NZ209700A - Amine and ammonium substituted polyvinyl alcohol polymer compositions and use in skin and hair conditioners and pharmaceutical formulations - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £09700 2 09"0 0 Priority DKelsJ: No.: Datt: , ^ Co,v.;;:cta S.-iecincaiion I .ioo: '••■» c, .,:CO%S% J -5 - ^ •" c Cfetb I .lou. ■ 1^:; ''' uo.ii'v 1®® t jJAN1988 l..'.t:on ; JJ ' ' " .... . ...:....vSO.5 | NO DRAWINGS F^bii-.'.vcn PO N.2. patent CFF. t %^27SEPI984 r.Tc.^v.v NEW ZEALAND PATENTS ACT, 1953 COMPLETE SPECIFICATION AMINE AND AMMONIUM NITROGEN CONTAINING POLYVINYL ALCOHOL POLYMERS HAVING IMPROVED LIPOPHILIC PROPERTIES FOR USE IN SKIN CONDITIONING, COSMETIC AND PHARMACEUTICAL FORMULATIONS jhW«, ICI AMERICAS INC. of Concord Pike & New Murphy Road, Wilmington, Delaware 19897, United States of America, a Company incorporated under the laws of the State of Delaware, United States of America hereby declare the invention for which we pray that a patent may be granted to rae^ua, and the method by which it ie to be performed, to be particularly described in and by the following statement:- - 1 . (followed by page la) atl.1579-1 2JJ70O -(cv.- amind and ammonium mitrogdh cowtaimimg pollyvihyij ALCOHOL POLYMERC iiavimq improved LIPOPHILie- pnopcnTiBa for use ihakih cowditionimGi cosmetic- amd pharmaceutical'pormulatiohg ■ 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 nitrogen 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 by evaporation they also behave as moisture retainers through the possible formation of hydrates at the quaternary ammonium 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 akin while they provide means for adjusting the hydrophilic/lipophilic 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.

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 from the general formulas: (a) -R-N+R1R2R3A", (b) -R-NR!R2, and (c) -R4 wherein R is alkylene, substituted alkylene preferably hydroxyalXylene, or acylene of formula weight ranging from 14 to about 3,000, Rl, R2» R3 are alkyl, alkenyl, aryl or arylalkyl radi 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 0.01-7.0% by weight. Such polymers have a random selection of (a,b) groups, (a,c) groups, (b,c) groups or (a,b,c) groups. Another object 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 alkylene groups such as, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, ethylhexylene, dodec^lene, tetradecylene, hexadecylene, octadecylene, and substituted alkylene groups such as hydroxypropylene, hydroxybutylene, carbonyl, oxoethylene, oxopropylene, oxobutylene, oxooctadecylene and oxooctadecylene.

Rl, R2, and R3 may be selected from the alkyl groups such as for example methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, octadecenyl, phenyl, or benzyl.

A~ may be selected from a large number of anion such as chloride, bromide, iodide, hydroxide, lower alkyl (1-6 carbon atoms) sulfate, tetrafluoro-borate, 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 carboxyl 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 synthesis 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 -.Ve'jwV v © \ « ■V* 12 mm V/> 209700 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 0-90% by weight. Depending on the amount of the -R-N+R21*2^3^" and -R4 groups the presence of -R-N-R1R2 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 quaternary ammonium or tertiary amine bearing groups some of the quaternary ammonium or tertiary amine groups may become oxy-linked to the -R4 pendant group inplace 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, octadecyl, hydroxyethyl, mono or dihydroxypropyl, mono or polyhydroxybutyl, mono or polyhydroxypentyl, mono or polyhydroxyhexyl, mono or polyhydroxyoctyl, mono or polyhydroxypentyl, mono or polyhydroxyhexyl, mono or polyhydroxyoctyl, mono or polyhydroxydecyl, mono or polyhydroxydodecyl, mono or polyhydroxytetra-decyl mono or polyhydroxyhexadecyl, mono or polyhyd-roxyactadecyl, carboxymethylene, carboxyethylene, carboxypropylene, carboxybutylene, carboxypentylene, carboxyhexylene, carboxyheptylene, carboxyoctylene, carboxydecylene, carboxydodecylene, carboxytridecylene, carboxytetradecylene, carboxypentadecylene, carboxyhexadecylene, carboxyheptadecylene, carboxyoctadecylene, carboxy (hydroxyethylene), carboxy(hydroxypropylene) carboxy(hydroxybutylene, I2NCVIM7S 209700 carboxy (hydroxypentylene) , carboxy (hydroxyhaxylan®), carboxy (hydroxyhaptylene) , carboxy (hydroxyoctylene) carboxy(hydroxydecylene) , carboxy (hydroxydodecylene) , carboxy (hydroxytridecylene), carboxy (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 following idealized structural formula: - [ (-CH2-CHORN+R1R2R3A~) C-CH2CHOH) ml (CH2CHOR4) CH2choh) m2(ch2choph+-e1r2r3a-) ]- or - [ ( CH2 CHORN+R1R2R3 A" ) (CH2 CHOH) pl(CH2 CHORNR1R2) CH2 choh) p2 (CH2CHOR4) -(CH2CHOH)p3 (C^CHORNR^R^A") ]- mi'm2 = 0-650 m^ + m2 = <650 Pl, P2' P3 = °-650 P1 P2+P3 = <65° R, R^,R2,R3,R4 and A are the same as above.

Preferred values for R in the pendant groups of general formulas (a) and (b) include the groups -CH2-CH0H-CH2- and -[CH2CH(CH2N+R1R2R3A") O]e-CH2CH(OH) CH2- wherein R^, R2 and R3 are selected from alkyl and arylalkyl radicals having 1 to 20 carbon atoms, A~ is a halide ion or a lower alkylsulfate ion and e = 1 to 20.

Preferred values for the pendant groups of general formula (a) include the group -coch2n+r1r2r3a" wherein R1# R2, R3 and A~ may take any of the values previously defined. fcHfj? "V 12 NOV 1967 thi -o- ^0970c r** Preferred values for the pendant groups of general formula (b) include: the groups —CH^CHOH—CHjNI^R^ / and - [CH2CH (CH2NR1R2) -0 ] eCH2-CH (OH) -CHjNR-JRJ wherein R1 and R2 are alkyl or arylalkyl radicals having 1 to 20 carbon atoms and e ■ 1 to 20; and the group -CJC^NR^ wherein R1 and R2 are alkyl or arylalkyl radicals having 1 to 20 carbon atoms.

Preferred values for the pendant groups of general formula (c) include: 1,9-dihydroxyoctadecyl and 1.10-dihydroxyoctadecyl; and 17-carboxyheptadecyl, 17-carboxy-lO-hydroxyheptadecyl, 17-carboxy-9-hydroxyheptadecyl, 17-carboxy-9,10-dihydroxy-heptadecyl and their salts and esters.

Preferred values for R^, R2 and R3 in the pendant groups of general formulas (a) and (b) include methyl, ethyl, n-propyl, iso-propyl and benzyl.

Illustrative examples of the numerous quatenary and tertiary amine groups and non-nitrogen containing groups in the randomly distributed units in the polyvinyl alcohol base chain may be given as follows: (1) -CH2-CH(OH)CH2N+(CH3)3Cl" (2 ) -CH2 CH [ CH2 N+ ( CH3) C1 ~J 0 J eCH2 CH (OH) CH2 N+ ( CH3 ) 3 CI ~ where e ■= 1-20 .+, (3) -(C=0)CH2N (CH CH3)3Br (4) -CH2 CH(OH)CH2 N ( CH3)2 CH2 Ph)Cl" (5) -CH2CH2N+(CH3) (CH2Ph)CH3S04~ 209700 O (6) -CH[(CH2)7CH3]CH(OH)(CH2)7CH2OH ( 7) -CH[CH2)7CH3]CH(OH)(CH2)7CH02CH2CH(OH)CH2N+(CH3)3 Cl" (8) -ch2ch[ch2n+(ch3)3ci_]och[(ch2)7ch3]ch(oh)(ch2 )7ch2 OH (9) -CH2CH(OH)CH3 (10) -CH2CH(CH3)[OCH2CH(OH)CH2N+(CH3)3C1" (11) -CH2CHCH2N+(CH3)3Cl"[OCH2CH(OH)CH3] (12) -CH2CH(OH)CH2N(CH2Ph)CH3 (13) -CH2CH[OCH2CH(OH)CH2N+(CH2Ph)CH3]CH2N+(CH3)3Cl- (14) -CH2CH[OCH2CH(OH)CH2N+(CH3)3Cl~]CH2N(CH2Ph) CH3 (15) -CH[ (CH2 ) 7CH3 ]CH[OCH2CH (OH) CK2N+ (CH3 ) 3C1" 3 (CH2)7CH20_CH2CH(0H)CH2N+(CH3)3C1" (16) -(C=0)(CH2)16CH3 (17) -(C=0) (CH2)8CH0H(CH2)7CH3 (18) -(C=0)(CH2)7CH=CH(CH2)7CH3 (19) -(C=0)(CH2)7CH(OH)CH(OH)(CH2)7CH3 where Ph = phenyl radical.

While 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 desired 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 R]_, R2, R3, in the above general formulas are all methyl radicals the effective nitrogen content may range from 0.05-5% by weight.

V 12N0V1987Zi! A /■' i v 209700 While many techniques have been employed in the art to add substituent groups to vary the polymer change or its hydrophilic-lipophilic balance four preferred methods for attaching the substituent groups to poly-vinyl alcohol involve the reaction of hydroxyl groups of the poly-vinyl alcohol base chain with an epoxy (oxirane) group, a halo-hydrin group in aqueous solution, or a lower molecular weight alkyl alcohol ester of the substituent in a dipolar aprotic solution or an acid halide in either a dipolar aprotic solvent or a two phase system in the presence of an appropriate acid or base catalyst.

While a number of methods may be utilized for the preparation of the PVA derivatives described in this invention, the use of non-aqueous solvents such as dimethyl formamide or similar polar materials is possible, but generally these solvents must be thoroughly removed from the final product. The use of aqueous solvents or mixed aqueous 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 PVA may affect the skin moisture barrier properties as well as the substantivity to skin. It is generally desirable to work in a pH range between 2-10 preferably from 5-9. 209700 Tha compositions of the present inven-tion may be prepared by a number of methods including: (i) 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 molecular 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 or substituted alkyl epoxide with the product of step (c) at 30-90°C; (ii) by the steps of: (a) reacting an alkyl or substituted alkyl epoxide with an aqueous solution of polyvinyl alcohbl having a number average molecular weight in the range of 25,000 - 150,000 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; (iii) by the steps of: (a) adding (chlorohydroxy-propyl) trialkylammonium halide 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; 0% o I +s- 209v0u (iv) by the steps of: (a) reacting an alkyl or substituted 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 (chloro-hydroxypropyl)tri-methylammonium halide in either aqueous solution or crystalline form at a temperature of 40-90°C; (v) 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 39-90°C; (vi) by the steps of: (a) reacting an alkyl or substituted 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 3 0-90°C until complete, and (b) reacting an aqueous solution of 2,3-epoxypropyltrialkylammonium halide with the product of step (a) at a temperature of 40-90°C in the presence of a catalytic amount of base in amounts wherein the mol ratio of said ammonium halide to 209 •ach mol of hydroxyl group on said product of step (a) ranges from 0.003 to 1; (vii) by the steps of: (a) reacting polyvinyl alcohol having a number average molecular weight of 25,000 - 150,000 with trimethyl-ethoxycarbonylmethylammonium halide in in dipolar aprotic solution in the presence of catalytic amounts of magnesium acetate at a temperature of 150°C, and (b) reacting said product of step (a) with an alkyl or substituted alkyl epoxide in aqueous reaction medium; (viii) by the steps of: (a) reacting polyvinyl alcohol having a number average molecular 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 trimethylethoxycarbonyl-methylammonium halide in dipolar aprotic solution in the presence of catalytic amounts of magnesium acetate at a temperature of 70 - 150°C; and (ix) by reacting an aqueous solution of polyvinyl alcohol polymer having a number average molecular weight of 25,000 -150,000 with 9,10-epoxyoctadecanol 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.

A'-: /v *12NW1987 209700 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 otherwise specified.

General Preparation I 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 commercially available product prepared by hydrolysis of polyvinyl acetate may have from 0-3 5% 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. 209700 The aqueous slurry is heated to 80 -100°C 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 50-75°C 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 mol per mol of hydroxyl groups on the polyvinyl alcohol chain and preferably from 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 80-90°C for a period generally ranging from 3 to 24 hours and preferably from 5 to 10 hours. The quaternary ammonium reagent such as 2,3-epoxypropyltrialkylammoniumhalide or (chloro-j hydroxypropyl)trimethylammoniumhalide either in aqueous solution or crystalline form may be added / either incrementally or all at once and stirred at a temperature of 40-90°C and preferably at 60-70°C for a period of about 4 hours or until the reaction is complete. 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 - ^ ^ t V ^ * v, «v- 14- 209700 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 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 themometer 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 vinylpyrolidone, acrylic and methacrylic acid and esters thereof.

The aqueous slurry is heated to 80-100°C 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 entire solution is then generally treated with a quaternary ammonium reagent when used at a temperature of 40-90°C for a period generally ranging from 3 to 24 hours and preferably from 5 to 10 hours. The quaternary ammonium reagent such as 2,3- V* /< - 209700 O epoxypropyltrialkylammoniumhalide or (chlorohydroxy-propyl)trimethylammoniumhalide either in aqueous solution cr crystalline form may be added either incrementally or all at once and stirred at a temperature of 40-90°C and preferably at 60-70°C for a period of about 4 hours or until the reaction is complete. 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 and 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 temperature if the addition of propylene oxide is intended or 50-75°C 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 mol per mol of hydroxyl groups on the polyvinyl alcohol chain and / 209700 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 to remove the catalyst, affording an aqueous dispersion that may be used as is or recovered by precipitation.

Example 1 —r4 « -ch2-ch(ch3)oh; -RN+R1R2R3A~ - -ch2-ch(0h)ch2N+(ch3)3c1 v- 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 85-90°C for one hour and potassium hydroxide (3.0 g in 15 ml H2O) was added. The solution was cooled to 35°C 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 50°C for 4 additional hours. The warm solution was then poured into acetone. The precipitate was collected by filtration, washed with acetone and methanol, and dried under vacuum. The yield was 113 g.

This propoxylated 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 (chlorohydroxypropyl) trimethylammonium chloride 80 ml of 48% aqueous 209 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%.

Example 2 -R4 - -CH2CH(OH)CH3 -R-N+R1R2R3A~ « -CHjCH(OH)CH2-N(CH3)3C1 A flask equipped with thermometer, mechanical stirrer, condenser and nitrogen sparger was charged with polyvinyl alcohol (88.0 g, 98% hydrolyzed, MW = 126,000) and distilled water (700 ml). Potassium hydroxide (3.0 g in 25 ml water) was added and the pot stirred at 35°C for one hour. Propylene oxide (58.0 g, 1.0 mol) was then added dropwise. The exotherm was allowed to bring the pot temperature to 55°C during the addition. When the addition was complete, the temperature was maintained at 55°C for an additional 4 hours. Recovery was accomplished by precipitation in acetone as described previously. Yield was 134.5 g.

The propoxylated polyvinyl alcohol (72.2 g) was charged to a flask equipped as above along with distilled water (500 ml). The pot was warmed to 55°C and potassium hydroxide (3.0 grams in 25 ml water) was added. After one hour, 2,3-epoxytrimethyl-ammonium chloride (78 ml of 48% aqueous solution) was added in one slug and the entire solution warmed for an additional 12 hours. Recovery was accomplished by precipitation from acetone as described previously affording a product with a nitrogen content of 1.71%. . ' ~r -*/ 209700 Example 3 -R4 ■ -CHC(CH2)7CH3]CH(OH)(CH2)8oh or -CH[CH2)8°H] CH(OH)(CH2)7CH3-RN+R1R2R3A" = -CH2CH(OH)CH2N(CH3)3CI A two liter flask equipped with mechanical stirrer, thermometer and efficient condenser was charged with oleyl alcohol (200 g, 85% purity) and methylene chloride (600 ml) and cooled to 5-10°C.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% 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 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 distilled water (3700 ml). The slurry was heated to 85°C and held until dissolution was complete. Potassium hydroxide (31.5 g in 100 ml water) was added and the pot cooled to 70°C. 9,10-Epoxyoctadecan-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 60°C and allowed to cool gradually to ambient temperature.

I' 209700 The resulting latex-like solution was neutralized 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 80°C. Potassium hydroxide (15.0 g in 50 ml) H2O) was added and the pot cooled to 60°C. Aqueous chlorohydroxypropyltrimethylammonium chloride (331.0 ml 48% aqueous solution) was then added all at once. The entire slurry was warmed at 60°C for an additional 4 hours and recovered by precipitation from acetone.

Example 4 -r4 « -ch[(ch2)70h]ch(oh)(ch2)7ch3 -rn+r1r2r3a" - -ch2-ch(oh)ch2n+(ch3)3ci 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 85°C for one hour and cooled to 80°C. Potassium hydroxide (3.0 g in 15 ml H2O) was added and the pot was cooled to 60°C. 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 previously described. The yield was 110 grams and the nitrogen content was 4.66%.

This quaternized polymer (40.0 g) was then charged to a similarly equipped flask with water (400 ml). The pot was heated to 60 - 65°C and potassium hydroxide (2.0 g in 5 ml H2O) was added. 9,10-Epoxyoctadecanol (8.5 g), prepared as described in Example 3, was added and the solution was stirred at 60°C for 16 hours. The product was then recovered from acetone and had a nitrogen content of 0.97%. v X -20- • 209700 Example 5 -R4 - -CH2CH(OH)CH3 ■rn"r1r2r3a" - -ch2ch(oh)ch2n+(ch3)3ci A flask equipped with a mechanical 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 - 90°C and sodium hydroxide (2.6 g in 20 ml H2O) was added. The solution was then cooled to 30°C. Propylene oxide (15.0 g) was added all at once. The solution was stirred one hour at 30°C and warmed to 70°C. 9,10-Epoxyoctadecanol (10.0 g) was then added along with glycidyltrimethyl-ammonium chloride (30.0 g). The entire solution was then stirred at 70°C for 3 hours, cooled to ambient temperature, and allowed to stand overnight. The product was recovered by precipitation in methanol.

Example fc -RNRxR2 ■ -CH2CH(OH)CH2N+(CH3)(CH2Ph) -rn+r1r2r3a~ = -ch2ch(oh)ch2n+(ch3)3ci A flask equipped as described in Example 5 was charged with polyvinyl alcohol (44.0 g) and water (400 ml) and heated to 85°C. After one hour, potassium hydroxide (3.1 g in 15 ml H20) was added and the pot cooled to 65°C. Glycidyltrimethylammonium 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 from methanol/acetone mixture to afford 62 g. The nitrogen content was 1.20%. ■* % r^W0VJ9l87^ 209700 Example 7 -rnr!r2 « -ch2-ch(oh)ch2n(ch3)(chjph) A flask equipped with a mechanical stirrer, thermometer, dropping funnel and condenser was charged with polyvinyl alcohol (44.0 g) (98% hydrolyzed, MW « 126,000) and water (400 ml). The slurry was warmed to 90°C for one hour and potassium hydroxide (3.0 g in 15 ml H20) was added. The solution was cooled to 75°C and freshly distilled benzyl-(2,3-epoxypropyl)-methylamine (44.3 g) was added dropwise over a 30 minute period. The entire solution was stirred 3 additional hours at 60-65°C 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 example is charged with polyvinyl alcohol 44.0 g (MW = 86,000, 100% hydrolyzed) and water (400 ml) and heated to 85 - 90°C. A catalytic amount of aqueous potassium hydroxide is added and the pot cooled to 70°C. Then 9,10-epoxyoctadecan-l-ol (14.2 g, 0.05 mol) is added and the entire slurry stirred for 3 hours, while gradually cooling to 60°C. Crystalline 2,3-epoxypropyltrimethylammonium chloride (151.5 g, 1.0 mol) is then added and the reaction mixture stirred 4 additional hours at 60°C. The product may then be recovered by precipitation or ultrafiltration to afford a product with a nitrogen content of 5.5% at an approximated yield of 84%. c «*V, 209700 Example 9 Another reaction done as described above except that the 2,3-epoxypropyltrimethylammonium chloride is reduced (75.8 g, 0.50 mol) should afford a product with a nitrogen content of 4.5% based on a reaction yield of 80%.

Example 10 A flask equipped as described in Example 5 may be charged with polyvinyl alcohol and distilled water. The aqueous slurry is heated to 80 - 90°C 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 - 90°C. At this point 9,10-epoxyoctadecanol is added and the reaction mixture is stirred for one hour. 2,3-Epoxypropyltrialkyl-ammonium halide can then be added incrementally or all at once. These two epoxides combined may be used in 0.05-1.0 mol 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 an additional period typically 4 hours at 60°C. The product may then be recovered by one of the methods described.

Example 11 illustrates the effect of the salt formed by HC1 neutralization on the skin moisture barrier properties. Note the substantial improvement of results based on the final dialyzed product. 23- 2097 Example 11 A flask equipped as described in the general example was charged with polyvinyl alcohol (44.0 g, MW * 86,000, 100% hydrolyzed) and water (400 ml) and heated at 85 - 90°C for one hour. The vessel was cooled to 80°C and potassium hydroxide (5.6 g in 15 ml H2O) is added. The vessel was cooled to 60°C over one hour and 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride (18.8 g) was added. The solution was stirred four hours at 60°C and dialyzed through a semi-porous membrane for five days. The nitrogen 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. equipped as described in the general example and heated to 80 - 85°C. Potassium hydroxide (0.56 g in 10 ml H2O) was added and the solution stirred for one hour. While cooling to 60°C, 9,10-epoxyoctadecan-l-ol (10.2 g) was added and the entire solution was stirred at 60°C for three hours. The resulting white dispersion was then split volumetrically into two aliquots. Solution A was neutralized with a small amount of concentrated HC1. This product was found to reduce the transpiration of water through the paper barrier by 42%. Solution B was dialyzed through a senti-porous membrane for 48 hours to pH = 7.9. This product was found to reduce the transpiration of water through the paper barrier by 83%.

The solution was then placed in a flask 209700 Moisture 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 1 Whatman filter paper was treated with aqueous solutions containing from 5 -10% by weight of the modified polymer as described in the examples to obtain a polymer film deposit amounting to about 0.1 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 room 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 100 grams of water and permitted to stand for 100 hours in a constant humidity and temperature room at 70°F 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 identical paper having no polymer treatment.

Considering the weight loss through untreated paper as 100 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 testing on animal skin. ? V ©, * • ^ - 209700 The materials prepared according to Examples 1 and through 7 when screened with the above described moisture barrier test on paper indicate a percent reduction in evaporation measuring from 3 5 to about 50% which compare favourably 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 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.

Such films can be applied to skin surfaces without detrimental affect upon elasticity. For example, the composition of Example 3 when applied to pigskin at a 5% film loading and thereafter subjected to thermo-mechanical analysis provides a value of 11.4 while compared with petroleum jelly which produces maximum 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 ^£*X I ; y 2( for these polymers is determined experimentally, in general those derivatized PVA polymers that contain high ratios of polyalkylene to quaternary groups in the side chain are more lipophilic and less moisture sensitive, whereas, those compositions containing higher levels of nitrogen containing side groups tend to be more hydrophilic in character and lend themselves more readily for formulation in systems containing higher 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 in a variety of compositions with or without the addition of lower molecular weight surfactants. The choice of the surfactant depends on the specific formulation and properties desired and will depend on the molecular weight of the PVA, the level of quaternary nitrogen, the ratio of lipophilic side chain in the composition and the level of oil or water desired in the final formulation. With these experimental parameters and guidelines it is possible to prepare formulations which afford utilization of the polymers of this 209700 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 makeup. 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 form to protect burned skin from loss of moisture or infection. polymer in film forming ointment bases and barrier creams 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 greasy 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. unmodified PVA in film forming bases are substantially overcome by the compositions of this invention in that they are easily dispersible in water are compatible with typical lotion formulations, and when applied to the surface of the skin, they dry quickly to form an elastic, smooth pellicle which The use of unmodified polyvinyl alcohol The problems associated with employing 887* retains its integrity over long periods of time and is easily removed with soap and water. Tests for cosmetic elegance is accomplished by applying typical moisture barrier 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 removal and a host of subjective factors. In most instances, the formulations evaluated do not adversely effect the film forming characteristics of the modified polyvinyl alcohol compositions of this invention. The aqueous moisture barrier compositions of the invention generally have a lotion consistency and 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 100°C 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 poptides, preservatives, alkaline agents, thickening agents, perfumes, stabilizers and antiseptics. 209700 One preferred composition of the invention is an amino modified polyvinyl alcohol polymer composition for use in skin conditioning, cosmetic and pharmaceutical formulations which comprises a polyvinyl alcohol base chain having a multiplicity of oxygen linked pendant groups of the general formula: -RNRiR2 wherein R is selected from a group consisting of an alkylene, a substituted alkylene or acylene radical, R1 and R2 are selected from the group consisting of alkyl or arylalkyl radicals having 1-2 0 carbon atoms, said polymer having a total nitrogen content ranging from 0.01-7% by weight. '209700 Th« skin conditioning lotions and ointments of the invention contain as an essential ingredient from 0.1 - 15% 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. an amount of from about 0.05 to about 8% and preferably from about 0.25 to about 5% to emulsify the oil components. Typical emulsifiers 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, polyoxyethylene fatty ether phosphates, fatty acid amides, phospholipids, polypropoxylated fatty ethers, acyllactates, polyethoxylated polyoxypropylene glycols, polypropoxylated polyoxyethylene glycols, polyoxyethylene, polyoxypropylene ethylene diamines, soaps and mixtures thereof. polyoxyethylene (8) stearate, myristyl ethoxy (3) myristate, myristyl 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, calcium stearoyl-2-lactate, and the PluoronicsR offered by BASF Wyandotte. 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 polyethylene (21) stearyl The lotions may contain an emulsifier in Examples of such emulsifiers include ether. 209700 The 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, esters 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 liquid or solid paraffins and mixtures thereof. Typical alcohols and fatty acids which are useful include those having from 12 to 22 carbon atoms such as cetyl alcohol, myristyl alcohol, stearyl alcohol, stearic acid and palmitic acid. Paraffins include, for example, mineral oil, 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 polymers of the invention may undergo decomposition 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. 209700 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 lotions contain 0.1-5.0% of the above described modified PVA polymers, 2 - 5% of an emolient, and 2-5% emulsifier in an aqueous emulsion.

Example A A portion of the aqueous 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 (BRIJR 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 75°C 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 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 preparin 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 N /Xx //« //> V z 'i 12 NOV 1987 r*%-. 33- 209700 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. When employed in hair treatment they facilitate untangling of wet hair and do not remain on dry hair as a sticky residue. In some instances they 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 agents, etc.

Example B A typical hair rinse formulation containing 5 grams of the modified polymer of Example 8, 7 grams cetyl alcohol, 3 grams of a linear polyoxyethylenated Ciq~c18 fatty alcohol, 2 grams of a casein derivative, 0.5 grams tetradecyltrimethyl-ammonium 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.

,/V C . V *12 NOV 1987, rc' >09700 Exanrole C A typical oxidation hair dye solution containing a 2.5 gram of the modified polymer of Example 9, 10 grams benzyl alcohol, 20 grams oleic acid, 3 grams polyoxyethylene (30), oleo cetyl alcohol, 7 grams oleic diethanolamide, 7.5 grams 2 -> octyldodecanol, 2.5 grams triethanolamine lauric sulfate, 10 grams ethanol, 18 millileters aqueous ammonium, 1 gram n, n-bis (2-hydroxy-ethanol Jparaphenyl-enediamine, 0.4 grams resorcin, 0.15 grams m-amino-phenol, .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 hydrogen 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 personal 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 employed in conventional formulations as hereinafter exemplified. 12 NOV W87, VU ./ -35-Example D 209700 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 (ARIAMOL R E by ICI Americas Inc.), 5.0 grams glycerol monostearate and polyoxyethylene stearate (ARLACEL R 165 by ICI Americas Inc.), and 10.0 grams of 70% sorbitol solutin (SORBO R by ICI Americas Inc.). After stirring for about 5 minutes at 7 5°C 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, was determined to have smooth, silky feel, drying time of less than 15 minutes and a film durability in excess of 2 days. Residual films and lotions are easily removed from the skin with soap and water.

Example E Roll-On Antiperspirant Ingredient % W/W Example 3 4.0 polyoxyethylene (21) stearylether 0.76 polyoxyehtylene (2) stearylether 3.24 water (deionized) 34.76 Dowicil 200 R, Dow Chemical 0.1 A1 Zr tetrachlorohydrex-Gly, Rezol 36G, Reheis 57.14 't e -A 12N0Ym7£1 Example F Aerosol Shave Cream Ingredient % W/W Example 3 5.0 Cetyl alcohol £.3 polyoxyethylene (21) stearylether 2.2 sorbic acid .17 water 74.9 fragrance .08 water 13.35 Example G Oil-in-water Sunscreen Lotion Ingredient W/W % mineral oil 18.8 cetyl alcohol 5.0 Arlocel 60 R emulsifier 2.5 Tween 60 R emulsifier 7.5 Amyl para-dimethylaminobenzoic acid 1.2 Example 4 2.0 water 63.0 Preservative q.s.

A N /• 309700

Claims (37)

- // -37- Example H Water-in-Oil Pigmented Makeup Ingredient W/W % Mineral Oil 10 Beeswax 1.5 Cevesin wax 1.0 Ax lacel 186 R emulsifier 3.2 Sorbo R sorbitol 28.8 Ti02 and other pigments 20.0 water 33.5 Example 6 2.0 Example 1 Calamine Lotion Calamine 80 gms Zinc Oxide 80 gms glycerine 20 mis bentonite magma 250 mis calcium hydroxide 950 mis (concentrated aqueous sol.) Example 1 50 gms 209700 r* ^ f 2 NOV 1967 209700 -38- • what we claim is:

1. A modified polyvinyl alcohol polymer composition useful in skin conditioning, cosmetic and pharmaceutical formulations which comprises a polyvinyl alcohol base chain having a multiplicity of oxygen-linked pendant groups comprising at least two types selected from the group consisting of the following general formulas: (a) -rn+r1r2r3a" (b) -RNR^, and (<=) -*4 wherein R is selected from the group consisting of an alkylene, a substituted alkylene or acylene radical, R1,R2,R3 are alkyl, alkenyl, aryl or arylalkyl radicals having 1-20 carbon atoms, R4 is selected from the group consisting of alkyl, alkylaryl, arylalkyl, substituted alkyl, substituted alkylaryl, and substituted arylalkyl radicals, and 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 total formula weight of all RNR^R2 groups is in the range of from 0 to 90% by weight of the total formula weights of all of said -RN+R1R2R3A~ groups. -39- 209700

5. A composition of claim 1 wherein R is a radical selected from the group consisting of -CH2CHOH-CH2- and -[ch2 ch(ch2n+r1r2r3 a~)0]ech2 ch(oh)ch2- wherein R1, R2 and R3 are alkyl or arylalkyl radicals having 1-20 carbon atoms, A~ is halide ion or (lower alkyl) S04~ 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-NR^Rj are selected from the group consisting of -CHjCHOH—CH2NR1R2 and [-C^CHCC^NR^)-0]eCH2~CH(OH)-CH2 NRiR2 wherein R^ 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-NR^R2 pendant groups are -COCH2NR1R2 wherein R1 and R2 are alkyl or arylalkyl radicals having 1-2 0 carbon atoms.

9. A composition of Claim 1 where R^^Rj and R3 are selected from the group consisting of -CH3, -CH2CH2CH3, -CH-CH3, and -CH2Ph ch3 where Ph is phenyl.

10. A composition of Claim 1 wherein the -R^ is selected from the group consisting of 1,9-dihydroxy octadecyl and 1,10-dihydroxy octadecyl.

11. A composition of Claim 1 wherein -R^ is selected from the group consisting of 17-carboxyheptadecyl, 17-carboxy-10-hydroxyheptadecyl, 17-carboxy-9-hydroxyheptadecyl/ 17-carboxy-9/10-dihydroxyheptadecyl and their salts and esters. i E U !/'*■ i2Hwmz -40 209700

12. A composition of Claim 10 wherein one or both of the hydroxy groups of the 1,9 or 1,10-dihydroxy octadecyl radical are oxy-linked to groups of the general formula -R-NR^R2 and/or -R-N+RiR2R3A~ where R, R], 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 octadecyl.

14. A composition of Claim 13 wherein one or both hydroxy groups of the dihydroxy octadecyl radical are oxy-linked to groups selected from the general formula -RNR^R2 and -R-N+R^R2R3A~ 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 OO O « »0H H -C-(CH2)I6-CH3,-C-(CH2)8-CH-(CH2)7-CH3,-C-(CH2)7 CH=CH-(CH2)7~CH3, and O M -C-(CH2)7CH-CH(CH2)7-CH3 I • OH OH

16. A composition of Claim 11 wherein part or all of any hydroxy groups present on fy are oxy-linked to -R-NR^R2 and/or -R-N+R1R2R3A~ groups where R, R^, R2, R3 and A~ groups are the same as in Claim 1. //« /v t « '2 H0VI967SI T -41- 209700

17. A composition of Claim 15 wherein part or all of any hydroxy groups present on tne -R4 pendant groups are oxy-linked to -RNRj^ and/or -R-N'^R^RjRjA-groups where R, R^, R2, R3 and A~ are the same as in Example 1.

18. A composition of Claim 1 wherein Rj_, R2 and R3 are methyl groups and the nitrogen content ranges from 0.05 to 5% 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 molecular 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 or substituted alkyl epoxide with the product of step (c) at 30-90°C.

20. A composition of Claim 1 when prepared by the steps of: (a) reacting an alkyl or substituted alkyl epoxide with an aqueous solution of polyvinyl alcohol having a number average molecular weight in the range of 25,000 - 150,000 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 halide in aqueous or crystalline form to an aqueous solution of polyvinyl alcohol having a number average molecular weight of tlN I* 12 NOV 1987 Vv // -42- 209 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. by the steps of: (a) reacting an alkyl or substituted 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)tri-methylammonium halide in either aqueous solution or crystalline form at a temperature of 40-90°C. 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. by the steps of: (a) reacting an alkyl or substituted 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 a temperature of 40-90°C in the presence of a catalytic amount of base in

22. A composition of Claim 1 when prepared

23. A composition of Claim 1 when prepared

24. A composition of Claim 1 when prepared -43- 209700 amounts wherein the mol ratio of said ammonium halide to each mol of hydroxyl group on said product of step (a) ranges from 0.003 to 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 trimethylethoxycarbonylmethylammonium halide in dipolar aprotic solution in the presence of catalytic amounts of magnesium acetate at a temperature of 150°C, and (b) reacting said product of step (a) with an alkyl or substituted 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 molecular 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-epoxyoctadecan-l-ol -

28. A composition when prepared according to Claim 23 or 24 wherein said ammonium halide is 2, 3-epoxypropyltrimethylammonium chloride and said alkyl epoxide is 9,10-epoxyoctadecan-l-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 2 5,000 - 150,000 with 9,10-epoxyoctadecanol and 2,3- •' ... -44- 209700 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 moles 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.

3 2. 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.

3 3. An aqueous hair conditioning composition comprising 0.01-153! 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 composition for use in skin conditioning, cosmetic and pharmaceutical formulations which comprises a polyvinyl/alcohol base chain havinq a multiplicity of oxyqen linked pendant groups of the general formula: -RNR1R2 wherein R is selected from a group consisting of an alkylene, a substituted alkylene or acylene radical, and R^ 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. \> '' < 309700 -45-

37. A composition of claim 1 wherein polyvinyl alcohol Is a copolymer comprising up to 252 by weight of repeating units derived from monomers selected from vinyl acetate, vinylpyrrolidone and (meth)acryl1c acid and the esters thereof. dated this «»»7 A J cj[ agents FOR THS APPLICANTS I I2N0VIW£|