WO2002009656A2 - Reshapable hair styling composition comprising acrylic emulsions - Google Patents

Reshapable hair styling composition comprising acrylic emulsions Download PDF

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Publication number
WO2002009656A2
WO2002009656A2 PCT/IB2001/001568 IB0101568W WO0209656A2 WO 2002009656 A2 WO2002009656 A2 WO 2002009656A2 IB 0101568 W IB0101568 W IB 0101568W WO 0209656 A2 WO0209656 A2 WO 0209656A2
Authority
WO
WIPO (PCT)
Prior art keywords
composition according
hair
composition
reshapable
monomers
Prior art date
Application number
PCT/IB2001/001568
Other languages
French (fr)
Other versions
WO2002009656A3 (en
WO2002009656A8 (en
Inventor
Isabelle Rollat-Corvol
Henri Samain
Original Assignee
L'oreal
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by L'oreal filed Critical L'oreal
Priority to AU8001701A priority Critical patent/AU8001701A/en
Priority to EP01958297A priority patent/EP1353627A2/en
Priority to CA002416907A priority patent/CA2416907A1/en
Priority to MXPA03000701A priority patent/MXPA03000701A/en
Priority to AU2001280017A priority patent/AU2001280017B2/en
Priority to BR0113020-0A priority patent/BR0113020A/en
Priority to JP2002515211A priority patent/JP2004521860A/en
Priority to KR10-2003-7001084A priority patent/KR20030017652A/en
Publication of WO2002009656A2 publication Critical patent/WO2002009656A2/en
Publication of WO2002009656A8 publication Critical patent/WO2002009656A8/en
Publication of WO2002009656A3 publication Critical patent/WO2002009656A3/en

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Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/06Preparations for styling the hair, e.g. by temporary shaping or colouring
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a reshapable hair styling composition.
  • Fixing the hairstyle is an important element in hair styling, and involves maintaining a
  • the term "hair styling composition” relates to
  • any kind of hair composition that can be used to effect hair styling, for example fixing
  • compositions shampoos, conditioners, permanent waving compositions, hair care
  • compositions comprising a
  • solution usually alcohol- or water-based, and one or more materials, generally
  • polymer resins One of the functions of polymer resins is to form links between the
  • This solution is generally packaged either in an appropriate aerosol
  • hair styling compositions include styling gels and mousses, which are known hair styling compositions.
  • compositions are essentially aqueous and their application wets the hair
  • the hairstyle has a tendency to take on an
  • hair conditioning benefits such as ease of combing and soft
  • a subject of the invention is a reshapable hair styling composition comprising,
  • At least acrylic polymer comprising: (a)
  • Another subject of the invention is a reshapable hair styling composition
  • the term "reshapable" hair styling composition means a hair styling
  • composition providing hair styling that can be restored or modified without new
  • “reshapable” effect means to provide a hair styling that can be restored or modified
  • composition without new material or heat being applied.
  • efficacy of the composition can be any organic compound or without new material or heat being applied.
  • reshapable include repositionable, remoldable,
  • emulsion means a stable mixture of two or more
  • All emulsions comprise a continuous phase
  • polyfunctional crosslinking agents means a
  • crosslinking agent having an average functionality greater than 1 , such as greater
  • the at least one emulsion comprises at least
  • At least one acrylic polymer comprising: (a) about 50 to about 90% by weight, such as
  • polymer further comprising up to about 50% by weight units derived from at least one
  • the at least one co-polymerizable monomer may be any co-polymerizable monomer.
  • the at least one co-polymerizable monomer may be any co-polymerizable monomer.
  • Alkylacrylate monomers may
  • methyl methacrylate examples include methyl methacrylate, isobomyl acrylate, ethyl acrylate, methyl acrylate,
  • Useful polar monomers include acrylic acid;
  • (meth)acrylamides such as N,N, -dimethyl acrylamides and N-octylacrylamide; dimethylaminoethyl methacrylate; acrylonitrile; 2-carboxyethyl acrylate; maleic
  • methoxypolyethylene glycol 550 monoacrylate available from Sartomer Co. under the
  • monomers include styrene and C1 -C4 vinyl esters such as vinyl acetate, vinyl
  • co-polymerizable ethylenically unsaturated free radically polymerizable monomers are present in the range up to about 30% by weight.
  • Polyfunctional crosslinking agents if included, may be copolymerizable with
  • the monomeric components of the acrylic polymer or may by added to the
  • copolymerizable crosslinking agents examples include
  • alkyl triacrylates and tetracrylates such as trimethylol propane triacrylate
  • copolymerizable crosslinking agent is 1 ,6-hexanediol diacrylate.
  • Post-additive crosslinking agents may also be used. Examples of
  • post-additive crosslinking agents include but are not limited to multifunctional
  • aziridine amides such as 1 ,1'-(1 ,3-phenylenedicarbonyl)bis[2-methyl aziridine],
  • the metal ion is copper, zinc, zirconium, and chromium.
  • the metal ion is copper, zinc, zirconium, and chromium.
  • crosslinkers are chosen from chelated esters of ortho-titanic acid sold under the
  • the TYZOR is TYZOR AA, which is titanium acetyl acetonate.
  • Crosslinking agents when used, comprise up to about 10 parts by weight,
  • emulsions of the present invention are initiators that, on exposure to heat, generate
  • water soluble initiators are preferred.
  • Suitable water-soluble initiators include but are not limited to those chosen from
  • potassium persulfate ammonium persulfate, sodium persulfate, and mixtures thereof;
  • persulfates and reducing agents such as those chosen from sodium metabisulfite and
  • the water-soluble initiator is potassium
  • Suitable oil-soluble initiators include but are not limited to those chosen from
  • the oil-soluble thermal initiator is (2,2'-azobis(isobutyronitrile)).
  • initiators may comprise from about 0.05 to about 1 part by weight, also
  • the copolymerizable mixture may optionally further comprise a chain transfer
  • useful chain transfer agents include but are not limited to those
  • the chain transfer agent is chosen from isooctylthioglycolate and carbon tetrabromide.
  • the emulsion mixture may further comprise up to about 0.5
  • a chain transfer agent typically about 0.01 weight percent to about
  • Polymerization via emulsion techniques may require the presence of an
  • emulsifier (which may also be called an emulsifying agent or a surfactant).
  • emulsifiers for the present invention include those chosen from anionic surfactants,
  • nonionic surfactants and mixtures thereof.
  • Useful anionic surfactants include but are not limited to those whose molecular
  • structure includes at least one hydrophobic moiety chosen from about C6 - to about
  • Said salts are chosen from alkali metal salts, ammonium salts, tertiary amino salts, and the like.
  • Representative commercial examples of useful anionic surfactants are chosen from alkali metal salts, ammonium salts, tertiary amino salts, and the like.
  • Useful nonionic surfactants include but are not limited to those whose
  • molecular structure comprises a condensation product of an organic aliphatic or alkyl
  • HLB Hydrophilic-Lipophilic Balance
  • the HLB of a surfactant is an
  • Rhone-Poulenc available from Rhone-Poulenc as the IGEPAL CA or CO series, respectively;
  • the emulsion polymerization of this invention is carried out
  • a useful range of emulsifier concentration is from about 0.5 to about 8 weight percent, preferably from about 1 to about 5 weight
  • the acrylic emulsions of the invention may also contain one or more
  • Preferred additives include plasticizers, dyes, fillers,
  • antioxidants and UV stabilizers.
  • Such additives can be used if they do not adversely
  • the acrylic emulsions of the present invention are prepared by a semi-continuous emulsion polymerization process. In the process, a
  • surfactant n-butyl acrylate monomers, hydroxyalkyl (meth)acrylate (b) monomers, and the optional components such as co-polymerizable monomers, polyfunctional
  • crosslinking agents chain transfer agents, pH modifiers, and other additives.
  • induction temperature typically about 50 °C to about
  • the first initiator is added to initiate the polymerization and the reaction is
  • the monomer pre-emulsion comprising Dl water, surfactant,
  • n-butyl acrylate monomers hydroxyalkyl (meth)acrylate (b) monomers, and the
  • optional components such as co-polymerizable monomers, polyfunctional crosslinking agents, chain transfer agents, and other additives is added to the stirred flask over a period of time, typically 2 to 4 hours, while the temperature is maintained.
  • the second initiator charge if used, is added to the
  • the mixture is cooled to room temperature (about 23 °C.) and the latex is
  • the pH of the latex prepared using this method is typically about 2 to about 3.
  • the acidity of the latex can be modified following latex formation using a pH modifier
  • a basic solution e.g., solutions of sodium hydroxide, ammonium hydroxide
  • buffer solutions e.g., sodium bicarbonate and the like
  • buffer solutions e.g., sodium bicarbonate and the like
  • the pH is 7 or less. In another embodiment, the pH is in
  • the acrylic polymers may be neutralized in one embodiment of the invention.
  • Suitable neutralizing agents may be chosen
  • organic, inorganic, and organomineral bases such as amino methyl propanols, sodium and potassium hydoxides, primary, secondary and tertiary amines, ammoniacs, derivatives thereof, and combinations thereof.
  • the acrylic has a glass transition
  • Tg temperature ranging from about -100 to about 15°C.
  • the Tg of the acrylic is obtained following the application of the acrylic
  • the glass transition temperature is determined by
  • DSC Differential Scanning Calorimetric method
  • composition according to the invention may comprise at least one other
  • perfumes perfumes; UV filters; active haircare agents; plasticizers; anionic, cationic,
  • amphoteric, nonionic, and zwitterionic surfactants such as
  • silicone fluids fatty esters, fatty alcohol, long chain hydrocarbons, emollients,
  • lubricants such as lanolin compounds, protein hydrolysates, and
  • polymers ; dyes; tints; bleaches; reducing agents; pH adjusting agents; sunscreens;
  • the appropriate cosmetically acceptable vehicle is adapted to the method of
  • the vehicle preferably comprises an appropriate solvent to
  • compositions according to the invention can be provided in any form
  • a vaporizable composition including in the form of a vaporizable composition, mousse, gel, or lotion.
  • composition may be in any of the conventional form including, but not
  • compositions hair dye compositions, hair straightening compositions, hair fixing
  • composition according to the invention may be vaporizable, for example
  • a pump or may be a pressurized aerosol composition. It may be vaporizable by
  • a dispensing valve controlled by a dispensing head, which in turn comprises a nozzle
  • a vaporizable composition according to the
  • the appropriate solvent comprises an appropriate solvent.
  • the appropriate solvent is selected from any solvent.
  • lower alcohol means a C1-C4 aliphatic alcohol, preferably
  • the vaporizable composition according to the invention is an aerosol
  • composition it additionally comprises an appropriate amount of propellant.
  • propellant comprises compressed or liquefied gases, which are normally employed
  • Suitable gasses include compressed air,
  • carbon dioxide nitrogen, and gases, which are soluble or otherwise in the composition, such as dimethyl ether, fluorinated or non-fluorinated hydrocarbons, and
  • the present invention additionally provides an aerosol device comprising a
  • an aerosol composition which comprises on the one hand a liquid phase (or juice) comprising at least one hair styling material as described above in an appropriate medium and on the other hand a propellant, and a dispenser for dispensing said aerosol composition.
  • the present invention additionally provides a method of treating keratinous
  • fibers, especially hair in which the composition according to the invention as defined above is applied to the hair before, during, or after the shaping of the hairstyle.
  • compositions according to the invention can be rinsed off or not rinsed off the hair.
  • present invention additionally provides the use of a composition as
  • composition according to the invention can be provided in any form known
  • a vaporizable composition a mousse, a gel, or a lotion.
  • hair styling composition can be determined by an in vivo test. Specifically, a
  • composition comprising the acrylic emulsion and a cosmetically
  • composition is in the form of a lotion
  • the in vivo test proceeds as follows. The hair of the model is washed and then divided into two
  • composition is applied to one
  • the reference composition may, for example, be chosen from
  • the hairdresser dries and styles both sides of the head.
  • the two sides of the head are
  • the hair is brushed in different directions to remove
  • composition is a reshapable hair styling composition.
  • a reshapable hair styling composition is a reshapable hair styling composition.
  • composition permits (1) the original hair styling to be restored after brushing and (2)
  • composition to be evaluated is in another form, such as a shampoo
  • the in vivo test can be appropriately modified by one skilled in the art.
  • in vivo testing may require testing on 10-20 different individuals.
  • HOA methyl methacrylate
  • MMA methyl methacrylate
  • RHODACAL DS- 10 sodium dodecyl benzene sulfonate surfactant
  • reaction mixture was then heated to 70 °C and maintained at this temperature for 20
  • This pre-emulsified mixture contained 345.6 grams of BA, 69.12 grams of
  • Example 2 To a 2000ml reactor was added 37.0 grams of n-butyl acrylate (BA), 7.68
  • HOA 2-hydroxyethyl acrylate
  • MMA methyl methacrylate
  • reaction mixture was then heated to 70 °C and maintained at this temperature for 20
  • This pre-emulsified mixture contained 295.8 grams of BA, 69.12 grams of
  • mousse or lotion were prepared using the components and amounts in weight percent listed hereafter. The testing was conducted on several models with one part
  • compositions were applied to wet hair after shampooing. In some instances, the composition was rinsed off after
  • the hair was then dried, brushed, and evaluated.
  • Example 1 4 % active material
  • Example 2 8 % active material
  • Example 1 8 % active material
  • Example 1 1 % active material
  • Formulation D imparted very good reshapable effect much better than the reference with very good cosmetic properties (soft hair with good touch).

Abstract

A reshapable hair styling composition comprising, in a cosmetic vehicle appropriate for hair, at least one emulsion comprising at least one acrylic polymer comprising: (a) units derived from n-butyl acrylate monomers and (b) units derived from at least one monomer chosen from 2-hydroxy ethyl acrylate, 2-hydrocy ethyl methacrylate, and hydroxy propyl acrylate monomers.

Description

RESHAPABLE HAIR STYLING COMPOSITION COMPRISING ACRYLIC EMULSIONS
The present invention relates to a reshapable hair styling composition.
Fixing the hairstyle is an important element in hair styling, and involves maintaining a
shaping that has already been carried out, or in simultaneously shaping and fixing the
hair.
In accordance with the invention, the term "hair styling composition" relates to
any kind of hair composition that can be used to effect hair styling, for example fixing
compositions, shampoos, conditioners, permanent waving compositions, hair care
products, and hair treatment products.
The most prevalent hair styling compositions on the cosmetic market for
shaping and/or maintaining the hairstyle are spray compositions comprising a
solution, usually alcohol- or water-based, and one or more materials, generally
polymer resins. One of the functions of polymer resins is to form links between the
hairs, these materials also being called fixatives, in a mixture with various cosmetic
adjuvants. This solution is generally packaged either in an appropriate aerosol
container, which is pressurized with the aid of a propellant, or in a pump flask.
Other known hair styling compositions include styling gels and mousses, which
are generally applied to the wetted hair before brushing or setting it. In contrast to
the conventional aerosol lacquers, these compositions have the disadvantage that
they do not allow the hair to be fixed in a shape created before their application. In fact, these compositions are essentially aqueous and their application wets the hair
and is therefore unable to maintain the initial shape of the hairstyle. In order to shape
and fix the hairstyle, therefore, it is necessary to carry out subsequent brushing
and/or drying. Such hair styling compositions all have the same disadvantage that
they do not allow the hairstyle to be later modified to a desired shape, which is other
than that formed initially, without starting the styling and fixing operations again.
Moreover, under various kinds of stress, the hairstyle has a tendency to take on an
undesirable permanent set, which cannot easily be modified. Also in the styling
process, one desires hair conditioning benefits, such as ease of combing and soft
hair feel appearance.
A subject of the invention is a reshapable hair styling composition comprising,
in a cosmetic vehicle appropriate for hair, at least acrylic polymer comprising: (a)
units derived from n-butyl acrylate monomers and (b) units derived from at least one
monomer chosen from 2-hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, and
hydroxy propyl acrylate monomers.
Another subject of the invention is a reshapable hair styling composition
comprising, in a cosmetic vehicle appropriate for hair, at least one emulsion
comprising at least one acrylic polymer comprising: (a) units derived from n-butyl
acrylate monomers and (b) units derived from at least one monomer chosen from
2-hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, and hydroxy propyl acrylate
monomers. The term "reshapable" hair styling composition means a hair styling
composition providing hair styling that can be restored or modified without new
material or heat being applied. For example, in order to restore or modify the
hairstyle in case of drooping or loss of setting (dishevelment), no new materials, such
as water or any form of fixing agent, or heat are required. Thus, to provide a
"reshapable" effect means to provide a hair styling that can be restored or modified
without new material or heat being applied. The efficacy of the composition can be
long lasting, such as 10-24 hours, giving rise to a durable styling effect. Other terms,
which may be synonymous with reshapable, include repositionable, remoldable,
restyleable, and remodellable.
As used herein, the term "emulsion" means a stable mixture of two or more
immiscible liquids held in suspension. All emulsions comprise a continuous phase
and a disperse phase.
As used herein, the term polyfunctional crosslinking agents means a
crosslinking agent having an average functionality greater than 1 , such as greater
than 1.8, and further such as about 2.0 or greater. But the average functionality is
less than about 6, such as less than about 4, and further such as about 3 or less.
In one embodiment of the invention, the at least one emulsion comprises at
least one acrylic polymer comprising: (a) about 50 to about 90% by weight, such as
about 70 to about 90% by weight units derived from n-butyl acrylate monomers and
(b) about 10 to about 50%, such as about 10 to about 30% by weight of units derived from at least one monomer chosen from 2-hydroxy ethyl acrylate, 2-hydroxy ethyl
methacrylate, and hydroxy propyl acrylate monomers.
In one embodiment the at least one emulsion comprises at least one acrylic
polymer further comprising up to about 50% by weight units derived from at least one
co-polymerizable monomer. The at least one co-polymerizable monomer may be
chosen from (i) alkylacrylate monomers, (ii) polar monomers and (iii) ethylenically
unsaturated free radically polymerizable monomers. Alkylacrylate monomers may
include methyl methacrylate, isobomyl acrylate, ethyl acrylate, methyl acrylate,
isooctylacrylate, 2-ethyl hexyl acrylate and mixtures thereof. In another embodiment,
units derived from the co-polymerizable alkylacrylate monomers are present in the range of up to about 30% by weight. Useful polar monomers include acrylic acid;
methacrylic-acid; itaconic acid; N-vinyl pyrrolidone; N-vinyl caprolactam; substituted
(meth)acrylamides, such as N,N, -dimethyl acrylamides and N-octylacrylamide; dimethylaminoethyl methacrylate; acrylonitrile; 2-carboxyethyl acrylate; maleic
anhydride; and mixtures thereof. Another example of useful polar monomers is
methoxypolyethylene glycol 550 monoacrylate available from Sartomer Co. under the
tradename CD553. Useful ethylenically unsaturated free radically polymerizable
monomers include styrene and C1 -C4 vinyl esters such as vinyl acetate, vinyl
propionate, and mixtures thereof. In yet another embodiment, the units derived from
the co-polymerizable ethylenically unsaturated free radically polymerizable monomers are present in the range up to about 30% by weight. Polyfunctional crosslinking agents, if included, may be copolymerizable with
the monomeric components of the acrylic polymer or may by added to the
polymerized latex product. Examples of copolymerizable crosslinking agents include
but are not limited to those chosen from divinylbenzene; alkyl diacrylates such as
those chosen from 1 ,2-ethylene glycol diacrylate, 1 ,4-butanediol diacrylate,
1 ,6-hexanediol diacrylate, 1 ,8-octanediol diacrylate, and 1 ,12-dodecanediol
diacrylate; alkyl triacrylates and tetracrylates such as trimethylol propane triacrylate
and pentaerythritol tetraacrylate; monoethylenically unsaturated aromatic ketones
such as 4-acryloxybenzophenone; and mixtures thereof. In one embodiment, the
copolymerizable crosslinking agent is 1 ,6-hexanediol diacrylate.
Post-additive crosslinking agents may also be used. Examples of
post-additive crosslinking agents include but are not limited to multifunctional
aziridine amides such as 1 ,1'-(1 ,3-phenylenedicarbonyl)bis[2-methyl aziridine],
2,2,4-trimethyladipoyl bis [2-ethyl aziridine], 1 , 1'-azelaoyl bis [2-methyl aziridine], and
2,4,6-tris(2-ethyl-1-aziridinyl)-1 ,3,5 triazine; and metal ion crosslinkers such as
copper, zinc, zirconium, and chromium. In one embodiment, the metal ion
crosslinkers are chosen from chelated esters of ortho-titanic acid sold under the
tradename TYZOR and commercially available from the E.I. du Pont de Numours Co.
In another embodiment, the TYZOR is TYZOR AA, which is titanium acetyl acetonate. Crosslinking agents, when used, comprise up to about 10 parts by weight,
typically about 0.1 to about 2 parts by weight of the copolymerizable emulsion mixture
based on 100 parts by weight of the (a) and (b) monomers and the co-polymerizable
monomer, when present.
Water-soluble and oil-soluble initiators useful in preparing the acrylic
emulsions of the present invention are initiators that, on exposure to heat, generate
free-radicals which initiate (co)polymerization of the n-butyl acrylate monomers,
hydroxyalkyl (meth)acrylate monomers, and optional comonomer and crosslinking
agent components. In one embodiment, water soluble initiators are preferred.
Suitable water-soluble initiators include but are not limited to those chosen from
potassium persulfate, ammonium persulfate, sodium persulfate, and mixtures thereof;
oxidation-reduction initiators such as the reaction product of the above-mentioned
persulfates and reducing agents such as those chosen from sodium metabisulfite and
sodium bisulfite; and 4,4'-azobis(4-cyanopentanoic acid) and its soluble salts (e.g.,
sodium, potassium). In another embodiment, the water-soluble initiator is potassium
persulfate.
Suitable oil-soluble initiators include but are not limited to those chosen from
azo compounds such as VAZO 64 (2,2'-azobis(isobutyronitrile) and VAZO 52
(2,2'-azobis(2,4-dimethylpentanenitrile)), both available from E.I. du Pont de Numours
Co.; and peroxides such as benzoyl peroxide, lauroyl peroxide, and mixtures thereof.
In one embodiment, the oil-soluble thermal initiator is (2,2'-azobis(isobutyronitrile)). When used, initiators may comprise from about 0.05 to about 1 part by weight, also
about 0.1 to about 0.5 part by weight based on 100 parts by weight of the total
copolymerizable mixture
The copolymerizable mixture may optionally further comprise a chain transfer
agent. Examples of useful chain transfer agents include but are not limited to those
chosen from carbon tetrabromide, alcohols, mercaptans, and mixtures thereof. In
one embodiment, the chain transfer agent is chosen from isooctylthioglycolate and carbon tetrabromide. The emulsion mixture may further comprise up to about 0.5
parts by weight of a chain transfer agent, typically about 0.01 weight percent to about
0.5 parts by weight, if used, also about 0.05 parts by weight to about 0.2 parts by weight, based upon 100 parts by weight of the total copolymerizable mixture.
Polymerization via emulsion techniques may require the presence of an
emulsifier (which may also be called an emulsifying agent or a surfactant). Useful
emulsifiers for the present invention include those chosen from anionic surfactants,
nonionic surfactants, and mixtures thereof.
Useful anionic surfactants include but are not limited to those whose molecular
structure includes at least one hydrophobic moiety chosen from about C6 - to about
C12 -alkyl, alkylaryl, and/or alkenyl groups and at least one anionic group chosen
from sulfates, sulfonates, phosphates, polyoxyethylene sulfates, polyoxyethylene sulfonates, polyoxyethylene phosphates, and the like, and the salts of such groups.
Said salts are chosen from alkali metal salts, ammonium salts, tertiary amino salts, and the like. Representative commercial examples of useful anionic surfactants
include sodium lauryl sulfates, available from Stepan Chemical Co. as POLYSTEP
B-3; sodium lauryl ether sulfates, available from Stepan Chemical Co. as POLYSTEP
B-12; sodium dodecyl benzene sulfonates, available from Rhone-Poulenc as
SIPONATE DS-10; and alkylene polyalkoxy ammonium sulfates, available from PPG
Industries as MAZON SAM-211.
Useful nonionic surfactants include but are not limited to those whose
molecular structure comprises a condensation product of an organic aliphatic or alkyl
aromatic hydrophobic moiety with a hydrophilic alkylene oxide such as ethylene
oxide. The HLB (Hydrophilic-Lipophilic Balance) of useful nonionic surfactants is
about 10 or greater, also from about 10 to about 20. The HLB of a surfactant is an
expression of the balance of the size and strength of the hydrophilic (water-loving or
polar) groups and the lipophilic (oil-loving or non-polar) groups of the surfactant.
Commercial examples of nonionic surfactants useful in the present invention include
but are not limited to nonylphenoxy or octylphenoxy poly(ethyleneoxy) ethanols
available from Rhone-Poulenc as the IGEPAL CA or CO series, respectively;
C11-C15 secondary-alcohol ethoxylates available from Union Carbide as the
TERGITOL 15-S series; and polyoxyethylene sorbitan fatty acid esters available from
ICI Chemicals as the TWEEN series of surfactants.
In one embodiment, the emulsion polymerization of this invention is carried out
in the presence of anionic surfactant(s). A useful range of emulsifier concentration is from about 0.5 to about 8 weight percent, preferably from about 1 to about 5 weight
percent, based on the total weight of all monomers.
The acrylic emulsions of the invention may also contain one or more
conventional additives. Preferred additives include plasticizers, dyes, fillers,
antioxidants, and UV stabilizers. Such additives can be used if they do not adversely
affect the reshapable properties of the composition.
In one embodiment, the acrylic emulsions of the present invention are prepared by a semi-continuous emulsion polymerization process. In the process, a
flask is charged with a seed monomer mixture comprising deionized (Dl) water,
surfactant, n-butyl acrylate monomers, hydroxyalkyl (meth)acrylate (b) monomers, and the optional components such as co-polymerizable monomers, polyfunctional
crosslinking agents, chain transfer agents, pH modifiers, and other additives. The
mixture is stirred and heated under an inert atmosphere such as a nitrogen blanket.
When the mixture has reached induction temperature, typically about 50 °C to about
70 °C, the first initiator is added to initiate the polymerization and the reaction is
allowed to exotherm. After the seed reaction is completed, the batch temperature is
then raised to the feed reaction temperature, about 70 °C to about 85 °C. At the feed
reaction temperature, the monomer pre-emulsion comprising Dl water, surfactant,
n-butyl acrylate monomers, hydroxyalkyl (meth)acrylate (b) monomers, and the
optional components such as co-polymerizable monomers, polyfunctional crosslinking agents, chain transfer agents, and other additives is added to the stirred flask over a period of time, typically 2 to 4 hours, while the temperature is maintained.
At end of the feed reaction, the second initiator charge, if used, is added to the
reaction to further reduce residual monomers in the latex. After an additional hour of
heating, the mixture is cooled to room temperature (about 23 °C.) and the latex is
collected for evaluation.
The pH of the latex prepared using this method is typically about 2 to about 3.
The acidity of the latex can be modified following latex formation using a pH modifier
such as a basic solution (e.g., solutions of sodium hydroxide, ammonium hydroxide
and the like) or buffer solutions (e.g., sodium bicarbonate and the like), to less acidic
levels. In one embodiment, the pH is 7 or less. In another embodiment, the pH is in
the range of 2 to 6.
In one embodiment of the invention, the acrylic polymers may be neutralized in
the emulsion and/or the composition. Suitable neutralizing agents may be chosen
from organic, inorganic, and organomineral bases, such as amino methyl propanols, sodium and potassium hydoxides, primary, secondary and tertiary amines, ammoniacs, derivatives thereof, and combinations thereof.
An embodiment of the invention provides a reshapable hair styling composition
comprising, in a cosmetic vehicle suitable for hair, at least one emulsion comprising
at least one acrylic polymer, leading to a styling material following application to the fibers and drying. It is a further subject of the invention to provide a method for treating hair,
characterized in that the composition according to the invention is applied to the hair
before, during, or after the shaping of the hairstyle.
In another embodiment of the invention, the acrylic has a glass transition
temperature (Tg) ranging from about -100 to about 15°C. According to the present
invention, the Tg of the acrylic is obtained following the application of the acrylic
emulsion to a substrate and drying. The glass transition temperature is determined by
the Differential Scanning Calorimetric method (DSC).
The composition according to the invention may comprise at least one other
constituent, which is conventional in cosmetics, chosen from preservatives;
perfumes; UV filters; active haircare agents; plasticizers; anionic, cationic,
amphoteric, nonionic, and zwitterionic surfactants; hair conditioning agents such as
silicone fluids, fatty esters, fatty alcohol, long chain hydrocarbons, emollients,
lubricants, and penetrants such as lanolin compounds, protein hydrolysates, and
other protein derivatives; anionic, cationic, amphoteric, nonionic, and zwitterionic
polymers; dyes; tints; bleaches; reducing agents; pH adjusting agents; sunscreens;
preservatives; thickening agents; and perfumes.
The appropriate cosmetically acceptable vehicle is adapted to the method of
application selected. The vehicle preferably comprises an appropriate solvent to
which may be added additives such as gelling agents, foaming agents, and silicones. It is understood that the person skilled in the art will know how to choose the
additional constituents and their amount in the composition according to the
invention, such as the constituents of the vehicle, so as not to adversely affect or
substantially affect its reshapable hair styling properties.
The compositions according to the invention can be provided in any form
known from the prior art, which is appropriate for their application to the hair,
including in the form of a vaporizable composition, mousse, gel, or lotion.
The composition may be in any of the conventional form including, but not
limited to, shampoos, hair rinses, permanent waving compositions, waving
compositions, hair dye compositions, hair straightening compositions, hair fixing
products, hair styling gel products, products to use before or after a hair dye
treatment, products to use before or after a permanent waving treatment, hair
straightening compositions, products to use before or after a hair straightening
treatment, and fixing foams.
The composition according to the invention may be vaporizable, for example
by a pump, or may be a pressurized aerosol composition. It may be vaporizable by
a dispensing valve controlled by a dispensing head, which in turn comprises a nozzle,
which vaporizes the aerosol composition. A vaporizable composition according to the
invention comprises an appropriate solvent. Advantageously, the appropriate solvent
comprises at least one solvent chosen from water and lower alcohols. In accordance with the invention, the term lower alcohol means a C1-C4 aliphatic alcohol, preferably
ethanol.
When the vaporizable composition according to the invention is an aerosol
composition, it additionally comprises an appropriate amount of propellant. The
propellant comprises compressed or liquefied gases, which are normally employed
for the preparation of aerosol compositions. Suitable gasses include compressed air,
carbon dioxide, nitrogen, and gases, which are soluble or otherwise in the composition, such as dimethyl ether, fluorinated or non-fluorinated hydrocarbons, and
mixtures thereof. The present invention additionally provides an aerosol device comprising a
vessel comprising an aerosol composition, which comprises on the one hand a liquid phase (or juice) comprising at least one hair styling material as described above in an appropriate medium and on the other hand a propellant, and a dispenser for dispensing said aerosol composition.
The present invention additionally provides a method of treating keratinous
fibers, especially hair, in which the composition according to the invention as defined above is applied to the hair before, during, or after the shaping of the hairstyle.
The compositions according to the invention can be rinsed off or not rinsed off the hair. The present invention additionally provides the use of a composition as
defined above in, or for the preparation of, a cosmetic reshapable hair styling
formulation.
The composition according to the invention can be provided in any form known
from the prior art, which is appropriate for their application to the hair, including in the
form of a vaporizable composition, a mousse, a gel, or a lotion.
The determination of whether an acrylic emulsion can provide a reshapable
hair styling composition can be determined by an in vivo test. Specifically, a
composition is prepared comprising the acrylic emulsion and a cosmetically
acceptable medium. The medium may be chosen, for example, from water, lower alcohols such as ethanol, and mixtures thereof. The composition typically comprises from about 1% to about 12% by weight active material. The compositions may be in any form noted above, including lotions.
Where the composition is in the form of a lotion, for example, the in vivo test proceeds as follows. The hair of the model is washed and then divided into two
symmetrical portions, the right and the left sides. The composition is applied to one
side of the head of the model, while a reference composition is applied to the other
side of the head. The reference composition may, for example, be chosen from
water, an existing commercial product, or another composition under study. The hairdresser dries and styles both sides of the head. The two sides of the head are
separately evaluated for the styling effect, the cometic properties, and the reshapable effect. For example, once dried, the hair is brushed in different directions to remove
the original styling. The hair is then brushed to restore the original styling. The process of removing the styling, restoring the styling, and evaluating the success of
restoring the styling is repeated at least one more time to determine whether the
composition is a reshapable hair styling composition. A reshapable hair styling
composition permits (1) the original hair styling to be restored after brushing and (2)
the creation of a new hair styling after brushing, which may also be restored after
brushing. If the composition to be evaluated is in another form, such as a shampoo
or conditioner, the in vivo test can be appropriately modified by one skilled in the art.
It is understood that the person skilled in the art would recognize that not all formulations would provide reshapable effect for all hair types during in vivo testing
and will know how to formulate and evaluate reshapable hair styling composition in
view of the various hair parameters, such as length (short versus long), diameter (thin
versus thick), structure (curly versus straight), condition (oily, dry, or normal); and whether the hair is colored, bleached, permed, or straightened. Thus, in vivo testing may require testing on 10-20 different individuals.
The invention may be understood more clearly with the aid of the non limiting
examples which follow, and which constitute an advantageous embodiment of the compositions in accordance with the invention.
EXAMPLES Hair compositions according to the invention were produced with different
acrylic emulsions.
) Preparation of the acrylic emulsions:
Example 1 :
38.40 grams of n-butyl acrylate (BA), 7.68 grams of 2-hydroxyethyl acrylate
(HEA), 5.12 grams of methyl methacrylate (MMA), 374 grams of Dl water and 0.5
gram of RHODACAL DS- 10 (sodium dodecyl benzene sulfonate surfactant
commercially available from Rhone- Poulenc) were added to a 2000 ml reactor. This
mixture was stirred under nitrogen and degassed 4 times. The temperature was
raised to 60 °C and 1.29 grams of potassium persulfate initiator was added. The
reaction mixture was then heated to 70 °C and maintained at this temperature for 20
min. to complete the seed reaction. The reaction temperature was further increased
to 80 °C. At 80 °C, a pre-emulsified monomer mixture was fed into the reactor for 2
hours. This pre-emulsified mixture contained 345.6 grams of BA, 69.12 grams of
HEA, 46.08 grams of MMA, 208 grams of Dl water and 5.29 grams of RHODACAL
DS-10. After the feeding of the monomer mixture, the reaction was continued at 80
°C for another 60 min.
Example 2: To a 2000ml reactor was added 37.0 grams of n-butyl acrylate (BA), 7.68
grams of 2-hydroxyethyl acrylate (HEA), 10.24 grams of methyl methacrylate (MMA),
374 grams of Dl water and 0.5 gram of RHODACAL DS- 10 (sodium dodecyl
benzene sulfonate surfactant commercially available from Rhone- Poulenc). This
mixture was stirred under nitrogen and degassed 4 times. The temperature was raised to 60 °C and 1.29 grams of potassium persulfate initiator was added. The
reaction mixture was then heated to 70 °C and maintained at this temperature for 20
min. to complete the seed reaction. The reaction temperature was further increased
to 80 °C. At 80 °C, a pre-emulsified monomer mixture was fed into the reactor for 2
hours. This pre-emulsified mixture contained 295.8 grams of BA, 69.12 grams of
HEA, 92.16 grams of MMA, 208 grams of Dl water and 5.29 grams of RHODACAL
DS-10. After the feeding of the monomer mixture, the reaction was continued at 80
°C for another 60 min.
2) Preparation of the hair styling compositions
Four hair styling compositions in accordance with the invention in the form of a
mousse or lotion were prepared using the components and amounts in weight percent listed hereafter. The testing was conducted on several models with one part
of the head receiving one of the two reference compositions and the other side of the
head receiving the tested composition. The compositions were applied to wet hair after shampooing. In some instances, the composition was rinsed off after
application. The hair was then dried, brushed, and evaluated.
Reference 1 :
AQ 1350 4 % active material
Ethanol 20 %
Water qsp 100 %
Reference 2:
Water 100%
Formulation A:
Example 1 4 % active material
Water qsp 100 %
Formulation A and Reference 1 were not rinsed off after application.
Formulation A imparted very good hairstyling and reshapable effect much better than
the reference with good cosmetic properties (soft hair with good touch).
Formulation B:
Example 2 8 % active material
Water qsp 100 %
Formulation B and Reference 2 were rinsed off after application. Formulation
B imparted good hairstyling and reshapable effect better than the reference with very
good cosmetic properties (soft hair with good touch). Formulation C:
Example 1 8 % active material
Water qsp 100 %
Formulation C and Reference 1 were rinsed off after application. Formulation
C imparted very good hairstyling and reshapable effect much better than the
reference with very good cosmetic properties (soft hair with good touch).
Formulation D:
Example 1 1 % active material
Water qsp 100 %
Formulation D and Reference 1 were not rinsed off after application.
Formulation D imparted very good reshapable effect much better than the reference with very good cosmetic properties (soft hair with good touch).

Claims

What is claimed is:
1. A reshapable hair styling composition comprising, in a cosmetic vehicle
appropriate for hair, at least one acrylic polymer comprising: (a) units derived from n-butyl acrylate monomers and (b) units derived from at least one monomer chosen
from 2-hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, and hydroxy propyl
acrylate monomers, wherein said composition provides a reshapable effect.
2. A reshapable hair styling composition according to claim 1 comprising, in a cosmetic vehicle appropriate for hair, at least one emulsion comprising at least
one acrylic polymer comprising: (a) units derived from n-butyl acrylate monomers and
(b) units derived from at least one monomer chosen from 2-hydroxy ethyl acrylate,
2-hydroxy ethyl methacrylate, and hydroxy propyl acrylate monomers, wherein said
composition provides a reshapable effect.
3. The composition according to claim 1 or 2, further comprising at least
one additional polymer.
4. The composition according to claim 3, wherein said at least one
additional polymer is chosen from anionic, cationic, amphoteric, nonionic, and zwitterionic polymers.
5. The composition according to claim 1 or 2, wherein the (a) units are
present in an amount about 50 to about 90% by weight of the polymer and the (b)
units are present in an amount about 10 to about 50% by weight of the polymer.
6. The composition according to claim 1 or 2, wherein said at least one
acrylic polymer further comprises units derived from at least one co-polymerizable
monomer.
7. The composition according to claim 6, wherein said at least one
co-polymerizable monomer is chosen from (i) alkylacrylate monomers, (ii) polar
monomers, and (iii) ethylenically unsaturated free radically polymerizable monomers.
8. The composition according to claim 6, wherein units derived from at
least one co-polymerizable monomer are present in an amount up to about 50% by
weight of the polymer.
9. The composition according to claim 2, wherein said at least one
emulsion further comprises at least one polyfunctional cross-linking agent.
10. The composition according to claim 2, wherein said at least one acrylic
emulsion has a pH less than or equal to 7.
11. The composition according to claim 2, wherein said at least one acrylic
emulsion has a Tg ranging from about -100 to about 15°C.
12. The composition according to claim 1 or 2, further comprising at least
one other constituent, which is conventional in cosmetics, chosen from preservatives,
perfumes, UV filters, active haircare agents, plasticizers, anionic, cationic,
amphoteric, nonionic, and zwitterionic surfactants, hair conditioning agents such as
silicone fluids, fatty esters, fatty alcohol, long chain hydrocarbons, emollients,
lubricants, and penetrants such as lanolin compounds, protein hydrolysates, and other protein derivatives, dyes, tints, bleaches, reducing agents, pH adjusting agents,
sunscreens, preservatives, thickening agents, and perfumes.
13. An aerosol device comprising a vessel, which comprises (i) an aerosol
composition, which comprises a liquid phase comprising at least one composition
according to anyone of the preceding claims, wherein said composition provides a
reshapable effect;
and at least one propellant, and (ii) a dispensor.
14. A method of cosmetically treating hair, comprising the application of a
composition according to anyone of the preceding claims 1 to 12, wherein said
composition provides a reshapable effect;
to the hair before, during, or after the shaping of the hairstyle.
PCT/IB2001/001568 2000-07-27 2001-07-12 Reshapable hair styling composition comprising acrylic emulsions WO2002009656A2 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
AU8001701A AU8001701A (en) 2000-07-27 2001-07-12 Reshapable hair styling composition comprising acrylic emulsions
EP01958297A EP1353627A2 (en) 2000-07-27 2001-07-12 Reshapable hair styling composition comprising acrylic emulsions
CA002416907A CA2416907A1 (en) 2000-07-27 2001-07-12 Reshapable hair styling composition comprising acrylic emulsions
MXPA03000701A MXPA03000701A (en) 2000-07-27 2001-07-12 Reshapable hair styling composition comprising acrylic emulsions.
AU2001280017A AU2001280017B2 (en) 2000-07-27 2001-07-12 Reshapable hair styling composition comprising acrylic emulsions
BR0113020-0A BR0113020A (en) 2000-07-27 2001-07-12 Removable hair styling composition, aerosol device and method for cosmetic hair treatment
JP2002515211A JP2004521860A (en) 2000-07-27 2001-07-12 Hair reforming hair styling composition containing acrylic emulsion
KR10-2003-7001084A KR20030017652A (en) 2000-07-27 2001-07-12 Reshapable hair styling composition comprising acrylic emulsions

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Application Number Priority Date Filing Date Title
US62705500A 2000-07-27 2000-07-27
US09/627,055 2000-07-27

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EP1321130A2 (en) * 2001-12-20 2003-06-25 L'oreal Reshapable hair styling composition comprising (meth)acrylic copolymers
EP1336401A1 (en) * 2001-12-20 2003-08-20 L'oreal Reshapable hair styling non rinsed compositions comprising (meth)acrylic copolymers
US6645478B2 (en) 2001-06-22 2003-11-11 L'oreal S.A. Reshapable hair styling composition comprising (meth)acrylic copolymers of four or more monomers
US6667378B2 (en) 2001-06-22 2003-12-23 L'oreal, S.A. Reshapable hair styling composition comprising heterogeneous (meth)acrylic copolymer particles
US6689346B1 (en) 2000-10-25 2004-02-10 L'oreal Reshapable hair styling composition comprising acrylic copolymers
AU2001280017B2 (en) * 2000-07-27 2004-07-08 L'oreal Reshapable hair styling composition comprising acrylic emulsions
EP1495749A2 (en) 2003-07-07 2005-01-12 Beiersdorf AG Fixing cosmetic composition allowing multiple reshaping of the hair
WO2007003784A1 (en) 2005-07-01 2007-01-11 L'oreal Neutralised cationic polymer, composition containing said polymer and a cosmetic treatment method
FR2924341A1 (en) * 2007-11-30 2009-06-05 Oreal Reshapable hair styling composition comprises (meth)acrylic copolymers comprising butyl (meth)acrylate monomer units, hydroxyalkyl (meth)acrylate monomer units and other copolymerizable monomer units, and fillers
FR2924336A1 (en) * 2007-11-30 2009-06-05 Oreal HAIR COMPOSITION COMPRISING (METH) ACRYLIC COPOLYMERS AND AT LEAST ONE OIL.
US8691199B2 (en) 2004-07-13 2014-04-08 L'oreal Ethylenic copolymers, compositions and methods of the same

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WO2002009656A2 (en) * 2000-07-27 2002-02-07 L'oreal Reshapable hair styling composition comprising acrylic emulsions

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US5919439A (en) * 1993-08-23 1999-07-06 The Procter & Gamble Company Silicone grafted thermoplastic elastomeric copolymers and hair and skin care compositions containing the same
EP0985405A2 (en) * 1998-09-11 2000-03-15 Rohm And Haas Company Stiff-feel hair styling compositions

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2001280017B2 (en) * 2000-07-27 2004-07-08 L'oreal Reshapable hair styling composition comprising acrylic emulsions
US6689346B1 (en) 2000-10-25 2004-02-10 L'oreal Reshapable hair styling composition comprising acrylic copolymers
US6645478B2 (en) 2001-06-22 2003-11-11 L'oreal S.A. Reshapable hair styling composition comprising (meth)acrylic copolymers of four or more monomers
US6667378B2 (en) 2001-06-22 2003-12-23 L'oreal, S.A. Reshapable hair styling composition comprising heterogeneous (meth)acrylic copolymer particles
US7048916B2 (en) 2001-06-22 2006-05-23 L'oreal S.A. Reshapable hair styling composition comprising heterogeneous (meth)acrylic copolymer particles
US7122175B2 (en) 2001-06-22 2006-10-17 L'oreal S.A. Reshapable hair styling composition comprising (meth)acrylic copolymers of four or more monomers
EP1321130A2 (en) * 2001-12-20 2003-06-25 L'oreal Reshapable hair styling composition comprising (meth)acrylic copolymers
EP1336401A1 (en) * 2001-12-20 2003-08-20 L'oreal Reshapable hair styling non rinsed compositions comprising (meth)acrylic copolymers
EP1321130A3 (en) * 2001-12-20 2003-07-02 L'oreal Reshapable hair styling composition comprising (meth)acrylic copolymers
EP1495749A2 (en) 2003-07-07 2005-01-12 Beiersdorf AG Fixing cosmetic composition allowing multiple reshaping of the hair
US8691199B2 (en) 2004-07-13 2014-04-08 L'oreal Ethylenic copolymers, compositions and methods of the same
US8722028B2 (en) 2004-07-13 2014-05-13 L'oreal Ethylenic copolymers, compositions and methods of the same
WO2007003784A1 (en) 2005-07-01 2007-01-11 L'oreal Neutralised cationic polymer, composition containing said polymer and a cosmetic treatment method
FR2924341A1 (en) * 2007-11-30 2009-06-05 Oreal Reshapable hair styling composition comprises (meth)acrylic copolymers comprising butyl (meth)acrylate monomer units, hydroxyalkyl (meth)acrylate monomer units and other copolymerizable monomer units, and fillers
FR2924336A1 (en) * 2007-11-30 2009-06-05 Oreal HAIR COMPOSITION COMPRISING (METH) ACRYLIC COPOLYMERS AND AT LEAST ONE OIL.

Also Published As

Publication number Publication date
EP1353627A2 (en) 2003-10-22
AU2001280017B2 (en) 2004-07-08
PL365575A1 (en) 2005-01-10
WO2002009656A3 (en) 2003-08-28
CA2416907A1 (en) 2002-02-07
WO2002009656A8 (en) 2002-05-30

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