WO2011057882A1 - Acrylic polymer - Google Patents
Acrylic polymer Download PDFInfo
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- WO2011057882A1 WO2011057882A1 PCT/EP2010/065744 EP2010065744W WO2011057882A1 WO 2011057882 A1 WO2011057882 A1 WO 2011057882A1 EP 2010065744 W EP2010065744 W EP 2010065744W WO 2011057882 A1 WO2011057882 A1 WO 2011057882A1
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- hair
- acrylic polymer
- polymer beads
- preparation
- beads
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/046—Aerosols; Foams
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions 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
- A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1803—C3-(meth)acrylate, e.g. (iso)propyl (meth)acrylate
Definitions
- the present invention relates to acrylic polymer beads having very low residual monomer content as well as to their use in hair care preparations in particular as styling agent.
- Acrylate Copolymers such as e.g. Luvimer ® (BASF), Balance ® (Akzo Nobel) or Acudyne ® (Rohm und Haas) are widely used in the Hair Care Industry as setting polymers for Aerosol and non-Aerosol Sprays.
- These polymers are prepared with emulsion polymerization technology which allows a good control over critical polymer parameters like molecular weight, particle size in the nm range (typically 50-300 nm) and residual monomer content. However, no micron sized particles are obtained during emulsion polymerisation.
- acrylic polymer beads are widely applied in the field of colorants, photographic applications, inks, or plastics the application in personal care products such as in particular hair care preparations is still limited due to toxicological issues resulting from the residual monomer content. Therefore, there is an ongoing need for a process for the preparation of acrylic polymer beads for cosmetic applications, in particular for hair care preparations with a very low residual monomer content such as below 250 ppm and in particular below 100 ppm. Furthermore, such acrylic polymer beads need to have a sufficiently high T g , of at least 45°C and in particular between 80-120°C in order to prevent the beads from sticking together during processing and storage.
- the beads In order to be industrially viable the beads should be obtainable by an efficient and economical attractive process without the necessity of applying elaborate purification processes in order to achieve the low monomer content. Furthermore, the beads should be preservative-free, non dusty, free-flowing, and exhibit easy solubilisation and no lumping even without the addition of separating agents.
- the acrylic polymer beads should be compatible with the customary cosmetic ingredients and readily formulated as pump or aerosol spray in solvents or solvent mixtures.
- the acrylic polymer beads applied to the hair should dry rapidly and impart good setting and prolonged hold to the hair (such as e.g. good curl retention) even at increased atmospheric humidity and have a good ability to be washed out.
- the treated hair should have good haptic properties such as, for example, a good feel to the touch and being non-sticky.
- the invention relates in a first embodiment to a process for the preparation of acrylic polymers beads comprising subjecting a monomer composition consisting of a mixture of methacrylic acid (MAA), n-butyl methacrylate (BMA), ethylacrylate (EA) and ethyl methacrylate (EMA) to suspension polymerization.
- MAA methacrylic acid
- BMA n-butyl methacrylate
- EA ethylacrylate
- EMA ethyl methacrylate
- polymer 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 ⁇ , preferably at least 150 ⁇ .
- the beads have a diameter between 50 and 1500 ⁇ such as in particular between 150 to 400 ⁇ .
- the monomer composition consists of a mixture 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 such as in particular of 15-25 wt.-% of methacrylic acid, 38-60 wt.-% of n-butyl methacrylate, 8-15 wt.-% of ethyl acrylate and 15-25 wt.-% of ethyl methacrylate such as even more in particular of 17-22 wt.-% of methacrylic acid, 44-56 wt.-% of n-butyl methacrylate, 9-15 wt.-% of ethyl acrylate and 15-25 wt.-% of ethyl methacrylate.
- Particular low monomer contents are obtained using monomer mixtures consisting of 15- 22 wt.-% of methacrylic acid, 44-56 wt.-% of n-butyl methacrylate, 9-15 wt.-% of ethyl acrylate and 18-22 wt.-% of ethyl methacrylate.
- the term 'consisting of as used according to the present invention means that the total amount of monomer ideally sum up to 100 wt.-%. It is however not excluded that small amount 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.
- the ratio of ethyl methacrylate (EMA) to ethyl acrylate (EA) (w/w) in the monomer compositions according to the invention and outlined above 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.
- the amount of methacrylic acid used in the monomer compositions according to the invention is less than 25 wt.-%, such as about 15 to 22 wt.-%, in particular about 17 to 22 wt.-% and even more in particular about 20 wt.-% based on the total amount of the monomers in order to further reduce the residual monomer content.
- Particular preferred are monomer compositions wherein the MAA content is selected in the range of about 15-22 wt.-%, in particular 17 to 22 wt.-% and the coefficient of EMA/ EA is selected in the range of about 2.0 to 1.3 as such polymer exhibit a good solubility in water or alcohols as well as mixtures thereof while having an extremely low residual monomer content.
- the invention relates to acrylic polymer beads obtainable by the process according to the invention.
- the to acrylic polymer beads according to the invention have a residual monomer content of less than 250 ppm such as in particular of less than 100 ppm.
- the acrylic polymer beads according to the invention are prepared by suspension polymerization (also known as granular, bead, or pearl polymerization due to the shape of the resultant polymer particles) according to known methods in the art as illustrated in the examples.
- Initiators for polymerizing the monomers to provide the acrylic polymer beads of the invention are those which are normally suitable for free-radical polymerization of acrylate monomers and which are oil-soluble and have low solubility in water such as e.g. organic peroxides, organic peroxyesters and organic azo initators.
- the initiator is generally used in an amount of about 0.01 to 1 wt.-% based on the total monomer content.
- Useful chain transfer agents include mercaptans, carbon tetrabromide, and mixtures thereof. Dodecylmercaptane is preferred.
- the chain transfer agent generally is used in an amount of about 0.01 to 1.0 wt.-%, preferably in an amount of 0.01 to 0.5 wt.-% based on the total monomer content.
- a water soluble inhibitor can be added to inhibit polymerization in the water phase in order to prevent the formation of too much polymer by emulsion and/or solution polymerization in the water phase, which can result in bead agglomeration or emulsion type polymerization.
- Suitable inhibitors include those selected from thiosulfates, thiocyanates, water soluble hydroquinones and nitrites.
- the water soluble inhibitor can generally be added in an amount of from about 0.01 to about 1 parts by weight based on 100 parts total monomer content.
- a water soluble or water dispersible polymeric stabilizer is needed to stabilize the suspension and in order to obtain stable beads.
- the stabilizer is preferably a synthetic water soluble or water dispersible polymer such as e.g. polyvinylalcohol, gelatine, starch, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, poly(meth)acrylic acid and their sodium salts, and the like.
- the stabilizer is preferably used in an amount of about 0.001 to 10 wt.-%, more preferable in an amount of about 0.01 to 1 wt-% based on the total monomer content.
- additives can optionally be used such as e.g. mono-, di- and trivalent metal salts, borax, urea, glyoxal and urea formaldehyde resin.
- Biocides both bactericides and fungicides
- the monomers, free-radical initiator, and any optional materials can be mixed together in the prescribed ratio to form a premix.
- the stabilizer can be combined with water and then with the premix to form an oil in water suspension.
- the resulting suspension typically comprises from about 10 to about 50 weight percent monomer premix and from about 90 to about 50 weight percent water phase.
- Bead-type suspension polymerization in accordance with the present invention is typically a thermally initiated polymerization and is preferably carried out with agitation for about 2 to about 16 hours at a temperature between about 40° C and 90° C.
- the beads are preferably subjected to an extended drying, preferably at about 40-100°C and more preferably at about 80-100°C in order to further reduce the residual monomer content to an amount of below 250 ppm such as in particular below 100 ppm.
- the drying can be performed by commonly known means to a person skilled in the art such as e.g. using a fluidized bed dryer or a conventional oven.
- the drying time can be easily adjusted by a person skilled in the art and is usually carried out over a period of 3 to 40h such as about 8 to 20h and in particular about 8 to 10h.
- the invention relates to the process according to the invention said process further comprising the isolation of the beads followed by an extended drying step at 40 to 100°C such as in particular at 80-100°C.
- the drying step is carried out over a period of 3 to 40h, more in particular of 8 to 20h such as e.g. of 8 to 10h.
- the acrylic polymer beads made according to the present invention typically have a molecular weight of about 100kDalton, a glass transition temperature of about 80-120 °C and a particle size of about 50 to 500 ⁇ such as e.g. 200 to 500 ⁇ (X-50). Due to high Tg of the acrylic polymer beads no anti-caking agent is needed to prevent the beads from sticking during storage even at elevated temperature. Furthermore, the residual monomer content prior to drying is low enough to come below the limit required for personal care applications after an extended drying step at about 80-100°C such as e.g. at 90°C, i.e. below 250 ppm and in particular even below 100ppm.
- the acrylic polymer beads according to the invention typically have an acid value of about 125-145 mg KOH/g.
- the glass transition temperature T g is the limit at which, according to G. Kanig (Kolloid- Zeitschrift & Zeitschrift fur Polymere, Vol. 190, page 1 , equation 1 ) the polymer changes from a glassy, brittle state to a rubbery state.
- Tg values of polymers may e.g. be determined experimentally using techniques such as differential scanning calorimetry DSC.
- Acrylic polymer beads according to the present invention are e.g. available at DSM Nutritional products Ltd. under the Tradename TILAMAR ® Fix A1000 (INCI: 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, CAS Number: 1070166- 98-1 ).
- the acrylic polymer beads according to the invention After neutralization e.g. with 2-amino-2-methylpropanol (AMP), the acrylic polymer beads according to the invention are perfectly soluble in water, in ethanol and in mixtures of both making them suitable for a wide range of applications.
- the acrylic polymer beads according to the invention exhibit a good compatibility with cosmetic ingredients making them especially suitable for cosmetic applications such as in particular hair care applications.
- the invention in a further embodiment relates to cosmetic compositions comprising acrylic polymer beads according to the invention and a cosmetically acceptable carrier.
- cosmetic composition refers in particular to cosmetic compositions that can be topically applied to mammalian keratinous tissue such as e.g. human skin or scalp.
- cosmetic composition refers to cosmetic compositions as defined under the heading "Kosmetika” in Rompp Lexikon Chemie, 10th edition 1997, Georg Thieme Verlag Stuttgart, New York as well as to cosmetic compositions as disclosed in A. Domsch, "Cosmetic Compositions", Verlag fur chemische Industrie (ed. H. Ziolkowsky), 4 th edition, 1992.
- cosmetically acceptable carrier refers to all carriers and/or excipients and/ or diluents conventionally used in cosmetic compositions.
- the amount of the acrylic polymer beads according to the present invention in the cosmetic compositions, in particular in the hair care preparations according to the invention may easily be chosen by a person skilled in the art in an amount suitable for the desired application.
- a concentration of 0.01-20 wt.-%, most preferred of 0.05-10 wt.-% such as in particular about 5 wt.-% based on the total weight of the cosmetic composition is used.
- the acrylic polymer beads according to the invention also show excellent hair styling properties such as e.g. excellent high humidity curl retention.
- the acrylic polymer beads according to the invention are in particular suitable for hair styling applications.
- the present invention relates to hair care preparations such as in particular hair styling preparations (e.g. aqueous hair styling preparations) comprising the acrylic polymer beads according to the invention.
- hair styling preparations e.g. aqueous hair styling preparations
- the hair care preparations according to the present invention may be in the form of a (aerosol) spray, (aerosol) foam, gel, gel spray, cream, lotion, liquid or a wax.
- Hair sprays comprise as well aerosol sprays as pump sprays without propellant.
- Hair foams comprise as well aerosol foams as pump foams without propellant.
- Hair sprays and hair foams comprise mainly or exclusively water soluble or water dispersible components. If the components used in hair sprays or hair foams according to the invention are water dispersible, then they may be in the form of micro dispersions with particle sizes of usually 1 -350 nm, preferably 1-250 nm.
- the solid content of such preparations is typically in the range of 0.5 to 20 wt.
- the hair styling preparations according to the invention are in the form of styling creams, styling gels, liquid hair-setting preparations, hair foams or hairsprays.
- the acrylic polymer beads according to the present invention further exhibit an excellent solubility in ethanol or water as well as in mixtures thereof which is a prerequisite for the formulation of hair styling preparations such as hairsprays. Furthermore, the compatibility of ethanol solutions comprising the acrylic polymer beads according to the invention with commercial propellants (propane/butane, DME) is comparable to that of Luvimer ® acrylate emulsion polymers and thus the beads are in particular suitable for use in aerosol hair sprays.
- the hair care preparations such as in particular the hair styling preparations may also contain other hair fixative resins, neutralizers, surfactants, solvents, propellants, other preservatives, thickeners, UV-filters and other additives usually employed in such preparations.
- the amount of the acrylic polymer beads according to the present invention in hair styling preparations is preferably selected within a concentration range of 0.01 -20 wt.-%, more preferably within a concentration range of 0.1-10 wt.-% such as in particular within a concentration range of 1 to 10 wt.-% such as about 5 wt.-% based on the total weight of the hair styling preparation.
- hair fixative resins may optionally be added to the hair care preparations 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 hair styling preparation.
- the other hair fixative resins may be present in the hair styling preparation at a concentration of from 0.5 to 6.0 weight percent, preferably from 1.0 to 3.0 weight percent, based on the total weight of the hair styling preparation.
- the other hair fixative resins which are suitable in the hair care preparation include for example butyl acrylate/ethyl acrylate/methacrylic acid copolymers; polyvinyl pyrrolidone, vinyl pyrrolidone/vinyl acetate copolymers; octylacrylamide /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
- Neutralizers are preferably present in the hair care preparation when the hair fixative resins contain acidic groups, such as carboxylic acid groups, to promote solubility of the resin in the aqueous hair styling composition.
- the acrylic hair fixative resin is preferably fully neutralized.
- Bases which will neutralize the hair fixative resins include for example 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.
- 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.
- the amount of neutralizer added to the hair care preparation is preferably that amount to provide solubility of the hair fixative resin in the hair styling composition.
- a hair styling preparation containing 35 weight percent or less VOC from 40 to 100 mole percent of the acid groups on the hair fixative resin are neutralized.
- a VOC hair styling composition containing greater than 35 weight percent VOC preferably greater than 50 mole percent of the acid groups on the hair fixative resin are neutralized.
- One or more surfactants may be added to the hair care preparation.
- surfactants are present in the hair care preparation, 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 care preparation include for example anionic, cationic, non-ionic, or amphoteric surfactants.
- 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.
- 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
- siloxane derivatives may be present in the hair care 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 care preparation of the present invention.
- the solvents may or may not be VOC.
- the amount of solvent added to the hair care preparation 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 care preparation.
- Suitable solvents include for example Ci to Ci 2 straight or branched chain alcohols such as methanol, ethanol, isopropanol, or propanol or combinations thereof.
- propellants are used.
- the propellants may or may not be VOC.
- the propellants are used at a total concentration of from 10 to 70 wt.-%; and more preferably from 30 to 60 wt.-% based on the total weight of the hair care preparation.
- Propellants include for example n-butane, isobutane, dimethyl ether; dimethoxymethane, difluoroethane, chlorodifluoroethane, chlorodifluoromethane, other chlorofluorocarbons or combinations thereof.
- Preferred propellants are dimethyl ether, 1 , 1-difluoroethane, n-butane, isobutane or combinations thereof. These propellants are commercially available.
- preservatives which may be used in the hair care preparation 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 care preparation.
- One or more thickeners may be desirable in a hair care preparation which is applied to the hair in form of a mousse or styling gel.
- Suitable thickeners include for example polycarboxylic acid thickeners such as acrylates/steareth-20 methacrylate copolymer, carbomers, acrylates copolymer, or acrylates C10-30 acrylate crosspolymer; polyethoxylated urethane thickeners, or polyamide thickeners.
- Other suitable thickeners are based on natural polymers such as polysaccharides or polyamides and can be chemically modified.
- Such thickeners include for instance hydroxyethyl celluloses, hydroxypropyl celluloses, xanthan gum, gelatine, agar- agar, carragenens, alginates or mixtures thereof.
- the thickeners are preferably used in an amount of about 0.001 to 5.0 wt.-% based on the total weight of the hair care preparation.
- One or more light screening agents may be desirable in a hair care preparation 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
- 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.-% with respect to the total weight of the composition.
- additives such as those commonly used by those skilled in the art may be added to the hair care preparation according to the invention.
- the other additives used in the hair care preparations will depend upon the type of hair care preparation desired.
- Other additives include for example fragrances; moisturizers such as sorbitol, propane diol, butylene glycol, glycerin, 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 care preparation.
- the polymerization reactions were conducted in a glass 3-necked reaction flask using stainless steel baffle and stirrer equipped with nitrogen inlet.
- Hydroxylethylcellulose stabilizer (2.4g) was weighed into the reaction flask containing distilled water (1 , 105g). 480g of a monomer mixture consisting of n-butylmethacrylate (BMA), ethylmethacrylate (EMA), ethylacrylate (EA) and methacrylic acid (MMA) in the ratios as indicated below was weighed into a separate stirred feedtank containing di-lauroylperoxide (3.6g) as chain starter and dodecylmercaptane chain transfer agent (1.9g). After homogenizing the feedtank, the mixture was transferred to the reaction flask and under constant nitrogen purge slowly heated to 75°C.
- BMA n-butylmethacrylate
- EMA ethylmethacrylate
- EA ethylacrylate
- MMA methacrylic acid
- reaction flask content was subsequently heated to 85°C and left at this temperature for another 2hrs. Accordingly the reactor contents were cooled, the final suspension polymer filtered, washed and allowed to dry at 40-50°C for 14-16hrs yielding the respective polymer beads in 90-95 % yield.
- the obtained acrylic polymer beads were furthermore subjected to an extended drying process at 90°C for another 14-16hrs resulting in residual monomer contents of less than 210ppm or even less than 100ppm.
- the residual monomer content was analysed via Headspace Gas Chromatographie, the molecular weight (MW) was determined by Gel Premeation Chromatographie, the Tg by Differential Scanning Calometrie (DSC) and the particle size (PS) determination is done via a so-called Malvern Hydro 2000 Mastersizer.
- This instrument optically (by laser diffraction) determines a volume distribution of the sample submitted in a water environment.
- the X50 mentioned is the average particle size of the total volume distribution as determined.
- the acrylic polymer beads according to the invention also exhibit a very low total monomer content when compared to the market benchmark for hair styling applications such as e.g. Luvimer ® 100P (acrylate emulsion polymer consisting of methacrylic acid, tert-butyl acrylate and ethyl acrylate) which exhibits a total monomer content of 425 ppm when measured according to the method described above.
- Luvimer ® 100P acrylate emulsion polymer consisting of methacrylic acid, tert-butyl acrylate and ethyl acrylate
- Example 2 Solubility of acrylic polymer beads in ethanol, in water and in mixtures thereof: Mixtures of Ethanol/Water were tested according to the US-VOC-guidelines as "VOC 80" and "VOC 55" formulation using the beads of table 2.
- the acrylic polymer beads can be easily incorporated either into the ethanol or into the water phase of the VOC formulation:
- the solubility of 5 wt.-% acrylic polymer beads in standard hair care preparations was determined by preparation of the formulations as indicated in table 3 according to standard procedures and determination of the turbidity with a HACH 2100 N IS Turbidimeter, 115 Vac according ISO 7027 (The threshold for turbidity is at NTU > 5. (NTU ⁇ 5 means visibly clear solution)). Furthermore, the solutions were assessed visually.
- High VOC acrylic polymer beads 5 wt.-%
- VOC 80 acrylic polymer beads 5 wt.-%
- VOC 55 acrylic polymer beads 5 wt.-%
- Switches Hair Tresses (Kerling; Art.Nr.826 500) are cut in switches of 2 cm width. Each switch is washed twice with 0.5 mL of a Cleansing Shampoo (10% Sodium Laureth Sulfate/ 4% Sodium Chloride): 30s foaming, 90s rinsing with warm water. The switches are combed 5 times and dried in a climate room at 20°C and 65% relative humidity for at least 4 hours. The weight of the switches is standardized under these conditions for 2g +/- 0.2g for hair (without rubber coating).
- a Cleansing Shampoo 10% Sodium Laureth Sulfate/ 4% Sodium Chloride
- the switch is dampened with 1 g water, and evenly wetted with 0.3g of polymer solution (5 wt.-% of TILAMAR ® Fix A1000 in EtOH, 100% neutralized with AMP-95): application with syringe from root to tip and comb 5 times. Then, the switch is curled with a spiral curler of 12 mm diameter (Basler Haarkosmetik Art. 12939).
- the curler with the hair is dried for 40 min at 45°C. Then, the curler is left in the climate room at 20°C/65% rel. humidity over night. The curl is removed carefully from the curler, lay at the table and the starting length L 0 is taken. Than, the curl is hung up at the rubber coating in the climate chamber at 20°C/ 90% rel. humidity, and the Length L t is taken after following times: 0 min, 15 min, 30 min, 45 min, 60 min, 90 min, 120 min, 240 min and 360 min. For each sample, three hair switches are prepared. The curl retention values are calculated as follow:
- the Curl Retention of one sample is obtained as the mean of the three calculated curl retention values of the three switches.
- the acrylic polymer beads according to the invention perform better than the market benchmark, i.e. an acrylate emulsion polymer consisting of MAA, tert-butyl acrylate and EA (Luvimer ® P100).
- All tests are carried out in a regular hairdresser studio with common equipment on 10 panellists.
- the models are treated according to common procedures of hair washing, cutting, colouring, bleaching, perming, drying (air or blow-dry) etc.
- Each model is styled according to his/her wishes.
- the Hairspray is finally sprayed from a distance of 20-30cm around the hair (not directly into eyes and face) at an application rate (mid-long hair, -15 cm) of 5s per half- side (increased for longer hair).
- Hair spray 'A' was assessed in a half side test against benchmark hair spray ⁇ '. As can be retrieved from table 6, hairspray 'A' comprising the inventive beads was overall rated significantly better in regard to its performance in view of hold, crosslinking, shine and creation of style.
- Test criteria One or two phases
- the acrylic beads according to the invention such as in particular TI LAMAR ® Fix A1000 (INCI: 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, CAS Number: 1070166-98-1 ) exhibits a unique product form, superior high humidity curl retention, excellent propellant compatibility, easy handling and a natural feel on hair.
- the acrylic beads according to the invention as in particular TILAMAR ® Fix A1000 can be incorporated into a great variety of product forms as illustrated below without being limited thereto:
- This solution is bottled in an appropriate can (aluminium, tinplate), crimped 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% H F 152A for a water-freeVOC.55 Hairspray. 7.7. Pump Shine & Hold Hair Spray with natural feel
- Part B with stirring: Add ethanol part I I into the solution. Add step by step all other ingredients and stir until.
- Part C Add propane/butane
- Neolone 950 Preservative Methylisothiazolinone 0.10
- Part B with stirring: Add ethanol part II into the solution. Add step by step all other ingredients and stir until. 7.1 1 . Chic Shine Hairspray luxurious gloss and addictive shine
- Part B with stirring: Add ethanol part I I into the solution. Add step by step all other ingredients and stir until.
- Part B with stirring: Add ethanol part I I into the solution. Add step by step all other ingredients and stir until.
- Part C Add propane/butane. 7.13. Chic Shine Hairspray luxurious gloss and addictive shine
- Part B with stirring: Add ethanol part I I into the solution. Add step by step all other ingredients and stir until.
- Part C after bottling and crimping, add propane/butane.
- 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.
- the polymers according to the resent invention such as in particular TILAMAR ® Fix A1000 can also be easily combined with other commercially available hair styling polymers in order to further improve the performance.
- Some basic formulation examples are given in the following part without being limited thereto.
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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BR112012011637A BR112012011637B1 (en) | 2009-11-16 | 2010-10-19 | acrylic polymer |
KR1020127015747A KR101726903B1 (en) | 2009-11-16 | 2010-10-19 | Acrylic polymer |
EP10768769.1A EP2501730B1 (en) | 2009-11-16 | 2010-10-19 | Acrylic polymer |
JP2012538266A JP5585856B2 (en) | 2009-11-16 | 2010-10-19 | Acrylic polymer |
CN201080051959.8A CN102666614B (en) | 2009-11-16 | 2010-10-19 | Acrylic polymer |
US13/503,768 US8741274B2 (en) | 2009-11-16 | 2010-10-19 | Acrylic polymer |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP09176064.5 | 2009-11-16 | ||
EP09176064A EP2322570A1 (en) | 2009-11-16 | 2009-11-16 | Acrylic Polymer |
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WO2011057882A1 true WO2011057882A1 (en) | 2011-05-19 |
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Family Applications (1)
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PCT/EP2010/065744 WO2011057882A1 (en) | 2009-11-16 | 2010-10-19 | Acrylic polymer |
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US (1) | US8741274B2 (en) |
EP (2) | EP2322570A1 (en) |
JP (1) | JP5585856B2 (en) |
KR (1) | KR101726903B1 (en) |
CN (1) | CN102666614B (en) |
BR (1) | BR112012011637B1 (en) |
WO (1) | WO2011057882A1 (en) |
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WO2013072118A2 (en) | 2011-11-17 | 2013-05-23 | Henkel Ag & Co. Kgaa | Composition for temporary deformation of keratinic fibres, based on a combination of specific film-forming polymers |
DE102011086529A1 (en) | 2011-11-17 | 2013-05-23 | Henkel Ag & Co. Kgaa | Means for temporary deformation of keratinic fibers based on a combination of specific film-forming polymers |
WO2014095165A2 (en) | 2012-12-20 | 2014-06-26 | Henkel Ag & Co. Kgaa | Foam aerosol for increasing volume |
WO2014108384A1 (en) * | 2013-01-09 | 2014-07-17 | Dsm Ip Assets B.V. | Aerosol hair spray compositions |
US20150190334A1 (en) * | 2012-08-06 | 2015-07-09 | Conopco, Inc., D/B/A Unilever | Shampoo composition |
US20150328126A1 (en) * | 2012-04-02 | 2015-11-19 | Dsm Ip Assets B.V. | Shampoo preparations |
WO2016142093A1 (en) * | 2015-03-09 | 2016-09-15 | Henkel Ag & Co. Kgaa | Product and method for the temporary shaping of keratin-containing fibers |
WO2016142092A1 (en) * | 2015-03-09 | 2016-09-15 | Henkel Ag & Co. Kgaa | Product and method for the temporary shaping of keratin-containing fibers |
US9468224B2 (en) | 2011-08-31 | 2016-10-18 | Avery Dennison Corporation | Removable polymer compositions |
US9783627B2 (en) | 2011-01-14 | 2017-10-10 | Avery Dennison Corporation | Removable composition with polymer microspheres |
WO2020035448A1 (en) | 2018-08-13 | 2020-02-20 | Dsm Ip Assets B.V. | Cosmetic composition comprising a hyperbranched copolymer and a hair styling polymer |
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WO2014044469A1 (en) * | 2012-09-18 | 2014-03-27 | Dsm Ip Assets B.V. | Novel process |
EP2868309B1 (en) * | 2013-10-31 | 2019-03-06 | Kao Corporation | Hair styling composition |
DE102014217207A1 (en) * | 2014-08-28 | 2016-03-03 | Henkel Ag & Co. Kgaa | Using a combination of AquaStyle SH-100 and Acudyne 1000 |
KR101939388B1 (en) | 2016-02-24 | 2019-01-16 | 주식회사 엘지화학 | Preparation method for acrylic acid- based polymer |
JP6723772B2 (en) * | 2016-03-10 | 2020-07-15 | ジャパンコーティングレジン株式会社 | Hairdressing composition |
CN111356501A (en) | 2017-11-20 | 2020-06-30 | 生活实验公司 | Properties to achieve durable cosmetic Performance |
ES2963357T3 (en) | 2019-06-12 | 2024-03-26 | Nouryon Chemicals Int Bv | Process for the production of diacyl peroxides |
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ES2963356T3 (en) * | 2019-06-12 | 2024-03-26 | Nouryon Chemicals Int Bv | Method for isolating carboxylic acid from an aqueous side stream |
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- 2010-10-19 WO PCT/EP2010/065744 patent/WO2011057882A1/en active Application Filing
- 2010-10-19 CN CN201080051959.8A patent/CN102666614B/en active Active
- 2010-10-19 BR BR112012011637A patent/BR112012011637B1/en active IP Right Grant
- 2010-10-19 KR KR1020127015747A patent/KR101726903B1/en active IP Right Grant
- 2010-10-19 JP JP2012538266A patent/JP5585856B2/en not_active Expired - Fee Related
- 2010-10-19 US US13/503,768 patent/US8741274B2/en active Active
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US20180055757A1 (en) * | 2015-03-09 | 2018-03-01 | Henkel Ag & Co. Kgaa | Product and method for the temporary shaping of keratin-containing fibers |
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JP2013510913A (en) | 2013-03-28 |
US8741274B2 (en) | 2014-06-03 |
CN102666614A (en) | 2012-09-12 |
KR20130026526A (en) | 2013-03-13 |
KR101726903B1 (en) | 2017-04-13 |
EP2501730A1 (en) | 2012-09-26 |
EP2322570A1 (en) | 2011-05-18 |
CN102666614B (en) | 2015-04-29 |
JP5585856B2 (en) | 2014-09-10 |
BR112012011637A2 (en) | 2016-06-28 |
EP2501730B1 (en) | 2013-08-28 |
BR112012011637B1 (en) | 2019-12-24 |
US20120207696A1 (en) | 2012-08-16 |
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