WO2014108384A1

WO2014108384A1 - Aerosol hair spray compositions

Info

Publication number: WO2014108384A1
Application number: PCT/EP2014/050120
Authority: WO
Inventors: Yevgen Blyumin; Dirk Weber
Original assignee: DSM IP Assets BV
Current assignee: DSM IP Assets BV
Priority date: 2013-01-09
Filing date: 2014-01-07
Publication date: 2014-07-17
Anticipated expiration: 2015-07-09

Abstract

The present invention relates to aerosol hair spray compositions comprising a not or only partially neutralized acrylate copolymer and a propellant as well as to their use for styling hair.

Description

Aerosol hair spray compositions

Many aerosol hair spray compositions comprising acrylate copolymers provide acceptable hair styling properties but exhibit polymer flaking after application to the hair which is highly unwanted. Thus, there is an ongoing need for aerosol hair spray compositions comprising acrylate copolymers which provide good hair styling properties and exhibit no or only very little flaking.

Surprisingly, it has been found that aerosol hair spray compositions comprising specific acrylate copolymers which are not or only partially neutralized show reduced flaking properties after application to hair.

Thus, the invention relates in a first embodiment to an aerosol hair spray composition comprising at least one propellant and at least one acrylate copolymer from monomers selected from the group consisting of (meth)acrylic acid, methyl (meth)acrylate, n-butyl (meth)acrylate, tert. -butyl (meth)acrylate and ethyl (meth)acrylate, characterized in that at most 85 mole-% of the carboxyl groups of the acrylate copolymer are neutralized.

In another embodiment the present invention relates to a method of styling hair, said method comprising the step of applying an aerosol hair spray composition according to the present invention to hair and appreciating the result.

In all embodiments of the present invention the monomers are preferably selected from the group consisting of methacrylic acid (MM), n-butyl methacrylate (BMA), ethyl acrylate (EA) and ethyl methacrylate (EMA). Even more preferably the acrylate copolymer is obtained by copolymerisation of 10-30 wt.-% of methacrylic acid, 35-65 wt.-% of n-butyl methacrylate, 5-15 wt.-% of ethyl acrylate and 10-35 wt-% of ethyl methacrylate, more preferably of 15-25 wt.- of methacrylic acid, 38-60 wt.-¾ of n-butyl methacrylate, 8-15 wt.-% of ethyl acrylate and 15-25 wt.-% of ethyl methacrylate, most preferably of 17- 22 wt.-¾ of methacrylic acid, 44-56 wt.-% of n-butyl methacrylate, 9-15 wt.- of ethyl acrylate and 15-25 wt.-% of ethyl methacrylate, with the proviso that the total amount of monomers sums up to 100 wt.-%. Most advantageously, in all embodiments of the present invention 15-22 wt.-% of methacrylic acid, 44-56 wt.-¾ of n-butyl methacrylate, 9-15 wt.-% of ethyl acrylate and 18-22 wt.-¾ of ethyl methacrylate are used. When the MM content is selected in the range of about 15-22 wt.-%, in particular 17 to 22 wt.-% it is further preferred to select the coefficient of EMA/ EA in the range of about 2.0 to 1.3. T e term 'with the proviso that the total amount of monomers sums up to 100 wt.-%' as used according to the present invention means that the total amount of monomers ideally sum up to 100 wt.-%. It is however not excluded that small amounts of impurities or additives may be present such as e.g. in amounts of less than 5 wt.- , preferably less than 3 wt.-% which are e.g. introduced via the respective raw materials.

In all embodiments preferably the ratio of ethyl methacrylate (EMA) to ethyl acrylate (EA) (w/w) is selected in the range of 4:1 to 1 :1 , preferably in the range of 2: 1 to 1 :1 , in particular in the range of 2:1 to 1.3:1.0, which can also be expressed as coefficient of EMA/ EA which accordingly should preferably be selected in the range of 4 to 1 , preferably in the range of 2 to 1 such as in particular in the range of about 2.0 to 1.3.

In all embodiments of the present invention preferably the acrylate copolymer is in the form of acrylate copolymer beads obtained by suspension polymerisation of the respective monomers. By the term "acrylate copolymer beads" in connection with the present invention is meant polymer particles that are simple to isolate e.g. by filtering or centrifuging. The polymer beads in connection with the present invention typically have an average diameter of at least 50 μηι, preferably of at least 150 μητι. Preferably the beads according to the present invention have a diameter between 50 and 150ΌμΓη such as in particular between 150 to 500μηη.

Particular suitable acrylate copolymer beads according to the present invention have a molecular weight of about 100kDalton, a glass transition temperature of about 80-120 ^*C and a particle size of about 50 to 1500 μηι, preferably of 150 to 500 μητι (X-50). Even more preferred acrylate copolymer beads according to the present invention have additionally an acid value selected in the range of 125-145 mg KOH/g.

Most suitable acrylate copolymer beads according to the present invention are e.g. disclosed in WO2011 /057882 which is included herein by reference. Particularly advantageous in all embodiments of the present invention are acrylate copolymer beads from monomers selected form the group consisting of methacrylic acid (M ), n-butyl methacrylate (BMA), ethyl acrylate (EA) and ethyl methacrylate (EMA) which exhibit a Tg of 98-108^' C and an acid value of 125-145 mg KOH/g. Such acrylate copolymer beads are e.g. commercially available under the tradename Tl LAMAR* FIX A 1000 at DSM Nutritional Products Ltd (CAS Number: 1070166-98-1 ; !NCi: Acrylates Copolymer; Chemical Name: polymer with 2-methyl-2-propenoic acid, butyl 2-methyl-2-propenoate, ethyl 2-methyl-2- propenoate and ethyl 2-propenoate).

Another suitable acrylate copolymer according to the present invention is the acrylate copolymer from tert. -butyl acrylate, ethyl acrylate and methacrylic acid which is commercially available as Luvimer* 100 P at BASF.

In all embodiments of the present invention, the neutralization level of the carboxyl groups of the acrylate copolymers is preferably selected in the range of 0-80 mole- , more preferably in the range of 0-75 mole-% and most preferably in the range of 0-35 mole-%. The amount of neutralizing agent necessary for achieving the desired neutralization level can easily be calculated by a person skilled in the art from the acid value of the respective acrylate copolymer.

The at least one propellant may or may not be VOC. Particularly suitable propellants according to the present invention are n-propane, isopropane, n-butane, isobutane, dimethyl ether; dimethoxymethane, difluoroethane, chlorodifluoroethane, chlorodifluoromethane, other chlorofluorocarbons or combinations thereof. Preferred propellants according to the present invention are either a mixture of n-propane and n- butane or dimethyl ether, most preferred is dimethyl ether (DME) as the use of DME as propellant results in least flaking as illustrated in the examples. Preferably, the at least one propellant is used at a total concentration of 10 to 70 wt.-¾; and more preferably of 30 to 60 wt.-% based on the total weight of the aerosol hair spray composition.

Suitable neutralization agents for the neutralization of the at least one acrylate copolymer encompass amines, alkali or alkaline earth metal hydroxides, ammonium hydroxide or combinations thereof. Suitable amine neutralizers include for example 2-amino-2-methyl propanediol, 2-amino 2-methyl propanol, N,N-dimethyl-2-amino-2-methyl-1 -propanol, mono-isopropanolamine, triiso-propanolamine, ethanolamine, triethanolamine, morpholine or combinations thereof. Suitable alkali or alkaline earth metal hydroxides include for example sodium hydroxide potassium hydroxide, or combinations thereof. Preferably, the neutralizer is selected from the group consisting of 2-amino 2-methyl propanediol, 2- amino-2-methyl propanol, N,N dimethyl 2-amino 2-methyl propanol, potassium hydroxide, triethanolamine, triisopropanolamine, or combinations thereof. Most preferably the neutralization agent is 2-amino-2-methylpropanol (AMP).

The total amount of the at least one acrylate copolymer in the aerosol hair spray compositions according to the present invention may easily be chosen by a person skilled in the art. Preferably, a concentration of 0.1 -10 wt.-%, more preferred of 1 -8 wt.-%, most preferred of about 2-5 wt.-% based on the total weight of the aerosol hair spray compositions is used.

The aerosol hair styling compositions according to the present invention are prepared according to standard methods in the art. Preferably, first a bulk solution of the at least one acrylate copolymer with all the definitions and preferences as given above in a suitable solvent or solvent mixture, optionally in the presence of other additives usually employed in aerosol hair spray composition is prepared which is subsequently mixed with the at least one propellant. Preferably the bulk solution consists mainly of the at least one acrylate copolymer, water and a Ci alcohol. Particularly suitable d.₄ alcohols include methanol, ethanol propanol and butanol. Most preferred is ethanol. Most preferably the bulk solution consists of 1 -15 wt.- of the at least one acrylate copolymer, 20-100 wt.-¾ of water, 0-80 wt.-% of ethanol and 0-10 wt.-% of other additives usually employed in aerosol hair spray composition.

Suitable additives usually employed in aerosol hair spray composition encompass in particular further hair fixative resins, neutralizes, synthetic or natural oils, siloxane derivatives, moisturizers, detangling aids, antistatic aids, conditioning agents, surfactants, further solvents, fragrances, preservatives, thickeners and UV-f liters as illustrated in the examples. Further hair fixative resins may optionally be added to the aerosol hair spray compositions to provide other properties which may be desired by the formulator, such as a "stiffer" hold of the hair. The other hair fixative resins may be soluble or insoluble in the aerosol hair spray composition. The other hair fixative resins may be present in the aerosol hair spray composition at a concentration of from 0.5 to 6.0 wt.-%, preferably from 1.0 to 3.0 wt.-%, based on the total weight of the aerosol hair spray composition.

The further hair fixative resins which are suitable in the aerosol hair spray composition include for example butyl acrylate/ethyl acrylate/methacrylic acid copolymers; polyvinyl pyrrolidone, vinyl pyrrolidone/vinyl acetate copolymers; octytacrylamide /acrylates / butyl-aminoethylmethacrylate copolymers; vinylcaprolactam/vinylpyrrolidone/ dimethylamino-ethylmethacrylate copolymers; methacryloyl ethyl- betaine/methacrylate copolymers; methacrylic acid/methacrylic ester copolymer; methacrylic acid /acrylic acid ester copolymers, alkylester of the copolymer of vinyl methyl ether and maleic anhydride; hydroxyethylcellulose quaternized with diallyl dimethyl ammonium chloride, quaternized vinyl pyrrolidone/ dimethylaminoethylmethacrylate copolymer, or combinations thereof.

One or more surfactants may be added to the hair spray composition. When surfactants are present in the hair spray composition, they are preferably present at a concentration of from 0.001 to 1.0 wt.-%, based on the total weight of the composition. The surfactants which may be used in the hair spray composition include for example anionic, cationic, non-ionic, or amphoteric surfactants. For example, suitable surfactants include PPG 28 Buteth 35, PEG 75 lanolin, perfluoropolymethyl isopropyl ether, octoxynol-9, PEG-25 hydrogenated castor oil, polyethylene terephthalate, polyethylene glycol 25 glyceryl trioleate, oleth-3 phosphate, PPG-5-ceteth-10 phosphate, PEG-20 methyl glucose ether, glycereth-7-triacetate, glycereth-7-benzoate, fatty acid ester of polysorbate (TWEEN), or n-alkyl substituted lactam such as n-octyl pyrrolidone, or combinations thereof.

One or more siloxane derivatives may be present in the hair spray formulation. When they are used, they are preferably present in a concentration from 0.001 to 1.0 wt.-%, based on the total weight of the composition. The siloxane derivatives include for example dimethicones, phenyl trimethicones, dimethiconols, amodimethicones, alkoxylated dimethicones e.g. PEG-12 dimethicone or methoxy PEG/PPG-7/3 aminopropyl dimethicone. One or more solvents may be added to the hair spray composition of the present invention. The solvents may or may not be VOC. The amount of solvent added to the hair spray composition can be selected in the range of about 100 wt.-% or less, such as in particular in the range of 55 wt.-% or less based on the total weight of the hair spray composition. Suitable solvents include for example Ci to C₁₂ straight or branched chain alcohols such as methanol, ethanol, isopropanol, or propanol or combinations thereof.

Other preservatives which may be used in the hair spray composition include for example isothiazolones, benzyl alcohol, or imidazolidinylurea. The other preservatives are preferably used in an amount of about 0.001 to 1 .0 wt.-% based on the total weight of the hair spray composition.

One or more light screening agents may be desirable in a hair spray composition according to the invention. The light screening agents are advantageously selected from UV-A, UV-B, UV-C and/ or broadband filters such as in particular from the commercially available and widely used UV-filter substances octocrylene (PARSOL* 340), 4-methyl benzylidene camphor (PARSOL* 5000), ethylhexyl methoxycinnamate (PARSOL* MCX), ethylhexyl triazone (Uvinul* T-150), diethylhexyl butamido triazone (Uvasorb* HEB), 2,2'-methylene- bis-(6-(2H-benzotriazole-2-yl)-4-(1 , 1 , 3, 3, -tetramethylbutyl)-phenol (Tinosorb* M) , bis- ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb* S), 2,2-(1 ,4-phenylene)bis-( 1 H- benzimidazol-4,6-disulfonic acid (NeoHeliopan* AP) , 2-(4-Diethylamino-2-hydroxy-benzoyl)- benzoic acid hexylester (Uvinul* A plus), polysilicone-15 (PARSOL* SLX), 2-phenyl benzimidazole sulfonic acid (PARSOL* HS), ethylhexyl salicylate (PARSOL* EHS), homomenthyl salicylate (PARSOL* HMS), Benzophenone-3 (Uvinul* M 40), Benzophenone-4 (Uvinul* MS 40), PEG-25 PABA, as well as mixtures thereof.

The light screening agents are generally present in the compositions according to the invention in proportions ranging from 0.001 to 5 wt. - , preferably ranging from 0.01 to 1 wt. -%, most preferably ranging from 0.02 to 0.5 wt. -¾ with respect to the total weight of the composition.

Additionally other additives, such as those commonly used by those skilled in the art may be added to the hair spray composition according to the invention. The other additives used in the hair spray compositions will depend upon the type of hair spray composition desired. Other additives include for example fragrances; moisturizers such as sorbitol, propanediol, butylene glycol, glycerine, hydrolyzed silk protein, or hydrolyzed wheat protein; detangling aids such as panthenol; conditioning agents such as those disclosed in US Patent 5, 164, 177 emulsifiers; antistatic aids, extracts, proteins, vitamins, dyes, tints, colorants or combinations thereof. The other additives are typically present from 0.005 to 5 wt.-%; more preferably from 0.01 to 1 wt„-% based on total weight of the hair spray composition.

Additional other additives, as well as additional surfactants, solvents, other preservatives, and thickeners, which may be suitable in hair care compositions, may be found in the International Cosmetic Ingredients Dictionary, 5th Edition, 1993, published by the CTFA in Washington D.C,

The following examples are provided to further illustrate the processes and compositions of the present invention. These examples are illustrative only and are not intended to limit the scope of the invention in any way.

Example

Amount of residue

Scale: 1 no flakes

2 very few flakes

3 few flakes

4 good visible flakes

5 many flakes

6 very many flakes

Used reagents

Acrylate copolymer: Ti LAMAR* FIX A 1000 [DSM Nutritional Products Ltd]

Neutralization agent: 2-Amino-2-methylpropanol (AMP) [ANGUS Chemie GmbH] Propellant: Demeon D (DME) [Akzo Nobel]

Propane-Butane [Shell]

Ethanol: Ethanol (96%) [Fluka]

Water demineralized (ion exchange)

Hair Swatches

Hair swatches (natural European hair, color 6.0) of 1 cm broadness and 12 cm overall length [Kerling].

Application From a distance of 25 cm, the respective hair spray was sprayed homogeneously over six hair swatches for 15s. The hair swatches were left to dry for 30 min and additionally in a conditioning chamber at 75%rH 20°C. Finally, the swatches were washed twice with simple SLS-Shampoo, dried at 20°C and evaluated visually for the degree of flaking. The results are presented in table 1 . As can be retrieved, the degree of flaking significantly increases with the neutralization level.

A: Ethanol based hair spray composition

Various solution consisting of partially neutralized Acrylate copolymer in the indicated concentration in ethanol were bottled in an appropriate can (aluminium, tinplate), crimped with an aerosol valve before the propeliant was added (ratio solution/propellant 60/40 (w/w)).

Results

A.1 . Propeliant: DME

same experiment was repeated using propane propane/butane mixture as propeliant

A.2. Propeliant: Propane-Butane

same experiment was repeated using different acrylate copolymer concentrations. A.3. Different polymer concentrations

As can be retrieved, the flaking always increases with an increased neutralization level.

B: Ethano /Water based hair spray composition

Various solution consisting of 4 wt.-¾ of partially neutralized Tl LAMAR* FIX A 1000 in water (indicated amounts) and ethanol (ad 100 wt.-%) were bottled in an appropriate can (aluminium, tinplate), crimped with an aerosol valve before the propellant was added (ratio solution/ propellant 60/40 (w/w)).

B.1. Propellant DME

The same degree of flaking in dependence of the neutralization level can be seen in ethanol/ water hair spray formulations.

Formulation examples

T! LAMAR^® Fix A1000 (!NC!: Acrylates Copolymer, Chemical Name: polymer with 2-Methyl-2- propanoic acid, butyl 2-methyl-2-propenoate, ethyl 2-methyl-2-propenoate and ethyl 2-propenoate, CAS Number: 1070166-98-1 ) can be incorporated into a great variety of product forms as illustrated below without being limited thereto: . Aerosol Hairspray "Strong Hold"

with an aerosol valve and a propellant is added. The propellant, the ratio of effective solution: propellant and the actuator are chosen according to the product requirements as spray rate, spray pattern, particle size and particle size distribution. A typical composition would be: 60% Effective Solution; 40% propane/butane 2.5 bar (high VOC) or 55% Effective solution & 45% HF 152A for a water-free VOC.55 Hairspray.

1 .2. Chic Shine Hairspray luxurious gloss and addictive shine

and stir until uniform. This part must be clear.

Part B, with stirring: Add ethanol part II into the solution. Add step by step all other ingredients and stir until. Part C, Add propane/butane 1 .3. Elastic Flexible Hold Hairspray with UV protection and pro- Vitamin B5

and stir until uniform. This part must be clear. Part B, with stirring: Add ethanol part II into the solution. Add step by step all other ingredients and stir until. Part C. Add propane/butane.

1 .4. Chic Shine Hairspray luxurious gloss and addictive shine

and stir until uniform. This part must be clear. Part B, with stirring: Add ethanol part II into the solution. Add step by step all other ingredients and stir until. Part C: after bottling and crimping, add propane/butane. 1 .5. Elastic Flexible Hold Hairspray VOC 55

and stir until uniform. This part must be clear. Part B, with stirring: Add water part II into the solution. Add step by step all other ingredients and stir until. Part C: After bottling and crimping, add DME.

Claims

1. Aerosol hair spray composition comprising at least one propellant and at least one acryiate copolymer from monomers selected from the group consisting of (meth)acrylic acid, methyl (meth)acrylate, n-butyl (meth)acrylate, tert. -butyl (meth)acrylate and ethyl (meth)acrylate, characterized in that the carboxyl groups of the acryiate copolymer are neutralized to the extent of at most 85 mole-1,

2. The aerosol hair spray composition according to claim 1 , characterized in that the monomers are selected from the group consisting of methacrylic acid, n-butyl methacryiate, ethyl acryiate and ethyl methacryiate.

3. The aerosol hair spray composition according to claim 2, characterized in that the acryiate copolymer is obtained by copolymerisation of 17-22 wt.-% of methacrylic acid, 44-56 wt.-% of n-butyl methacryiate, 9-15 wt.-% of ethyl acryiate and 15-25 wt.-¾ of ethyl methacryiate, with the proviso that the total amount of monomers sum up to 100 wt.-%.

4. The aerosol hair spray composition according to claim 2 or 3 characterized in that the acryiate copolymer is in the form of acryiate copolymer beads.

5. The aerosol hair spray composition according to claim 4 characterized in that the acryiate copolymer beads have a Tg of 98-108T and an acid value of 125-145 mg KOH/g.

6. The aerosol hair spray composition according to any one of claims 1 to 5, characterized in that the carboxyl groups are neutralized to the extent of 0-80 mole-%.

7. The aerosol hair spray composition according to 6, characterized in that the carboxyl groups of the acryiate copolymer are neutralized to the extent of 0-35 mole-%.

8. The aerosol hair spray composition according to any one of claims 1 -7, characterized in that the propellant is selected from the groups consisting of n-propane, isopropane, n- butane, isobutane, dimethyl ether; dimethoxymethane, difluoroethane, chlorodifluoroethane, chlorodifluoromethane, other chlorofluorocarbons or combinations thereof.

9. The aerosol hair spray composition according to claim 8, characterized in that the propellant is a mixture of n-propane and n-butane or is dimethyl ether.

10. The aerosol hair spray composition according to any one of claims 1 to 9, characterized in that the acrylate copolymer is neutralized with a neutralizer selected from the group consisting of 2-amino 2-methyl propanediol, 2-amino-2-methyl propanol, N,N dimethyl 2-amino 2-methyl propanol, potassium hydroxide, triethanolamine, triisopropanolamine, or combinations thereof,

11 . The aerosol hair spray composition according to any one of claims 1 to 10, characterized in that the acrylate copolymer is used in a concentration of 1 -8 wt.-% based on the total weight of the aerosol hair spray composition.

12. The aerosol hair spray composition according to any one of claims 1 to 11 , characterized in that the propellant is used in a concentration of 30 to 60 wt. - based on the total weight of the aerosol hair spray composition.

13. The aerosol hair spray composition according to any one of claims 1 to 12, characterized in that the composition is manufactured by preparation of a bulk solution consisting of 1 -15 wt.-% of the acrylate copolymer, 20-100 wt.-% of water, 0-80 wt.-¾ of ethanol and 0-10 wt.-% of other additives usually employed in aerosol hair spray composition followed by mixing the resulting solution with the at least one propellant.

14. The aerosol hair spray composition according to any one of claims 1 to 13 characterized in that said preparation further comprises at least one additional hair fixative resin.

15. A method of styling hair, said method comprising the step of applying an aerosol hair spray composition as defined in any one of claims 1 to 14 to hair and appreciating the result.