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Publication numberUS3406238 A
Publication typeGrant
Publication dateOct 15, 1968
Filing dateJan 5, 1965
Priority dateJan 5, 1965
Also published asDE1617484A1
Publication numberUS 3406238 A, US 3406238A, US-A-3406238, US3406238 A, US3406238A
InventorsHarlan B Freyermuth, Wilmer E Van Horn
Original AssigneeGaf Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Emollient preparations containing alkylated polymers of heterocyclic n-vinyl monomers
US 3406238 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States P21031 Delaware No Drawing. Filed Jan. 5, 1965, Ser. No. 423,603 12 Claims. (Cl. 424-40) ABSTRACT OF THE DISCLOSURE Toiletry and cosmetic compositions are provided which are smooth in texture and which impart a softening and soothing effect to the skin and the appendages of the skin.

The said compositions contain as an essential component from 0.1 to about 50% by Weight thereof of an alkylated polymer of an N-vinyl heterocyclic monomer wherein on an average at least of the N-vinyl heterocyclic monomer units in said polymer are alkylated with an alkyl group of from 10 to 42 carbon atoms.

This invention relates to emollient preparations containing alkylated polymers of heterocyclic N-vinyl monomers which impart a much smoother texture to the preparation together with a softening and soothing effect when applied to the skin and the appendages of the skin.

It is known that emollients and cosmetics for the skin and hair include all preparations for conditioning or embellishment such as cleansing creams, quick-liquefying creams, emollient creams, cleansing lotions, cream and paste rouges, lipsticks, anti-perspirants, facial masks, massage oils, hair .oils and creams, hair removers (epilating Waxcompositions), eye shadow, sunburn preventives, etc. Many of such preparations, other than normal soap bars, contain petroleum hydrocarbons in one form or another, such as mineral oil, petroleum (solid or liquid), and paraffin wax or a mixture of two or all of such hydrocarbons. Although these preparations are satisfactory for skins and scalps that tend toward oiliness, it is well established that the presence of mineral oils, liquid and solid petrolatums in such preparations is drying to the skin. As a consequence, such preparations require modification wit-h vegetable oils or with cholesterol, lecithin or an absorp: tion base. Paraffin and substances with similar proper-. ties are not recommended for use in cosmetic skin preparations because they may clog the pores and cause them to become enlarged or infected. Moreover, many of such preparations are neither sufficiently smooth in texture nor do they impart to the normally dry skin a softening and soothing effect.

The cosmetic industry has and is expending considerable amounts of money in research and development of a product or products which, when incorporated into toiletry preparations, will impart a much smoother texture as well as a softening and soothing effect on the skin and the appendages of the skin. The problems involved are manifold. The cosmetic chemist must consider the nature of the skin, i.e., whether normally dry or oily to which the preparation is to be applied. He must also consider the nature or character of the developed product, its compatibility with other components constituting the preparation and the effect ;when applied ot the skin or the appendages thereof.

It is the principal object of the present invention to provide toiletry preparations, i.e., emollients, cosmetics, and soaps, which are smooth in texture and which impart a softening and soothing elfect to the skin and the appendages of the skin.

Another object is to provide cosmetic preparations for the conditioning of nails of the toes and fingers.

. A further object isto provide cosmetic preparations for the conditioning and grooming of hair which will leave the hair soft, lustrous, alive-looking and manageable.

Other objects and advantages will become manifest from the following description.

We have discovered that products obtained by the alkylation of polymers of heterocyclic N-vinyl monomers or by the simultaneous polymerization and alkyl-ation of heterocyclic N-vinyl monomers and co-monomers thereof are excellent additives to soaps and cosmetic preparations of the cleansing, conditioning, and embellishing type which will impart a smooth texture as Well as a softening and soothing effect to the skin and skin appendages. The additives range from viscous oils to soft and relatively hard waxes. They can be used in place of, and in addition to, petroleum hydrocarbons, i.e., mineral oils, petrolatums and paraffin waxes. They are not only soluble in these petroleum hydrocarbons, but also soluble in other unctuous materials such as fatty acids; stearic, myristic oleic acids, etc.; glyceryl monostearate (Glycosterin); lanolin (wool fat); beeswax and other animal and vegetable waxes; higher alcohols, such as hexanol, myristyl alcohol, etc.; polyoxyalkylene glycols, e.g., polyoxyethylene glycol, polyoxypropylene glycol; methyl ethyl ketone, Cellosolve (2-ethoxyethanol), butyrolactone, etc, which are employed in toiletry preparations of this type. They are readily emulsified by the usual re-agents employed in toiletry manufacture. By virtue of this solubility, emulsifiability and broad compatibility With other components of the toiletry preparation, they substantially reduce or eliminate the drying tendency of mineral oils and petrolatums present in such preparations. Regardless whether the toiletry preparation contains any one or all of these petroleum hydrocarbons, vegetable oils', lanolin, and/or other unctuous components, or is free from such components, etc., the presence of the additive in such preparation imparts a much smoother texture to it with the attendant softening and soothing effect when applied to the skin and a softening effect when applied to skin appendages.

In some people, overproduction or underproduction of sebum causes excessively oily or excessively dry skin. In very cold weather the sebum congeals on its way to the surface and the skin becomes dry and chapped. In old age, sebum production drops very low and skin fibers lose much of their elasticity. Any toiletry preparation of the cleansing, conditioning or embellishing type containing the additive will keep the skin soft and pliable. Even though the toiletry preparation is removed from the skin or scalp by washing with water and soap, the soft and soothing effect persists. The same effect persists after several washings. The same effect is also noted when the additive is present in hair preparations. The hair remains soft, lustrous and alive-looking. In finger-nail preparations, the additive imparts a softening and smoothing effect. In lipsticks, the additive displays dye-binding properties as well as softening and soothing effects. It also retards drying out of the lipstick. In soaps and synthetic soap bars, the presence of the additive imparts a soft and pliable effect on skin and scalp and a soft effect on hair after rinsing with water. The same effect is felt after several rinses with water. Toiletry preparations, especially skin cosmetics, containing the additive and applied to the skin, resist the penetration of oils and of fine dust and other dirt particles which imbed themselves in the skin pores.

The unusual properties of the additive are not-clearlystearate, glycerine, the currently used emollients, hair- 3 oils and creams, etc., may be due to both the hydrophilic character of the component of the N-heterocyclic ring and the hydrophobic character of the alkyl chain or chains in said ring of the polymer molecule. The hydrophobic character imparts the solubility and compatibility in oils, fats, waxes, and other unctuous materials, as well as smoothness; Whereas the hydrophilic character may contribute to the softening and soothing eiiects.

The additives employed in accordance with the present invention are prepared by reacting one mole of a monomer or polymer of a (homopolymer or copolymer) of a a heterocyclic N-vinyl monomer with 0.5 to 4, preferably 1 to 3, moles of an a-olefin of from 10 to 42 carbon atoms in solution of an organic solvent common to the monomer and its polymer (homopolymer or copolymer) in the presence of 0.025 to 0.30 mole of an organic peroxide catalyst per mole of iii-olefin at a temperature ranging from 100 to 200 C. for a period of time ranging from 3 to 60 hours. The percent of a-olefin reacted is determined by the percent of the a-olefin consumed and may range from about 50% to 100% of the a-olefin charged. Alkylated polymers of heterocyclic N-vinyl monomers with emollient properties are obtained in which a minimum of 25% to a maximum of 400% of the monomeric units in the polymer are alkylated. In other words, alkylated homopolymers are obtained containing an average of 0.25 to 4 alkyl groups of 10 carbon atoms per monomer unit. In the case of a copolymer of 60% by weight of heterocyclic N-vinyl monomer and 40% by weight of a non-heterocyclic monomer, alkylated copolymers with emollient properties are obtained in which a minimum of 30% to a maximum of 240% of the heterocyclic N-vinyl units in the copolymer are alkylated, i.e., containing at least 0.25 alkyl groups of 10 carbon atoms per monomeric unit in the copolymer. In alkylating such copolymers to obtain the best emollient properties, it is preferred that 1-3 moles of a-Olefin be reacted with one mole of copolymer to yield an alkylate in which at least 30% of the heterocyclic N-vinyl units in the copolymer are alkylated. The resulting solution of the alkylated polymer is subjected to vacuum distillation to remove the organic solvent. The residue, alkylated polymer, ranges from a viscous oil to a soft and substantially hard wax.

The homopolymers of heterocyclic N-vinyl monomers, which are alkylated with an a-olefin of from 8 to 42 carbon atoms and employed as additives, include homopolymers of N-vinyl suecinimide, N-vinyl diglycolylimide, N- vinyl glutarimide, N-vinyl-3-morpholinone, N-vinyl-- methyl-B-morpholinone, N-vinyl-5-ethyl-3-morpholinone, and N-vinyl lactams having the following formulae:

l CH=CH1 wherein R represents an alkylene bridge, i.e.,

N-vinyl thiolactams and these can be used in the alkylation process.

(IJOCRFCHZ wherein R represents either hydrogen or methyl group and R and R have the same value as above. Illustrative compounds, obtained by the conventional reaction of a 5-, 6-, or 7-membered lactam with acryloyl or methacryloyl chloride or bromide in the presence of a hydrogen halide acceptor such as pyridine, dimet'hylaniline, etc., are N-methacryloyl-pyrrolidone, -piperidone and -caprolactam; N-methacryloyl-5-methylpyrrolidone, N-methacryloyl-6-methylpiperidone and N-methacryloyl-7-methyl caprolactam and their corresponding 5-, 6-, and 7-ethyl derivatives; N-acryloyl-pyrrolidone, -piperidone and -caprolactam; N-acryloyl-5-methylpyrrolidone, N-acryloyl-6-methylpiperidone and N-acryloyl-7-methyl caprolactam and their corresponding 5-, 6- and 7-ethyl derivatives; acrylic esters having the structure:

Ri-C

t lnmnmmcocnpom wherein R, R and R have the same values as above, in is an integer of from one to four, and n is an integer of from one to four when m has a value of one and from two to four when m has a value greater than one. Illustrative compounds are N-acryloxy-methyl-pyrrolidone, -piperidone and -caprolactam; N-methacryloxyethoxy-ethyl-pyrrolidone, -piperidone and -caprolactam; N methacryloxy propyl pyrrolidone, -piperidone and -caprolactam; N-methacryloxy-ethyl-pyrrolidone, -piperidone, and -caprolactam; N-methacryloxy-methyl-S-methyl-pyrrolidone, -6-methylpiperidoue and -7-methy1-caprolactam, including amidoalkyl lactams of the structure:

J H:,NR:i-COCR;=CH: wherein R, R and R have the same value as above, R represents hydrogen, alkyl group of from 1 to 12 carbon atoms or phenyl, and Y represents an integer of from 2 to 3. Illustrative compounds of this type are N-methacrylamidomethyl-, N-methacrylamidoethyl-, N-methacrylamidopropyl and N (N phenylacrylamidopropyl) pyrrolidones, -piperidones and -caprolactams, which are readily prepared by reacting acryloyl or methacryloyl chloride or bromide with an N-(aminoalkyD-lactam, wherein the alkyl is from 1 to 12 carbon atoms, in the presence of any conventional base to take up the hydrogen halide.

The individual homopolymers of the foregoing heterocyclic N-vinyl monomers may be alkylated as such or in admixture. The proportions constituting the mixture are immaterial since such mixture of homopolymers is readily alkylated and yields a product with emollient properties. However, where a mixture of any one of the foregoing heterocyclic N-vinyl monomers is copolymerized prior to alkylation with an a-olefin, with a non-heterocyclic monomer containing a polymerizable vinyl group, it is preferable that the comonomer mixture contain at least 60% by weight, i.e., from 60% to by weight of any one of the foregoing heterocyclic N-vinyl monomers with up to 40% by Weight, i.e., from 5 to 40% by weight of a non-heterocyclic monomer. The non-heterocyclic monomers containing a polymerizable vinyl group which are copolymerized with any one of the foregoing heterocyclic N-vinyl monomers, prior to alkylation, including vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl lactate, vinyl caproate, vinyl caprylate, vinyl oleate, and vinyl stearate; vinyl chloride; vinylidene chloride; acrylonitrile; styrene; acrylic acid; 'acrylate ester monomers of the formula CH CHCOOR wherein R represents either a straight or branched alkyl of from 1 to 18 carbon atoms or an alkoxyalkyl in which the total number .of carbon atoms in the alkyl groups range from 3 to 6. As examples of such acrylate esters the following are illustrative: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, Z-methyl-l-butyl, 3- methyl-l-butyl, Z-ethyl-l-butyl, amyl, 3-pentyl, 2-methyll-pent'yl, 4-methyl-2-pentyl, hexyl, Z-ethylhexyl, heptyl, 2-heptyl, octyl, 2-octyl, nonyl, 5-ethyl-2-nonyl, decyl, 2- methyl-7 ethyl-4-undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, 2-methoxyethyl, 2-ethoxyethyl and 2-butoxyethyl acrylate; methacrylate monomers such as methacrylic acid, methyl methacrylate, cyclohexyl methacrylate, isobutyl methacrylate, isoamyl methacrylate, fi-methoxy ethyl methacrylate and a-(o-chlorophenyl) ethyl methacrylate, B-phenoxyethyl methacrylate, a-phenylethyl methacrylate, phenyl methacrylate, o-cresyl methacrylate, pcyclohexylphenyl methacrylate, 2-nitro-2-methyl propyl methacrylate, diethylaminoethyl methacrylate, ethylidene acetate methacrylate and glycidyl methacrylate, including esters of halo acrylic acids, such as methyl-a-chloroacrylate, ethyl-a-chloro-acrylate, phenyl-a-chloro-acrylate, a-ethylacrylic acid; methacrylonitrile; acrylamide; methacrylamide, as well as N-alkyl and N-aryl substituted acrylamides such as N-methyl acrylamide, N-ethyl acrylamide, N-propyl acrylamide, N-n-butyl acrylamide, N-ndodecyl acrylamide, N-n-octadecyl acrylamide, N,N-dimethyl acrylamide, N,N-diethyl acrylamide, N,N,-di-n butyl acrylamide, N,N-diisobutyl acrylamide, N-cyclohexyl acrylamide, N,N-dicyclohexyl acrylamide, N- phenyl acrylamide, N-p-nitrophenyl acrylamide, N-ocnaphthyl acrylamide, N-fi-naphthyl acrylamide, N-methyl-N-p'henyl acrylamide, N,N-diphenyl acrylamide, N- benzyl acrylamide, N,N-dibenzyl acrylamide; and grafted monomers on the polyvinyllactam of the type disclosed in United States Patents 3,029,219; 3,035,009; 3,036,033, and the like. Both the homopolymers and copolymers should have a K value of 10 to 140 for the alkylation reaction, preferably of 20 to 100. r

It is to be noted that the nature or character of the non-heterocyclic polymerizable monomers is immaterial so long as such monomers are capable of copolymerization in the aforestated proportions with the heterocyclic N-vinyl monomers and yield copolymers which can be alkylated.

In the alkylation of the polymers of heterocyclic N-vinyl monomers, i.e., homopolymers and copolymers, any a-olefin having a molecular weight from about 140 to about 588 may be employed in the alkylation reaction. In other words, alpha-olefins (straight chain or branched), ranging from l-dodecene, l-tetradecene, l-hexadecene, l-heptadecene, l-ocetadecene, l-nonadecene, l-eicosene, l-docosene, l-tetracosene, l-pentacosene to trimerized a-tetradecene may be used.

While linear a-olefins are preferred because of their. commercial availability, numerous isomers of a-olefins ranging from l-pentene to l-pentacosene as well as polybutenes may also be employed in the alkylation reaction. The only precaution required in such case is that the isomer contain an ethylenic unsaturation in the a-position thereof.

Instead of employing any one of the foregoing individual a-olefins; a mixture of commercially available linear a-OlCfiHS produced by cracking petroleum wax orby polymerizing lower olefins may also be used as the alkylating agent. The commercial product composition contains a mixture of linear olefins ranging from 11 to 15 carbon atoms, and as high as 15 to 22 carbon atoms.

In lie-u of the individual a-olefins of from 10 to 42 carbon atoms or mixtures thereof, alkylated polymers of heterocyclic N-vinyl monomers suitable for the purpose of the present invention are also obtained by alkylating the polymer (homoand co-polymer) with at least 5 moles to as high as 16 moles of ethylene for each mole of polymer to yield an alkylate wherein the ethylene propagates itself to a minimum average chain length of 10 carbon atoms. A minimum average chain length of 10 carbons is also obtained by alkylation with l-p-ropene, l-butene, l-pentene, l-hexene, l-heptene, l-octene or l-nonene. In determining for each mole of polymer the required number of moles of such oz-Olefin, i.e., from 2 to 9 carbon atoms to obtain the minimum average chain length of 10 carbon atoms, the following formula may be used:

wherein M represents the number of moles of the -olefin and C represents the number of carbon atoms in the a-olefin. I Inste'adof employing ethylene as the alkyl-ating agent, chlorinated and/or fluor'inated a-olefins such as, for example, dichlorovinylidene fluoride, chlorovinylidene fluoride, chlorotrifluoroethylene, tetrafluoroethylene, vinylidene fluoride and the like may be used.

In the alkylation of polymeric heterocyclic N-vinyl compounds with an alpha-olefin or mixtures thereof, an organic solvent is employed which is common to the polymer and alpha-olefin(s). As solvents, various alcohols such as methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, amyl alcohol, hexanol, 2-ethyl-1ahexanol, ethylene glycol, 1,2-butanediol, 4-butanediol, etc. may be employed. Other solvents such as d-iacetone alcohol, diethylene glycol, ethylene glycol monomethyl ether acetate, methylene chloride and the like may also be employed. It is to be noted that the nature or character of the organic solvent is immaterial so long as it is a liquid, forms a solution with the polymer and alkylating a-olefin(s), and is not susceptible to alkylation.

The amount of organic solvent employed is not critical. Any amount which will yield a solution of the polymeric material and a-olefin(s) will suflice. However, for purposes of expediency, for every part by weight of solid homopolymer or.copolymer of N-vinyl lactam, from 2 to 10 parts of organic solvent, either by volume or by weight, are sufficient to yield a workable solution.

As peroxide catalyst (initiator) for the alkylation reaction, any one of the known tertiary-alkyl organic peroxides such as, for example, t-butyl hydro-peroxide, di-t-butyl peroxide, t-butyl perbenzoate, di-ti-butyl peroxide, t-butyl perbenzoate, di-ti-butyl perphthalate, t-butyl-pentamethylethyl peroxide, tbutyl-triphenylmethyl peroxide, di-t-amyl peroxide, bis-(triethylmethyl) peroxide, bis-(triphenylmethyl) peroxide, 2,5dimethylhexyl-2,S-dihydro-peroxide, 2,5 dimethyl-2,5-di(t-butyl peroxy) hexane, 2,5-dimethy1- hexyl-2,5-di(peroxy benzoate), and the like may be used.

The alkylation procedure for both the homopolymers and copolymers of the foregoing heterocyclic :N-vinyl monomers is more fully described in the co-pend-ing applications of Ashot Merijan, Frederick Grosser and Eugene Hort, Ser. No. 340,786, filed on Jan. 28, 1964, entitled Process of Alkylating Polymer N-Vinyl Lactams, now abandoned, the complete disclosure and teachings of which are incorporated herein by reference thereto. Alkylated homopolymers and copolymers with emollient properties are also obtained by the procedure described in the copending application of Ashot Merijan and Frederick Grosser, Ser. N0. 358,406, filed on Apr. 8, 1964, and entitled, Simultaneous Polymerization and Alkylation of Heterocyclic N-Vinyl Monomers, now abandoned, the complete disclosure and teachings of which are incorporated herein by reference thereto.

Where it is desired that the alkylated polymer be in solution of a mineral oil of the type employed in toiletries, the alkylation of the polymers or the simultaneous polymerization and alkylation reaction of the monomer(s) is preferably conducted in the presence of hexanol. As the latter is being removed during vacuum distillation, it is replaced with a refined mineral oil and the resulting solution of the alkylated polymer employed as the additive. Any refined mineral oil used by the pharmaceutical and cosmetic trade is ideally suited as a replacement during the removal of the hexanol by vacuum distillation.

The following examples will show how some of the alkylated polymeric N-vinyl lactams are prepared.

EXAMPLE I Into a one-liter, four-necked flask equipped with stirrer, thermometer, nitrogen inlet, and reflux condenser, the following ingredients were charged and the system then purged with nitrogen:

Grams Polyvinyl-Z-pyrrolidone (K-30) (1.0 mole) 111 a-Eicosene (1.0 mole)-.. 280 Methyl isobutyl carbinol 200 Di-t-butyl peroxide .(0.1 mole) 14.6

The contents were maintained at 130-135" C. for 16 hours and then a second addition of 7.3 grams (0.05 mole) peroxide was made and reaction continued for eight more hours. (Total peroxide=21.9 grams, 0.15 mole.) The solution was cooled and analyzed. The analytical data showed only 5.48% of unreacted u-eicosene. The contents were subjected to vacuum distillation and the methyl isobutyl carbinol removed. A waxy solid weighing about 350 grams was obtained.

EXAMPLE II Into a one-liter, four-necked flask equipped with stirrer, thermometer, nitrogen inlet and reflux condenser, the following materials were charged:

Grams Polyvinyl-2-piperidone (K-30) (1.0 mole) 125 a-Octadecene do 252 Normal butanol 200 Di-to-butyl peroxide (0.1 mole) 14.6

The flask was purged thoroughly with nitrogen and heated. The contents were maintained at reflux (120 C. pot) for 30 hours and then cooled and analyzed. The analyses showed the presence of only 3.05% of a-octadecene in the solution, corresponding to 18 grams unreacted olefin.

When all the n-butanol was stripped in vacuum, a very clear, oily, somewhat hard gel, weighing about 353 grams, was obtained.

EXAMPLE III Into a one-liter, four-necked reaction flask, equipped with stirrer, thermometer, nitrogen inlet and reflux condenser, the following materials were charged:

Grams Polyvinyl-e-caprolactam (K-30) (1.0 mole) 139 a-Octene do 112 Methyl isobutylcarbinol 200 Di-t-butyl peroxide (0.09 mole) 13.1

The flask was then purged thoroughly with nitrogen, heated and maintained at 125-135 C. for 24 hours. The contents when analyzed showed the presence of only 4.54% of u-octene, corresponding to about 21 grams of the unreacted olefin. The solvent was stripped in vacuum and about 210 grams of a clear, oily gel was obtained.

EXAMPLE IV Into a one-liter, four-necked flask equipped with stirrer, thermometer, nitrogen inlet and reflux condenser, the following materials were charged:

Grams Polyvinyl-Z-pyrrolidone (K-30) (0.5 mole)" 55.5 C a-olefin obtained by the trimerization of a-tetradecene (0.5 mole) 294 Methyl isobutylcarbinol 120 Di-t-butyl peroxide (0.1 mole)-..

The flask was purged thoroughly with nitrogen and heated. The contents were maintained at reflux for 24 hours and then cooled and analyzed. The analysis showed the presence of 7.75% of the C a-olefin in the solution corresponding to 37.5 grams of unreacted olefin.

When all the solventwas stripped in vacuum, about 350 grams of a white wax were obtained.

EXAMPLE V Into a one-liter, four-necked flask equipped with stirrer, thermometer, nitrogen inlet and reflux condenser, after a thorough nitrogen purge, the following ingredients were charged and heated:

Grams Polyvinyl-5-methyl-2-pyrrolidone (K-45) (1.0 mole) 125. Hexanol (mixture of isomeric hexanols) 200 a-Octadecene (1.0 mole) 252 Di-t-butyl peroxide (0.1 mole) 15 The solution was maintained at 120-140 C. for 30 hours and then cooled and analyzed. It was found to contain only 4.56% a-octadecene, corresponding to 27 grams, or a 89.4% consumption of the u-Olefin charged. When the solvent was removed in vacuum, about 348 grams of a waxy material were obtained.

EXAMPLE VI An /20 (by weight) copolymer of N-vinyl-e-capro lactam and ethyl acrylate weighing grams was dissolved in 200 grams of normal amyl alcohol and after the addition of 252 grams (1.5 mole) of u-dodecene and 22 grams (0.15 mole) of di-t-butyl peroxide, the solution was heated and maintained at 140 C. for 10 hours. The reaction mixture was then cooled and analyzed. It was found to contain 4.2% of unreacted a-dodecene, corresponding to 90.5% alkylation based on the dodecene used. The product is a soft waxy substance.

EXAMPLE VIII Into a one-liter, four-necked flask equipped with stirrer, thermometer, nitrogen inlet and reflux condenser, the following materials were charged:

Grams Polyvinyl-Z-pyrrolidone (K 60) 1.0 mole) 111 a-Octene ..(2.0 mole) 224.42 Normal butanol 200 Di-t-butyl peroxide (0.2 mole) 29.2

The flask was purged thoroughly with nitrogen and heated. The contents were maintained at reflux for 30 hours and then cooled and analyzed. The analysis showed the presence of only 4.97% of u-octene in the solution corresponding to 28 grams of unreacted olefin.

When all the solvent was stripped in vacuum and substituted with 450 grams of refined mineral oil (pharmaceutical grade), a very clear, oily solution, weighing 751 grams was obtained.

EXAMPLE IX Example I was repeated with the exception 1 mole of aeicosene was replaced by 1 mole of a commercial mixture of oc-OlefinS in the C -C carbon range. The product is a waxy substance.

9 EXAMPLE x Into a one-liter, four-necked flask equipped with stirrer, thermometer, nitrogen inlet and reflux condenser, the follow-ing ingredients were charged:

Grams N-vinyl-2-pyrrolidone (0.5 mole) 55.5 N-vinyl-3-morpholinone do 63.5 Methyl isobutylcarbinol 200 cz-Octadecene (1.25 mole) 315 t-Butyl hydroperoxide (0.12 mole) 11 The flask was purged with nitrogen thoroughly and heated. The contents were maintained at 130-140 C. for 12 hours and then 11.0 more grams of peroxide were added and heated continually for another 12 hours. (Total peroxide=22 grams or 0.24 mole.) In analysis of the contents, no trace of N-vinyl-2-pyrrolidone or N-vinyl-3-morpholinone were found but only the presence of 11.6% of a-octadecene was detected which indicates a residual of 76 grams unreacted olefin. The contents were then transferred into a two-liter flask and the solvent stripped in vacuum and substituted with 434 grams 100 sec. solvent. The final 50% solution was a clear amber liquid weighing 860 grams.

EXAMPLE XI Into a one-liter, four-necked flask equipped with stirrer, thermometer, nitrogen inlet and reflux condenser, the following ingredients were charged:

Grams N-vinyl succinimide (0.5 mole) 62.5 Methyl isobutylcarbinol 150 a-Eicosene (0.65 mole) 182 Di-t-butyl peroxide (0.1 mole) 15 The flask was purged with nitrogen, heated and maintained at a range of 120-140 C. for 30 hours. The contents were then cooled and analyzed and found to contain only a trace of N-vinyl succinimide and 3.66% (equivalent to 15.0 grams unreacted only) of u-eicosene by weight of the solution. Then 244.5 grams of 100 sec. solvent were added and the solvent stripped in vacuum. The final 50% solution obtained was clear and weighed 485 grams. (Theory: 489.0 grams.)

EXAMPLE XII Into a one-liter, four-necked flask equipped with stirrer, thermometer, nitrogen inlet and reflux condenser, after a thorough nitrogen purge, the following ingredients were charged and heated:

The mixture (clear phase) was maintained at reflux (117- 125 C.) for 20 hours and then another 5.0 grams peroxide added (total peroxide=15.0 grams, 0.1 mole) and refluxing continued for 16 more hours. The contents were then cooled and analyzed. The analysis showed the total absence of the monomer and only 3.0% (equivalent to 12.0 grams unreacted) of a-eicosene. The solvent Was then stripped in vacuum and substituted with 186 grams 100 sec. solvent. The final 50% solution in the 100 sec. solvent was clear and weighed 371 grams. (Theory=372 grams.)

The alkylated polymers of heterocyclic N-vinyl monomers prepared as above described, and in accordance with the foregoing illustrative examples, are soluble in all of the unctuous materials used in toiletry preparations such as vegetable and mineral oils, fatty acids, fatty acid esters, waxes, polyoxyalkylene glycols, higher alcohols of from 6 carbon atoms and up, including compounds having similar boiling points of the type employed in the alkylation reaction. They are also partially soluble in hot lower alcohols such as ethanol and propanol. Solutions of the product of Example I in hot ethanol and in hot propanol are cooled to room temperature, the ethanol contains about 0.1% of alkylated polymer, whereas the propanol contains about 0.3% of the alkylated polymer. Their partial solubility in such alcohols provides an excellent means for incorporation into non-unctuous materials. The alkylated polymers are added at any suitable stage of conventional toiletry manufacture. In other words, if the toiletry preparation comprises an unctuous base the alkylated polymer is dissolved in such base by gentle heating and stirring until solution is attained. For example, where such unctuous material is a liquid such as mineral oil, myristyl alcohol, etc., the alkylated polymer is dissolved therein'at room temperature with or without gentle heating and stirring. Where such unctuous components are solids such as solid petrolactams, paraflin wax, natural and synthetic waxes, fatty acid, fatty acid esters, lanolin, etc., they are first heated to the liquid state and the alkylated polymer dissolved therein with stirring. The temperature of heating may vary from 50 to C., depending upon the nature or character of the unctuous material. If a water phase is included in such preparation such as triethanolamine, borax, sodium or potassium hydroxide, and any other water soluble components, the oil phase is added slowly to the water phase or vice versa with good agitation.

The amount of alkylated polymer that is employed to effect the desired results (smoother texture with softening and soothing effects) ranges from about 0.1% to about 50% by weight based on the total weight of the completed toiletry preparation. The alkylated polymers are added at any stage of manufacture of cold creams, cleansing creams, emollient creams, finishing creams, skin-softening lotions, hand cleaners, lubricating creams, overnight creams, iabsorption-base creams, hand creams and lotions, foot creams, baby creams, baby skin oils; special creams, such as astringent creams, bleaching creams, acne creams, protective creams (industrial creams), vanishing creams, foundation creams, brushless shaving creams, shaving preparations, after-shave lotions and sprays, medicated creams, deodorants and anti-perspirants, such as deodorant creams and lotions, roll-on deodorants, sunburn preventives, suntan preparations, paste or lotion rouges, cream rouges, massage oils, facial masks, depilatories, i.e, hair removers (epilating wax compositions) and hair removing creams, paste or lotion face make-up, face powders; eye makeup, i.e., eye shadows and eyebrow creams; fingernail creams and cleaners, hair bleaches and tints, cuticle softeners, hair conditioners, wave sets, hair dressings, hair brilliantines; hair oils, hair sprays, creams and shampoos, nail polish removers, lipsticks, perfume sticks, facial soaps, synthetic soap bars, antiseptic soaps (tincture of green soap), insect repellents, protective hand creams, waterless hand cleaners, dentifrice, pet shampoos, bath tales, and the like.

The alkylated polymers are effective pigment dispersers and act as color receptors. In hair preparations the presence of the alkylated polymer improves the softness, water repellency and manageability of the hair. In hair conditioners, the alkylated polymers may be added to creams, foams or gels and the resulting preparations pressurized with nitrogen, argon, or the usual liquefied fluorochloro-hydrocarbons.

In each of the following toiletry preparations, the presence of the alkylated polymer rendered the preparation smoother in texture and easier in application to the skin the skin or scalp, the preparations left the skin soft and pliable with a soothing effect which remained after the EXAMPLE XIII Cold cream l =52 grams of liquid petroleum, 14 grams of beeswax and.5 grams of the alkylated polymer of Example I were heated on a steam bathto 87 C. in a 250 ml. beaker and stirred with a small propeller-type stainless steel stirrer-for about five minutes until the beeswax had completely dissolved. I s

I 1 gram of borax (sodium tetraborate) was dissolved in 33 ml. of water by heating to the boil in a 100 ml. beaker. The borax solution was poured in a small steady stream into the white mineral oil-'beeswax-iadditive-solution which was being rapidly stirred. The hot solution was cooled to 49 C. and poured into 'threel-ounce bottles and then allowed to cool to room temperature.

EXAMPLE XIV Brushless shaving cream.

10 grams of white mineral oil, 10 grams of glyceryl monostearate and 3.5 grams of the alkylated polymer of Example I were creamed on a steam bath with stirring to 66 C. for 10 minutes or until a complete solution had resulted. With very rapid stirring, by a stainless steel propeller type stirrer, 50 ml. of boiling distilled water was slowly added in a small stream. Rapid stirring was continued while allowing the cream to cool to room temperature. The brushless shaving cream was transferred to a suitable glass jar.

EXAMPLE XV Hand lotion (liquid) grams of boric acid was dissolved in 30 grams glycerine by heating the mixture in a 100 ml. beaker to 105 C. with an electromagnetic-type electrically heated stirrer. 30 grams of lanolin and 10.5 grams of the alkylated polymer of Example I were dissolved in 40 grams of white mineral oil in a 250 ml. beaker by heating to 60 C. on a steam bath while stirring with a small stainless steel stirrer. After rninutes stirring at 60 C., and

after the lanolin and additive had completely dissolved,

the glycerine solution of boric acid was slowly added in a thin stream to the solution of lanolin, additive and mineral with rapid agitation.

EXAMPLE XVI Vanishing cream EXAMPLE XVII Cleansing cream 10 grams of petrolatum, 27.5 grams of white mineral oil, 12.5 grams of parafiin wax and 5 grams of the alkylated polymer of Example I were melted together in a 100 ml. beaker while stirring and heating on a steam bath to 12 72 C. The melted solutionwas poured into a glass jar and allowed to cool undisturbed overnight.

EXAMPLE XVIII Hand lotion (salve) 2 grams of boric acid were dissolved in 12 grams of glycerine by heating to'105 C. with stirring in a 30 ml. beaker. 16 grams of petrolatum, 12 grams of lanolin and 42 grams of the alkylated polymer of Example I were melted and dissolved in each other by heating to 70 C. while stirring in a 100 ml. beaker. The boric acid-glycerine solution was added slowly to the petrolatum-lanolin-addirive-solution with continual stirring with a stainless steel agitator. The hot C.) molten salve was poured into a jar and allowed to cool undisturbed to room temperature.

EXAMPLE XIX Emollient cream This cream was prepared from the following ingredients in percent by weight: Y

7 Grams Beeswax 8 Cetyl alcohol 2 Cocoa butter 2 Lanolin (anhydrous) 10 Olive oil 50 Lecithin 1 Alkylated polymer of Example II 7 were dissolved in admixture by heating to 87 C. The resulting solution was allowed to reach room temperature to which was added 1 gram of rose perfume. Sufiicient distilled water was added with agitation to make 100 parts by weight of finished emollient cream.

EXAMPLE XX Quick-liquefying cream Percent by 'weight Mineral oil '40 Parafiin wax 18 Beeswax 9 Petrolatum 23 Alkylated polymer of Example III 10 The foregoing components were heated to 87 C. with stirring. The hot solution was poured into a jar and allowed to cool to room temperature.

EXAMPLE XXI Paste rouge Percent by weight Ceresin 20 I Mineral oil 45 Petrolatum 21 Spermaceti 3 Finely divided certified color 1 Oil solution of alkylated polymer of Example VIII 10 The above mixture was heated to C. in a' stainless steel beaker untilall components were dissolved. The mixture was allowed to cool about the solidification point and the massrun through an ointment mill and poured into a container.

1.3 The oil phase washeated fto yield a solution. The color was added and the mixture cooled above the solidification point and poured in lipstick molds. t

w EXAMPLE XXIII Anti-perspirant stick 1 5, Percent by weight Alum 5 1' ThBiOll phase was heated to the liquid state and the mixture of alum, hydroxyquinoline' sulfate, titanium dioxide, talc and zinc phenol sulfonate added with stirring. The resulting mixture was allowed to cool above the solidification point and poured into stick molds and th sticks mounted in asuitable holder.

EXAMPLE XXIV Synthetic soap bar 30% by weight of stearic acid and 10% by weight of the alkylated polymer of Example I were melted and emulsified with 8% by weight of water. To the emulsion were added, with agitation, 30% by weight of myristic sodium isethionate, 5% by weight of ethoxylated nonyl phenolcontaining 80% by weight of ethylene oxide and by weight of sodium tallowate. The resulting mixture was cooled and subjected to soap bar formation by the conventional injection molding.

EXAMPLE XXV Total sunscreen lotion Percent by weight Mineral oil 40.0 Beeswax 1 6.0 Oil solution of alkylated polymer of Example X 19.5 Water 33.5 2,2, 4,4'-tetrahydroxy-benzophenone 0.5 Sodium hydroxide 0.5

The oil phase and alkylated polymer were heated to 70 -C. and the water phase, including the sunscreen agent and sodium hydroxide to the same temperature. The oil phase was added slowly to the'water phase with good agitation. A'creamy emulsion resulted.

EXAMPLE XXVI Hair shampoo Percent by weight Stearic acid 3.5 Myristic acid 2 90% of the above concentrate maybe pressurized with a 60/ 40 mixture of propellents 114/ 12 at 10% concentration. If desired, a small amount from about 0.2 to 0.5%

14 EXAMPLE XXVII Nail polish remover v t The solvent mixture has the following composition:

' Percent by weight Butyrolactone Ethylene glycol-monomethylether 50 Ethylene glycol monobutylether 10 Diethyl glycol 5 Alkylated polymer of Example VI 5 The solvent mixture was adjusted to a pH of approximately 8.0-8.5% with caustic soda to insure stability. If desired, perfume to further enhance the product may be added to the mixed solvents.

EXAMPLE XXVIII Cuticle softener Percent by weight Stearyl alcohol n 22.0

. Cetyl alcohol u 22.0 Alkylated polymer of Example VII 50.0 "llriethanolamine 2.0 Propylene glycol 4.0

by weight of polyvinyl pyrrolidone may be incorporated in the shampoo so that in addition to functioning as a shampoo, it will also serve as a grooming agent by permitting curl retention. a

The first three components were gently heated until a clear solution was obtained. To the solution the last two components were added with stirring and allowed to cool to room temperature.

EXAMPLE XXIX Bath talc One gram of alkylated polymer of Example -I was dissolved in 250 grams of hot ethanol. While maintaining the ethanol solution hot, 50 grams of talcum powder were added slowly with constant agitation. After the addition of the talc was complete, the slurry was permitted to cool to room temperature, a few drops of perfume added wit-h mixing, and the slurry filtered, dried and the small lumpy particles broken by milling in a hammer mill. The dried fine powder was passed through the customary talc sieve and stored in a container. The a1- cohol may also be removed by vacuum distillation of th slurry while maintaining good agitation.

EXAMPLE XXX After-shave lotion Percent by weight The ethanol was heated to about the boil and the alkylated polymer added slowly until dissolved. The'homo genous cloudy solution was allowed to cool with agitation and the perfume added when the solution reached room temperature. 60% by weight of the resulting concentrate was charged in the conventional manner with 40 parts by weight of a mixture consisting of 30% by weight of propellent 12 and 10% by weight of propellent 114. The aerosol preparation was clear in view of the higher solubility of the alkylated polymer in the propellent mixture.

EXAMPLE XXXI Hair spray Percent'by weight Ethanol SDA-40 anhydrous u 200.0 Alkylated polymer of Example I 0.2 Myristyl alcohol 0.2

The components were heated to the boil of ethanol, 5 grams of polyvinylpyrrolidone K-30 added with stirring, quickly cooled to room temperature, perfume added and 30% by weight of the cooled solution pressurized in the conventional manner with 70% by weight of a mixture 15 of propellents containing 35% by weight of propellent 12 and 65% by weight of propellent 11.

In this spray the alkylated polymer also functions as plasticizer for the polyvinylpyrrolidone (or copolymers thereof with vinyl acetate) and as water repellent for the film. It imparts softness and lubricity to the hair. It also reduces the tack when the polymeric film former concentration is around by weight or higher in the hair spray composition.

EXAMPLE XXXII Oil-free hair groom (gel) 0.5 gram of polyacrylic acid were dissolved in 90 grams of water at room temperature. The pH was adjusted to 7.0 with concentrated ammonium hydroxide. 5.2 grams of 45% aqueous solution of polyvinylpyrrolidone K-3O were added with moderate agitation until a homogeneous gel was obtained.

3.8 grams of polyethylene glycol having a molecular weight of 550 were melted and 0.5 gram of the alkylated polymer of Example I added with gentle heating until a solution was obtained. The resulting solution and one drop of geranium perfume were blended with the gel until a homogenous gel was obtained.

EXAMPLE XXXIII Waterless hand cleaner (gel) Percent by weight Bayol 50 mineral oil (highly refined white mineral oil) 50.0 Solution of alkylated polymer of Example XI 8.0 Nonylphenol ethoxylated with 3 moles of ethylene oxide 12.0

The mixture was gently heated until a clear solution was obtained. To the resulting oil phase was added 30% by weight of water containing 0.25% by weight of potassium hydroxide with stirring until gelled.

This cleaner is useful for removing heavily embedded grime, oil, grease and stains.

EXAMPLE XXXIV Dentrifice Percent by weight Calcium carbonate 51.3

Alkylated polymer of Example I 0.5 Sodium lauryl sulfoacetate 2.1 Glycerine 28.7 Water 17.4 Gum and flavor q.s.

The calcium carbonate was mixed with the water and glycerine to yield a uniform suspension. To the suspension was added in sufficient quantity the customary gum and peppermint fiavor to yield a paste. The alkylated polymer was mixed with the sodium lauryl sulfoacetate and incorporated into the paste with thorough mixing.

EXAMPLE XXXV The preparation of the paste rouge of Example XXI was repeated with the exception that the oil solution of alkylated polymer of Example VIII was replaced by the same amount of the oil solution of the alkylated polymer of Example XII.

From Examples XIII to XXXV it is evident that the alkylated polymers (homopolymers and copolymers) of heterocyclic N-vinyl monomers are not only soluble in, but also compatible with, a large variety of currently used and acceptable toiletry carriers (cosmetics and soaps) to yield compositions having new, novel and desirable properties.

Because of their softening and soothing effects, the alkylated polymers may be employed in the preparation of pharmaceutical salves, ointments and suppositories. Such preparations may contain the usual antiseptic, germicidal and medicinal agents.

. 16 a I The alkylated polymers display their desirable emollient effects in all types of ointments, salves, lotions, antiseptics, disinfectants, and other medicinal preparations for external use. The alkylated polymers are especially adaptable in the preparation of non-irritating detergent emulsions as skin cleansers for removing grease and oils from the skin. They manifest their softening and soothing effects when incorporated in hemorrhoidal preparations. They can be incorporated into unctuous materials and employed as lubricants to aid the passage of cathethers or enema tubes. They can be incorporated into salves and ointments used in the treatment of burns. Due to the water insolubility of the alkylated polymers, a continued softening (emollient) effect is noted even after several washings of the skin with soap and water.

While the present specification has shown the new and useful application of a large class of alkylated polymers of heterocyclic' N-vinyl monomers in cosmetics and soaps, alkylated polymers (homoand co-polymers) of other heterocyclic N-vinyl monomers containing a a o I II group in the ring may be employed as additives in accordance with the present invention. Such monomers include the N-vinyl monomers of alkyl substituted derivatives of lactams such as, for example, 4,4-dimethyl-2- pyrrolidone, 3,3-dimethyl-2-pyrrolidone, 3-ethyl-2-pyrrolidone, 3,5-dimethyl-2-pyrrolidone, 3-ethyl-2-pyrrolidone, 4-acryl-2-pyrrolidone, 5-ethyl-2-pyrrolidone, 3- methyl-Z-pyrrolidone, 4-methyl-2-pyrrolidone, 3,3,5-trimethyl 2 pyrrolidone, 5,5-diethyl-2-piperidone, 5,6-dimethyl-Z-piperidone, 4-ethyl 2 piperidone, 6-ethyl-3- methyl-Z-piperidone, 3-methyl-2-piperidone, 4-methyl-2- piperidone, 5-methyl-2-piperidone, 3,6-dimethyl-2-caprolactarn, 4,6-dimethyl-2-caprolactam, 4,7-dimethyl-2-caprolactam, 7,7-diethyl-2-caprolactam, 3-ethyl-2-capro1actam, 5-ethyl-2-caprolactam, 6-ethyl-2-caprolactam, 4-ethyl-6- methyl-2-caprolactam, 6-methy1-2-caprolactam, G-ethyl- 4-methyl-2-caprolactam, 3-methyl-2-caprolactam, 4-methyl-2-caprolactarn, S-methyl 2 caprolactam; 6-methyl-2- caprolactam; N-vinyl monomers of 3,5-dimethyl-3-morpholinone, 2-oxazinidinone (US. Patent 2,905,660 and US. Patent 3,097,087), 5-ethyl-2-oxazinidinone, 5-phenyl- 2-oxazinidinone, 4,5-dimethyl 2 oxazinidinone, 5,5-dimethyl-Z-oxazinidinone, 2,S-diphenyl-2-oxazinidinone, 2- pheny1-4-oxothiazolidone, 2,2-diphenyl 4 oxothiazolidone, 2,2-dimethyl 4 oxothiazolidone, 2-oxazolidinone (US. Patent 2,905,690 and US Patent 2,891,058), 5- methyl-2-oxazolidinone, 4-methyl 2 oxazolidinone, 5- ethyl 2 oxazolidinone, 4,5-dimethyl 2 oxazolidinone, 2-phenyl-2-oxazolidinone, 5-butyl-2-oxazolidinone, S-propyl-2-oxazolidinone, 4,5-diethyl-2-oxazolidinone, Z-piperazonone (JACS 62, 1202 (1940), 3,3-dimethyl-2-ketopiperazine and 3-methyl-2-ketopiperazine, 4-thiazolidone (JACS 76, 578 (1954), Z-thiazolidone (J. Chem. Soc. 1949, 2367), 2-methyl 4 thiazolidinone, 2-phenyl-4- thiazolidinone dioxide, 3-thiamorpholinone, 2-pyrimidone (J. Chem. Soc. 1959, 525), 2-imidazolidones (e.g. Ann. 232, 227 (1886), N,N-ethylenethioureas (J. Biol. Chem. 163, 761 (1946); tetrahydro-(ZH, l,3)-oxazin-3-ones (US. Patent 2,940,971), and the like.

In preparing alkylated polymers (homoand copolymers) of the foregoing N-vinyl monomers, it is preferred to follow the simultaneous polymerization and alkylation procedure described in the aforementioned application of Merijan and Grosser, Serial No. 358,406 while adhering to the proportions of co-reactants described herein. By the term skin, as employed in the following claims, is meant skin in general, which is the external covering or integument of the body and includes the scalp which isan integument of the upper part of the head. Since hair is the natural covering of the head growing from the skin and since nails (modified epidermis,

17 skin) grow on the upper side of the ends of fingers and toes, the term appendages of the skin includes hair and nails.

We claim:

1. A composition for application to a member of the group consisting of skin and appendages of theskin containing as an essential component in a toiletry carrier from 0.1 to about 50% by weight of said carrier of an alkylated polymer of an N.-vinyl heterocyclic monomer wherein on an average of at least 25% of the N-vinyl heterocyclic monomer units in said polymer are alkylated with an alkyl chain of from-10 to 42 carbon atoms, said alkylated polymer being selected from the class consisting of polymers prepared by (a) the simultaneous polymerization and alkylation of one mole of a monomer selected from the group consisting of at least one N-vinyl heterocyclic monomer and a mixture of monomers containing from 60 to 95% by weight of said N-vinyl heterocyclic monomer and from to 40% by weight of a non-heterocyclic polymerizable monoethylenically unsaturated monomer, and v (b) by the alkylation of one mole of a polymer selected from the group consisting of homopolymer of said N-vinyl heterocyclic monomer and copolymer of said N-vinyl heterocyclic monomer and said non-heterocyclic polymerizable monoethylenically unsaturated monomer, with 0.5 to 4 moles of an alpha-olefin of from to 42 carbon atoms in solution of an organic solvent common to said selected monomer, mixture of monomers, homopolymer and copolymer, and alpha-olefin in the presence of 0.025 to 0.30 mole of an organic peroxide catalyst per mole of said alpha-olefin at a temperature ranging from 100 to 200 C., said heterocyclic N-vinyl monomer is selected from the glass consisting of N-vinyl succinimide, N-vinyl diglycolylamide, N-vinyl glutaramide, N- vinyl 3-rnorpholinone, N-vinyl 5-methyl-3-1morpholinone, N-vinyl 5-ethyl-3-morpholinone and monomers of' the following formulae:

Hg NRrCOCRz=CHz wherein R represents an alkylene bridge of from 2 to 4 carbon atoms to complete a 5-, 6- and 7-membered heterocyclic ring system, R represents a member selected from the class consisting of hydrogen, methyl and ethyl, R represents a member selected from the class consisting of hydrogen and methyl, R represents a member selected from the class consisting of hydrogen, alkyl of from 1 to 12 carbon atoms and phenyl, m is an integer of from 1 to 4, n is an integer of from 1 to 4 when m has a value of 1, and from 2 to 4 when m has a value greater than 1, and y is an integer of from 2 to 3, and the said non-heterocyclic polymerizable monoethylenically unsaturated monomer is selected from the class consisting 18- of vinyl esters, vinyl chloride, vinylidene' chloride, acrylonitrile, styrene, acrylic acid, acrylate esters, methacrylic acid, .methacrylate esters, methacrylonitrile, acrylamides and methacrylamides. 2. A composition for application to a member of the group consisting of skin and appendages of the skin containing as an essential component in a toiletry carrier from 0.1 to about 50% by weight of said carrier of an alkylated poly-mer of an N-vinyl lactam monomer Wherein on an average ofat least 25% of the N-vinyl lactam monomer units in said polymer are alkylated with an alkyl chain of from 10 to 42 carbon atoms, said alkylated polymer being selected. from the class consisting of polymers prepared by I -('a) the simultaneous polymerization and alkylation of one mole of amonomer selected from the class consisting of at least one N-vinyl lactam monomer and a mixture of monomers containing from to 95% by weight of said N-vinyl'lactam monomer and from 5% to 40% by weight of a non-heterocyclicpolym- 'erizable monoethylenically unsaturated monomer, and a (b) by the alkylation of one mole of a polymer selected from the group consisting of homopolymer of said N-vinyl lactam monomer and copolymer of said N-vinyl lactam monomer and said non-hetero cyclic polymerizable monoethylenically unsaturated monomer, i with 0.5 to 4 moles of an alpha-olefiin of from 10 to 42 carbon atoms in solution of an organic solvent common to said selected monomer, mixture of monomers, homopolymer, copolymer and alpha-olefin in the presence of 0. 025 to 0.30 mole of an organic peroxide catalyst per mole of said alpha-olefin at a temperature ranging from 100 to 200 C., and said N-vinyl lactam monomer is selected from the class consisting of monomers of the fol lowing formulae:

lil Hz NRaC O C Rg=CHz wherein R represents an alkylene bridge of from 2 to 4 carbon atoms to complete a 5-, 6- and 7-mem-bered-heterocyclic ring system, R represents a member selected from the class consisting of hydrogen, methyl and ethyl, R represents a member selected from the class consisting of hydrogen and methyl, R represents a member selected from the class consisting of hydrogen, alkyl of from 1 to 12 carbon atoms and phenyl, m is an integer of from 1 to 4, n is an integer of from 1 to 4 when m has a value of l, and from 2 to 4 when m has a value greater than 1, and y is an integer of from 2 to 3, and the said non-heterocyclic polymerizable monoethylenically unsaturated monomer is selected from the class consisting of vinyl esters, vinyl chloride, vinylidene chloride, acrylonitrile, styrene, acrylic acid, acrylate esters,

methacrylic acid, methacrylate esters, methacrylonitrile,

acrylamides and-methacrylamides'. Y I

3;A cosmetic cream for softening and 'soothingthe skin containing as an essential component in a dermatologically acceptable carrier from 0.1% to about 50% by-weight of'said carrier of an alkylated polymer of an N- vinyl heterocyclic monomer'prepared by the process defined in claim 1. .j '1 4. A soap for conditioning and softeningthe skin containing as an essential component in a dermatologically acceptable carrier from 0.1% to about 50% by weight of said carrier of-an alkylated polymer "of an N-vinyl heterocyclic monomer prepared bythe process defined in claim 1. g

5. A lotion for-conditioning and softening the skin containing as an essential component in a dermatologically acceptable carrier vfrom 0.1% to about 50% by weight of said carrier of an alkylated polymer of an N- vinyl heterocyclic monomer prepared by the process defined in claim 1. 1 6. A cuticle softener for conditioning and softening the cuticles of the nails of fingers and toes containing as an essential component in a dermatologically acceptable carrier from 0.1% to about 50% ,by weight of said cartier of an alkylated polymer of an N-vinyl heterocyclic monomer, prepared by the process defined in claim 1. 7. A hair groomingcomposition for imparting softness, lubricity, lustre and manageability to the hair containing as an essential component in a dermatologically acceptable carrier from 0.1% to about 50% by weight of said carrier of an alkylated polymer of an N-vinyl heterocyclic monomer preparedwby the process defined in claim 1. 2

8. A toiletry preparation for application to a member selected from the group consisting of skin and appendages of the skin containing as an essential component in a toiletry carrier from 0.1% to about 50% by weight of said carrier of an alkylated homopolymer of N-vinyl-2- pyrrolidone, wherein on the average of at least 50% of the N-vinyl-2-pyrrolidone units in said homopolymer are alkylated with an alkyl group of from 10 to 42 carbon atoms, prepared by the alkylation of one mole of the homopolymer of N-vinyl-2-pyrrolidone with 0.5 to 4 moles of an u-olefin of from 10 to 42 carbon atoms in solution of an organic solvent common to said homoof an organic peroxide catalyst per mole of said a-olefin at a temperature ranging from 100 to 200 C.

9. A toiletry preparationfor application to a member selected from the group consisting of skin and appendages of the skin containing as an essential component in a toiletry carrier from 0.1% to about 50% by weight of said carrier of an alkylated homopolymer of N-vinyl- 5-methyl-2-pyrrolidone, wherein on the average of at least 50% of the N-vinyl-5-methyl-2-pyrrolidone units in said homopolymer are alkylated with an alkyl group of from to 42 carbon atoms, prepared by the alkylation of one mole of the homopolymer oi N-vinyl-S-methyl-2-pyrrolidone with 0.5 to 4 moles of an a-olefin of from 10 to 42 carbon atoms in solution of an organic solvent common to said homopolymer and a-olefin in the presence of 0.025 to 0.3 mole of an organic peroxpolymer and u-olefin in the presence of 0.25 to 0.3 mole 5 of the skin containing as an essential component in a toiletry-carrier from 0.1% to abo ut 50% by weight'of said :carrier of an alkylated homopolymer ofN-vinylpiperidone, wherein on the average of at least 50% of the N-vinyl-piper'idone units in said homopolymer are alkyl- 10 ated with an alkyl group'of from '10 to 42 carbonatoms,

prepared by the'-'alkyla tion'-- of one'mole of the homopolymer of N vinylpiperidone with 0.5 to '4 moles-of an tat-olefin of fromlO to 42'carbon atoms in solution of an organic solvent common to said'homopolyrner and a 15 olefin-in the presence of 0.025 to'0.3 mole of an organic peroxide 'catalystper mole of said 'a-ol'efinat a temperature ranging'from 100to 200 C. 0

11. A toiletry preparation for'applica'tion to ainember selected from the group cunsisting of 'skinand appendages of the skin-containing as an essential component in a toiletry carrier from 0;l%-to about 50% by weight of said carrier of an alkylated homopolymer of N-vinyl-e-caprolactam, wherein=on the average of at least 50% of the N vinyl-e-caprolactam units in said homopolymer are alkylated with an alkyl group of from 10 'to 42 carbon atoms, prepared by the alkylationof one mole 'of the homopolymer of N-vinyl-e-caprolactam with 0.5to 4 moles of an a-olefin of from 10 to 42 carbon atoms in solution of an organic solvent common to said homopolymer and u-olefin in the present of 0.025 to 0.3 'mole of an organic peroxide catalyst per mole of said a-olefin at a temperatur'eranging from 100 to 200 C.

12. A toiletry preparation for application to a member selected from the group consisting of skin and appendages of'the skin containing as an essential component in a toiletry carrier from 0.1% to about 50% by weight of said, carrier of an alkylated homopolymer of Nwinyl-Z- pyrrolidone, wherein on the averageof at least 50% of the N-vinyl-Z-pyrrolidone units in said homopolymer are 0 alkylated with an alkyl group of from 10 to 42 carbon atoms, prepared by the simultaneous polymerization and alkylation of one mole of N-vinyl-Z-pyrrolidone with 0.5 to 4 moles of an a-olefin of from 10 to 42 carbon atoms in solution of an organic solvent common to said pyrrolidone and a-olefin in the presence of 0.025 to 0.3 mole of an organic peroxide catalyst per mole of said a-olefin at a temperature ranging from 100 to 200 C.

References Cited UNITED STATES PATENTS ALBERT T. MEYERS, Primary Examiner.

V. C. CLARKE, Assistant Examiner.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2723248 *Oct 1, 1954Nov 8, 1955Gen Aniline & Film CorpFilm-forming compositions
US3250680 *Jul 19, 1960May 10, 1966Gillette CoHeat-generating cosmetic composition
US3309365 *Oct 9, 1964Mar 14, 1967Gen Aniline & Film CorpAlkylated cyclic imides and processes for their production
CA519669A *Dec 20, 1955Colgate Palmolive CoDentifrice containing polyvinylpyrrolidone
DE850328C *Aug 10, 1944Sep 22, 1952Basf AgGeformte Wasch- und Reinigungsmittel
GB797992A * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3479417 *Nov 16, 1966Nov 18, 1969Gaf CorpGraft copolymers of alpha-olefins and preformed,water-insoluble,homopolymer of n-vinyl-2-pyrrolidone
US3878135 *Oct 15, 1973Apr 15, 1975Warner Lambert CoDenture adhesive preparation containing an anionic protein material
US3906091 *Oct 12, 1973Sep 16, 1975OrealHair-setting lotion containing a reducing agent
US3911105 *Jun 7, 1974Oct 7, 1975OrealFatty compositions for use in cosmetic makeup compositions and said cosmetic makeup compositions
US3926870 *Jan 15, 1975Dec 16, 1975Warner Lambert CoDenture adhesive preparation containing an anionic protein material
US3937811 *Jun 7, 1974Feb 10, 1976Societe Anonyme Dite: L'orealFatty compositions for use in cosmetic makeup compositions and said cosmetic makeup compositions
US3988110 *May 20, 1975Oct 26, 1976Societe Anonyme Dite: L'orealHair coloring and hair-setting lotion containing a direct dye, a reducing agent and a solar filter
US4075131 *Sep 17, 1976Feb 21, 1978Minnesota Mining And Manufacturing CompanyConditioning shampoo
US4172122 *Jul 29, 1977Oct 23, 1979Minnesota Mining And Manufacturing CompanySubstantive sunscreening compositions
US4268499 *Jun 7, 1979May 19, 1981Dow Corning CorporationAntiperspirant emulsion compositions
US4507280 *Feb 12, 1982Mar 26, 1985Clairol IncorporatedHair conditioning composition and method for use
US4701322 *Feb 28, 1985Oct 20, 1987The Procter & Gamble CompanyConditioning shampoo
US5004598 *May 31, 1989Apr 2, 1991The B. F. Goodrich CompanyStable and quick-breaking topical skin compositions
US5011681 *Oct 11, 1989Apr 30, 1991Richardson-Vicks, Inc.Facial cleansing compositions
US5026540 *Jun 4, 1987Jun 25, 1991Chesebrough-Pond's Usa Co.Sunscreen composition
US5304317 *Nov 23, 1992Apr 19, 1994Fospur LimitedFroth flotation of fine particles
US5690918 *May 24, 1996Nov 25, 1997Maybelline, Inc.Solvent-based non-drying lipstick
US6740316Oct 19, 2001May 25, 2004L'orealAnhydrous pigment paste and its use in cosmetics
USRE29871 *Mar 11, 1977Dec 26, 1978L'orealFatty compositions for use in cosmetic makeup compositions and said cosmetic makeup compositions
USRE38441 *Mar 22, 1999Feb 24, 2004Maybelline, Inc.Solvent-based non-drying lipstick
EP2022805A2Jul 16, 2008Feb 11, 2009Basf SeCopolymers based on N-vinyllactams and olefins as their use as solubilizers for slightly water-soluble compounds
WO2002032382A1 *Oct 19, 2001Apr 25, 2002Rolf KluckerAnhydrous pigment paste and its use in cosmetics
WO2013156385A2 *Apr 11, 2013Oct 24, 2013L'orealWater resistant compositions containing a heterocyclic compound and a compound having at least one functional group chosen from an amino group and a hydroxyl group
Classifications
U.S. Classification424/70.15, 510/157, 510/152, 526/263, 526/260, 510/500, 510/137, 424/70.16, 424/59, 510/119, 510/158, 525/283, 526/264, 8/160, 424/63, 424/70.11, 510/475, 525/264
International ClassificationA61Q19/00, A61Q1/06, A61Q19/10, A61Q1/12, A61Q9/02, A61Q5/02, A61Q17/04, A61K8/81, A61Q3/04, A61Q11/00, C08F26/06, A61Q5/06, A61Q3/00, A61Q15/00, C08F8/00
Cooperative ClassificationA61Q3/00, A61K8/8182, A61Q9/02, C08F8/00, A61K8/8152, A61Q5/02, A61Q11/00, C08F26/06, A61Q1/12, A61Q19/00, A61Q5/06, A61Q19/10, A61K8/817, A61Q19/002, A61Q3/04, A61Q17/04, A61Q15/00, A61Q1/06
European ClassificationC08F26/06, C08F8/00, A61Q1/12, A61K8/81R, A61K8/81K4, A61K8/81R4, A61Q19/00, A61Q5/06, A61Q11/00