be done at 20 to 150 0. usually 40 to 90 C.

When cross-linked polymers are prepared the method of polymerization is not critical and the monomers can be polymerized in Water by suspension polymerization, in organic solvent or without any solvent. However, when hydrophilic soluble thermoplastic polymers are desired they are preferably prepared by suspension polymerziation of the hydrophilic monomers in a non-polar medium such as silicone oil, mineral oil, xylene, toluene, benzene or the like. Alternatively they can be polymerized while in solution in ethyl alcohol, methyl alcohol, propyl alcohol, isopropyl alcohol, formamide, dimethyl sulfoxide or other appropriate solvent.

In the suspension polymerization procedure the catalyst containing monomer is dispersed in the non-polar medium in the form of small droplets which are polymerized to form finely divided spheres or beads. The beads are dissolved in the polar organic solvents, e.g., ethyl alcohol, isopropyl alcohol, ethyl alcohol-water (e.g. 95:5 or 70: glycols and glycol ethers for use as sprays, etc. or are mixed with other ingredients to make creams, powders or the like.

Suspension polymerization is preferably carried out at 50-405 C. until bead formation is completed. The ratio of suspension oil to monomer can be varied widely, but preferably is from 5:1 to 20: 1. As stated the catalyst to monomer ratio is preferably from 0.05 to 1.0 parts per 100 parts of monomer.

One method of incorporating the hydrophilic polymeric powders with cosmetic ingredients or essences dissolved in an appropriate solvent is to place the mixture on a mechanical roller so that the solution becomes intimately mixed with the powder. The mixture is dried by air evaporation or forced heat. Upon evaporation of the solvent the cosmetic ingredients and/or essences are retained by the powder.

EXAMPLE 1 Into a flask equipped with an agitator and a heating mantle was charged 1000 grams of silicone oil (polydimethyl silicone); 100 grams of 2-hydroxyethyl methacrylate and 0.33 gram of isopropyl percarbonate. The flask was placed under a nitrogen atmosphere and the contents were rapidly agitated and heated to 100 C. After 15 minutes at 100 C., the polymer slurry obtained was filtered hot to isolate the polymer. The polymer powder was reslurried in 300 ml. of xylene, filtered and dried. A 98% yield of 2 to 5 micron particle size powder was obtained.

EXAMPLE 2 The thermoplastic, solvent soluble poly-(2-hydroxyethyl methacrylate) polymeric powder formed in Example 1 was mixed with an oil of orchids perfume essence and the resultant mixture placed on a mechanical roller for approximately 8 hours. The polymeric powder thus absorbed the essence. The mixture was filtered and the residue dried at room temperature.

EXAMPLE 3 Example 1 was repeated using xylene in place of the silicone oil. The amount of Z-hydroxyethyl methacrylate was increased from 100 grams to 300 grams and the quantity of isopropyl percarbonate was increased to 0.99 gram. An yield of polymer beads was obtained.

EXAMPLE 4 Example 1 was repeated using mineral oil in place of the silicone oil, the amount of Z-hydroxyethyl methacrylate was increased from grams to 200 grams and the quantity of isopropyl percarbonate was increased from 0.33 to 0.66 gram. A 98% yield of polymer beads ranging in diameter from 2 to 5 microns was obtained.

EXAMPLE 5 800 grams of ethylene glycol monomethyl ether, grams of Z-hydroxyethyl methacrylate, 20 grams of acrylic acid and 2 grams of t-butyl peroctoate were charged into a flask. The solution was heated and stirred under a carbon dioxide atmosphere at 85 C. for 6 hours. The thermoplastic hydrophilic polymer formed was precipitated by pouring the reaction solution into 10 liters of rapidly agitated water. The precipitated polymer was isolated by filtration and dried. The product of this example while thermoplastic and solvent soluble has the capability of curing to cross-linked solvent insoluble polymer by further heating, particularly if additional catalyst is added. In contrast, the polymers of Examples 1, 3, and 4 are permanently thermoplastic and solvent soluble. The copolymers formed in Examples 7-13 are all cross-linked.

EXAMPLE 6 The procedure of Example 1 was repeated replacing the 2-hydroxyethyl methacrylate by 100 grams of Z-hydroxypropyl methacrylate to produce a thermoplastic solvent soluble hydrophilic finely divided bead polymer.

EXAMPLE 7 This example shows the preparation of a cross-linked polymer prepared with the aid of a foaming agent. The use of a foaming agent, e.g. sodium bicarbonate, potassium bicarbonate, azodicarbonamide, benzene sulfonyl hydrazide, azo-bis-isobutyronitrile, etc. aids in preparing polymers which are in the form of a foam which is easily disintegrated to form a fine powder by means of a shearing action. Quantities of 0.5 to 10 grams of foaming agent per 100 grams of reactants are adequate.

100 grams of 2-hydroxyethyl methacrylate, 0.15 gram of t-butyl peroctoate, 0.20 gram of ethylene glycol dimethacrylate and 1 gram of sodium bicarbonate were heated to 70 C. and the resulting solid friabe polymeric foam ground into a powder of 80 mesh size (U.S. Standard Sieve).

EXAMPLE 8 100 grams of purified Z-hydroxyethyl methacrylate was mixed with 0.2 gram of ethylene glycol dimethacrylate and 1 gram of benzoyl peroxide. The mixture was sprayed via a nozzle which forms fine droplets into a chamber containing nitrogen at 150 C. After spraying of the monomer was concluded, 36 grams of polymer beads were recovered.

EXAMPLE. 9

An aqueous solution was prepared from 15% acrylamide, 10% ethylene glycol monomethacrylate, 0.1% ethylene glycol dimethacrylate and the balance water. One liter of this solution was mixed with 10 ml. of an aqueous 2% solution of sodium thiosulfate and 15 ml. of an aqueous 2% solution of ammonium persulfate and the mixture allowed to polymerize at room temperature. The resulting gel was then finely divided to give a cross-linked hydrophilic polymer.

EXAMPLE 10 A polymerization mixture was prepared from 15 parts methacrylamide, 80 parts ethylene glycol monomethacrylate, 0.4 part ethylene glycol bis-methacrylate and parts of dibenzoyl peroxide. The mixture was rotated at 400 rpm. in a helium atmosphere at 80 C. for 6 hours to give a cross-linked copolymer. The polymer was then finely divided (below 100 mesh).

EXAMPLE 11 97 parts of ethylene glycol monomethacrylate, 0.25 part ethylene glycol bis-methacrylate, 0.25 part diethylene glycol bis-methacrylate, 2 parts ethylene glycol and 0.2 part diisopropyl percarbonate were rotated 80 minutes at 420 r.p.m. in a carbon dioxide atmosphere at 60 C. to produce a cross-linked hydrophilic copolymer. The polymer was then finely divided, i.e. to less than 100 mesh.

EXAMPLE 12 15 parts of a monomer mixture consisting of 99.7% ethylene glycol monomethacrylate and 0.3% ethylene glycol bis-methacrylate as a cross-linking agent, 85 parts glycerol and 0.1 part diethyl percarbonate as a catalyst was heated at 65 C. for 20 minutes to form a crosslinked hydrophilic polymer.

EXAMPLE 13 50 ml. of a mixture of 98% ethylene glycol monomethacrylate, 0.3% diethylene glycol bis-methacrylate and 1% ethylene glycol were mixed with 50 ml. formamide and an amount of azo-bis-isobutyronitrile corresponding to 0.2% of the combined monomers. Polymerization was performed at 75 C. for 50 minutes to give a cross-linked hydrophilic polymer.

EXAMPLE 14 30 grams of the solvent soluble, thermoplastic hydrophilic poly(2-hydroxyethyl methacrylate) prepared in Example 1 was dissolved in 70 ml. of methanol. To the solution was added 4.0 grams of peppermint oil. The viscous solution was coated on an impervious plate and allowed to dry to form a film 1.0 mil thick. The dry film was stripped from the plate and ground to form minute platelets. These were incorporated in an amount of about 1% in Crest-type toothpaste devoid of flavoring to provide prolonged release of the peppermint flavor on contact of the product with an aqueous medium, e.g. in the normal brushing of teeth.

10 The toothpaste formula was:

Parts Hydrophilic polymer platelets containing pepermint oil Calcium pyrophosphate 39 Sodium carboxymethyl cellulose 1.20 Magnesium aluminum silicate 0.40 S rbitol 20.00 Sodium coconut monoglyceride sulfonate 0.81 Sodium lauryl sulfate 0.70 Saccharin 0.12 Stannous pyrophosphate 1.00 Water 25.77

EXAMPLE 15 A hair setting composition was prepared from 1.90 parts of the poly 2-hydroxyethyl rnethacrylate prepared in Example 1, 0.10 part of perfume (oil of orchids) and 28 parts of ethyl alcohol. This solution (50% of the total formulation) was packaged in a conventional aerosol pressure can container together with 45.5 parts (32% of the total formulation) of monofluorotrichloromethane and 24.5 parts (18% of the total) of methylene chloride.

The aerosol was sprayed on hair held in a desired configuration and allowed to dry, the formulation was found to provide satisfactory set-holding characteristics even under conditions of high humidity. The sprayed hair was natural looking, non-sticky, non-static and exhibited holding power for a relatively long period of time.

EXAMPLE 16 A 5% solution of the polymeric Z-hydroxyethyl methacrylate prepared in Example 1 in ethyl alcohol (95% alcohol, 5% water) was applied to kinky hair. The hair was relaxed and then rolled on rollers and held in tension until dried. When dry the hair was set and could be combed in conventional fashion. The permanent remained until the hair was wet.

Drying can be accomplished with or without a conventional hair dryer. In place of the rollers of any other conventional means for holding the hair in tension can be employed.

EXAMPLE 17 A more flexible wave can be obtained by incorporating 5 to based on the polymer, of glycerol, sorbitol, diethylene glycol, dipropylene glycol, ethylene glycol, propylene glycol or other liquid polyhydric alcohol as a plasticizer.

Thus a more flexible wave than that of Example 16 was obtained by applying to the hair, a solution of 5 parts of the poly 2-hydroxyethyl methacrylate, 100 parts of 95% ethyl alcohol and 0.75 part of glycerol. After the hair was relaxed it was held in tension until dried using a hair dryer. The hair was thus set .and was combed in conventional manner. Not only was a more flexible wave obtained, but the use of glycerol prevented flaking of the polymer when the hair was combed.

EXAMPLE 18 To impart greater sheen to the hair a small amount, e.g. 23% of silicone oil can be added to the formulation. Thus the formulation of Example 17 was modified by adding 3% of dimethyl polysiloxane oil based on the 2-hydroxyethyl methacrylate polymer to give a flexible permanent wave having a high sheen.

The hair straightener compositions can be brushed on the hair, poured on the hair or combed on the hair. The preferred solvent is ethyl alcohol with or without minor amounts of water. There can also be employed other solvents such as isopropyl alcohol, monomethyl ether of ethylene glycol, monoethyl ether of ethylene glycol, normal or isopropylene glycol monomethyl ether, normal or isopropylene glycol monoethyl ether.

1 1 EXAMPLE 19 A hair setting gel was produced having the following formulation:

Parts Hydrophilic Z-hydroxyethyl methacrylate polymer of Example 1 10 Ethyl alcohol (95%) 144 Water 36 Carbopol 940 (sucrose acrylate polymer having free acrylic acid groups) 1.2 Glycerine 1.4

Solulan 98 (acetylated polyoxyethylated lanolin) 1.0

Triton X-100 (polyoxyethylene (l)-nonylphenol condensate) Essence (lavender oil) 0.6

The polymer was dissolved in the alcohol-water mixture to form a solution. The solution was then mixed with the remaining ingredients by rapid stirring and the pH of the mixture adjusted to a pH of about 7.2 by adding a 10% solution of diisopropanolamine in 95 ethyl alcohol. This gel was suitable for setting hair. Thus a sample of curly hair was straightened by heat and pressure, coated with the above gel and soaked in water. A control sample of the curly hair was also straightened, but remained uncoated when soaked in water. The control sample returned to its original curly configuration after 30 seconds while the coated sample remained straight for about 3 minutes.

In place of the diisopropanolamine there can also be used triethanolamine, diethanolamine or tripropanolamine as a gelling agent in this example.

EXAMPLE 20 Into a bottle equipped with an agitator and a heating mantle was charged 20 liters of 2-hydroxy ethyl methacrylate, 50 liters of methanol, 30 liters of water and 10 grams of t-butyl peroctoate. The kettle was flushed with carbon dioxide and the contents were rapidly agitated and heated to 75 C. After 8 hours at 75 C. the polymer, representing an 85% polymeric conversion, was isolated. The polymer solution was precipitated from 500 liters of water, filtered and dried at room temperature.

EXAMPLE 21 A cosmetic emulsion with the following formulation was prepared.

Two solutions were formulated:

Solution A: Parts Polymer produced according to Example 20 30 Ethanol 95% 61.34

Water 75.02

Essence 0.5

Solution B:

Mineral oil I 30 Atlas polysorbate 80 2.96 Triton X-100 0.68

Solution A is added slowly to solution B with rapid stirring for minutes. A stable emulsion results which could be applied to the hands or face. Polysorbate 80 is polyoxyethylene (20) sorbitan monooleate.

EXAMPLE 22 An insect repellant sun screen lotion was prepared with the following formulation:

Parts Hydrophilic polymer of Example 1 1 Ethanol (95%) 60 Water 38 2-ethyl-l,3-hexandiol 0.5 2-ethoxyethyl-p methoxy cinnamate 0.5

EXAMPLE 23 100 parts of the hydrophilic polymer prepared in Example 1 containing parts of essence (oil of orchids) 12 was homogeneously mixed with 5 parts of hexachlorophene. 75 parts of the resulting mixture was mixed with a conventional toilet soap (Ivory) to provide a composite soap having a pleasant smell, antiseptic and increased lubricity characteristics.

EXAMPLE 24 The hydrophilic polymers of the present invention in powder form can be incorporated in a fat or oil or lanolin in an amount of 1 to 40% to release a fragrance on contact with water. Thus 1 part of perfume was absorbed in 10 parts of the cross-linked hydrophilic polymer prepared in Example 7 and this was incorporated with 100 parts of lanolin.

EXAMPLE 25 A sun screen aerosol was made from 1 part of the poly Z-hydroxyethyl mothacrylate prepared in Example 1, 30 parts of ethyl alcohol, 0.5 part of Z-ethoxyethyl-pmethoxy cinnamate and 68.5 parts of dichlorotetrafluoroethane. The aerosol was sprayed from the container onto the body and acted as an effective sun screen.

EXAMPLE 26 20 parts of aluminum chlorohydrol, in parts of water, 10 parts of hydroxyethyl methacrylate containing 1 part of perfume (e.g. rose oil) and 0.04 part of isopropyl percarbonate were polymerized at 70 C. for two hours. The solid obtained was ground to a powder-less than 300 mesh and was useful as a deodorant by applying the same to the body.

EXAMPLE 28 A nail enamel was prepared by making a 10% solution of the polymer prepared in Example 1 in alcohol together with a small amount of red dye. The resulting solution was applied to fingernails and allowed to dry.

EXAMPLE 29 A cleansing cream was prepared from a mixture of 5 parts almond oil, 15 parts lanolin, 5 parts of the hydrophilie 2-hydroxyethyl methacrylate polymer prepared in Example 1, 30 parts paraffin wax, 5 parts borax and 35 parts distilled water.

EXAMPLE 30 Another cleansing cream was prepared from 25 parts almond oil, 10 parts beeswax, 15 parts lanolin, 8 parts spermaceti, 12 parts of the hydrophilic cross-linked polymer of Example 11 and 30 parts of rose water.

EXAMPLE 31 A cleansing cream was prepared from 7 parts beeswax, 30 parts mineral oil, 15 parts soyabean oil, 10 parts spermaceti, 1 part borax, 8 parts of the hydrophilic polymer prepared in Example 6 and 29 parts of rose water.

EXAMPLE 32 A vanishing foundation cream was prepared from 8 parts glycerol, 1 part potassium hydroxide, 20 parts stearic acid, 0.5 part perfume, 7 parts of the hydrophilic polymer of Example 1 and 63.5 parts of water.

EXAMPLE 33 A vanishing cream Was prepared from 0.5 part cetyl alcohol, 5 parts glycerol, 4 parts lanolin, 3 parts mineral oil, 20 parts stearlc acid, 2 parts triethanolamine, 0.5 part 13 part oil of orchids, 3 parts of the hydrophilic polymer prepared in Example and 62 parts of water.

EXAMPLE 34 A quick-liquefying hand cream was made from 12 parts cresin, 85 parts mineral oil and 3 parts of the hydrophilic polymer prepared in Example 4.

EXAMPLE 35 An emollient cream for softening the skin was prepared from 5 parts lanolin, 4 parts beeswax, parts cocoa butter, 10 parts almond oil, 35 parts solid petrolatum, 5 parts spermaceti, 3 parts of the hydrophilic polymer prepared in Example 1, 0.5 part of perfume, 0.2 part preservative and 27.3 parts water.

"EXAMPLE 36 A face powder was made from 10 parts precipitated chalk, 75 parts talc, 5 parts of the hydrophilic polymer of Example 1, 5 parts zinc oxide and 5 parts zinc stearate.

EXAMPLE 37 A loose face powder was prepared from 3 parts kaolin, 70 parts talc, 1.5 parts magnesium stearate, 2 parts of D & C Red No. 2 (lake) 20% in talc, D & C Red No. 3 (lake) 10% tale, 1 part yellow iron oxide 20% in talc and 1 part rose oil absorbed in 4.5 parts of the hydrophilic polymer of Example 7.

EXAMPLE 38 A cake type face powder was prepared from 10 parts kaolin, 5 parts zinc stearate, 10 parts zinc oxide, 3 parts magnesium carbonate, 61 parts talc (French), 1.4 parts of the hydrophilic polymer prepared in Example 1, 2 parts light mineral oil, 1 part cetyl alcohol, 0.3 part lanolin, 2.7 parts D & C Orange No. 4 (lake), 10% in talc, 0.8 part D & C No. 2 (lake), 20% in tale, 1 part brown iron oxide, 20% in talc and 0.8 part perfume.

EXAMPLE 39 A baby powder was prepared from 80 parts tale, 9 parts zinc stearate, 5 parts boric acid and 0.25 part perfume absorbed in 5.75 parts of the hydrophilic polymer prepared in Example 1.

EXAMPLE 40 A lipstick was prepared from 12 parts beeswax, 3 parts of the hydrophilic polymer of Example 1, 5 parts Carnauba wax, 20 parts ceresin, 5 parts lanolin, 28 parts lard, parts mineral oil, 2 parts of dibrorno fluorescein and 10 parts of lakes (a mixture of equal parts of D 8: C No. 9 and D & C Orange No. 4).

In addition to the polymers set forth supra, it has also been found that hair spray and hair setting compositions can be prepared from other hydrophilic copolymers, the term copolymers being employed generically to cover polymers of 2, 3, 4 or more reactants. Such copolymers include copolymers of hydroxyalkyl monoacrylates or methacrylates of the type set forth supra, e. g. hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl methacrylate with 1 to 50%, preferably 5 to 25% of lower alkyl acrylates and methacrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, sec. butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate and sec. butyl methacrylate.

Other suitable copolymers include copolymers of the hydroxyalkyl acrylates or methacrylates as set forth supra with 1 to 60%, preferably 5 to 25 of lower alkoxy lower alkyl acrylates and methacrylates where the lower alkyl has at least 2 carbon atoms, e.g. methoxyethyl acrylate, ethoxyethyl acrylate, propoxyethyl acrylate, butoxyethyl acrylate, methoxypropyl acrylate, methoxybutyl acrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, propoxyethyl methacrylate, butoxyethyl methacrylate, ethoxypropyl methacrylate. Preferably methoxyethyl and ethoxy ethyl acrylates are employed.

There can also be employed copolymers of the hydroxyalkyl acrylates and methacrylates as set forth supra with 0.1 to 25% usually at least 1% and preferably 5 to 15% of ethylenically unsaturated amines.

As the ethylenically unsaturated amine there can be used p-aminostyrene, o-aminostyrene, 2-amino 4 vinyltoluene, alkylamino alkyl acrylates and methacrylates, e.g. diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, t-butylaminoethyl acrylate, t-butylaminoethyl methacrylate, piperdinoethyl acrylate, piperidinoethyl methacrylate, morpholinoethyl acrylate, morpholinoethyl methacrylate, 2-vinylpyridine, 3-vinyl pyridine, 4- vinyl pyridine, 2-ethyl-5-vinylpyridine, dimethylamino propyl acrylate, dimethylamino propyl methacrylate, clipropylaminoethyl acrylate, dipropylaminoethyl methacrylate, di-n-butylaminoethyl acrylate, di-n-butylaminoethyl methacrylate, di-sec. butylaminoethyl acrylate, di-sec. butylaminoethyl methacrylate, dimethylaminoethyl vinyl ether, dimethyl aminoethyl vinyl sulfide, diethylaminoethyl vinyl ether, diethylaminoethyl vinyl sulfide, aminoethyl vinyl ether, aminoethyl vinyl sulfide mono methylaminoethyl vinyl sulfide, monoethylaminoethyl vinyl ether, N-(gamma-monomethylamino) propyl acrylamide, N-(beta-monomethylamino) ethyl acrylamide, N-(betamonomethylamino) ethyl methacrylamide, l0aminodecyl vinyl ether, 8-aminooctyl vinyl ether, S-aminopentyl vinyl ether, 3'aminopropyl vinyl ether, 4-aminobutyl vinyl ether, 2-aminobutyl vinyl ether, monoethylaminoethyl methacrylate, N-(3,5,5-trimethylhexyl) aminoethyl vinyl ether, N-cyclohexylarninoethyl vinyl ether, 2-(1,1,3,3- tetramethylbutylamino) ethyl methacrylate, N-t-butylaminoethyl vinyl ether, N-methylaminoethyl vinyl ether, N-Z-ethylhexylaminoethyl vinyl ether, N-t-butylaminm ethyl vinyl ether, N-t-octylaminoethyl vinyl ether, 2-pyrrolidinoethyl acrylate, 2-pyrrolidinoethyl methacrylate, 3- (dimethylaminoethyl)-2-hydroxypropyl acrylate, 3'(dimethylaminoethyl) 2 hydroxypropyl methacrylate, 2- aminoethyl acrylate, 2 -aminoethyl methacrylate. The presently preferred amino compounds are alkylaminoethyl acrylates and methacrylates, most preferably t-butyl aminoethyl methacrylate.

Furthermore, there can be employed copolymers of the hydroxyalkyl acrylates and methacrylates as set forth supra with 0.1 to 15%, usually at least 1% and preferably 5 to 15% of ethylenically unsaturated carboxylic acids such as those set forth supra, e.g. acrylic acid, methacrylic acid, itaconic acid, 2-hydroxyethy1 itaconate, etc.

Of Course, there can be used a plurality of the alkyl acrylates and/or methacrylates; alkoxyalkyl acrylates and methacrylates, etc. A particularly preferred mixture of alkoxyalkyl acrylates and methacrylates contains 20 to ethoxyethyl acrylate or methaerylate and 80 to 20% methoxyethyl acrylate or methacrylate based on the total amount of this constituent employed.

Useful terpolymers include terpolymers of (l) at least 50% of the hydroxy alkyl acrylate or methacrylate (2) l to 49.9% of the alkyl acrylate or methacrylate and (3) 0.1 to 15%, preferably at least 1%, of the ethylenically unsatuarted acid or 0.1 to 25%, preferably at least 1%, of the ethylenically unsaturated amine or terpolymers of (l) at least 50% hydroxyalkyl acrylate or methacrylate, (2) l to 49.9% of lower alkoxy lower alkyl acrylate or methacrylate (where the lower alkyl has at least 2 carbon atoms) and (3) 0.1 to 15%, preferably at least 1%, of the ethylenically unsaturated acid or 0.1 to 25%, preferably at least 1%, of the ethylenically unsaturated amine.

Tetrapolyrners are also useful which are like the terpolymers of the preceding paragraph but which contain both the unsaturated acid and amine in the proportions specified, e.g. a tetrapolymer of hydroxyethyl methacrylate, ethyl acrylate, 5% dimethylaminoethyl acrylate and 5% methacrylic acid.

Additional useful polymers are terpolymers of alkoxyalkyl acrylates or methacrylates as specified above with 1 to 49.9% of lower alkyl acrylates or methacrylates and 0.1 to preferably at least 1%, of ethylenically unsaturated acids as specified above, particularly acrylic acid or methacrylic acid, and terpolyrners of alkoxyalkyl acrylates or methacrylates as specified above with 1 to 49.9% of lower alkyl acrylates or methacrylates and 0.1 to 25%, preferably at least 1%, of ethylenically unsaturated amines as specified above. Similarly tetrapolymers can be employed containing both the acid and amine.

Furthermore, there can be employed copolymers of 1 to 99%, preferably to 80% of ethoxyethyl acrylate or methacrylate with 99 to 1%, preferably 80 to 20%, of methoxyethyl acrylate or methacrylate. Likewise, there can be employed terpolymers containing the ethoxyethyl acrylate or methacrylate and the methoxyethyl acrylate or methacrylate in the above indicated ranges in relation to each other (i.e. 1 to 99%) together with 0.1 to preferably at least 1%, of ethylenically unsaturated amine or 0.1 to 15%, preferably at least 1%, of ethylenically unsaturated acid based on the total amount of monomers. There can also be employed tetrapolymers wherein both the unsaturated amine and unsaturated acid are employed in the proportions specified.

Polymers containing a major proportion of hydroxy alkyl acrylate or methacrylate have the desired properties of adequate adhesion to hair and adequate control or holding power for many purposes. The incorporation of relatively hydrophobic species such as alkyl acrylates or methacrylates increases the holding power where this is desire-d and also maintains the holding power at relatively high humidities.

The incorporation of ethoxyethyl and methoxyethyl acrylate or methacrylate and similar alkoxyalkyl acrylates and methacrylates provides softer films on the hair which result in a more natural feel.

The incorporation of minor quantities of ethylenically unsaturated amino containing monomers enhances adhesion to hair and the incorporation of ethylenically unsaturated carboxylic acid group containing monomers assures easy removal of the film cast on hair by employing mildly alkaline shampoos as pointed out supra.

The polymers are conveniently prepared by solution polymerization in lower aliphatic alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol and isopropyl alcohol as set forth supra using the same catalysts as previously set forth as well as diisopropyl percarbonate and azo bis isobutyronitrile for example.

EXAMPLE 41 A reactor was charged with 80 kilograms of ethyl alcohol, 15 kilograms of hydroxyethyl methacrylate, 4 kilograms of methyl methacrylate and 1 kilogram of dimethylaminoethyl methacrylate. 100 grams of t-butyl peroctoate was added, the reactor purged with nitrogen and heated to 80 C. After stirring at 80 C. for 7 hours a conversion of 98.5% of the monomers to polymer achieved.

EXAMPLE 42 100 grams of polymer solution of Example 41 was diluted with 300 grams of ethyl alcohol. 100 grams of the dilute solution was placed in an aerosol can along with grams of methylene chloride, 70 grams of Freon-l2 (dichlorodifluoromethane) propellant and 0.1 gram of perfume oil.

The formulation was sprayed on hair on the head to provide high holding power at relatively high humidities.

The solvent soluble polymers employed in the present invention generally have an intrinsic viscosity as measured in Methyl Cellosolve of 0.1 to 0.6. All of the organic solvent soluble polymers in the specific examples had intrinsic viscosities within that range.

16 EXAMPLE 4:

20 parts of hydroxyethyl methacrylate containing about 0.2% ethylene glycol dimethacrylate, parts of methanol and 0.01 part of t-butyl peroctoate were heated at C. to get about 87-90% conversion to the polymer. The polymer had an intrinsic viscosity of 0.37 measured in Methyl Cellosolve.

The polymer was precipitated by the addition of water and the precipitate dried and ground to form a powder. parts of the powder were dissolved in 300 parts of ethyl alcohol and placed in an aerosol can together with 30 parts of methylene chloride and 70 parts of Freon-12 to provide a hair spray.

EXAMPLE 44 A reactor was charged with 80 kilograms of ethanol, 17 kilograms of hydroxyethyl methacrylate, 2 kilograms of 2-ethoxyethyl methacrylate and 1 kilogram of dimethylaminoethyl methacrylate. The reactor was heated to 70 C. and grams of t-butyl peroctoate was added. After purging with nitrogen, the reactor was closed, and heated to 92 C. and allowed to stir for 6 hours to achieve a conversion of 96% of the monomer to polymer. The reaction mixture was then cooled to room temperature. A small sample was isolated by precipitation in water. This was dried, and dissolved in ethylene glycol monomethyl ether (Methyl Cellosolve) to determine the intrinsic viscosity. A value of 0.42 was obtained.

One hundred grams of the reaction mixture solution was diluted to 400 grams with ethanol. 100 grams of the dilute solution was placed in an aerosol can along with 30 grams of methylene chloride, 70 grams of Freon-12 propellant and 0.1 gram of perfume oil.

The formulation, sprayed on hair, provided good holding power and control of hair style, while maintaining a soft feel.

EXAMPLE 45 Example 44 was repeated using a monomer charge of 17 kilograms of hydroxyethyl methacrylate, 2 kilograms of ethoxyethyl methacrylate and 1 kilogram of acrylic acid. The polymer was obtained in 92% conversion after 7 hours at 93 C. and had an intrinsic viscosity of 0.38 measured in Methyl Cellosolve.

A spray formulated in accordance with Example 44 exhibited good holding power on hair and easy removal with mildly alkaline shampoo.

EXAMPLE 46 Example 44 was repeated using a monomer charge of 15 kilograms of hydroxyethyl methacrylate, 3 kilograms of ethoxyethyl methacrylate, 1.5 kilograms of dimethylaminoethyl methacrylate, and 0.5 kilogram of methacrylic acid. The reaction was carried to 87% conversion after 7 hours at 92 C.

An aerosol spray formulated in accordance with Example 44 exhibited excellent adhesion to hair with no flaking when combed, and was easily removed with shampoo.

EXAMPLE 47 Into a 2 liter flask, equipped with a stirrer and reflux condenser, was charged 800 grams of ethanol, grams of 2-ethoxyethyl methacrylate, 20 grams of ethyl acrylate and 20 grams of t-butylaminoethyl methacrylate. One gram of benzoyl peroxide was added and the flask was heated and stirred at reflux for 6 hours. A conversion of 78% was achieved. The polymer was isolated by precipitation in water and drying.

Ten grams of the polymer was dissolved in 90 grams of ethanol. This solution was added to an aerosol along with 100 grams of a 50:50 mixture of Freon-l1 (trichloromonofluoromethane) and Freon-12 propellant and 0.1 gram of perfume oil.

The resulting hair spray showed excellent substantivity to hair and provided good control at high humidities and 17 a soft feel to the rair. In addition, the spray showed rapid drying characteristics.

EXAMPLE 48 Example 47 was repeated using Z-methoxyethyl methacrylate in place of ethyl acrylate. A conversion of 83% was obtained. A hair spray formulated in accordance with Example 47 aflForded similar results.

EXAMPLE 49 EXAMPLE 50 A 2-liter flask, equipped with a stirrer and reflux condenser was charged with 800 grams of ethanol, 180 grams of hydroxypropyl methacrylate and 20 grams of dimethylaminoethyl methacrylate. One gram of t-butylperoctoate was added and the flask was heated at reflux for 7 hours. The polymer was isolated by precipitation in water and dried. A yield of 183 grams was obtained.

A hair spray formulated in accordance with Example 44 yielded similar results.

EXAMPLE 1 Example 50 was repeated using a monomer charge of 100 grams of hydroxyethyl methacrylate, 80 grams of ethoxyethyl methacrylate, and 20 grams of hydroxypropyl acrylate. The polymer, obtained in 84% yield was formulated into a spray in accordance with Example 44. This spray afforded an exceptionally soft feel to the hair, and was unaffected at high humidities.

EXAMPLE 52 Example 51 was repeated using a monomer charge of 95 grams of hydroxyethyl methacrylate, 75 grams of ethoxyethyl methacrylate, 20 grams of hydroxypropyl acrylate, and grams of methacrylic acid. This polymer, obtained in 79% yield was formulated into a spray in accordance with Example 44. This spray, in addition to providing a very soft feel to hair, was very easily removed by shampoo.

EXAMPLE 53 Using the procedure of Example 44, hair spray formulations were made from copolymers prepared from the following monomer mixtures in the presence of about 0.4% t-butyl peroctoate based on the monomers and 400 parts ethanol as a solvent in accordance with the polymerization technique of Example 44.

(a) 98 parts hydroxyethyl methacrylate 2 parts methacrylic acid (b) 90 parts hydroxyethyl methacrylate 10 parts ethoxyethyl methacrylate (c) 90 parts hydroxyethyl methacrylate 1 0 parts diethylene glycol methacrylate (d) 90 parts hydroxyethyl methacrylate 10 parts methacrylic acid (e) 100 parts hydroxypropyl methacrylate (f) 90 parts hydroxyethyl methacrylate 10 parts dimethylaminoethyl methacrylate (g) 85 parts hydroxyethyl methacrylate parts methyl methacrylate (h) 60 parts hydroxyethyl methacrylate 40 parts methyl methacrylate (i) 50 parts hydroxyethyl methacrylate 40 parts methyl methacrylate 10 parts methacrylic acid (j) 85 parts hydroxyethyl methacrylate 10 parts ethoxyethyl methacrylate 5 parts dimethylaminoethyl methacrylate (k) 70 parts hydroxyethyl methacrylate 15 parts ethoxyethyl methacrylate 15 parts methyl methacrylate (l) 50 parts hydroxyethyl methacrylate 50 parts ethoxyethyl methacrylate (m) 50 parts ethoxyethyl methacrylate 50 parts methoxyethyl methacrylate (n) parts hydroxyethyl methacrylate 15 parts dimethylaminoethyl methacrylate (o) 85 parts hydroxyethyl methacrylate 15 parts t-butylaminoethyl methacrylate (P) 50 parts hydroxyethyl methacrylate 40 parts ethoxyethyl acrylate 10 parts hydroxypropyl methacrylate (q) 85 parts hydroxyethyl methacrylate 15 parts t-butylaminoethyl methacrylate.

While all of the formulations in Example 53 (a) through 53(q) Were useful in preparing hair spray compositions, the formulation in Example 53(j) was particularly useful. The formulation in Example 53(i) was relatively ineffective and is about at the limit of utility according to the invention.

What is claimed is:

1. A process comprising applying to hair a cosmetic preparation, in a nontoxic lower aliphatic saturated alcohol and/0r polyhydric alcohol organic solvent system for the polymer selected from the group consisting of (1) a copolymer of a hydrophilic hydroxy lower alkyl acrylate or methacrylate with 1 to 50% of a lower alkyl acrylate or methacrylate, (2) a copolymer of a hydrophilic hydroxy lower alkyl acrylate or methacrylate with 1 to 60% of a lower alkoxy lower alkyl acrylate or methacrylate having at least 2 carbon atoms in the lower alkyl group, (3) a copolymer of a hydrophilic hydroxy lower alkyl acrylate or methacrylate with 0.1 to 25% of an ethylenically unsaturated amine, (4) a copolymer of a hydrophilic hydroxy lower alkyl acrylate or methacrylate with 0.1 to 15% of an ethylenically unsaturated carboxylic acid, (5) a terpolymer of (a) at least 50% of a hydrophilic hydroxy lower alkyl acrylate or methacrylate with (b) 1 to 49.9% of a lower alkyl acrylate or methacrylate, and either (c) 0.1 to 15% of an ethylenically unsaturated carboxylic acid or (d) 0.1 to 25% of an ethylenically unsaturated amine, (6) a terpolymer of (a) at least 50% of a hydrophilic hydroxy lower alkyl acrylate or methacrylate with (b) 1 to 49.9% of a lower alkoxy lower alkyl acrylate or methacrylate having at least 2 carbon atoms in the lower alkyl group and either (c) 0.1 to 15 of an ethylenically unsaturated carboxylic acid or (d) 0.1 to 25% of an ethylenically unsaturated amine, (7) a tetrapolymer of 5(a), (b), (c) and (d), (8) a tetrapolymer of 6(a), (b), (c) and (d), (9) a terpolymer of (a) at least 50% of a lower alkoxy lower alkyl acrylate having at least 2 carbon atoms in the lower alkyl group with (b) 1 to 49.9% of a lower alkyl acrylate or methacrylate and either (0) 0.01 to 15% of an ethylenically unsaturated carboxylic acid or (d) 0.1 to 25% of an ethylenically unsaturated amine, (10) a tetrapolymer of 9(a), (b), (c) and (d), (11) a copolymer of 1 to 99% ethoxyethyl acrylate or methacrylate with 99 to 1% of methoxyethyl acrylate or methacrylate, (12) a terpolymer of (a) ethoxyethyl acrylate or methacrylate with (b) methoxyethyl acrylate or methacrylate in the ratio of 99:1 to 1:99 and either (c) 0.1 to 15% of an ethylenically unsaturated carboxylic acid or (d) 0.1 to 25% of an ethylenically unsaturated amine; and (13) a tetrapolymer of 12(a), (b), (c) and (d).

2. A process according to claim 1 wherein the polymer is applied to the hair in a nontoxic lower aliphatic saturated alcohol and a minor amount of water as solvent.

3. A process according to claim 1 wherein the polymer is applied to the hair in the form of an aerosol spray.

4. A process according to claim 1 wherein the polymer is selected from groups (1), (2), (3), (4), (5), (6), (7)

19 and (8) and the hydrophilic acrylate or methacrylate is selected from the group consisting of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.

5. A process according to claim 4 wherein the polymer is in group (1).

6. A process according to claim 4 wherein the polymer is in group (2).

7. A process according to claim 4 wherein the polymer is in group (3).

8. A process according to claim 4 wherein the polymer is in group (4).

9. A process according to claim 4 wherein the polymer is in group (5).

10. A process according to claim 9 wherein component (c) or (d) is the carboxylic acid.

11. A process according to claim 9 wherein component (0) or (d) is the amine.

12. A process according to claim 4 wherein the polymer is in group (6).

13. A process according to claim 12 wherein component (c) or (d) is the carboxylic acid.

14. A process according to claim 12 wherein component (c) or (d) is the amine.

15. A process according to claim 4 wherein the polymer is in group (7).

16. A process according to claim 4 wherein the polymer is in group (8).

17. A process according to claim 1 wherein the polymer is in group (9) and component (c) or (d) is the carboxylic acid.

18. A process according to claim 1 wherein the polymer is in group (9) and component (c) or (d) is the amine.

19. A process according to claim 1 wherein the polymer is in group (10).

20. A process according to claim 1 wherein the polymer is in group (11).

21. A process according to claim 1 wherein the polymer is in group (12) and component (c) or (d) is the carboxylic acid.

22. A process according to claim 1 wherein the polymer is in group (12) and component (c) or (d) is the amine.

23. A process according to claim 1 wherein the polymer is in group (13).

24. A packaged material suitable for applying to the hair comprising a cosmetic preparation, in a nontoxic lower aliphatic saturated alcohol and/or polyhydric alcohol organic solvent system for the polymer selected from the group consisting of (1) a copolymer of a hydrophilic hydroxy lower alkyl acrylate or methacrylate with 1 to 50% of a lower alkyl acrylate or methacrylate, (2) a copolymer of a hydrophilic hydroxy lower alkyl acrylate or methacrylate with 1 to 60% of a lower alkoxy lower alkyl acrylate or methacrylate having at least 2 carbon atoms in the lower alkyl group, (3) a copolymer of a hydrophilic hydroxy lower alkyl acrylate or methacrylate with 0.1 to 25% of an ethylenically unsaturated amine,

(4) a copolymer of a hydrophilic hydroxy lower alkyl acrylate or methacrylate with 0.1 to 15% of an ethylenically unsaturated carboxylic acid, (5) a terpolymer of (a) at least 50% of a hydrophilic hydroxy lower alkyl acrylate or methacrylate with (b) 1 to 49.9% of a lower alkyl acrylate or methacrylate, and either (c) 0.1 to 15% of an ethylenically unsaturated carboxylic acid or (d) 0.1 to 25% of an ethylenically unsaturated amine, (6) a terpolymer of (a) at least 50% of a hydrophilic hydroxy lower alkyl acrylate or methacrylate with (b) 1 to 49.9% of a lower alkoxy lower alkyl acrylate or methacrylate having at least 2 carbon atoms in the lower alkyl group and either 0.1 to 15 of an ethylenically unsaturated carboxylic acid or (d) 0.1 to 25% of an ethylenically unsaturated amine, (7) a tetrapolymer of 5(a), (b), (c) and (d), (8) a tetrapolymer of (a), (b), (c) and (d), (9) a terpolymer of (a) at least 50% of a lower alkoxy lower alkyl acrylate having at least 2 carbon atoms in the lower alkyl group with (b) 1 to 49.9% of a lower alkyl acrylate or methacrylate and either (c) 0.1 to 15 of an ethylenically unsaturated carboxylic acid or (d) 0.1 to 25% of an ethylenically unsaturated amine, (10) a tetrapolymer of 9(a), (b), (c) and (d), (11) a copolymer of 1 to 99% ethoxyethyl acrylate or methacrylate with 99 to 1% of methoxyethyl acrylate or methacrylate, 12) a terpolymer of (a) ethoxyethyl acrylate or methacrylate with (b) methoxyethyl acrylate or methacrylate in the ratio of 99:1 to 1:99 and either (c) 0.1 to 15% of an ethylenically unsaturated carboxylic acid or (d) 0.1 to 25 of an ethylenically unsaturated amine; and (13) a tetrapolymer of 12(a), (b), (c) and (d) packaged in an aerosol container also containing a propellant.

25. A packaged material according to claim 24 including a lower aliphatic saturated alcohol and a minor amount of water as solvent for the polymer.

26. A packaged material according to claim 24 wherein the polymer is selected from the group consisting of (l), and

27. A packaged material according to claim 24 wherein the polymer is selected from the group consisting of (9), (10 (11 (12 and 13 References Cited UNITED STATES PATENTS 2,542,897 2/ 1951 Brown et al. 424-81 2,624,690 l/ 1953 Leader 424-81 2,804,073 8/1957 Gallienne et al. 424-81 2,976,576 3/ 1961 Wichterle et al 18-5 8 3,025,219 3/1962 Maeder 424-81 3,220,960 11/1965 Wichterle et al. 260-25 3,269,903 8/1966 Von Fienot et al. 424-81 3,400,890 9/ 1968 Gould 239-36 3,428,043 2/1969 Shepherd 128-268 SHEP K. ROSE, Primary Examiner US, Cl. X.R. 424-71, 81

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3893988 *May 10, 1973Jul 8, 1975Hydron LtdCopolymers of alkoxy and hydroxy alkyl methacrylates and a process for their preparation
US3927199 *Aug 13, 1973Dec 16, 1975Nat Starch Chem CorpHair fixing compositions containing N-alkyl acrylamide or methacrylamide interpolymer
US3935303 *Nov 1, 1972Jan 27, 1976Gennady Lvovich KhromovBase for ophthalmological medicinal preparations and on ophthalmological medicinal film
US3937802 *Aug 23, 1973Feb 10, 1976Sanyo Chemical Industries, Ltd.Sprayable hair-setting composition containing a sulfonate containing hydrophilic copolymer
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Classifications
U.S. Classification424/47, 424/70.17, 424/DIG.100, 424/70.16, 424/DIG.200
International ClassificationA61Q11/00, A61K8/81, A61K8/00, A61Q5/00, A61Q5/06
Cooperative ClassificationY10S424/02, A61K8/8152, Y10S424/01, A61Q5/06, A61Q11/00
European ClassificationA61Q11/00, A61Q5/06, A61K8/81K4