WO1993014024A1

WO1993014024A1 - Hair care compositions

Info

Publication number: WO1993014024A1
Application number: PCT/US1992/008601
Authority: WO
Inventors: Robert B. Login; John J. Merianos; Michael W. Helioff; Carmen D. Bires; Stephen L. Kopolow; Edward W. Walls, Jr.; Mohammed Tazi; Yoon T. Kwak
Original assignee: Isp Investments Inc.
Priority date: 1992-01-13
Filing date: 1992-10-09
Publication date: 1993-07-22
Also published as: AU2778792A

Abstract

A hair care composition comprising: (a) about 3-8 % of a water soluble or dispersible alkylated polyvinylpyrrolidone copolymer powder comprising: (i) about 90-95 % polyvinylpyrrolidone having a K-value of 30-90, and (ii) 5-10 % of an alkylene having 4 carbon atoms; (b) about 50-95 % water; and (c) about 0-60 % alcohol.

Description

HAIR CARE COMPOSITIONS

(1) A hair spray composition is provided herein which is capable of delivering a fine finishing mist at a high resin solids level. The composition is substantially moisture resistant, provides a stiff resin film having excellent hair holding power, and has a relatively low concentration of volatile organic compounds therein. The composition of the invention attains its unique attributes by including therein a water soluble or dispersible alkylated polyvinylpyrrolidone (PVP) copolymer powders having a predetermined blend of two monomer components, one being PVP having a defined molecular weight (K-value 15-120, preferably 30-90) and concentration (80-99%, preferably 90-95%) and the other being an alkylene having a selected number of carbon atoms (C₄-C₁₀, preferably C₄-C₈) , linear or branched, in a defined concentration (1-20%, preferably 5-10%) .

The pump hair spray resin composition of the invention consists essentially of:

(a) said water soluble or dispersible alkylated PVP copolymer powder, in an amount of about 0.5-10% by weight;

(b) water in an amount of about 10-99% by weight; and

(c) alcohol in an amount of about 0-60% by weight of the composition.

In the form of an aerosol, the hair spray resin composition of the invention consists essentially of about 50-80% by weight of the concentrate as defined above and about 20-50% by weight of a suitable propellant. In the preferred form of the invention, (a) is a copolymer derived from the copolymerization of vinylpyrrolidone monomer (K 30-90, 90-95%) and an alkylene monomer (C₄-C₈, 5-10%) in the amount of about 3-8%; (b) is present in an amount of about 50-95%; and (c) is ethanol in the amount- of about 5-50%, by weight of the composition.

The pump hair spray composition of the present invention comprises:

Component Suitable Preferred

(a) Water soluble alkylated PVP copolymer (1) PVP K=15-120 K=30-90 80-99% 90-95%

(2) Alkylene ^C4~^C10 ^C4 ^C8

1-20% 5-10%

Concentration (% by weight) 0.5-10 3-8

(b) Water

(% by weight) 10-99 50-95

(c) Alcohol

(% by weight) 0-60 5-50

The aerosol hair spray composition comprises:

(1) Hair spray concentrate 50-80% 60-70% 65%

(2) Propellant 20-50% 30-40% 35%

Suitable aerosol propellants include aliphatic hydrocarbons, e.g. butane, propane; C0₂, nitrous oxide, dimethyl ther and difluoroethane, and mixtures thereof. A preferred copolymer resin for use in the hair spray composition of the invention is:

Ganex^® 904 (International Specialty Products, Wayne, NJ) which is a water soluble copolymer powder derived from the copolymerization of 90% vinylpyrrolidone (K-30) and 10% butylene in t-butylperoxide.

EXAMPLE 1

The following composition of the invention was prepared and tested for effectiveness as a pump hair spray product.

EXAMPLE NO.

A f- a.

Component Wt.

Ganex^® 904 5.0 8.0 3 3 5 5

(PVP K-30, 90%, and Butylene 10%)

Ethanol - 8 19 19 47.5

Water 95 92 89 78 76 47.5

100.0 100.0 100.0 100.0 100.0 100.0

The above formulations were one-phase systems. Upon testing as a pump hair spray, they were observed to develop spray patterns which were fine, broad and dry. The curl retention properties at 90% RH and 80°F. were excellent even after 90 minutes.

EXAMPLE 2

PVP (K-15) , PVP (K-60) , PVP (K-90) and PVP (K-120) were substituted for PVP (K-30) in the compositions of Example 1. The hair spray formulations thus produced exhibited water solubility, good viscosity and gave excellent spray patterns.

PROCEDURE FOR PREPARING COMPOSITIONS OF INVENTION

A. Pump Spray

The pump hair spray compositions of the invention were prepared by first providing an ethanol solution including the neutralizing agent and dissolving the resin therein. Then the requisite amount of water was added. The composition then was packaged into a plastic bottle fitted with a suitable pump actuator, such as the commercial CALMAR MARK II pump actuator.

B. Aerosol Compositions

The aerosol hair spray resin compositions of the invention were prepared from 65% by weight of the concentrate of the pump spray formulation of Example l and a 35% by weight of dimethylether propellant. In summary, the structure of the alkylene used herein, linear or branched, can play an important role in the stiffness of the resin film. Use of a branched alkylene herein promotes a stiffer resin film in the presence of water, whereas a linear alkylene provides a softer film.

(2) In accordance with this invention, there is provided a hair styling composition having pronounced hair conditioning properties which comprises a hydrolyzed crosslinked aleic anhydride/C-_j^ to C_g alkyl vinyl ether copolymer in the form of a gel, having a Brookfield viscosity of between about 5000 and about 150,000 cps and containing between about 0.01 and about 0.8 weight %. of a quaternized amino lacta . In most cases the composition has a substantially neutral or slightly alkaline pH, thus accounting for its high affinity for hair which carries a pH of about 5.

Representative examples of the copolymer gels employed in the present composition are the copolymers of maleic anhydride and a lower alkyl vinyl ether which are crosslinked to between about 1 to about 10 mole %, based on the alkyl vinyl ether, with a suitable difunctional crosslinking agent such as a hydrocarbon diene, e.g. 1,9-decadiene, 1,7-octadiene, 1,5-hexadiene, and other known crosslinking agents. The preferred copolymer at about 0.5% solids in a hydrolyzed aqueous gel has a Brookfield viscosity of between about 10,000 and about 130,000 cps and is 2 to 8% crosslinked. The crosslinked, lactam complexed copolymer is formed as a substantially neutralized gel in aqueous solution wherein its concentration is between about 0.10 and about 3 weight %. Generally the present copolymer contains between about 40 and about 70 weight %, preferably between about 33 and about 66 weight %, of maleic anhydride; the remainder being alkyl vinyl ether and crosslinking agent.

The quaternized amino lactam is added to the neutralized aqueous gel solution, preferably in an amount between about 0.05 and about 0.3 weight %, is mixed until the lactam is uniformly distributed and complexed with the . polymer. Suitable quaternized amino lacta s include quaternized amino derivatives of an N-alkyl pyrrolidone, N-alkyl caprolacta , N-alkyl hexahydroazepinone, N-alkyl octahydroazecinone, N-decahydroazecinone and N-alkyl octahydroazoninone which represent heterocyclic ring structures of from 5 to 10 members. The quaternized derivatives of these compounds include mono- and poly- quaternized amino derivatives which optionally contain cyclic, ether, a ido and additional quaternized amino groups. Such compounds and methods for their preparation are described in U.S. Patents 4,732,990; 4,830,850; 4,834,970; 4,837,013; 4,883,655; 4,885,158; 4,886,890; and 4,952,559.

Preferred of the above quaternized amino lactam derivatives are the pyrrolidone derivatives and, of this group, those most preferred are defined by the formula

wherein m has a value of from 1 to 4, n has a value of from 0 to 3, A~ is an anion of a chloride, bromide, iodide or toluene sulfonic acid onohydrate; R₄ is lower alkyl and R-^, R₂ and ₃ are each independently a radical having from 1 to 30 carbon atoms which is selected from the group of alkyl, alkyloxy alkyl, alkyloxy alkenyl, hydroxy alkyl, aryl, aralkyl, alkaryl, alkylamido alkyl, alkylcarbamoyl alkyl, aryl a ido alkyl, and aryl carbamoyl alkyl radicals and alternatively R₂ and R₃ together with the quaternized nitrogen can form an N-heterocyclic moiety. One of the most preferred quaternized amino lactams is stearamidopropyl pyrrolidonyl dimethyl ammonium halide, e.g. chloride, although any of the corresponding C₁₀ to C₁₇ amido lower alkyl pyrrolidonyl dialkyl ammonium salts are suitable.

The present quaternized amino lactam is added to the neutralized copolymer aqueous gel concentrate, preferably containing between about 0.8 and about 1.5 weight % of the copolymer, to form a complexed solution. The concentrate is then diluted to desired viscosity with an inert carrier such as water, an aqueous alcohol solution, propylene glycol, dipropylene glycol and the like.

One of the highly recommended concentrate compositions of the present invention is an aqueous gel containing maleic anhydride/methyl vinyl ether copolymer in a mole ratio of about 1:1, complexed with between about 0.05 and about 0.3 weight % of an alkylamidoalkyl-2-pyrrolidonyl mono- or di- methyl ammonium halide, as described in U.S. patent 4,837,013, e.g. dimethyl stearaminopropyl[(2-pyrrolidonyl) methyl] ammonium chloride. The hydrolyzed crosslinked maleic anhydride-C-L-Cg alkyl vinyl ether copolymer gel is prepared by polymerizing maleic anhydride, a C₁-C₆ alkyl vinyl ether and a crosslinking agent in the presence of a suitable free radical initiator.

Different solvents may be used for the polymerization, including benzene, toluene, xylene, acetone, methyl ethyl ketone and methylene chloride; however, it is preferred to use a mixture of a carboxylic acid ester and a saturated cycloaliphatic hydrocarbon. A particularly preferred solvent system is a mixture of ethyl .acetate and cyclohexane, preferably in the weight ratio of about 35 to 55% ethyl acetate to about 45 to 65% cyclohexane.

In this solvent system, the crosslinked copolymer product is provided in pu pable slurry form, from which dry, fine, white powders can be obtained easily. The copolymer powders can be readily hydrolyzed to clear gels of high viscosities with good stability and excellent salt tolerance.

The amount of crosslinking agent used in polymerization generally varies from about 1 to about 10 mole percent based on the monovinyl alkyl ether. Examples of suitable crosslinking agents include diunsaturated compounds such as the divinyl ethers of an aliphatic diol, e.g. the divinyl ethers of. 1,2-ethanediol; 1,3-propanediol; 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol; 1,7-heptanediol; 1,8-octanediol; 1,9-nonanediol; 1,10-decanediol; 1,11-undecanediol; and 1,12-dodecanediol, as well as the divinyl ethers of diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol; hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol and other polyalkylene glycols up to a molecular weight of about 5900. Other suitable crosslinking agents include 1,7-octadiene, 1,9-decadiene, divinylbenzene, N,N-bis-methylene acrylamide, acrylates such as polyethylene glycol diacrylate, trimethylolpropane triacrylate, propylene glycol diacrylate, polyhydric alcohols esterified once or twice with acrylic acid triallylamine, tetraallylethylenediamine, diallyl phthalate, and the like.

In the polymerization reaction it is recommended that a 10-20 molar excess of the alkyl vinyl ether be employed to assure complete reaction to approximately a 1:1 molar ratio of maleic anhydride and alkyl vinyl ether.

The polymerization is conveniently carried out at a temperature within the range of from 50° to 100°C. , particularly about 60°-80°C, by preparing the mixed solvent solution of the monomers and adding a catalytic amount (generally from about 0.001 to about 1.0%) of an organic free radical-generating initiator. The resulting solution then is mixed thoroughly and heated sufficiently so that the polymerization reaction takes place. At the completion of the polymerization reaction, the precipitated interpolymer is isolated by any suitable means such as by filtration or distillation of solvent, then washed with fresh solvent and vacuum dried.

Suitable organic free radical-generating initiators includes azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide, caprylyl peroxide, acetyl peroxide, acetyl benzoyl peroxide, di-tert-butyl peroxide, t-butyl peroxypivalate, azobis(2,4-dimethyl-valeronitrile) and the like. Mixtures of such catalysts are also suitable in the process of making the interpolymers of the invention. After obtaining the dry powder copolymer, the anhydride groups thereof are hydrolyzed and at least partially neutralized in aqueous basic solution at a suitable temperature, e.g. from about 30°C. to about 85°C. Suitably, a 0.15 to 3% by weight of a crosslinked copolymer gel is obtained. For example, about 1 g. of the copolymer can be dissolved in about 2.4-3.0 g. of a 10% aqueous NaOH solution and 96-97.6 g. of water to produce the gel product.

The selected quaternized lactam is then added to the resultant aqueous solution at a temperature of less than 50°C. , e.g. at between about 25° and about 45°C. , and mixed therein until a uniform composition is obtained as a gel-like complex of the quaternized component. The pH of the clear gel suspension is about 4.5-8, more often a pH of 6-8, which is ideally suited for hair conditioning.

The resulting, complexed gel concentrate then can be diluted with an inert carrier to form a solution containing between about 0.1 and about 3 weight % solids, more desirably between about 0.4 and about 2 weight % solids, depending upon the type application on the hair.

Other water soluble additives may also be included in the final styling composition. For example, as fixatives there may be added polyvinylpyrrolidone (PVP) , poly(vinylpyrrolidone/vinyl acetate) , acrylate/polyvinylpyrrolidone, acrylate/steareth-20, acrylate/vinyl acetate, and vinyl acetate/crotonate copoly ers, vinyl acetate/crotonate/propionate terpolymer or a quaternized polymer, e.g. dimethyl sulfate quaternized vinylpyrrolidone/dimethyl a inoethylmethacrylate copolymer (polyquaternium-11, 22 and 28) and others in the polyquaternium series. A conventional preservative e.g. imidazolidinyl urea, and a standard UV absorber such as a sulfonated benzophenone e.g. benzophenone-4 or 5, can also be added to the present formulation, if desired. Further, a chelating agent such as di-, tri- or tetra- sodium ethylenediamine tetraacetic acid and the like, as well as fragrance and color additives, can be included in the formulation. These optional components can be added to the composition individually in amounts up to about 10 weight %, preferably not more than about 5 weight %.

The present composition provides effective hair fixative and conditioning properties with enhanced shine, hair softness and combability. The conditioning properties of the quaternized lactam markedly reduces frizzing and holds the hair style under conditions of high humidity in a soft natural look while eliminating the drying affects of prior styling gels.

A typical hair styling and conditioning gel formulation of this invention is illustrated by the following:

% by weight

Component Suitable Preferred

POLYMER COMPLEX MA/alkyl VE Copolymer 0.2-1.2 0.5-1.0 Crosslinking agent 0.5-10.0 2.0-5.0 Quat. amino lactam 0.05-0.5 0.2-0.3

Solvent 78.15-98.64 87.2-93.5

ADDITIVES Chelating agent 0.01-0.25 0.05-0.1 UV absorber 0.01-0.3 0.15-0.2 Fixative 0.5-8.0 3.0-5.0 Preservative 0.05-1.5 0.5-1.0 Fragrance 0.05-0.30 0.1-0.2 It will be understood that solvent vehicles or carriers other than deionized water can be used for dilution in the final compositions, when desired. Accordingly, aqueous alcoholic solutions can be used as well as glycols and other inert carriers.

EXAMPLE 7

About one g. of a 50/50 maleic anhydride/methyl vinyl ether copolymer crosslinked with 2.5% of 1,9-decadiene was hydrolyzed in 89.8 ml water at 80°C. with agitation for about 35 minutes to form the corresponding crosslinked maleic acid/methyl vinyl ether polymer. The aqueous polymeric solution was then neutralized to about pH 7 with an inorganic hydroxide, in this case 10% sodium hydroxide, after which 0.50 wt. % of quaternized amino lactam, in this case stearamidopropyl pyrrolidonyl dimethyl ammonium chloride based on polymer, was added to the polymer solution and mixed at about 70-80°C. for about 30 minutes. The resulting neutralized crosslinked polymer complexed gel is then recovered.

If desired modifying adjuvants in aqueous solution can then be added and blended into the above complexed copolymeric gel at between about 35° and about 75°C. with agitation for a period of from about 5 to about 20 minutes, preferably at between about 50° and about 65°C. for a period of from about 7 to about 15 minutes or until a clear composition is obtained. The following Table (I) discloses a typical formulation (A) which was prepared using the above complexed copolymer gel.

TABLE I FORMULATION A

Ingredients Wt. %

Fixative resin PVP/VA W-735 6.00

10% aq. NaOH neutralizer 2.30

Suttocide A preservative * 0.30

Oleth 20 Fragrance Solubilizer ** 0.50

Fragrance 0.10

Copolymer complex of Ex. 7 60.00

Deionized H₂0 30.80

* Sodium hydroxymethyl glycinate

** Polyethylene glycol ether of oleyl alcohol,

CH₃(CH₂)₇CH₂(0CH₂CH₂)_n0H (n average=20)

The above formulation is prepared by adding and blending preservative, then fixative and finally a mixture of fragrance and fragrance solubilizer to the crosslinked copolymer complex of Example 7 at about 60°C. over a period of about 10 minutes. The resulting mixture is cooled to room temperature and mixing is continued until a clear composition is obtained. The Brookfield viscosity of the above formulation was found to be about 60,000 cps with TE spindle at 10 rpm.

Formulation A possesses good holding power, exceptional hair conditioning properties and other superior properties as subsequently shown. EXAMPLE 8

Example 7 was repeated except that a maleic anhydride/methyl vinyl ether copolymer in a mol ratio of 1:2 was substituted for the 1:1 copolymer at the beginning of the process. When formulated as in A above, the resulting composition provides a hair styling gel having similar conditoning and holding power.

EXAMPLE 9

Example 7 was repated except that the addition of the quaternized amino lactam was omitted. A formulation of this copolymr gel, similar to formulation A, except for the inclusion of the quaternized amino lactam, was prepared and designated as formulation B.

EXAMPLE 10

Formulations A and B were tested by half head evaluation which involved uniformly applying 0.5 teaspoon amount of each formulation (A and B) to opposite sides of wet human hair. After the treated hair had dried, the results were evaluated on a scale of 1 (poor) to 5 (exceptional) . These results are reported in following Table II

EXAMPLES 11-13

The following formulations were made up and found to have the same holding and conditioning properties as formulation A. In general the same procedure as in Example 7 was carried out.

EXAMPLE 11

FORMULATION C

Phase A % Weight

DI Water

50/50 MA/MVE copolymer

Polyglycerylmethacrylate and Propylene glycol (LUBRAJEL MS)

10% aqueous NaOH

Suttocide A, 50% solution

Tetrasodium ethylene diamine tetraacetic acid

Phase B DI Water

Calendula Extract Chamomile Extract Spirulina Allantoin

Phase C

DI Water

PVP (PVP K-30)

Phase D

PVP/VA Copolymer (PVP/VA W735)

DI Water

Phase E

Dimethicone Copolyol (Dow Corning 193 Polyether) 0.10

Phase F

PEG-60 Almond Glycerides (Crovol A-70) 0.50

Fragrance 0.05

100.00 PROCEDURE

(1) The copolymer was added to water and heated to 80°C. and the mixture agitated for 40 minutes.

(2) The solution was then cooled to 50°C. and the other Phase A ingredients added sequentially.

(3) Phase B components were premixed at 50°C. and then added to (2) .

(4) Phase C components were premixed and added, after which PVP/VA W735 was diluted with water and added. This was followed by the addition of Dow Corning 193 polyether.

(5) Finally, the components of Phase F were premixed and added to the above and the entire composition was mixed until uniform.

EXAMPLE 12

FORMULATION D

Phase A % Weight

DI Water

50/50 MA/MVE copolymer

Polyglycerylmethacrylate and Propylene glycol (LUBRAJEL MS)

Suttocide A, 50% solution

Tetrasodium ethylene diamine tetraacetic acid

Phase B DI Water

Calendula Extract Chamomile Extract Spirulina Allantoin

Phase C

DI Water 10.00

PVP (PVP K-30) 2.00

Phase D

PVP/VA Copolymer (PVP/VA W735) 5.00

DI Water 5.00

Phase E

Dimethicone Copolyol (Dow Corning 193 Polyether) 0.10

Phase F

PEG-60 Almond Glycerides (Crovol A-70) 0.50

Fragrance 0.05

100.00

The same procedure as described in Example 11 was repeated.

EXAMPLE 13

FORMULATION E

Ingredients % Weight

Deionized Water 89.80

50/50 MA/MVE copolymer 1.00

PVP/VA W-735 6.00

NaOH, 10 % aqueous solution 2.30

Suttocide A 0.30

Oleth 20 0.50

Fragrance 0.10 100.00

PROCEDURE

The copolymer was added to half of the required deionized water and mixed well after which the mixture was heated to 80°C. and held for 40 minutes with agitation. The remaining water at 60°C. was then added and mixed for 7-10 minutes, after which NaOH and Suttocide A were added sequentially. PVP/VA W-735 was then added with constant agitation followed by the addition of premixed Oleth 20 and fragrance. The resulting composition was cooled to room temperature and mixed well, until uniform.

The Brookfield viscosity of Formulation E was found to be 108,500 cps with a TE spindle at 10 rpm and the pH was 5.57. The pH of the above formulations can be adjusted by changing the concentration of the NaOH solution. (3) A hair bleaching composition, designed to be used in combination with an aqueous hydrogen peroxide solution, includes about 1-20% by weight of a stable, high purity, free-flowing, fine white powder of a substantially anhydrous complex of PVP and H-_>0₂ in about a 1:1 molar ratio, respectively, in a suitable powdered bleach vehicle, which complex can provide both enhanced hair bleaching action and hair conditioning, and, particularly, substantially accelerates the time required to complete the desired bleaching action.

In accordance with the invention, a base powdered bleaching composition which is designed to be used in combination with an aqueous hydrogen peroxide solution is provided. The base bleaching composition provides a suitable thickening agent and basic component for the aqueous hydrogen peroxide solution. In this invention, a bleach enhancer is included in the base bleaching composition to accelerate the rate of bleaching and to provide a hair conditioning effect during the bleaching process.

The bleach enhancer is a stable, high purity, free-flowing, fine, white powder of a substantially anhydrous complex of PVP and H₂0- in about a 1:1 molar ratio of its constituents, respectively. This complex is described by Merianos in U.S. Patents Nos. 5,008,093 and 5,066,488. Suitably the complex is present in the base composition in an amount of about 1-20% by weight thereof, preferably, about 5-10%. EXAMPLE 14 CONTROL (A)

BASE HAIR BLEACH COMPOSITION

Ingredient % by Weight

Ammonium Persulfate 3.00

Potassium Hydrogen Tartrate 3.00

Sodium Carbonate 3.00

Non-ionic Surfactant 1.00

Carboxymethylcellulose 5.00

Magnesium Hydroxide qs to 100

Procedure - The base powder was mixed to a paste with 20 volume hydrogen peroxide just prior to use. The resultant composition was spread evenly over those parts of the hair which are desired to bleach. The bleach-hair sections were wrapped in aluminum foil and the patron was kept under a hair dryer using medium to high heat. The bleaching action required 40 minutes.

EXAMPLE 15 CONTROL (B)

BASE HAIR BLEACH COMPOSITION

Ingredient % by Weight

Potassium Persulfate 8.00

Potassium Hydrogen Oxylate 8.00

Sodium Carbonate 13.00

Non-ionic Surfactant 1.00

Magnesium Hydroxide qs to 100 Procedure — Mix the powder to a paste with 20 volume hydrogen peroxide just prior to use. Spread evenly over those parts of the hair which it is wished to bleach. Wrap the bleach sections in aluminum foil and place the patron under the dryer at medium to high heat. Check sections after 15 minutes. Continue checking in intervals of 15 minutes up to 40 minutes. The bleaching action required 40 minutes.

EXAMPLE 16 CONTROL (C)

BASE HAIR BLEACH COMPOSITION

A commercial Basic White^® (Clairol^®) extra strength powdered lightener was the base bleach composition. After treatment of hair as described in Examples 14 and 15, it was observed that the bleaching action took 40 minutes.

EXAMPLES 17-19 INVENTION

The above base powders (Controls A, B and C) were blended with 5% PVP-H₂0₂ complex to a paste with 20 volume creme hydrogen peroxide developer. Virgin DeMao Brothers (8 inch length) brown hair swatches were wrapped in aluminum foil with the above preparation. The benefits of the bleach composition with PVP/H₂0₂ follow: 1. Bleaching time decreased from 40 minutes to 25 minutes.

2. The swatch was easier to comb and generally more conditioned.

3. PVP/H₂0₂ acted as a thickener for the hair preparation.

4. Swatches were softer to the touch and the hair "brighter" but not brassy.

(4) In accordance with the present invention, a fluidized bed containing a charge of suitable copolymer powders is reacted with an aqueous solution of concentrated hydrogen peroxide. Such copoly ers for use herein are copolymers of vinyl pyrrolidone and a quaternary ammonium monomer, which can be made by copolymerizing vinyl pyrrolidone with the quaternary ammonium monomer by solution polymerization in water ethyl alcohol or isopropyl alcohol, or by precipitation polymerization in cyclohexane or heptane, and under conditions which provide high molecular weight copolymers, i.e. about 100,000 to about 2,000,000 Daltons.

Suitable quaternary ammonium monomers for copolymerization with vinyl pyrrolidone include acrylamido, acrylate, vinyl and alkyl quaternary ammonium monomers, in an amount of about 1-30 mole %, preferably 5-15 mole %, of the copolymer. Additional comonomers also may be included in the copolymer, in an amount up to about 10% by weight thereof, and these comonomers are selected from acrylate esters, vinyl amides and vinyl esters. Representative commercially available quaternary ammonium monomers include the following:

DADMAC - Diallyldimethyl ammonium chloride DMAEMA(Q) - Dimethylaminoethyl methacrylate, quaternized DMAEA(Q) - Dimethylaminoethyl acrylate, quaternized MAPTAC - Methacrylamidopropyltrimethylammonium chloride DADEAC - Diallyldiethylammoniu chloride

Preferably, the quaternary ammonium monomer should contain a minimum amount of residual tertiary amine therein, which could react with peroxide and cause instability problems for the complex.

A preferred copolymer for use herein is the copolymer of vinyl pyrrolidone and MAPTAC, known as GAFQUAT^® HS-100 resin (International Specialty Products) , which is used herein in the form of powders thereof.

The hydrogen peroxide solution used herein usually contains about 30 to 85% hydrogen peroxide. A 50 to 70% H₂0₂ solution, however, is preferred because of the inherent danger present in use of the higher H₂0₂ concentrations.

The fluidized bed of copolymer powders can be maintained in the fluidized condition by directing a current of dry air through the powders, by mechanical agitation of the powders, or by a combination of both techniques.

The fluidized bed also is maintained at a suitable bed (reaction) temperature at which formation of the desired copolymer-H₂0₂ complex product can occur readily without affecting the powdery state of the copolymer, and at which temperature excess water from the H₂0₂ solution can be quickly removed both from the product and the copolymer bed itself. The selected bed temperature also will enhance the formation of a free-flowing powder rather than a gum. Such suitable reaction temperatures range from ambient temperature to about 60°C, preferably about 35° to 50°C.

The aqueous, concentrated H₂0₂ solution preferably is contacted with the copolymer powders as finely divided droplets of liquid. Such desired droplets may be formed by pumping the H₂0₂ solution through a spray nozzle and onto the copolymer bed at a selected rate and for a predetermined period of time. Any spray nozzle capable of producing a fine dispersion of droplets may be used for this purpose. If necessary, however, a stream of air may be introduced into such nozzle with the solution to assist in atomizing the solution into finely divided droplets.

The spray solution of aqueous H-_>0₂ thus formed preferably is introduced into the fluidized bed of copolymer powders at a selected rate such that excess water can be removed therein during formation of the complex without retaining free H₂0₂ therein. A suitable feed rate for introduction of the H₂0₂ solution herein is about 1-10 g H₂0₂ solution/minute/kg copolymer, preferably about 2-5 g H₂0₂ solution/minute/kg copolymer. Under these selected flow rate conditions, a free-flowing powder of the desired copolymer-H₂0₂ complex is obtained containing about 10-20% H₂0₂, and about 5% or less water therein.

In the preferred form of the process of the invention, the spray solution of H₂0₂ is directed onto the copolymer bed for a period sufficient to form a free-flowing powder having an H₂0₂ content of about 10 to 20% by weight, which corresponds to a complex having about a 1:1 molar ratio of copolymer to H₂0₂. At this point in the process, the feed is discontinued to preclude the formation of excess water and/or free H₂0₂ on the free-flowing powder which can cause it to become gummy. The appearance of a gummy product is indicative of the presence of undesired excess water and/or free H₂0₂ in the product. The spray solution of H₂0₂ may be directed onto the fluidized bed as a vertical, horizontal or by downward flow of droplets.

If a fluidizing air stream is used to create the fluid bed, it is usually directed upwardly against the copolymer powders. Such air currents also can assist in carrying water away from the bed. An exhaust suction system also may be used to aid in removal of water in the air stream. The fluidized state of the bed also may be maintained using mechanical agitation, or a combination of both air and mechanical means.

The process of the invention can be carried out in one or two steps, i.e. removal of water from the product and bed can take place either (a) simultaneous with, or after mixing, of the reaction components in the same apparatus, or (b) in a downstream drying step, or (c) by a combination of both steps. The particular method of drying will depend upon the type of equipment used. For example, if a fluidized bed mixer is used, such as a plowshare, belt screw or paddle mixer, then the moist copolymer-H₂0₂ product can be dried further in a separate dryer. This sequence is characterized as a two-step process. Any suitable dryer can be used for this purpose, such as a vacuum, radiant heat or contact dryer.

Furthermore, if desired, application of the spray H₂0₂ solution onto the copolymer bed, followed by downstream drying, may be carried out in several stages in order to increase the H₂0₂ content of the product towards the desired 1:1 molar ratio, and to reduce its water content.

Moreover, a fluid bed dryer may be used in the process which has the dual capabilities of providing both the fluidized bed and drying functions. Accordingly, drying of the product will begin and be completed during reaction between the copolymer charge and the aqueous H₂0₂ solution. Such a process may be considered as taking place in a one-step. Preferably, reaction and dehydration are continued until the product reaches a desired H₂0₂ content, suitably about 10-20% H₂0₂, with less than about 5% water. Moreover, it is essential that the product remain in the desired free-flowing state after completion of addition of the H₂0₂ solution.

EXAMPLE 20

200 g of a powdered copolymer of GAFQUAT^® HS-100 (International Specialty Products) , which is the copolymer of 85% vinyl pyrrolidone and 15% 3-methacrylamidopropyl trimethylammonium chloride, was charged into a fluid bed dryer apparatus. Then, with the assistance of an air stream, 80 g. of a 50% aqueous H₂0₂ solution was sprayed onto the fluidized bed of the copolymer at the rate of 2 g of the solution/minute/kg copolymer at 50°C. Vacuum was applied during the application of the peroxide solution to remove water from the air stream. The product was a free-flowing powder of the complex of the copolymer and H₂0₂, in a yield of 253 g. The peroxide content was 16%; and it contained 5% water.

EXAMPLE 21

The procedure of Example 20 is repeated using equivalent amounts of a copolymer of vinyl pyrrolidone and diallyldimethyl ammonium chloride, quaternized dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl acrylate, and diallyldiethylammonium chloride, optionally, with up to 10% by weight of a comonomer selected from an acrylate ester, vinylamide and a vinylester, with similar results.

Claims

WHAT IS CLAIMED IS:

1. A hair care composition comprising: (a) about 3-8% of a water soluble or dispersible alkylated polyvinylpyrrolidone copolymer powder comprising: (i) about 90-95% polyvinylpyrrolidone having a K-value of 30-90, and

(ii) 5-10% of an alkylene having 4 carbon atoms,

(b) about 50-95% water; and

(c) about 0-60% alcohol.

2. A hair care gel composition comprising:

(1) a hydrolyzed, crosslinked copolymer of maleic anhydride and a C-_^ to C₆ alkyl vinyl ether having a Brookfield viscosity of from about 5000 to about 150,000 cps and a pH of from about 4.5 to about 8, and

(2) between about 0.01 and about 0.8 weight % of a quaternized amino lactam such as in an aqueous solution.

3. The gel composition of claim 2 wherein the copolymer contains between about 40 and about 70 weight % of maleic anhydride, and said quaternized amino lactam is complexed in an aqueous solution of said copolymer gel containing from about 1 to about 8 weight % solids such as an alkylaminoalkyl-2-pyrrolidonyl mono- or di- methyl ammonium halide, for example, dimethyl stearylamido- propyl[(-2-pyrrolidonyl) methyl] ammonium chloride.

4. A hair care composition which can form a thickened formulation with aqueous hydrogen peroxide solution having both enhanced hair bleaching and hair conditioning within one active compound therein comprising

(a) a powdered hair bleach vehicle, and

(b) about 1-20% by weight of a stable, high purity, free-flowing, fine white powder of a substantially anhydrous PVP-H₂0₂ complex in about a 1:1 molar ratio, respectively.

5. A process making a hair care material comprising free-flowing powders of a copolymer of vinyl pyrrolidone and a quaternary ammonium monomer complexed with H₂0₂ by reacting a fluidized bed of said copolymer maintained at a reaction temperature of from ambient temperature to about 60°C. with finely divided droplets of a 30 to 85% by weight aqueous solution of H₂0₂, and drying the product introduced at a selected feed rate such that excess water can be removed during formation of said product, and wherein introduction of said solution is continued until the resultant product contains about 10 to 20% by weight H₂0₂, for example, wherein the feed rate of the H₂0₂ solution is about 1-10 g of solution/minute/kg copolymer, optionally, wherein air is used to assist in forming spray droplets of the H₂0₂ solution, wherein said copolymer includes an acrylamido, acrylate methylacrylate vinyl or allyl quaternary ammonium monomer, for example, selected from methacrylamidopropyl trimethyl ammonium chloride, diallyldimethyl ammonium chloride, quaternized dimethylaminoethyl acrylate or methacrylate and diallyldiethylammonium.

6. A hair care material which is a free-flowing powder product which is a copolymer of vinyl pyrrolidone and an acrylamido, acrylate, methacrylate, vinyl or alkyl quaternary ammonium monomer complexed with hydrogen peroxide.

7. A hair care free-flowing powder product according to claim 6 which is a copolymer of vinyl pyrrolidone and an acrylamido quaternary ammonium monomer such as complexed with hydrogen peroxide, methacrylamidopropyl trimethyl ammonium chloride, diallyldimethyl ammonium chloride, quaternized dimethylaminoethyl acrylate or methacrylate, or diallyldiethylammonium chloride.

8. A hair care free-flowing powder product according to claim 6 wherein said copolymer includes up to about 10 % by weight of a comonomer or selected from acrylate esters, vinyl amides and vinyl esters.