CA1246788A - Amine and ammonium nitrogen containing polyvinyl alcohol polymers having improved lipophilic properties for use in skin conditioning, cosmetic and pharmaceutical formulations - Google Patents

Abstract

ABSTRACT

Polyvinyl alcohol polymers having oxy-linked pendant quaternary ammonium or tertiary amine groups provide a thin film which aids in reducing moisture loss when applied to skin as conditioning lotions or ointments in cosmetic and pharmaceutical formulations.

Description

` i24~788 ~ ?E A~D A~lO~IUM NITROGE~ CO~TAINI~IG
POLYVINYL AI,COHOL POL~ERS HAVIt~G IMPROVED
LIPOPHILIC PP~OPERTIES FOP~ USE IN S~
CO~ITIO~I~IG, COSMETIC AIID PI~RMACEUTICAL FORMULATIQ~S

The present invention is directed to skin conditioning polymers which when applied to skin form retentive films which aid in reducing moisture loss. The invention relates in general to film forming polyvinyl alcohol polymer derivatives and specifically to those having certain amine and quaternary ammonium nitroger containing pendant groups or a combination of these nitrogen containing groups. Of particular interest are polymers having a polyvinyl alcohol backbone or base chain with randomly distributed pendant substituent nitrogen containing groups comprising at least two oxygen linked groups selected from tertiary amines, quaternary ammonium, alkyl, arylalkyl, hydroxy alkyl, alkyl acids and hydroxy alkyl acids.
As a result of the presence of quaternary ammonium groups in the polymer, thin film coatings on animal skin penetrate the outer layers of the skin to provide sufficient adhesive properties while remaining sufficiently elastomeric to avoid discomfort after drying. While the thin films act as a partially impenetrable barrier to prevent loss of moisture bv evaporation they also behave as moisture retainers through the possible formation of hydrates at the quaternary am7~onium sites and by inclusion of water molecules through hydrogen bonding on the hydrophilic polymer matrix. Other pendant groups on the polyvinyl alcohol chain selected from the tertiary amines and the alkyl groups further enhance the comfort of the dry thin film on the skin while thcy provide means for adjusting the hydrophilic/lipo-philic balance to provide for compatability with specific solvents thereby permitting the polymer to be formulated in a wide number of skin conditioning, cosmetic and pharmaceutical formulations.
Furthermore, the polymers act as suspending agents for insoluble pigments and pharmaceutical actives contained in such formulations in high concentrations.

ICI Americas Inc.
Docket ~o. 1579-1

-2~ 46788 It is an object of the invention to provide for a quaternary nitrogen or tertiary amine containing polyvinyl alcohol polymer base chain (having a number average molecular weight of at least 2,000 and preferably up to about 200,000 and higher when unmodified) and a multiplicity of oxy-linked pendant groups and at least-two being selected ~rom the general formulas:

(a) -R-N RlR2R3A , (b) -R-NRlR2, and (c) -R4 wherein R is alkylene, substituted alkylene preferably hydroxyalkylene, or acylene of formula weight ranging from 14 to about 3,000, Rl, R2, R3 are alkyl or arylalkyl radicals, having 1-20 carbon atoms which may be the same or different, A is an anion, and -R4 is alkyl, arylalkyl or specific substituents bearing alkyl ; or arylalkyl radicals such that the total nitrogen content in the resin polymer ranges from 0.01-7.07, by weight. Such polymers have a random selection of (a,b) groups, (a,c) groups, (b,c) groups or (a,b,c) groups. Another ob3ect is to provide for a preferred process for the synthesis of such compositions. It is still another object to provide for aqueous solutions containing 0.1-30% by weight of these polymers which are useful in skin conditioning lotions, ointments, cosmetic and pharmaceutical formulations for application to hair, skin and nails. Another object provides for a film forming polymer which also performs as a dispersant for insoluble particulates in such formulations.
R in the above formula may be selected from alkyl groups such as methylene, ethylene, propylene, butylene, pentylene, hexylene, ethylhexylene, dodecylene, tetradecylene, hexadecylene, octadecylene, and substituted alkyl groups such as hydroxy-:

`^ 12~788 propylene, hydroxybutylene, acetyl, propionyl, butyryl, octa-decanoyl, and octadecenoyl and their equivalents.
Rl, R2, and R3 may be selected from the alkyl Rroups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, octadecenyl, phenyl, or benzyl and their equivalents.
A may be selected from a large number of anion such as chloride, bromide, iodide, hydroxide, lower alkyl (1-6 c~rb~n atoms) sulfate, tetrafluoroborate, nitrate and perchlorate to name a few.
~ R4 may be selected from a number of groups such as alkyl, alkylaryl, substituted alkyl and substituted alkylaryl radicals primarily alkyl or arylalkyl radicals bearing hydroxy or carboxyl groups or a combination of hydroxyl and cfirboxyl groups having a formula weight up to about 3000 and preferably less than 1000. The cumulative formula weight of the pendant groups are controlled in the snythesis of the polymer such that total nitrogen content ranges from 0.01-7% by weight. The overall proportion of R4 groups added to the polyvinyl alcohol base chain are controlled such that their cumulative formula weight comprises from 0.5-50% by weight of the total product polymer weight and the ratio (b/a) of the cumulative formula weight of tertiary amine groups to the total formula weight of quatenary ammonium containing groups may vary from 0-9OZ by weight. Depending on the amount of the -R-~RlR2R3A and -R4 groups the presence of -R-N-RlR2 group may not be needed for certain applications. If the hydroxy or carboxy bearing -R4 type pendant groups are attached to the polyvinyl alcohol base chain prior to the reaction with quatenary ammonium or tertiary amine bearing groups some of the quatenary ammonium or tertiary amine groups may become oxy-linked to the -R4 pendant group in place of being oxy-linked directly to the polyvinyl alcohol base chain.
Specific R4 groups may be selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyldecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, oxtadecyl, hydroxyethyl, mono or dihydroxypropyl, mono or polyhydroxybutyl, mono or polyhydroxy-4 lZ~7~38 pentyl, mono or polyhydroxyhexyl, mono or polyhydroxyoctyl, monoor polyhydroxypentyl, mono or polyhydroxyhexyl, mono or poly-hydroxyoctyl, mono or polyhydroxydecyl, mono or polyhydroxy-dodecyl, mono or polyhydroxytetradecyl, mono or polyhydroxyhexa-decy:l, mono or polyhydroxvoxtadecyl, carboxymethylene, carboxy-ethylene, carboxypropylene, carboxybutylene, carboxypentylene, carbdxyhexylene, carboxyheptylene, carboxyoxtylene, carboxy-decylene, carboxydodecylene, carboxytridecylene, carboxytetra-decylene, carboxypentadecyler.e, carboxyhexadecylene, carboxv-heptadecylene, carboxyoxtadecylene, carboxy(hydroxethylene), carboYy(hydroxypropylene), carboxy(hydroxybutylene), carboxy-(hydroxypentylene), carboxv(hvdroxyhexylene), carboxy(hydroxy-heptylene), carboxy(hydroxyoctylene), carboxy(hydroxydecylene), carboxy(hydroxydodecylene), carboxy(hydroxytridecylene), carboY.y-(hydroxytetradecylene), carboxy(hydroxypentadecylene), carboxy-(hydrohexadecylene), carboxy(hydroxyheptadecylene), and carboxy-(hydroxyoctadecylene).
The quaternary nitrogen containing polyvinyl alcohol polymer compositions of the invention may be represented by a typical polymer segment having the following idealized structural formula:

[( CH CHo~ +RlR2R3A-)(-c~l2cHoH)ml(cH2cHoR4)(cH2c )m2 2 RlR2R3A ) ]

or [(CH CHORN+RlR2R3A ~(CH2CHOH)pl(CY.2CHOR~RlP~2)(CH2 p2 2 4 (CH2CHOH)p3 (CH2cHoRNRlR2R3A ) ] -ml, m2 = 0-650 ml + m2 = <650 Pl~ P2, p3 = 0-650 Pl + P2 + P3 = <650 -"`` lZ~6788 R, Rl, R2, R3, R4 and A are the same as above.

Illustrative exa~ples of the numerous quatenary and tertiàry amine groups and non-nitrogen containing groups in the randomly distributed units in the polyvinyl alcohol base chain may be gi~en as follows:

(1) -CH2CH(OH)CH2N (CH3)3Cl 2CH[CH2~ (C~3~3C; ~o)ecH2cH(oH)cH2N~(cH3)3 where e = 1-20 ~3)~ -(C=O)CH2N (CH2CH3)3Br : (4) -CH2CH(OH)CH2N (CH3)2( 2 ( ) CH2CH2N (CH3)(CH2CH3)(CH2Ph)CH3SO4-(6) -cH[(cH2)7cH3]cH(oH)(c~2)7cH2oH

(7) -CH[(CH2)7CH3]CH(OH)(CH2)7CH2OCH2CH(OH)CH2N (CH3)3CI

8) -CN2CH[CH2N (CH3)3Cl ]OCH[(CH2)7CH3]CH(OH)(CH~)7CH2OH

(9) -CH2CH(OH)CH3 : ~ +
(10) -CH2CH(CH3)tOCH2CH(OH)CH2N (CH3)3Cl CH2CHCH2N (CH3)3C1 10CH2CH(OH)CH3]
(12) -CH2CH(OH)CH2N(CH2Ph)CH3 (13) -CH2CHlOCH2CH(OH)CH2N+(CH~Ph)CH3]CH2N+(CH3)3Cl-; (14) -CH2CHlOCH~CH(OH)CH2N+(CH3)3Cl ]CH2N(CH2Ph)CH3 ~' ~

124!6788 (15) -CH~(CH2)7CH37CH[OCH2CH(OH)CH2N (CH3)3C1 3(CH2)7CH2O-CH2CH(OH)CH~N (CH3)3Cl (16) -(C=O)~CH2)16CH3 (17); -(c=o)(c~2)8cH(cH2)7cH3 (l8) -(C=O)(CH2)7CH=CH(CH2)7 3 (19) -(C=O) (CH2)7CH(OH)C~(OH) (CH2)7C1~3 where Ph = phenyl radical.

l~ile the above structures serve to illustrate the types of pendant groups which can be added to the polyvinyl alcohol (PVA) base chain it is apparent to one skilled in the art that many other arrangements of similar chemical structure can be added. It has been found that each of the above types of groups used in combination with one or more of the others as a substituent on the polyvinyl alcohol base chain yields the desire(l combination of products having the right moisture barrier properties especially when the nitrogen content of the final product ranges from 0.01-7% by weight. Depending on the type of radical attached to the nitrogen of the quaternary group the effective range of the nitrogen content could be even more specific. It has been found for example that when the Rl, ~2 R3, in the above general formulas are all methyl radicals the effective nitrogen content may range from O~1-5~o by weight.
While many techniques have been employed in the art to add substituent groups to vary the polymer change or its hydro-philic-lipophilic balance four preferred methods for attaching the substituent groups to poly-vinyl alcohol involve the reaction of hydroxyl groups of the poly-vinvl alcohol base chain with an epox~-(oxirane) group, a halo-hydrin group in aqueous solution, or a lower molecular weight alkyl alcohol ester of the substituent in a i2~6788 dipolar aprotic solution or an acid halide in either a dipolar aprotic solvent or a two phase svstem in the presence of an appropriate acid or base catalyst.
While a number of methods mav be utilized for the prep~aration of the PVA derivatives described in this invention, the u:se of non-aqueous solvents such as dimethyl formamide or similar polar materials is possible, but gener~lly these sol~ents must be thoroughly removed from the final product. The use of aqueous solvents or mixed agueous systems is preferable but, in this case, yields must be optimized because of competitive reactions of the quaternary ammonium compounds with water as well as PVA hydroxyls in the presence of catalyst. Improved yields can be obtained by increasing the PVA concentration in water, adding the oxirane compound as a concentrate and reducing to a minimum the amount of base used to catalyze the addition reaction. Salt formed during the reaction is preferentially removed from the final product, since it may have a deleterious effect on the skin moisture barrier properties and its formulation. It has also been found that the pH of the derivatized P~A may affect the skin moisture barrier properties as well as the substantivity to skin.
It is generally desirable to work in a p~l range between 2-10 preferably from 5-a.
The product can be obtained in a dry form by precipitation, filtering, drying and grinding. The precipitation is accomplished by adding the reaction mixture to a nonsolvent such as acetone, methanol, ethanol and the like. The product also finds use in the form of the aqueous solution or suspension which can preferably be obtained by dialyzing the reaction mass to free it from salts and low molecular weight unreacted intermediates.
To obtain a better understanding of the preparative techniques found to be most satisfactory attention is drawn to the following generalized and specific preparations which are intended to illustrate but not limit the invention and wherein all proportions mentioned are based on weight unless other~7ise specified.

-8- 12 ~7 8 8 General Preparation I

A flask equipped with a water cooled condenserr mechanical stirrer and thermometer is charged with polyvinyl alcohol and distilled water to form an aqueous suspension or slurry. The polyvinyl alcohol which is generally a commercially available product prepared by hydrolysis of polyvinyl acetate may have from 0-35% by weight residual acetate groups and preferably from 2-15% by weight. The number average molecular weight of the starting material may range from 2,000 up to 200,000 and higher and preferably from 25,000-150,000. In addition and for the purpose of this invention, a polyvinyl alcohol base chain may include up to 25% by weight of another comonomer such as vinyl-pyrolidone, acrylic and methacrylic acid and esters thereof.
The aqueous slurry is heated to 80-100C and then a catalytic amount of an alkaline hydroxide such as sodium or potassium hydroxide or acidic material when appropriate as a catalyst is added. The solution is then cooled to near ambient temperature if the addition of propylene oxide is intended or 50-75C when fatty epoxides or tertiary amine epoxides are to be added. These reagents may be used either singly or in combinatior.
in amounts ranging from 0-0.95 mol per mol of hydroxyl groups or.
the polyvinyl alcohol chain and preferably ~rom 0.001-0.5 mol per mol of hydroxyl on the base chain. The entire solution is then generally treated with a quaternary ammonium reagent when used at a temperature of 80-90C for a period generally ranging from 3 to 24 hours and preferably from 5 to 10 hours. The qu&ternary ammonium reagent such as 2,3-epoxypropyltrialkylammoniumhalide or (chlorohydroxypropyl)trimethylammoniumhalide either in aqueous solution or crystalline form may be added either incrementally or all at once and stirred at a temperature of 40-90C and preferably at 60-70C for a period of about 4 hours or until the reaction is complete. These quaternary ammonium halide reagents are typicall,~
used in amounts of 0.003-0.95 mol per mol of hydroxyl and preferably from n . l-o . 3 mols per mol of hydroxyl group remaining unreacted on the polyvinyl alcohol base chain.

~Z4~788 g The reaction mixture is freed from all species below a certain molecular wei~ht by dialysis or ultra~iltration. Two methods may be used, one a static and one a dynamic. Inrthe static method the reaction mixture is placed inside a commercial semi-porous dialysis tube and the tubes are submerged in distilled water-typically for periods of 12 to 48 hours. The contents of the tube are then recovered and the product may be used as is or dryed. In the dynamic system a pressure pump is used to move water fro~. the reaction mixture through a semi-porous me~hrane.
The water carries out any inorganics and low molecular weight organics. The resulting concentrated product is then collected and may be used as is in cosmetic formulations or dried by conventional techniques to form a highly dispersable solid.

General Preparation II

A flask equipped with a water cooled condenser, mechanical stirrer and thermometer is charged with polyvinyl alcohol and distilled water to form an aqueous suspension or slurry. The polyvinyl alcohol which is generally a co~mercially available product prepared by hydrolysis of polyvinyl acetate ~ay have from 0-35% by weight residual acetate groups and preferably from 2-15~ by weight. The number average molecular weight of the starting material may range from 2,000 up to 200,000 and higher and preferably from 25,000-150,0nO. In addition and for the purpose of this invention, a polyvinyl alcohol base chain may include up to 25% by weight of another comonomer such as vinyl-pyrolidone, acrylic and methacrylic acid and esters thereof.
The aqueous slurry is heated to 80-100C and then a catalytic amount of an alkaline hydroYide such as sodium or potassium hydroxide or acidic material when appropriate as a catalyst is added. The entire solution is then generally treated with a quaternary ammonium reagent when used at a temperature of -` 12~788 40-90C for a period generally ranging from 3 to 24 hours and preferably from 5 to lO hours. The quaternary am~onium reagent such as 2,3-epoxyprop~ltrialkylamr.oniumhalide or (chlorohydroxy-propyl)trimethyla~ oniumhalide either in aqueous solution or crys~alline form may be added either incrementally or all at once and stirred at a temperature of 40-90C and preferably at 60-70C
for a' period of about 4 hours or untll the react~on is co~plete.
These quaternary ammonium halide reagents are typically used in amounts of 0.003-0.95 mol per mol of hydroxyl and preferably from 0.1-0.3 mols per mol of hydroxyl group remaining unreacted on the polyvinyl alcohol base chain.
The reaction mixture is freed from all species below a certain molecular weight by dialysis or ultrafiltration. Two methods may be used, one a static and one a dynamic. In the static method the reaction mixture is placed inside a commercial semi-porous dialysis tube and the tubes are submerged in distilled water typically for periods of 12 to 48 hours. The contents of the tube are then recovered and the product may be used as is or dryed. In the dynamic system a pressure pump is used to move water from the reaction mixture through a semi-porous membrane.
The water carries out any inorganics and low molecular weight organics. The resulting concentrated product is then collected an,d may be used as is in cosmetic formulations or may be then alkylated in the fashion described in the previous example.
The solution is then cooled to near ambient temperat~re if the addition of propylene oxide is intended or 50-75C when fatty epoxides or tertiary amine epoxides are to be added. These reagents may be used either singly or in combination in amounts ranging from 0-0.95 ~ol per mol of hydroxyl groups on the poly-vinyl alcohol chain and preferably from 0.001-0.5 mol per mol of hydroxyl on the base chain. A catalytic amount of alkaline hydroxide is used.
To obtain the optimum moisture barrier properties, the resulting solution is then treated by dialysis or ultrafiltration `~ ~Z~788 to remove the catalyst, affording an aqueous dispersion that mzy be used as is or recovered by precipitation.

Example 1 ; + -R4 = -cH2-cH(cH3)oH;
-RN RlR2R3A = -CH2-CH(OH)CH2N (CH3)3Cl A flask equipped with mechanical stirrer, thermometer, efficient condenser, and dropping funnel was charged with commercial polyvinyl alcohol (88.0 g) and distilled water (500 ml). The PVA contained 2~ residual acetate groups and had a number average molecular weight of 126,000. The slurry was heated to 85-90DC for one hour and potassium hydroxide (3.0 g in 15 ml H2O) was added. The solution was cooled to 35C and propylene oxide (35.0 g) was added dropwise at such a rate to prevent refluxing. When the addition was complete, the temperature was raised to 50C for 4 additional hours. The warm solution was then poured into acetone. The precipitate wss collected by filtration, washed with acetone and methanol, and dried under vacuum. The yield was 113 g.
This propoxyiated polyvinyl alcohol (56.5 g) was then charged to another flask equipped as described above along with water (500 ml), potassium hydroxide (3.0 g), and (chlorohydrox~-propyl)trimethylammonium chloride 80 ml of 48% aqueous solution).
The entire solution was then stirred at 60~C for 16 hours. The product was recovered by precipitation from acetone described previously. The nitrogen content was found to be 0.88%.

EY.ample 2 -R4 = -CH2CH(OH)CH3 -R-N RlR2R3A = -C~2CH(OH)CH2-N(CH3)3Cl A flask equipped with thermometer, mechanical stirrer, condenser and nitrogen sparger was charged with polyvinyl alcohol lZ~Ç~788 (88.0 g, 98% hydrolyzed, ~ = 126,000) and distilled water ~700 ml). Potassium hydroxide (3.0 g in 25 ml water) was added and the pot stirred at 35C for one hour. Propylene oxide (58.0 r~ 1.0 mol) was then added dropwise. The exotherm was allowed to bring the pot temperature to 55C during the addition. When the addit;ion was complete, the temperature was maintained at 55C for an additional 4 hours. Recovery was acco~plished by precipitation in acetone as described previously. Yield was 134.5 g.
The propoxylated polyvinyl alcohol (72.2 g) was char~ed to a flask equipped as above along with distilled water (500 ml~.
The pot was warmed to 55C and potassium hydroxide (3.0 grams in 25 ml water) was added. After one hour, 2,3-epoxytrimethyl-ammonium chloride (78 ml of 4~% aqueous solution) was added in one slug and the entire solution warmed for an additional 12 hour.
Recovery was accomplished by precipitation from acetone as described previously affording a product with a nitrogen content of 1.71%.

Example 3 .
-R4 = -CH[(CH2)7CH3]CH(OH)(CH2)8OH or -CH[(CH2)8OHlCH(OH)(CH2)7CH3 ~i -RN~RlR2R3A = -CH2CH(OH~CH2N~CH3~3Cl A two liter flask equipped with mechanical stirrer, thermometer and ef,icient condenser was charged with oleyl alcohol (200 g, 85% purity) and methylene chloride (600 ml) and cooled to 5-10C. 3-Chloroperoxybenzoic acid (135 g, 85% purity) was then added through a powder funnel in four equal portions spaced at 20 minutes intervals. The slurry was stirred an additional 3 hours allowing the temperature to rise gradually to ambient. The solution was then filtered and the filtrate extracted with 10/o aqueous sodium bicarbonate (3 x 500 ml) and distilled water (2 x 500 ml). The organic layer was then collected, dried over anhydrous magnesium sulfate, and concentrated under vacuum to afford a pale yellow oil (212 g, 99~ yield) which solidified to a ~24Ç~788 colorless wax on standing. This wax was used without further purification.
A five liter, four necked flask equipped with ~
thermometer, condenser and mechanical stirrer was charged with polyvinyl alcohol (500 g, 98~ hydrolyzed, MW = 126,000) and disti-lled water (3700 ml). The slurry was heated to 85C and held until dissolution was complete. Potassium hydroxide (31.5 g in 100 ml water) was added and the pot cooled to 70C. 9,10-Epoxy-octadecan-l-ol (235 g, 0.83 mol) was then added and the pot cooled to 70~C. The opaque solution was stirred an additional 3 hours at 60C and allowed to cool gradually to ambient temperature.
The resulting latex-like solution was neutralize~ with a small amount of 6M H2SO4, and bottled. Half of this solution, measured volumetically, was then charged to similarly equipped three liter flask and warmed to 80C. Potassium h~droxide (15.0 g in 50 ml H2O) was added and the pot cooled to 60C. Aqueous chlorohdyroxypropyltrimethylammonium chloride (331.0 ml 482 aqueous solution) was then added all zt once. The entire slurry was warmed at 60C for an additional 4 hours and recovered by precipitation from acetone.

Exanple 4 -R4 = -CH[(CH2)70HlCH(OH)(CH~)7CH3 lR2R3A -CH2-CH(OH)CH2~ (CH3)3Cl A flask equipped with A mechanical stirrer, thermometer, and condenser was charged with polyvinyl alcohol (44.0 g, 98~
hydrolyzed, MW = 126,000) and water (400 ml). The pot was heated to 85C for one hour and cooled to 80C. Potassium hydroxide (3.0 g in 15 ml H2O) was added and the pot was cooled to 60C.
Glycidyltrimethylammonium chloride (75.8 g) was then added, and the resultant solution stirred for 5 additional hours. The product was recovered by precipitation from acetone (1500 ml) as ~: 12~Ç~788 previously described. The yield was 110 grams and the nitrogen content was 4.66~.
This quaternized polymer (40.0 g) was then cha~ged to a similarly equipped flask with water (400 ml). The pot was heated to 60-65C and potassiu~ hy~roxide (2.0 g in 5 ml H2O) was added.
9,10-~poY~yoctadecanol (8.5 g), prepared as described in Example 3, was added and the solution was stirre~ at 60C for 16 hours. ~h~
product was then recovered from acetone and had a nitrogen content Oc 0.97Z.

Example S

-R~ = -CH2CH(OH)CH3 -RN RlR2R3A = -CH2CH(OH)CH2~ (CH3)3Cl A flask equipped with a mecha~ical stirrer, condenser, thermometer, and dropping funnel was charged with 44.0 g polyvinyl alcohol (100% hydrolyzed, MW = 78,000) and water (400 ml). The solution was warmed to 85-90C and sodium hydroxide (2.6 g in 20 ml H2O) was added. The solution was then cooled to 30C.
Propylene oxide (15.~ g) was added all at once. The solution was stirred one hour at 30C and warmed to 7QC. 9,10-Epoxyocta-decanol (10.0 g) was then added along with glycidyltrimethyl-ammonium chloride (30.0 g). The entire solution was then stirred at 70C for 3 hours, cooled to ambient temperature, and allowed to stand overnight. The product was recovered by precipitation in methanol.

Example 6 -RNRlR2 = -CH~CH(OH)CH2N+(CH3)(CH2Ph) -RN RlR2R3A = -CH2CH(OH)CY2N (CH3)3Cl A flask equipped as described in Example 5 was charged with polyvinyl alcohol (44.0 g) and water (400 ml) an~ heated to 124~788 85C. After one hour, potassium hydroxide (3.1 g in 15 ml H2O) was added and the pot cooled to 65C. Glycidyltrimethylam~onium chloride (30.0 g) was added all at once and the pot was stirred for one hour. Benzyl-(2,3-epoxypropyl~-methylamine was then added dropwise over a 30 minute period and the entire solution was stirred an additional 3 hours. The product was precipitated fro~
methanol/acetone mixture to afford 62 g. The nitrogen content waC
1.20~.

Example 7 -RNRlR2 = -CH2-CH(OH)CY.2N(CH3) (CH2Ph) A flask equipped with a mechanical stirrer, thermometer, dropping funnel and condenser was charged with polyvinyl alcohol (44.0 g) (g8% hydrolyzed, h~ = 126,000) and water (400 ml). The slùrry was warmed to 90C for one hour and potassium hydroxide (3.0 g in 15 ml ~i2O) was added. The solution was cooled to 75C
and freshly distilled benzyl-(2,3-epoxypropyl)-methylamine (44.3 g) was added dropwise over a 30 minute period. Thc entire solution was stirred 3 additional hours at 60-65C and recovered from acetone. The yield was 49.0 g and the nitrogen content was 0.25%.
~, .
Example 8 A flask equipped as described in the general ex2mple is charged with polyvinyl alcohol 44.0 g (~ = 86,000, 100%
hydrolyzed) and water (400 ml) and heated to 85-90C. A catalytic amount of aqueous potassiu~ hydroxide is added and the pot cooled to 70C. Then 9,10-epoxyoctadecan-1-ol (14.2 g, 0.05 mol) is added and the entire slurry stirred for 3 hours, while gradually cooling to 60C. Crystalline 2,3-epoxypropyltrimethylammonium chloride (151.5 g, 1.0 mol) is then added and the reaction mixture stirred 4 additional hours at 60C. The product may then be ~, 124Ç~788 recovered by precipitation or ultrafiltration to afford a product with a nitrogen content of 5.5Y at an approximated yield of 84%.

Example 9 Another reaction done as described above except that the 2,3-e'poxypropyltrimethylammonium chloride is reduced (~5.8 g, 0.50 mol) should afford a product with a nitrogen content of 4.5% based on a reaction yield of 8070.

Example lO

A flask equippe~ as described in Example 5 may be charged with polyvinyl alcohol and distilled water. The aqueous slurry is heated to 80-90C and held for one hour or until the polymer is completely dispersed or solvated. A catalytic amount of an acid such as sulfuric acid or any proton acid or Lewis acid or aluminum hydrosilicate is added and the pot cooled to 40-90C.
At this point 9,lC-epoxyoctadecanol is added and the reaction mixture is stirred for one hour. 2,3-Epoxypropyltrialkylammonium halide can then be added incrementally or all at once. These two epoxides combined may be used in 0.05-l.0 mcl ratio preferably from 0.1-0.3 mol per mol of hydroxyl group on the polyvinyl alcohol base chain. The entire mixture is then stirred for ar.
additional period typically 4 hours at 60~C. The product may then be recovered by one of the methods described.

Example ll illustrates the effect of the salt formed by HCl neutralization on the skin moisture barrier properties. ~lote the substantial improvement of results based on the final dialyzed product.

124~7~8 ~

Example ll A flask equipped as described in the general e~ample was charged with polyvinyl alcohol (44.0 g, ~ = 86,000, 100Z
hydrolyzed) and water (400 ml) and heated at 85-90C for one hour.
The vessel was cooled to 80C and potassium hydroxide (5.6 g in 15 ml H2O) is added. The vessel W2S cooled to 60C over one hour and

3-chloro-2-hydroxypropyltrimethyl ammonium chloride (1~.8 ~) was added. The solution was stirred four hours at 60C and dialyzed through a semi-porous membrane for five days. The nitrogcn content was 0.15~. Improvement in product yields and a significant reduction in reaction time is achievable by using the oxirane derivative followed by addition to a concentrated PVA
solution.
The solution was then placed in a flask equipped as described in the general example and heated to 80-85C. Potassiuhl hydroxide (0.56 g in 10 ml H2O) was added and the solution stirred for one hour. While cooling to 60C, 9,10-epoxyoctadecan-1-ol (10.2 g) was added and the entire solutior was stirred at 60C for three hours. The resulting white dispersion was then split volumetrically into two a'iquots. Solution A was neutralized with a small amount of concentrated HCl. This product was found to reduce the transpiration of weter through the paper barrier by 42X. Solution B was dialyzed through a semi-porous membrane for 48 hours to pH = 7.9. This product was found to reduce the transpiration of ~ater through the paper barrier by 83~.

~loisture Barrier Test On Paper While the modified polyvinyl alcohol polymers of the invention are best tested for retentivity, substantivity and moisture barrier film forming properties on living animal skin an indication of their effectiveness as a moisture barrier can be obtained by testing on filter paper. In the test results listed in the following Table 1 a 2.5 inch circle of number l Whatman ..

,, 12~788 filter paper was treated with aqueous solutions containin~ from 5-10% by weight of the modified polymer as described in the examples to obtain a polymer film deposit amounting to ahout Q.l gram when dried at room temperature. The test is carried out by taking about 2 grams of aqueous solution of the modified polymer and dropping it over a water wet circle of filter paper from one side.' The saturated paper is permitted to dry overnight at roor temperature and weighed. Depending on the concentration of solution the procedure may be repeated until the weight pickup is about 0.1 gram so that each filter paper is treated with substantially an equal amount of polymer. The dry paper is sealed over the opening of a test cell containing lO0 gra~s of water and permitted to stand for 100 hours in a constant humidity and temperature room at 70F at 40% relative humidity. The weight of water passing through the paper under these conditions is measured by weighing the amount of water remaining in the test cell. Each test employs a control cell containing the identicai paper having no polymer treatment. Considering the weight loss through untreated paper as lO0 the test results which are listed as percentage reduction in evaporation of water are calculated from the water remaining in the cell. The paper test results provide a rough indication of effectiveness as a moisture barrier for further tes~ing on animal skin.
The materials prepared according to Examples l through 7 when screened with the above described moisture barrier test on paper indicate a percent reduction in evaporation measuring from 35 to about 50% which compare favorably with the 40-50% obtained with unmodified polyvinyl alcohol films. Of these, the product of Example 3 gave a result of 48% reduction.
In-vitro tests on animal skins having 5 weight percent of the modified polyvinyl alcohol polymers of this invention indicate comparable results with regard to water vapor transmission (WVT) on Neo-Natal Rat Stratum Corneum when compared with unmodified polyvinyl alcohol films. For example, when corneum membrane having a 5% film polymer as made according to . ,~ -19-Example 3 is tested, a 72.2~ reduction in transmission is obtainable when compared with unmodified PVA (molecular weight of 126,000) having a 66.7% reduction. r Such films can be applied to skin surfaces without detrimental affect upon elasticity. For example, the composition of Ex~mple 3 when applied to pigskin at a 5% film loading and thereafter subjected to thermo-mechanical analysis provides a value of 11.4 while when compared with petroleum jelly which produces maxi0um elasticity gives a value of 28 units.
The polymers of this invention can be varied over a wide range to control the film forming properties and the formulation properties which are affected by the molecular weight of the PVA, the level of quaternary nitrogen, and the concentration of lipophilic groups attached to the PVA backbone. The exact hydrophile/lipophile ratio to achieve a balance of moisture retention, film properties, skin retention, wash off and formulation properties for these polymers is determined experimentally. In general those derivatized PVA polvmers that contain high ratios of polyalkylene to quaternary groups in the side chain are more lipophilic and less moisture sensitive, whereas, those compositions containin& higher levels of nitrogen containing side groups tend to be more hydrophilic in character and lend themselves more readily for formulation in systems containing kigher levels of water, glycerine or other hydrophilic molecules. There is no upper limit to the molecular weight of PVA
that can be used to compare the polymers of this invention. In general it is found that above a molecular weight of several thousand, PVA film properties are sufficiently good to afford functional products. The film properties of PVA above 200,000 are excellent and may be used in the practice of this invention.
However, practical limitations on availability of such starting materials and higher working viscosities make these materials somewhat less attractive.
Certain products of this invention may be polymeric surfactants in addition to moisture barriers and may be formulated 12~788 in a variety of compositions with or without the addition of lower molecular weight surfactants. The choice of the surfactant depends on the specific formulatior. and properties desir~d and will depend on the molecular weight of the PVA, the level of quatèrnary nitrogen, the ratio of lipophilic side chain in the composition and the level of oil or water desired in the final form~lation. With these experimental parameters and guidelines it is possible to prepare formùlations which afford utilization of the polymers of this invention in a variety of applications including soap formulations, skin care products, vehicles for cosmetic formulations including pigments, powders, dyes, etc.
useful in eye shadows, lotions and make-up. The products of this invention may also be used as vehicles for the inclusion of biocides, germicides, sunscreens and other biologically or chemically active molecules in film or particle fo m to protect burned skin from loss of moisture or infection.
The use of unmodified polyvinyl alcohol polymer in film forming ointment bases and barrier crea~s for use in protecting the skin against the action of external irritants has met with only limited success (J.B. Ward and G. J. Sperandio, "American Perfumer and Cosmetics" Volume 79, pages 53-55 (1964)). Film forming creams are difficult to produce with polyvinyl alcohol since they are either very difficult to formulate because of their poor mixing characteristics or they form poor films. Lotions and creams made with polyvinyl alcohol in general lack elegance, that is, the in-vitro films made from ointments and lotions containing about 15% polyvinyl alcohol are either slow drying, become grea~
and tacky and eventually leave a film which is hard and leathery.
Furthermore, good PVA moisture barrier films usually are very hard to remove from the skin because they are difficult to remove with soap and water.
The problems associated with employing unmodified PVA in film forming bases are substantially overcome by the composition~
of this invention in that they are easily dispersible in water are compatible with typical lotion formulations, and when applied to ~Z~788 the surface of the skin, they dry quickly to form an elastic, smooth pellicle which retains its integrity over long periods of time and is easily removed with soap and wa~er. Tests f~r cosmetic elegance is accomplished by applying typical moisture barr-ier lotion formulas to the back of the hand and making observations with respect to ease of application, feel on the skin,` time of drying, durability of the film, ease of remo~ral an~l a host of subjective factors. In most instances, the formulations evaluated do not adversely effect the film forming characteristics oi the modified polyvinyl alcohol compositions of this invertion.
The aqueous moisture barrier compositions of the invention generally have a lotion consistency ~nd may be in the form of oil-in-water or water-in-oil emulsions with the former being preferred because oF their more pleasing cosmetic properties. The lotions are preferably made by first preparing the oil phase then preparing the water phase and thereafter adding the water phase to the oil phase. Usually the aqueous phase materials are heated to a temperature of about 75 to about 100C and then added slowly with stirring to the oil phase which is heated to about the same temperature.
The oil phase components may contain a variety of materials including emulsifiers, emollients, oils, waxes, perfumes, lanolins, polyalkylenes, stearols and the like.
Water phase components may contain many different materials which include humectants, modified PVA moisture barrier components of the invention, proteins and polypeptides, preservatives, alkaline agents, thickening agents, perfumes, stabilizers and antiseptics.
The skin conditioning lotions and ointments of the invention contain as an essential ingredient from 0.1-15Z by weight and preferably from .5-5% by weight of the above described modified polyvinyl alcohol polymers of the invention when used as cosmetics and pharmaceutical compositions. They may be added as aqueous compositions or as dry powder.

~2~788 The lotions may contain an emulsifier in an amount of from about 0.05 to about 8~ and preferably from about 0.25 to about 5% to emulsifv the oil components. Tvpical emulsi~iers are selected from the group consisting of polyethoxylated fatty acids having less than about 30 mols of ethylene oxide per mol of fatty acid,; ethyoxylated esters, unethoxylated sugar esters, polyoxy-ethylene fatty ether phosphates, fatty acid amides, phosphol7pids, polypropoxylated fatty ethers, acyllactates, polyethoxylated poly-oxypropylene glycols, polypropoxylated polyoxyethylene glycols, polyoxyethylene, polyoxypropylene ethylene diamines, soaps and mixtures thereof.
Examples of such emulsifiers include polyoxyethylene (~) stearate, myristyl ethoxy (3) myristate, myristvl ethoxy (3) palmitate, methyl glucose sesquistearate, sucrose distearate, sucrose laurate, sorbitan monolaurate, polyoxyethylene (3) oleyl ether phosphate, polyoxyethylene (10) oleyl ether phosphate, lauric diethenyl amide, stearic monoethyl amide, lecithin, lanolin alcohol propoxylates, sodium stearoyl-2-lactate, calciun stearoyl-2-lactate, and the Pluoronics~ offered by BASF ~yandotte.
Soaps such as alkaline metal or triethanolamine salts of long chain fatty acids which include sodium stearate, triethanolamine stearate and similar salts of lanolin fatty acids. A preferred emulsifier is polyoxyethylene (21) stearyl ether.
~ he lotion formulations may contain an emollient material in an amount ranging from 0.2 to 25~ and more often 1 to 8~ by weight. One function of the emollient is to ensure that the modified polyvinyl alcohol polymer is classified sufficiently to allow it to be in a film-like state on the surface of the skin.
Typical emollients are selected from the group consisting of fatty alcohols, ester~ having fewer than about 24 carbon atoms (for example, isopropylpalmitate), branch chain esters having greater than about 24 total carbon atoms (for example, cetearyl octonate), squalane, liquid or solid paraffins, mixtures of fatty acids and squalane, mixtures of fatty acids and liquid or solid paraffins and mixtures thereof. Typical alcohols and fatty acids which are :,, ~ lZ91~788 useful include those having from 12 to 2~ carbon atoms such as cetyl alcohol, myristvl alcohol, stearyl alcohol, stearic acid an~
palmitic acid. Paraffins include, for eY.ample, mineral ~il, petrolatum and paraffin wax.
: The lotions and ointments are particularly stable and effective when adjusted to a pH of 6-8.
' Because of their high amine content some of the polyrlers of the invention may undergo decompositior. in sunlight and air to form products which import an undesirable odor to the formulation.
To overcome this there should be incorporated with the polymer a minor portion of a material which will inhibit the formation of such decomposition products. These inhibitors/antioxidant materials include nordihydrogucaretic acid, citric acid, ascorbic acid, hydroquinone, butylated hydroxy anisole, butylated hydroxytoluene, and any other suitable antioxidant.
The following formulations will serve to demonstrate but not limit the formulations containing the modified polyvinyl alcohol film forming moisture barrier polymer of the invention.
Typical lotionE contain 0.1-5.0% of the above described modified PVA polymers, 2-5b of an emolient, and 2-SZ emulsifier in an aqueous emulsion.

Example A

A portion of the aaueous solution prepared according to Example 4 containing 0.5 grams of modified PVA polymer was diluted with water and added to an aqueous solution containing 2.4 grams cetyl alcohol, 1.6 grams stearyl alcohol and 3.0 grams of polyoxyethylene (21) stearyl ether (BRIJC 721 surfactant by ICI
Americas Inc.). Additional water was added to bring the water concentration to 92.5~. After stirring for about five minutes at 75C the emulsion is permitted to cool to room temperature and stored. The lotion was tested subjectively for cosmetic elegance by applying the product to the back of the hand and arm. It was determined to have smooth, silky feel, drying time of less than 15 ~2gL~788 minutes and a film durability in excess of two days. Residual films and lotions are easily removed from the skin with soap and water.
As mentioned above the polymers of the invention had advantageous cosmetic properties that permit them to be used in prepa;ring cosmetic formulations either as ready to use compositions or concentrates which have to be diluted before use.
Therefore, the cosmetic formula may contain the modified polyvinyl alcohol polymers in concentrations ranging from 0.01-15% by weight. The solution of these polymers are particularly useful when they are applied to hair, either alone or with other active substances during a treatment such as shampooing, dyeing, setting, blow drying, permanent waving, etc. They may improve notably the quality of the hair. ~hen employed in hair treatment they facilitate untangling of wet hair and do not remain on dry hair as a sticky residue. In some instances thev are expected to give dry hair additional life, a soft feel, a glossy appearance and resistance to tangling.
Hair treating formulations containing dilute aqueous, alcohol or dilute alcohol solutions of the modified polyvinyl alcohol polymer can be employed. Furthermore, they may be employed as creams, lotions, gels or as aerosol sprays. They may be used in combination with perfumes, dyes, preserving agents, sequestering agents, thickening agents, emulsifying agentC~ etc.

Example B

A typical hair rinse formulatior. containing 5 grams of the modified polymer of Example 8, 7 grams cetyl alcohol, 3 gramC
of a linear polyoxyethylenated C10-Cl8 fatty alcohol, 2 grams ot~ a casein derivative, 0.5 grams tetradecyltrimethylammonium chloride and 82.5 grams of water and a minor amount of hair dye can be used to treat hair having improved looks and anti-static properties.

-25- 12gL6788 Example C

A typical oxidation hair dye solution containi~g a 2.5 gram of the modified polymer of Example 9, 10 grams benzyl alcobol, 20 grams oleic acid, 3 grams polyoxyethylene (30), oleo cetyl; alcohol, 7 grams oleic diethanolamide, 7.5 grams 2 octyldo-decanol, 2.5 grams triethanolamine lauric sulfate, 10 grams ethanol, 18 millileters aqueous ammonium, 1 gram n,n-bis(2-hydroxy-ethanol)paraphenylenediamine, 0.4 grams resorcin, 0.15 grams m-aminophenol, .4 grams alphanaphthol, 0.1 grams hydro-quinone, 0.24 grams ethylene diamine tetracetic acid, 1 milliliter sodium bisulfite, and water sufficient to make 100 grams is a typical ammonia oil composition for use as an oxidation hair dye when 130 grams of the solution is mixed with 30 grams of hydroger.
peroxide bleach. After hair is treated with the material and allowed to stand for 30-40 minutes and thereafter rerinsed the hair is expected to untangle easily and have a silky touch.
The modified polyvinyl alcohol compositions of the invention may be employed to improve the elegance and stability of pers~nal care products such as liquid and bar soaps, shaving creams, bath products, antiperspirants, sunscreens, cleansing creams and as a suspending agents for insoluble pigments and pharmaceutical actives. Improvement is generally realized when from 0.5-5~ by weight of the compositions of this invention are em.ployed in conventional formulations as hereinafter exemplified.

Example D

A portion of the aqueous solution prepared according to Example 3 containing 0.5 grams of fatty alcohol modified quaternized PVA was diluted with water and added to an aqueous solution containing 4.0 grams stearic acid, 2.0 grams polyoxyethylene (15) stearyl ether (ARLAMOL~ E by ICI Americas Inc.), 5.0 grams glycerol monostearate and polyoxyethylene stearate (ARLACEL~ 165 by ICI Americas Inc.), and 10.0 grams of -26- 12~L~788 70~ sorbitol solutin (SORBO~ by ICI A~ericas Inc.). After ~tirring for abo~t 5 ~inutes at 75C the emulsion is perm~tted to cool to room temperature and stored. The lotion was teseed sub3ectively for cosmetic elegance by applying the product to the back:of the hand and arm, was determined to have snooth, silky feel, drying time of less than 15 minutes and a film durability in excess of 2 days. Residual films a~d lotions are easily remove~
from the skin with soap ar.d water.

Ex~mple E

Roll-On Antiper~pirant In~redient % W/~1 Example 3 4.0 polyoxyethylene (21) stearylether 0.76 polyoxyehtylene (2) stearylether 3.24 water (deionized) 34.76 Do~icil 200~, Dow Chemical 0.1 Al Zr tetrachlorohydrex-Gly, Rezol 36G*, Reheis 57.14 Example F

Aerosol Shave Cream In~redient ~ WIW
Exa~.ple 3 5.0 Cetyl alcohol ` 4.3 polyoxyethylene (21) stearylether 2.2 water 74 97 water 13 385 * Reg. TM

~
.

-27~ 788 Example G

Oil-in-water Sunscreen Lotion : ~gredient W/W %
miner~al oil 18.8 cetyl alcohol 5.0 Arlocel 60~ emulsifier 2.5 Tween 60~ emulsifier 7.5 Amyl para-dimethylaminobenzoic acid 1.2 Example 4 2.0 water 63.0 Preservative q.s.

Example H

Water-in-Oil Pigmented ~lakeup Ingredient W/~ Z
~iineral Oil 10 Beeswax 1.5 Cevesin wax 1.0 Arlacel 186~ emulsifier 3.2 Sorbo~ sorbitol 28.8 TiO and other pigments 20.0 water 33.5 Example 6 2.0 Example I

Calamine Lotion Calamine 80 gms Zinc Oxide 80 gms glycerine 20 mls bentonite magma 250 mls calcium hydroxide 950 mls (concentrated aqueous sol.) Example l 50 gms

Claims (37)

What is claimed is:

1. A modified polyvinyl alcohol polymer useful in skin conditioning, cosmetic and pharmaceutical formulations which comprises a polyvinyl alcohol base chain having a multiplicity of oxygen-linked pendant groups selected from the group consisting of at least two of the following general formulas:

(a) -RN+ R1R2R3A-, (b) -RNR1R2, (c) -R4 wherein R is selected from the group consisting of an alkylene, or acylene radical, R1, R2, R3 are alkyl or arylalkyl radicals having 1-20 carbon atoms, R4 is selected from the group consisting of alkyl, alkylaryl or arylalkyl radicals bearing hydroxy or carboxyl groups or a combination of hydroxy and carboxyl groups, A- is an anion, said polymer having a total nitrogen content ranging from 0.01-7.0% by weight.

2. A composition of Claim 1 wherein said polyvinyl alcohol base chain has a number average molecular weight which ranges from 2,000-200,000.

3. A composition of Claim 1 wherein the cumulative formula weights of all R4 groups are from 0.5-50% by weight of said polymer.

4. A composition of Claim 1 wherein the ratio of the total formula weights of all -RNR1R2 groups to the total formula weights of all of said -RN+R1R2R3A- groups range from 0-90% by weight.

5. A composition of Claim 1 wherein R is a radical selected from the group consisting of -CH2-CHOH-CH2- and -[CH2CH(CH2N+R1R2R3A-)O]e CH2CH(OH)CH2-wherein R1, R2 and R3 are alkyl or arylalkyl radicals having 1-20 carbon atoms, and A is halide ion or (lower alkyl) SO4 and e =
1-20.

6. A composition of Claim 1 wherein said (a) group is -COCH2N+R1R2R3A-.

7. A composition of Claim 1 wherein the pendant groups R-NR1R2 are selected from the group consisting of -CH2CHOH-CH2NR1R2 and (-CH2CH(CH2NR1R2)-O]eCH2-CH(OH)-CH2NR1R2 wherein R1 and R2 are alkyl or arylalkyl radicals having 1-20 carbon atoms and e = 1-20.

8. A composition of Claim 1 wherein the -R-NR1R2 pendant groups are -COCH2NR1R2 wherein R1 and R2 are alkyl or arylalkyl radicals having 1-20 carbon atoms.

9. A composition of Claim 1 where R1, R2 and R3 are selected from the groups consisting of -CH3, -CH2CH3, -CH2CH2CH3, , or -CH2Ph where Ph is phenyl.

10. A composition of Claim 1 wherein the -R4 is selected from the group consisting of 1,9-dihydroxy octadecane and l,10-dihydroxy octadecane.

11. A composition of Claim 1 wherein -R4 is selected from the group consisting of octadecanoic acid, 9-hydroxy octadecanoic acid, 10-hydroxy octadecanoic acid, 9,10-dihydroxy octadecanoic acid and their salts or esters.

12. A composition of Claim 10 wherein one or both of the hydroxy groups of the 1,9 or 1,10-dihydroxy octadecane are oxy-linked to groups selected from the general formula -R-NR1R2 and -R-N+R1R2R3A- where R, R1, R2, R3 and A- are the same as in Claim 1.

13. A composition of Claim 5 wherein -R4 is selected from the group consisting of 1,9-dihydroxy and 1,10-dihydroxy octadecane.

14. A composition of Claim 13 wherein the one or both hydroxy groups of the dihydroxy octadecane are oxy-linked to groups selected from the general formula -RNR1R2 and -R-N+R1R2R3A-where R, R1, R2, R3 and A- are as in Claim 1.

15. A composition of Claim 1 wherein R4 is selected from the group consisting of and

16. A composition of Claim 11 wherein part or all of the hydroxy groups on R4 are oxy-linked to groups selected from -R-NR1R2 and -R-N+R1R2R3A- groups where R, R1, R2, R3 and A- groups are the same as in Claim 1.

17. A composition of Claim 15 wherein part or all of the hydroxy group of the -R4 pendant groups oxy-linked to groups selected from -RNR1R2 and -R-N+R1R2R3A- groups where R, R1, R2, R3 and A- are the same as in Claim 1.

18. A composition of Claim 1 wherein R1, R2 and R3 are methyl groups and the nitrogen content ranges from 0.05 to 3% by weight.

19. A composition of Claim 1 when prepared by the steps of (a) reacting equal molar quantities of epichlorohydrin with aqueous trimethylamine at temperatures below 25°C, (b) forming an aqueous solution of polyvinyl alcohol having a number average moleculare weight of 2,000-200,000 containing catalytic amount of potassium hydroxide, (c) mixing the solutions of step (a) with step (b) at a temperature of 40-90°C, and (d) mixing an alkyl epoxide with the product of step (c) at 30-90°.

20. A composition of Claim 1 when prepared by the steps of: (a) reacting an alkyl epoxide with an aqueous solution of polyvinyl alcohol having a number average molecular weight in the range of 25,000-100,000 containing a catalytic amount of potassium hydroxide at a temperature of 30-90°C, (b) reacting epichlorohydrin with an aqueous solution of trimethylamine at a temperature below 25°C, (c) reacting the product of step (a) with product of step (b) at a temperature of 40-90°C.

21. A composition of Claim 1 when prepared by the steps of: (a) adding (chlorohydroxypropyl)trialkylammonium chloride in aqueous or crystalline form to an aqueous solution of polyvinyl alcohol having a number average molecular weight of 2,000-200,000 in the presence of a catalytic amount of potassium hydroxide at a temperature of 40-90°C, and (b) reacting said solution of step (a) with an alkyl epoxide at a temperature of 30-90°C.

22. A composition of Claim 1 when prepared by the steps of: (a) reacting an alkyl epoxide with aqueous polyvinyl alcohol having a number average molecular weight of 2,000-200,000 in the presence of a catalytic amount of potassium hydroxide at 30-90°C, and (b) reacting said reaction product of step (a) with (chlorohydroxypropyl)trimethylammonium chloride in either aqueous solution or crystalline form at a temperature of 40-90°C.

23. A composition of Claim 1 when prepared by the steps of: (a) reacting in aqueous solution of polyvinyl alcohol having a number average molecular weight in the range of 25,000-150,000 with an aqueous solution of 2,3-epoxypropyltrialkylammonium halide in the presence of a catalytic amount of alkaline material at a temperature of 40-90°C such that the mol ratio of said ammonium halide to each mol of hydroxyl group on said polyvinyl alcohol polymer ranges from 0.003-1, and (b) reacting said product of step (a) with an alkyl epoxide at a temperature of 30-90-C.

24. A composition of Claim 1 when prepared by the steps of: (a) reacting an alkyl epoxide with aqueous polyvinyl alcohol having a number average molecular weight in the range of 25,000-150,000 in the presence of catalytic amounts of potassium hydroxide at 30-90°C until complete, and (b) reacting an aqueous solution of 2,3-epoxypropyltrialkylammonium halide with the product of step (a) at 2 temperature of 40-90°C in the presence of a catalytic amount of base in amounts wherein the ratio of said ammonium halide to each mol of hydroxyl group on said polyvinyl alcohol polymer ranges from 0.003-1.

25. A composition of Claim 1 when prepared by the steps of: (a) reacting polyvinyl alcohol having a number average molecular weight of 25,000-150,000 with trimethylethoxycarbonyl-methylammonium halide in dipolar aprotic solution in the presence of catalytic amounts of magnesium acetate at a temperature of 150°, and (b) reacting said product of step (a) with an alkyl epoxide in aqueous reaction medium.

26. A composition of Claim 1 when prepared by the steps of: (a) reacting polyvinyl alcohol having a number average moleculare weight of 25,000-150,000 with an alkyl epoxide in aqueous solution containing catalytic quantities of alkaline hydroxide, and (b) reacting the reaction product of step (a) with trimethylethoxycarbonylmethylammonium halide in dipolar aprotic solution in the presence of catalytic amounts of magnesium acetate at a temperature of 70-150°C.

27. A composition when prepared according to Claim 21 or Claim 22 wherein said ammonium halide is (chlorohydroxypropyl)-trimethylammonium chloride and said alkyl epoxide is 9,10-epoxy-octadecane-1-ol.

28. A composition when prepared according to Claim 23 or 24 wherein said ammonium halide is 2,3-epoxypropyltrimethyl-ammonium chloride and said alkyl epoxide is 9,10-epoxyoctadecane-1-ol.

29. A composition of Claim 1 when made by reacting an aqueous solution of polyvinyl alcohol polymer having a number average molecular weight of 25,000-150,000 with 9,10-epoxyocta-decanol and 2,3-epoxypropyltrialkylammonium halide at a temperature of 40-90°C in the presence of a catalytic amount of acid wherein the combined mols of said epoxides to the mols of hydroxyl groups on the polyvinyl alcohol polymer ranges from 0.003-1.

30. A composition of Claim 1 when purified in aqueous solution by dialysis or ultrafiltration.

31. An aqueous dispersion containing from 0.1-30% by weight of a composition of Claim 1.

32. An aqueous skin conditioning composition comprising 0.1-5% by weight of a composition of Claim 1, 2-5% by weight of an emulsifier and 2-5% by weight of an emollient.

33. An aqueous hair conditioning composition comprising 0.1-5% by weight of a composition of Claim 1.

34. A cosmetic composition containing from 0.5-5% by weight of a composition of Claim 1.

35. A pharmaceutical composition which comprises from 0.5-5% by weight of a composition of Claim 1.

36. An amine modified polyvinyl alcohol polymer for use in skin conditioning, cosmetic and pharmaceutical formulations which comprises a polyvinyl base chain having a multiplicity of oxygen linked pendant groups of the general formula:

wherein R is selected from a group consisting of an alkylene or acylene radical, R1 and R2 are selected from the group consisting of alkyl or arylalkyl radicals having 1-20 carbon atoms, said polymer having a total nitrogen content ranging from 0.01-7% by weight.

37. A composition of Claim 1 wherein polyvinyl alcohol is a copolymer having up to 25% by weight of poly-vinyl acetate, polyvinylacrylate, polyvinylmethacrylate or polyvinylpyrolidone.