WO1999053891A1

WO1999053891A1 - Hairspray systems with lower alkyl acetate

Info

Publication number: WO1999053891A1
Application number: PCT/EP1999/001961
Authority: WO
Inventors: Francis Jones
Original assignee: Unilever Plc; Unilever N.V.; Hindustan Lever Limited
Priority date: 1998-04-16
Filing date: 1999-03-22
Publication date: 1999-10-28
Also published as: AU3520999A; AR019058A1

Abstract

A hairspray product is provided which includes a container with a spray nozzle and a hairspray composition stored within the container. The composition includes water, a film-forming resin, and a first and second organic solvent. The first organic solvent is a C1-C6 alkyl acetate. The second organic solvent is selected from short chain alkanols and ketones, particularly acetone.

Description

HAIRSPRAY SYSTEMS WITH LOWER ALKYL ACETATE

BACKGROUND OF THE INVENTION

Field of the Invention

The invention concerns hairspray products formulated to reduce volatile organic compounds and meet environmental standards .

The Related Art

Hairsprays are a widely used consumer product . They are formulated with volatile organic compounds such as ethanol and hydrocarbons. Environmental concerns have forced replacement of these highly volatile organic solvents with less volatile materials usually in combination with water.

Of course, mere lower volatility is an insufficient criteria for choice of a solvent. Many factors are to be considered. The solvent must be capable of solubilizing or at least suspending hair resins and other necessary functional components so as to avoid clogging of spray nozzles. Aesthetics must not be compromised. Solvents should not interfere with lustre, conditioning or leave the hair wet to the touch. They must allow the composition to quickly dry, be humidity resistant, hold hair all day and minimize curl droop. Smell must be acceptable. Stability of the solvent is also important; this material must not be subject to ready hydrolysis. When intended for packaging within steel cans, the solvent must not contribute to corrosion problems. 2 -

Accordingly, it is an object of the present invention to provide a hairspray product with a composition utilizing as a vehicle water and an organic solvent which can deliver functional hair ingredients without compromising sprayability and aesthetics.

Another object of the present invention is to provide a hairspray product with a composition which is quickly drying, humidity resistant, holds hair all day and minimizes curl droop.

Yet another object of the present invention is to provide a hairspray product with a composition utilizing as a vehicle water and an organic solvent stable against hydrolysis and breakdown into byproducts of unpleasant odor.

Still another object of the present invention is to provide a hairspray product with a composition utilizing as a vehicle water and an organic solvent which can be storable in metal cans without fear of significant corrosion problems .

These and other objects of the present invention will become more readily apparent from the following summary and detailed description.

SUMMARY OF THE INVENTION

A hairspray product is provided which includes 3 -

(a) a container with a spray nozzle; and

(b) a hairspray composition stored within the container, the composition including:

(i) from 0.01 to 95% water;

(ii) from 0.1 to 20% by weight of a hairspray resin; (iii)a first organic solvent of a Cι-C₆ alkyl acetate; and (iv) a second organic solvent selected from the group consisting of Cι~C₄ alkanol, C₃-C₆ ketone and mixtures thereof, the first and second solvent being present in a weight ratio of 20:1 to 1:20.

DETAILED DESCRIPTION OF THE INVENTION

Now it has been discovered that hairspray products meeting many of the objects of this invention are achievable by formulating a hairspray resin in a liquid carrier that includes water and a mixture of first and second organic solvents. The first of these solvents must be a Cι-C₆ alkyl acetate and the second a Cι-C₄ alkanol or C₃-C₆ ketone.

Suitable alkyl acetates for the present invention are methyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, t-butyl acetate, neopentyl acetate, hexyl acetate and combinations thereof. Most preferred are methyl acetate and t-butyl acetate. Methyl acetate is available from the Eastman Chemical Company, Tennessee. Tert-butyl acetate is available from the Arco Chemical Company, Philadelphia, Pennsylvania. Amounts of the alkyl acetate may range from about 0.1 to about 80%, preferably from about 1 to about 60%, more preferably from about 10 to about 40%, optimally from about 20 to about 35% by weight.

The second organic solvent necessary for the present invention is either a Cι-C₄ alkanol, a C₃-C₆ ketone or mixtures thereof. Alkanols especially useful for this invention are ethanol , isopropanol or tertiary-butanol or any mixture thereof. Most preferred is ethanol. Suitable ketones include acetone and methyl ethyl ketone, with acetone being preferred. Amounts of the second organic solvent may range from about 1 to about 80%, preferably from about 15 to about 60%, more preferably from about 25 to about 55%, optimally from about 35 to about 45% by weight.

Amounts of the first and second organic solvent will usually be present in weight ratios ranging from 20:1 to 1:20, preferably 10:1 to 1:10, more preferably from 2:1 to 1:2, optimally from 1:1 to 1:2.

Water will be a further carrier present in compositions of this invention. Amounts of water will range from about 0.01 to about 95%, preferably from about 5 to about 85%, optimally from about 30 to about 60% by weight. Normally, water will be second only in amount to the combined first and second organic solvents. Preferably the alkyl acetate will be the major solvent.

Film- forming polymeric hairspray resins are the key active of the hairspray compositions. Hairspray resins are - 5

polymers which function through film formation by holding the hair of the user in place after evaporation of solvent and other carrier volatile components. They may have a very wide average molecular weight range covering from 5,000 to 1 million, but usually going no higher than 100,000 with

10,000 to 50,000 being preferred. These resins may either be nonionic, anionic, cationic or amphoteric type hair fixative polymers. They may be vinyl polymerized compounds or condensation polymers. Amounts of the resin may range from about 0.1 to about 20%, preferably from about 0.8 to about 10%, optimally from about 2 to about 6% by weight.

Examples of anionic hair fixative polymers are the copolymers of vinyl acetate and crotonic acid, terpolymers of vinyl acetate, crotonic acid and a vinyl ester of an alpha-branched saturated aliphatic monocarboxylic acid such as vinyl neodecanoate; copolymers of methyl vinyl ether and maleic anhydride (molar ratio about 1:1) wherein such copolymers are 50% esterified with a saturated alcohol containing from 1 to 4 carbon atoms such as ethanol or butanol; and acrylic copolymers, terpolymers, etc., containing acrylic acid or methacrylic acid as the anionic radical-containing moiety and esters of acrylic or methacrylic acid with one or more saturated alcohols having from 1 to 22 carbon atoms such as methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, t-butyl acrylate, n-butyl acrylate, t-butyl methacrylate, n-butyl methacrylate, n-hexyl acrylate, n-octyl acrylate, lauryl methacrylate and behenyl acrylate. One specific example is the emulsion polymerized terpolymer of methacrylic acid, n- butyl acrylate and ethyl acrylate (e.g. in a weight percent 6 -

ratio of 31:42.27, respectively). Another specific example is Ultrahold^® (CTFA-Cosmetic Toiletries and Fragrance Association-designation of Acrylate/Acrylamide Copolymer) .

Amphoteric polymers which can contain cationic groups derived from monomers such as t-butyl aminoethyl methacrylate as well as carboxyl groups derived from monomers such as acrylic acid or methacrylic acid can also be used in the present invention. One specific example of an amphoteric hair fixative polymer is Amphomer^® sold by the National Starch and Chemical Corporation.

Examples of nonionic hair fixative polymers are homopolymers of N-vinylpyrrolidone and copolymers of N-vinylpyrrolidone with compatible nonionic monomers such as vinyl acetate and terpolymers of ethyl acrylate, butyl methacrylate and methyl methacrylate. Nonionic polymers containing N- vinylpyrrolidone in various weight average molecular weights are available commercially from ISP Corporation (formerly GAF Corporation) such as homopolymers of N-vinylpyrrolidone having an average molecular weight of about 630,000 sold under the trademark PVP K-90 and those having an average molecular weight of about 1,000,000 sold under the trademark of PVP K-120.

Examples of cationic hair fixative polymers are copolymers of amino-functional acrylate monomers such as lower alkylaminoalkyl acrylate or methacrylate monomers such as dimethylaminoethyl methacrylate with compatible monomers such N-vinylpyrrolidone, vinyl caprolactam, or alkyl methacrylates such as methyl methacrylate and ethyl - 7 -

methacrylate and alkyl acrylates such as ethyl acrylate and n-butyl acrylate. Cationic hair fixative polymers containing N-vinylpyrrolidone are commercially available from ISP Corporation such as those sold under the trademarks of Copolymer 845 and Copolymer 937 (copolymers of N- vinylpyrrolidone and t-butylaminoethyl methacrylate of average molecular weight about 1,000,000) and Gafquat^® 755 and 755N (quaternary ammonium polymers formed by the reaction of dimethyl sulfate and a copolymer of N- vinylpyrroldione and dimethylaminoethyl methacrylate of average molecular weight about 1,000,000) .

Where the film-forming resins are formed through vinyl polymerization, the monomers may best be selected from the group consisting of styrene, acrylic acid and Cι-C₂₀ esters, methacrylic acid and Cι-C₂o esters, vinyl acetate, crotonic acid and Cι-C₂₀ esters, vinyl neodecanoate, acrylamide, methacrylamide, maleic acid/anhydride and Cι-C₂₀ esters, vinyl caprolactam and combinations of these.

Resins of the present invention may also be of the condensation polymer type. Illustrative are caprolactam derived polyamides and phthalate polyesters, an example of the latter being an isophthalic acid/sulfoisophthalic acid/diethylene glycol polyester commercially available as AQ55 resin from the Eastman Chemical Company.

With certain of the polymers, it may be necessary to neutralize some acidic groups to promote solubility/dispensability. Examples of suitable neutralizing agents include 2-amino-2-methyl-l, 2-propanediol - 8 -

(AMPD) ; 2-amino-2-ethyl-l, 2-propanediol (AEPD) ; 2-amino-2- methyl-1-propanol (AMP) ; 2-amino-l-butanol (AB) ; monoethanolamine (MEA) ; diethanolamine (DEA) ; triethanolamine (TEA) ; monoisopropanolamide (MIPA) ; diisopropanol-amine (DIPA) ; triisopropanolamine (TIPA) ; and dimethyl stearamine (DMS) . Amounts of the neutralizing agents when present will range from about 0.001 to about 10% by weight .

Acetate solvents may have a tendency to hydrolyze breaking down into by-products of unpleasant odor and undesirable acidity. Thus, advantageously the compositions may be stabilized with a buffering agent to avoid reaction between water and the acetates. Amounts of the buffering agent may range from 0.001 to 40%, preferably from 0.01 to 20%, optimally from about 0.1 to about 5% by weight of the composition.

Buffering agents may be selected from ammonium salts, molybdate salts, and phosphate salts. Typical ammonium salts are those formed from Cι-C₀ amines neutralized with a counterion forming substance. For instance, the amines may be ammonia, cyclohexylamine, morpholine and isopropylamine . Counterion forming substances may be non-polymeric Cι-C₂o organocarboxylates such as acetate or benzoate, hydrogen such as to form ammonium hydroxide, and phosphates. A typical molybdate salt is sodium molybdenate. Further examples of buffering agents or inhibitors can be found in U.S. Patent 4,604,226 (Bartlett) , U.S. Patent 4,584,021 (Bartlett) and U.S. Patent 4,263,275 (Nandagiri) , all of which are herewith incorporated by reference. 9 -

Small quantities of surfactant ranging anywhere from 0.01 to about 10%, preferably from about 0.1 to about 1%, optimally about 0.3% by weight may be present in the compositions of the invention. The surfactant may be an anionic, nonionic or cationic emulsifier. Particularly preferred are nonionic emulsifiers which are formed from alkoxylation of hydrophobes such as fatty alcohols, fatty acids and phenols. Illustrative of such material is Triton X-100^®, an isoctyl phenyl polyethoxyethanol .

Alkoxylated silicone copolyols can be formulated with the resins to improve delivery onto the hair. These silicone copolyols may range from 500 to 30,000, preferably 2,000 to 5,000 in average molecular weight. Illustrative of this invention are the Silwet^® products such as Silwet^® L-7500.

Silicone oils may also be included as adjunct components. These silicones may either be volatile or nonvolatile. Representative of the volatile category are cyclomethicones and dimethicone . Non-volatile silicones may be materials such as Dow Corning 200, a polyorgano siloxane. Amounts of these materials may range anywhere from 0.01 to 10%, preferably from 0.1 to 5%, optimally from 0.5 to 1% by weight .

The present hair treatment compositions may be formulated as sprays in aerosol or non-aerosol forms. if an aerosol hairspray is desired, a propellant must be included in the composition. This agent is responsible for expelling the other materials from the container and forming the hairspray character. 10

The propellant gas can be any liquefiable gas conventionally used for aerosol containers. Preferably the density of the propellant or mixture thereof is less than the hairspray concentrate so that pure propellant is not emitted from the container. Examples of suitable propellants include dimethyl ether, propane, n-butane, isobutane, halocarbons, nitrogen, carbon dioxide used singly or admixed. Hydrocarbons are preferred because of their lower corrosion inducing properties.

The amount of the propellant gases is governed by normal factors well known in the aerosol art. For hairsprays the level of propellant is generally from about 3 to about 70%, preferably from about 5 to about 45%, optimally from 10 to 30% of the total composition.

Hairspray compositions of the invention can be dispensed from containers which are propellant-charged aerosol cans or pump spray bottles. They are commercially available from various manufactures including the American National Can Corp. and Continental Can Corp.

Resins when deposited upon hair quite often impart dullness. Counteraction of the dullness effect may be achieved by incorporating low levels of Cι₀-C₀ fatty alcohol esters. Particularly preferred is cetearyl octanoate. Amounts of these luster imparting agents when present will range from about 0.001 to about 1%, preferably from about 0.01 to about 0.5%, optimally from about 0.02 to about 0.1% by weight. 11

The compositions may also employ a Cι₂-C₃₀ long chain amine such as laurylamidopropyl dimethylamine for neutralizing resins containing carboxyl groups. Preferably up to 40% of the carboxyl groups present in the resin are neutralized with the long chain amine and the remainder of the carboxyl groups are then neutralized with another water soluble amine such as aminomethyl propanol . Hairspray compositions possessing improved adhesion for the hair can be obtained through the use of such long chain amine neutralizing agents.

Compositions of this invention may contain any other ingredient normally used in hairsprays. These other ingredients may include antifoam agents, proteins, antioxidants, fragrances, antimicrobials and sunscreens. Each of these ingredients will be present in an amount effective to accomplish its purpose.

Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material ought to be understood as modified by the word "about" .

The following Examples will more fully illustrate the embodiments of this invention. All parts, percentages and proportions referred to herein and the appended claims are by weight unless otherwise indicated. - 12

EXAMPLE 1

An aerosol hairspray is prepared according to the following formula and incorporated into a tin-plated steel can.

TABLE I

COMPONENTS WEIGHT %

Ethanol 35.00

Methyl Acetate 30.00

Propellant A85 15.00 (propane/isobutane)

Deionized Water 13.63

Resyn 28-29-30^® 5.50

AMP 95^® 0.54

Fragrance 0.13

Ammonium Benzoate 0.10

Ammonium Hydroxide 0.10

EXAMPLE 2

Another aerosol hairspray is prepared according to the following formula and incorporated into a tin-plated steel can. 13

TABLE II

COMPONENTS WEIGHT %

Acetone 38.97

Methyl Acetate 20.00

Dimethyl Ether 20.00

Deionized Water 16.00

Amphomer^® 4.25

AMP 95^® 0.78

Sodium Molybdenate 0.50

EXAMPLE 3

A non-aerosol hairspray is prepared according to the following formula which is incorporated into a mechanical spray pump .

14

TABLE III

COMPONENTS WEIGHT %

Tert-Butyl Acetate 50.00

Demineralized Water 30.00

Ethanol 13.00

Ultrahold^® 6.00

Oleyl Amine Neutralized with 1.00

Phosphoric Acid

EXAMPLE 4

Another non-aerosol hairspray is prepared according to the following formula and incorporated into a mechanical spray pump.

TABLE IV

COMPONENTS WEIGHT %

Methyl Acetate 40.00

Demineralized Water 30.00

Ethanol 23.00

Ultrahold^® 6.00

Oleyl Diamine Neutralized with 1.00

Acetic Acid

EXAMPLE 5

A series of consumer tests were conducted on methyl acetate aerosol hairspray formulations to evaluate whether they would meet California's (CARB) 55% VOC regulations. Comparisons were performed against an 80% VOC commercial control and a series of relatively high water/low alcohol 15

hairsprays designed to meet the 55% VOC regulations. Each formulation was reviewed

by a representative sample of approximately 150 women, ages 18-65 who were aerosol hairspray users at least three times a week.

Panelists were provided with two formulations. A control (Suave^® Extra Hold) and a test formulation. The panelists were instructed to use each hairspray for seven days, beginning with the control . After using each product they were asked to complete a questionnaire, evaluating the product on overall ratings as well as key attributes of hold, hair feel, build-up, manageability, application, body and speed of drying. The evaluated formulations are reported in Table V.

TABLE V ∞

SO

Aerosol Hairspray Formulations

INGREDIENTS A B C D E F

Ethyl Alcohol 47.8503 48.5268 29.0 33.01 29.00 32.13

AMP-95 0.5124 0.617 0.82 0.65 1.09 0.88

Resyn 4.70 5.67 2.24 3.00 28-2930^®

I

Amphomer 2.24 3.00 LV-71^®

Acrylic Copolymer 11.54 15.38

Methyl Acetate 40.7996 39.5485

Water 5.5 5.0 57.335 60.707 52.885 59.497

Fragrance 0.1765 0.1765 0.01 0.01 0.01 0.01

Ammonium Benzoate 0.1156 0.1156

Ammonium Hydroxide 0.1156 0.1156

Citric Acid

Sodium Benzoate 0.308 0.308 0.308 0.308

Ajidew N50^® 0.15

DC 245 (Cyclomethicone) 0.23 0.23 0.30 0.30 0.30 0.30

Silwet L720^® 0.30 0.30 O

H

Propellant A-75 A-75 DME DME DME DME

v© n w

TABLE VI 00 v©

Comparisons With Suave Extra Hold Hairspray

COMPARATIVE A B C D E F PROPERTIES

Strength of Hold Parity JAR, Parity JAR, Too weak Parity JAR, Too strong Too weak si. stronger stronger

Stronger

Duration of Hold Parity JAR, Parity JAR, Too short Parity JAR, Too long Too short si . Longer longer longer I

Feel of Hair Parity Too stiff Not stiff Sit. Too Too stiff Parity JAR, after Spray has enough stiff less stiff dried

Amount of Body Parity Parity Not Parity Too much Not enough enough

Manageability Parity Needs Advantage Parity Parity Advantages

Slight s

Improved

Build-Up Needs Needs Parity Needs Needs Needs Improvement Improvement Improvement Improvement Slight

Improvement O H

Speed of Drying Advantage Parity Too slow Slower Too slow Parity

Application Heavier Heavier Heavier Heavier Heavier Heavier so

Feel of Spray Parity Parity Similar Wetter Too wet Parity vø When First (Drier) (wetter) as

SB SO

D Wi

Applied 00 v©

Overall Fragrance Needs Needs Parity Parity Needs Needs Improvement Improvement Improvement Improvement

Strength of Too Strong Stronger SI. Lower and Parity Stronger

Fragrance Stronger JAR

* JAR = Just About Right

oo

I

O

H v© v©

V©

- 19

Formulations based on methyl acetate as determined by the study were at or close to parity compared to the commercial control (80% VOC Suave^® Extra Hold) . For some key properties such as application, build-up and the speed of drying, the methyl acetate formulations (A and B) were slightly better. Low VOC alternatives C through F were generally wetter in feel and slow to dry. In general, C through F were directionally poorer than those employing methyl acetate .

The foregoing description and examples illustrate selected embodiments of the present invention. In light thereof variations and modifications will be suggested to one skilled in the art, all of which are within the spirit and purview of this invention.

Claims

20WHAT IS CLAIMED IS:

1. A hairspray product comprising:

(A) a container with a spray nozzle; and (B) a hairspray composition stored within the container, the composition comprising: (i) from 0.01 to 95% water; (ii) from 0.1 to 20% by weight of a hairspray resin; (iii)a first organic solvent of a Ci-C╬▓ alkyl acetate; and (iv) a second organic solvent selected from the group consisting of C1-C4 alkanol, C₃-C₆ ketone and mixtures thereof, the first and second solvent being present in a weight ratio of 20:1 to 1:20.

2. The product according to claim 1 wherein the hairspray resin is a polymer constituted from a monomer selected from the group consisting of vinylacetate, crotonic acid, vinyl neodecanoate, methyl vinyl ether, acrylic acid and C╬╣-C₀ esters thereof, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, t-butyl acrylate, acrylamide, methacrylamide, t-butyl amino ethyl methacrylate, N-vinyl pyrrolidone, vinyl caprolactam and combinations thereof.

3. The product according to claim 1 wherein the resin is a polyester or polyamide.

4. The product according to claim 1 wherein the resin is selected from the group consisting of polyvinylpyrrolidone, 21

polyvinylacetate, octylacrylamide/acrylates/butyl amino ethyl methacrylate copolymer, vinyl acetate/crotonic acid/vinyl neodecanoate, acrylate/acrylamide copolymer, isophthalic acid/sulfoisophthalic acid/diethylene glycol polyester and combinations thereof.

5. The product according to claim 1 wherein the second organic solvent is ethanol .

6. The product according to claim 1 wherein the second organic solvent is acetone.

7. The product according to claim 1 wherein the acetate is methyl acetate.

8. The product according to claim 1 wherein the acetate is tert-butyl acetate.

9. The product according to claim 1 wherein the first organic solvent is present in an amount from about 20 to about 35% by weight.