US20120213724A1 - Agent for temporarily styling keratin-containing fibres containing a non-ionic starch modified by propylene oxide and a chitosane - Google Patents

Agent for temporarily styling keratin-containing fibres containing a non-ionic starch modified by propylene oxide and a chitosane Download PDF

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US20120213724A1
US20120213724A1 US13/453,393 US201213453393A US2012213724A1 US 20120213724 A1 US20120213724 A1 US 20120213724A1 US 201213453393 A US201213453393 A US 201213453393A US 2012213724 A1 US2012213724 A1 US 2012213724A1
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Prior art keywords
nonionic
starch
propylene oxide
agent according
cosmetic agent
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US13/453,393
Inventor
Burkhard Mueller
Pamela KAFTAN
Rolf Bayersdoerfer
Matthias Schweinsberg
Ralf Roenisch
Mathias Schriefers
Carine Dogan
Thorsten Knappe
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority claimed from DE102009045925A external-priority patent/DE102009045925A1/en
Priority claimed from DE102009045933A external-priority patent/DE102009045933A1/en
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of US20120213724A1 publication Critical patent/US20120213724A1/en
Assigned to HENKEL AG & CO. KGAA reassignment HENKEL AG & CO. KGAA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DOGAN, CARINE, BAYERSDOERFER, ROLF, KAFTAN, PAMELA, KNAPPE, THORSTEN, MUELLER, BURKHARD, ROENISCH, RALF, SCHRIEFERS, MATTHIAS, SCHWEINSBERG, MATTHIAS
Abandoned legal-status Critical Current

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    • 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
    • A61K8/73Polysaccharides
    • A61K8/732Starch; Amylose; Amylopectin; Derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/046Aerosols; Foams
    • 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
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/60Sugars; Derivatives thereof
    • A61K8/608Derivatives containing from 2 to 10 oxyalkylene groups
    • 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
    • A61K8/8147Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
    • 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
    • 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
    • A61K8/8158Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
    • 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
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54Polymers characterized by specific structures/properties
    • A61K2800/542Polymers characterized by specific structures/properties characterized by the charge
    • A61K2800/5422Polymers characterized by specific structures/properties characterized by the charge nonionic
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54Polymers characterized by specific structures/properties
    • A61K2800/542Polymers characterized by specific structures/properties characterized by the charge
    • A61K2800/5424Polymers characterized by specific structures/properties characterized by the charge anionic

Definitions

  • the present invention relates to cosmetic agents for temporary deformation of keratinic fibers containing, in a cosmetic carrier, a combination of at least one chitosan compound and at least one nonionic starch modified with propylene oxide.
  • Styling agents for deformation of keratinic fibers have been known for some time and are used in various embodiments to build up, refresh, and fix in place hairstyles that, for many types of hair, can be obtained only using setting active substances.
  • An important role is played by hair treatment agents used for permanent shaping and those used for temporary shaping of the hair.
  • Temporary shaping operations intended to yield good hold without impairing the healthy appearance of the hair such as its shine can be achieved, for example, using hair sprays, hair waxes, hair gels, blow-dry waves, etc.
  • Corresponding agents for temporary shaping usually contain synthetic polymers as a shaping component. Preparations having a dissolved or dispersed polymer can be applied onto hair using propellant gases or a pump mechanism. Hair gels and hair waxes, however, are not applied directly onto the hair but instead distributed in the hair using a comb or one's hands.
  • Synthetic polymers usually used in agents for temporary shaping are manufactured from corresponding synthetically accessible monomers. These monomers are obtained from fossil substances such as petroleum by conversion to the corresponding polymer modules, in some cases with expenditure of energy.
  • nature-based substitute polymers should impart volume to the fiber collective and retain the elasticity and smoothness of the keratin-containing fibers that are fixed as to shape. Formation on keratin-containing fibers of polymer particles visible to the naked eye should be avoided. In addition, the keratin-containing fibers must not give a dull impression, but should have a natural shine.
  • the present invention therefore provides a cosmetic composition that brings about very strong and durable shape retention, has a high volume effect, provides good fiber care, and does not exhibit the above disadvantages.
  • a further intention is to be able to dispense, predominantly or as entirely as possible, with use of synthetic polymers based on fossil raw materials.
  • a first subject of the invention is therefore a cosmetic agent for temporary deformation of keratinic fibers, particularly human hair, containing, in a cosmetic carrier
  • Keratinic fibers refer to furs, wool, feathers, and particularly human hair.
  • Chitosans represent biopolymers and are hydrocolloids. In chemical terms, they are partially deacetylated chitins of various molecular weights.
  • chitosans proceeds from chitin, preferably crustacean shell residues, which are available in large quantities as cheap raw materials.
  • the chitin is usually first deproteinated by addition of bases, demineralized by adding mineral acids, and lastly deacetylated by adding strong bases.
  • Molecular weights can be distributed over a broad spectrum. It is preferable to use those grades having an average molecular weight (weight average) from 800,000 to 1,200,000 Dalton, a viscosity per Brookfield (1-wt % in glycolic acid) 5000 mPa ⁇ s or less, a degree of deacetylation from 80 to 88%, and an ash content of 0.3 wt % or less.
  • chitosan derivatives are cationically derivatized chitosans (e.g., quaternization products) or alkoxylated chitosans.
  • Preferred agents include as a chitosan at least one neutralization product of chitosan with at least one organic carboxylic acid, such as in particular formic acid, acetic acid, citric acid, lactic acid, pyrrolidonecarboxylic acid, tartaric acid, glycolic acid, nicotinic acid, hydroxyisobutyric acid, hydroxyisovaleric acid, or mixtures of these acids.
  • the organic carboxylic acid are chosen from lactic acid, formic acid, pyrrolidonecarboxylic acid, nicotinic acid, hydroxyisobutyric acid, hydroxyisovaleric acid, or mixtures of these acids.
  • This neutralization product can be manufactured, for example, in an aqueous medium by adding chitosan and the corresponding organic carboxylic acid.
  • Suitable chitosans are readily commercially available, for example, under the commercial designations Hydagen® CMF (1 wt % active substance in aqueous solution with 0.4 wt % glycolic acid, molecular weight 500,000 to 5,000,000 g/mol, Cognis), Hydagen® HCMF (chitosan (80% deacetylated), molecular weight 50,000 to 1,000,000 g/mol, Cognis), Kytamer® PC (80 wt % active substance as chitosan pyrrolidone carboxylate (INCI name: Chitosan PCA), Amerchol), and Chitolam® NB/101.
  • Hydagen® CMF 1 wt % active substance in aqueous solution with 0.4 wt % glycolic acid, molecular weight 500,000 to 5,000,000 g/mol, Cognis
  • Hydagen® HCMF chitosan (80% deacetylated), molecular weight 50,000 to 1,000,000
  • the chitosans orderivatives thereof are present in agents according to the present invention preferably in an amount from 0.01 wt % to 5 wt %, more preferably 0.05 wt % to 2.0 wt %, very preferably 0.1 wt % to 1 wt %, based on weight of the agent according to the invention.
  • Starch is a reserve carbohydrate that is stored by many plants in the form of large starch grains (granules), usually 1 to 200 ⁇ m in size, in various parts of the plant, for example, in tubers or roots, cereal seeds, fruits and in the pith.
  • a nonionic starch modified with propylene oxide that can be used according to the invention can be obtained from the starch of potatoes, corn, rice, peas, acorns, chestnuts, barley, wheat, bananas, sago, millet, sorghum, oats, barley, rye, beans, yams, arrowroot or cassava.
  • nonionic tapioca starch modified with propylene oxide or nonionic potato starch modified with propylene oxide or with mixtures of these two starches are achieved with nonionic tapioca starch modified with propylene oxide or nonionic potato starch modified with propylene oxide or with mixtures of these two starches.
  • the agent contains at least one nonionic potato starch modified with propylene oxide.
  • Starch belongs to the homoglycan family and is a polycondensation product of D-glucose. Starch is made up of three structurally different polymers of d-glucopyranose, namely amylose, amylopectin, and an intermediate fraction. Higher plants contain 0 to 45 wt % amylose, based on dry substance.
  • the intermediate fraction also referred to as “anomalous amylopectin,” is structurally intermediate between amylose and amylopectin.
  • the quantitative indications defined in this Application for amylopectin include the intermediate fraction.
  • nonionic starch modified with propylene oxide has an amylose content of 25 wt % or less, particularly 20 wt % or less, based on weight of the modified starch. It has become apparent that a starch having 17 to 22 wt % amylose and 78 to 83 wt % amylopectin is particularly suitable for achieving the effect according to the present invention.
  • Amylose is made up of predominantly linear ⁇ -1,4-glycosidically linked d-glucose, M r 50,000 to 150,000. The resulting chains form double helices in the starch.
  • Amylopectin also contains, in addition to the ⁇ -1,4 links described for amylose, ⁇ -1,6 bonds (in an amount from 4 to 6%) as branching points.
  • the average spacing between the branching points is equal to approximately 12 to 17 glucose units.
  • the molar mass of 10 7 to 7* 10 5 corresponds to approx. 10 5 glucose units, making amylopectin one of the largest biopolymers.
  • the branching points are distributed over the molecule in such a way that a bundle structure, with relatively short side chains, develops. Each double helix is formed by two of these side chains. As a result of the many branching points, amylopectin is relatively easily soluble in water.
  • Nonionic starch modified with propylene oxide is a reaction product of a starch with propylene oxide.
  • a reaction product of this kind includes at least one structural unit of formula (PS)
  • R, R′, or R′′ is a group of the formula
  • Nonionic starches modified with propylene oxide are provided, for example, by reacting a natural starch with propylene oxide. Before modification with propylene oxide, the starch can have been exposed to a variety of physical or chemical processes such as heat treatment, shear, a thermal, acid-hydrolytic, oxidizing, or enzymatic cleavage, etc.
  • the nonionic starch modified with propylene oxide is not present in the agent according to the present invention as individual starch grains (granules). Accordingly, the starch grains are disintegrated, for example, by heat or shear and the corresponding polysaccharide molecules are released from the composite material. The released polysaccharide molecules can be modified with propylene oxide after or before release.
  • the nonionic starch modified with propylene oxide is gelatinized.
  • a tangential swelling of the bodies is then observed at a critical temperature or pressure, with loss of birefringence, a change in X-ray structure, and an abrupt rise in the viscosity of the solution. This phenomenon is called “gelatinization.”
  • Nonionic starches according to the present invention modified with propylene oxide are present in the agent in a molecular weight distribution.
  • Preferred nonionic starches modified with propylene oxide have an average molecular weight from 50 to 2500 kDa (weight average).
  • the molecular weight distribution is determined experimentally by gel filtration chromatography against dextran.
  • the weight average is an average molecular weight that takes into account the total weight of the molecules of various molecular weights, and not simply the number of molecules.
  • weight break For statistical calculation of the weight average, firstly the “weight break” is defined:
  • M w [ ⁇ ( N i M 2 i )/[ ⁇ ( N i M i )].
  • Particularly preferred agents contain nonionic starches modified with propylene oxide having an average molecular weight (weight average) from 100 to 2000 kDa, particularly 500 to 1800 kDa, very preferably from 700 to 1000 kDa.
  • the starch is subjected to a mechanical and/or chemical treatment before or after modification with propylene oxide.
  • the aforesaid starch can be crosslinked.
  • Crosslinking of the nonionic starch modified by means of propylene oxide exists when the linear or branched polysaccharide macromolecules of the starch are linked covalently by means of a crosslinking agent, forming a three-dimensional, insoluble, and still swellable polymeric network.
  • Natural starch is generally considered uncrosslinked, and, if crosslinking were desirable, requires artificial crosslinking by means of synthesis chemistry. Artificial crosslinking of this kind can be carried out using crosslinking agents. (Nonionic) starches (modified with propylene oxide) that do not exhibit such crosslinking are uncrosslinked.
  • Crosslinking occurs, for example, using the crosslinking agent epichlorohydrin.
  • epichlorohydrin a mixture (42-wt % in water) of starch modified with propylene oxide is produced, into which mixture the desired amount of epichlorohydrin is stirred at room temperature.
  • the target viscosity is reached after a stirring time of 1 to 5 hours with viscosity monitoring, the crosslinked starch is isolated using ordinary methods.
  • agents according to the present invention contain at least one uncrosslinked nonionic starch modified with propylene oxide as a modified nonionic starch.
  • the starches are preferably exposed to mechanical cleavage, enzymatic cleavage (particularly using ⁇ -amylase, ⁇ -amylase, glucoamylase, or debranching enzymes), acid-hydrolytic cleavage (particularly using hydrochloric acid, sulfuric acid, or phosphoric acid), thermal cleavage, or reaction with oxidizing agents (such as periodate, hypochlorite, chromic acid, permanganate, nitrogen dioxide, hydrogen peroxide, or organic percarboxylic acid, preferably with hydrogen peroxide).
  • oxidizing agents such as periodate, hypochlorite, chromic acid, permanganate, nitrogen dioxide, hydrogen peroxide, or organic percarboxylic acid, preferably with hydrogen peroxide.
  • Kneaders, extruders, stator/rotor machines, and/or agitators are suitable for mechanical cleavage of the starch.
  • Oxidative cleavage using hydrogen peroxide is preferred.
  • nonionic starch modified with propylene oxide is added to water, heated to 50 to 70° C., hydrogen peroxide is added, and stirring occurs at 70 to 85° C. for 2 to 5 hours.
  • Propylene oxide content of the starch affects the fine-tuning of the hairstyle hold and hairstyle flexibility, as well as stability of the cosmetic agents.
  • the parameters can be further optimized if the nonionic starch modified with propylene oxide has, based on weight of the modified starch, a propylene oxide content from 1 to 20 wt %, more preferably from 4 to 12 wt %, very preferably from 9.5 to 10.5 wt % or from 4.0 to 6.0 wt %.
  • Propylene oxide content can be determined, for example, by carrying out a Hodges cleavage using the method according to DIN EN 13268.
  • Cosmetic agents containing nonionic starches modified with propylene oxide having, in a 43-wt % aqueous solution, a preferred viscosity from 150 to 1,500,000 mP ⁇ s (Brookfield viscosimeter, spindle 7 at 20° C. and 20 rpm) are outstandingly suitable for the invention.
  • Particularly suitable starches modified with propylene oxide have viscosities from 10,000 to 200,000 mPa ⁇ s, more preferably from 25,000 to 180,000 mPa ⁇ s (measured under the conditions recited above).
  • the cosmetic agent contains the nonionic starch modified with propylene oxide in an amount from 0.1 wt % to 10 wt %, more preferably from 0.2 wt % to 5.0 wt %, very preferably from 1.0 to 3.0 wt %, based on weight of the agent.
  • Agents according to the present invention contain their active substances in a cosmetic carrier, preferably in a water-containing cosmetic carrier, an alcoholic cosmetic carrier, or an aqueous alcoholic cosmetic carrier.
  • a cosmetic carrier preferably in a water-containing cosmetic carrier, an alcoholic cosmetic carrier, or an aqueous alcoholic cosmetic carrier.
  • such carriers include lotions, water-in-oil emulsions, oil-in-water emulsions, creams, gels, foams, pomades, waxes, or other preparations that are suitable for use on the hair.
  • the carrier is a water-containing cosmetic carrier or an aqueous alcoholic cosmetic carrier.
  • the cosmetic carrier of the agent according to the present invention contains at least 50 wt % water, based on the weight of the entire agent.
  • “Aqueous alcoholic” carriers for purposes of the present invention are aqueous compositions containing 3 to 70 wt % of a C 1 to C 4 alcohol, particularly ethanol or isopropanol.
  • Agents according to the present invention can additionally contain further organic solvents such as methoxybutanol, benzyl alcohol, ethyl diglycol, 1,2-propylene glycol, or 1,3-propylene glycol. All water-soluble organic solvents are preferred in this context.
  • the agent according to the present invention additionally contains at least one film-forming and/or setting polymer.
  • Additional film-forming and/or setting polymers of this embodiment are different from the chitosan(s) (derivatives) and the nonionic starch modified with propylene oxide.
  • Film-forming and/or setting polymers can be nonionically, anionically, amphoterically, or cationically charged, preferably nonionically or cationically charged.
  • Polymers are compounds constructed from a plurality of molecules wherein one type or several types of atoms or atom groupings (“constituent units,” “basic modules,” or “repeating units”) are repeatedly serially arranged, and that have a molecular weight of at least 10,000 g/mol.
  • the polymers are obtained by polyreaction, which can occur artificially (i.e., synthetically) or naturally.
  • Film-forming polymers are those polymers that, upon drying, leave behind a continuous film on the skin, hair, or nails. Film-formers of this kind can be used in a very wide variety of cosmetic products such as face masks, make-up, hair setting agents, hair sprays, hair gels, hair waxes, hair therapies, shampoos, or nail polishes. Those polymers having sufficient solubility in water, alcohol or in water/alcohol mixtures are particularly preferred. It is possible in this way to produce corresponding solutions that can easily be utilized or further processed.
  • “Film-forming polymers” are also those polymers that, when applied in a 0.01- to 20-wt % aqueous, alcoholic, or aqueous alcoholic solution, are capable of depositing a transparent polymer film on the hair.
  • Setting polymers contribute to hold and/or buildup of hair volume and hair fullness of the overall hairstyle. These polymers are at the same time also film-forming polymers and are therefore generally typical substances for shape-imparting hair-treatment agents such as hair setting agents, hair foams, hair waxes, and hair sprays. It is certainly possible for film formation to be localized, and for only a few fibers to be connected to one another.
  • the additional film-forming and/or setting polymers are present preferably in an amount from 0.1 wt % to 10 wt %, particularly 1.0 wt % to 8.0 wt %, very preferably from 2.0 to 6.0 wt %, based on weight of the agent.
  • agents according to the present invention contain at least one nonionic film-forming and/or nonionic setting polymer as an additional film-forming and/or setting polymer.
  • the additional nonionic film-forming and/or nonionic setting polymers are present in the agent preferably in an amount from 0.1 wt % to 10 wt %, more preferably from 1.0 wt % to 8.0 wt %, very preferably from 2.0 to 6.0 wt %, based on weight of the agent.
  • Nonionic film-forming and/or nonionic setting polymers are preferably chosen from at least one polymer of
  • Suitable polyvinylpyrrolidones include commercial products such as Luviskol® K 90 or Luviskol® K 85 of the BASF SE company.
  • Suitable polyvinyl acetate is marketed, for example, as an emulsion under the trade name Vinac® by the Air Products company.
  • Agents having as a nonionic film-forming and/or nonionic setting polymer at least one polymer chosen from
  • agents according to the present invention having as a nonionic film-forming and/or nonionic setting polymer at least one polymer chosen from
  • copolymers of N-vinylpyrrolidone and vinyl esters of carboxylic acids having 2 to 18 carbon atoms are used, it is preferred if the molar ratio of the structural units of the polymer based on the N-vinylpyrrolidone monomer to the structural units of the polymer based on the monomer that is vinyl esters of carboxylic acids having 2 to 18 carbon atoms (particularly vinyl acetate), is from 20:80 to 80:20, particularly 30:70 to 60:40.
  • Suitable copolymers of vinylpyrrolidone and vinyl acetate are obtainable, for example, under the trademark Luviskol® VA 37, Luviskol® VA 55, Luviskol® VA 64, and Luviskol® VA 73 from the BASF SE Company.
  • Agents according to the present invention preferably contain as an additional film-forming and/or setting polymer, at least one cationic film-forming and/or cationic setting polymer. It is preferred according to the present invention if at least a combination of
  • “Cationic polymers” are polymers having in the main chain and/or side chain a group that can be “temporarily” or “permanently” cationic. According to the present invention, those polymers having a cationic group regardless of the pH of the agent are referred to as “permanently cationic.” These are polymers having a quaternary nitrogen atom, for example, in the form of an ammonium group. Preferred cationic groups are quaternary ammonium groups. Those polymers in which the quaternary ammonium group is bonded via a C1-4 hydrocarbon group to a main polymer chain constructed from acrylic acid, methacrylic acid, or derivatives thereof have proven particularly suitable.
  • a cationic film-forming and/or cationic setting polymer preferably suitable according to the present invention is at least one cationic film-forming and/or cationic setting polymer that contains at least one structural element of formula (M9) and additionally at least one structural element of formula (M10)
  • physiologically acceptable anions such as chloride, bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate, or p-toluenesulfonate, triflate, serve to compensate for the positive polymer charge.
  • Cationic film-forming and/or cationic setting polymers are further selected from cationic quaternized cellulose derivatives.
  • Cationic quaternized cellulose derivatives are further suitable as film-forming and/or setting polymers.
  • cationic quaternized celluloses having more than one permanent cationic charge in a side chain are particularly advantageous for purposes of the invention.
  • these cationic celluloses those having the INCI name Polyquaternium-4, marketed, for example, under the designations Celquat® H 100, Celquat® L 200 by the National Starch Company are particularly suitable.
  • cationic polymers particularly preferred for use for the invention are those cationic film-forming and/or cationic setting copolymers having at least one structural element of formula (M11)
  • R′′ is a (C 1 to C 4 ) alkyl group, particularly a methyl group, and additionally at least one further cationic and/or nonionic structural element.
  • physiologically acceptable anions such as chloride, bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate, or p-toluenesulfonate, triflate, serve to compensate for the positive polymer charge.
  • At least one copolymer (c1) having besides at least one structural element of formula (M11) and additionally a structural element of formula (M6)
  • R′′ is a (C 1 to C 4 ) alkyl group, particularly a methyl group, is present as an additional cationic film-forming and/or cationic setting polymer.
  • Very particularly preferred cationic film-forming and/or cationic setting polymers as copolymers (c1) contain 10 to 30 mol %, preferably 15 to 25 mol %, and particularly 20 mol % structural units according to formula (M11), and 70 to 90 mol %, preferably 75 to 85 mol % and particularly 80 mol % structural units according to formula (M6).
  • copolymers (c1) in addition to polymer units resulting from incorporation of structural units according to formulae (M11) and (M6) into the copolymer, a maximum of 5 wt %, preferably a maximum of 1 wt %, contain polymer units based on the incorporation of other monomers.
  • N-methylvinylimidazole/vinylpyrrolidone copolymers are then referred to according to INCI nomenclature as Polyquaternium-16 and are obtainable e.g. from BASF under the trade names Luviquat® Style, Luviquat® FC 370, Luviquat® FC 550, Luviquat® FC 905, and Luviquat® HM 552.
  • N-methylvinylimidazole/vinylpyrrolidone copolymers are then referred to according to INCI nomenclature as Polyquaternium-44 and are obtainable e.g. from BASF under the trade names Luviquat® UltraCare.
  • agents according to the present invention can also contain copolymers (c2) that, proceeding from copolymer (c1), contain structural units of formula (M7) as additional structural units:
  • compositions according to the present invention contain, as a cationic film-forming and/or cationic setting polymer, at least one copolymer (c2) having at least one structural unit according to formula (M11-a), at least one structural unit according to formula (M6), and at least one structural unit according to formula (M7)
  • copolymers (c2) in addition to polymer units resulting from incorporation of structural units according to formulae (M11-a), (M6), and (M7) into the copolymer, a maximum of 5 wt %, preferably a maximum of 1 wt %, contain polymer units based on the incorporation of other monomers.
  • Copolymers (c2) are preferably constructed exclusively from structural units of formulae (M11-a), (M6), and (M7).
  • N-methylvinylimidazole/vinylpyrrolidone/vinylcaprolactam copolymers are then referred to according to INCI nomenclature as Polyquaternium-46 and are obtainable, for example, from BASF under the trade name Luviquat® Hold.
  • Very particularly preferred copolymers (c2) contain 1 to 20 mol %, preferably 5 to 15 mol %, and particularly 10 mol % structural units according to formula (M-11 a), and 30 to 50 mol %, preferably 35 to 45 mol %, and particularly 40 mol % structural units according to formula (M6), and 40 to 60 mol %, preferably 45 to 55 mol %, and particularly 60 mol % structural units according to formula (M7).
  • agents according to the present invention can also contain as a cationic film-forming and/or cationic setting polymer, copolymers (c3) having as structural units structural units of formulas (M11-a) and (M6), as well as further structural units from the group of the vinylimidazole units and from the group of the acrylamide and/or methacrylamide units.
  • compositions according to the present invention contain, as an additional cationic film-forming and/or cationic setting polymer, at least one copolymer (c3) that contains at least one structural unit according to formula (M-11a), at least one structural unit according to formula (M6), at least one structural unit according to formula (M10) and at least one structural unit according to formula (M12)
  • copolymers (c3) contain, besides polymer units that result from incorporation of the aforesaid structural units in accordance with formulas (M11-a), (M6), (M8), and (M12) into the copolymer, a maximum of 5 wt %, preferably a maximum of 1 wt %, polymer units based on incorporation of other monomers.
  • Copolymers (c3) are preferably constructed exclusively from structural units of formulae (M11-a), (M6), (M8), and (M12).
  • physiologically acceptable anions such as chloride, bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate, or p-toluenesulfonate, triflate, serve to compensate for the positive polymer charge of component (c3).
  • N-methylvinylimidazole/vinylpyrrolidone/vinylimidazole/methacrylamide copolymers are referred to according to INCI nomenclature as Polyquaternium-68 and are obtainable, for example, from BASF under the trade name Luviquat® Supreme.
  • Very particularly preferred copolymers (c3) contain 1 to 12 mol %, preferably 3 to 9 mol %, and particularly 6 mol % structural units according to formula (M-11 a), and 45 to 65 mol %, preferably 50 to 60 mol %, and particularly 55 mol % structural units according to formula (M6), and 1 to 20 mol %, preferably 5 to 15 mol %, and particularly 10 mol % structural units according to formula (M8), and 20 to 40 mol %, preferably 25 to 35 mol %, and particularly 29 mol % structural units according to formula (M12).
  • cationic film-forming and/or setting polymers chosen from cationic polymers having at least one structural element of formula (M11-a), those considered preferred are:
  • cationic polymers preferably usable in agents according to the present invention are “temporarily cationic” polymers. These polymers usually contain an amino group that is present at certain pH values as a quaternary ammonium group and therefore cationically.
  • n 1 or 3 are preferred in this context.
  • Cosmetic agents very particularly preferred according to the present invention conform to at least one of the following embodiments A) to O):
  • G A cosmetic agent for the temporary deformation of keratinic fibers, particularly human hair, containing, in a cosmetic carrier,
  • K A cosmetic agent for the temporary deformation of keratinic fibers, particularly human hair, containing, in a cosmetic carrier,
  • Preferred organic carboxylic acids of the neutralization product of chitosan in accordance with embodiments A) to O) are chosen from lactic acid, formic acid, pyrrolidonecarboxylic acid, nicotinic acid, hydroxyisobutyric acid, hydroxyisovaleric acid, or mixtures of said acids.
  • At least one nonionic surfactant can already, according to the present invention, have an emulsifying effect.
  • Nonionic surfactants contain as a hydrophilic group, for example, a polyol group, a polyalkylene glycol ether group, or a combination of a polyol and polyglycol ether group.
  • a hydrophilic group for example, a polyol group, a polyalkylene glycol ether group, or a combination of a polyol and polyglycol ether group.
  • Such compounds include:
  • R 1 CO is a linear or branched, saturated and/or unsaturated acyl residue having 6 to 22 carbon atoms
  • R 2 is hydrogen or methyl
  • R 3 is linear or branched alkyl residues having 1 to 4 carbon atoms
  • w is a number from 1 to 20
  • Nonionic surfactants are present in the agent preferably in an amount from 0.005 wt % to 10 wt %, particularly from 0.01 wt % to 2 wt %, based on the weight of the agent according to the present invention.
  • the agent according to the present invention has acceptable hair-care properties even without further care-providing substances.
  • the agent can additionally contain at least one cationic surfactant.
  • cationic surfactants usable in the agents include quaternary ammonium compounds.
  • Ammonium halides are preferred, particularly chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides, and trialkylmethylammonium chlorides (e.g., cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, and tricetylmethylammonium chloride).
  • alkyltrimethylammonium chlorides e.g., dialkyldimethylammonium chlorides
  • trialkylmethylammonium chlorides e.g., cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, and tricetylmethylammoni
  • estersquats such as the methylhydroxyalkyldialkoyloxyalkylammonium methosulfates marketed under the trade names Dehyquart® and Stepantex®, can also be used.
  • Agents according to the present invention are preferably present as foam.
  • the agents are packaged in a delivery apparatus that is either a pressurized-gas container additionally filled with a propellant (“aerosol container”) or a non-aerosol container.
  • aerosol container Pressurized-gas containers from which a product is distributed through a valve due to the internal gas pressure of the container are referred to as “aerosol containers.”
  • a “non-aerosol container” is defined, conversely to the “aerosol” definition, as a vessel under standard pressure from which a product is distributed by mechanical action by way of a pump system.
  • Agents according to the present invention are present particularly preferably as aerosol hair foam in an aerosol container.
  • the agent therefore preferably additionally contains at least one propellant.
  • embodiments A) to O) are likewise considered, in particular, as preferably suitable compositions packaged in an aerosol container with at least one propellant for providing aerosol foam.
  • Agents according to the present invention that are present in the form of an aerosol product can be manufactured in usual fashion. All constituents of the agent except for the propellant are introduced into a suitable pressure-tight container. The latter is then sealed with a valve. Lastly, the desired quantity of propellant is introduced using conventional techniques.
  • propellants suitable according to the present invention include N2O, dimethyl ether, CO2, air, alkanes having 3 to 5 carbon atoms such as propane, n-butane, isobutane, n-pentane, and isopentane, and mixtures thereof.
  • alkanes having 3 to 5 carbon atoms such as propane, n-butane, isobutane, n-pentane, and isopentane, and mixtures thereof.
  • the aforesaid alkanes, mixtures of the aforesaid alkanes, or mixtures of the aforesaid alkanes with dimethyl ether are used as the only propellant.
  • the invention also expressly includes, however, the concurrent use of fluorochlorocarbon propellants, particularly fluorocarbons.
  • Dimethyl ether, propane, n-butane, isobutane, and mixtures thereof are preferred.
  • mixtures of propane and butane are used as the only propellant at a weight ratio of propane to butane from 70:30 to 15:85. These mixtures are used in the agents preferably in an amount from 3 to 15 wt %, based on total weight of the agent.
  • “Butane” according to the present invention is n-butane, isobutane, and mixtures of n-butane and isobutane.
  • the sizes of the foam bubbles and the respective size distribution can be adjusted by the quantitative ratio between the propellant and the other constituents of the preparations.
  • aerosol foam products contain the propellant preferably in amounts from 1 to 35 wt %, based on total product. Quantities from 2 to 30 wt %, particularly 3 to 15 wt %, are particularly preferred.
  • Isopentane is preferably suitable as a propellant for foaming gel-type agents in a two-chamber aerosol container, said propellant being is incorporated into the agents according to the present invention and being packaged in the first chamber of the two-chamber aerosol container.
  • Packaged in the second chamber of the two-chamber aerosol container is at least one further propellant different from isopentane that builds up in the two-chamber aerosol container a higher pressure than isopentane.
  • Propellants of the second chamber are preferably chosen from N2O, dimethyl ether, CO2, air, alkanes having 3 or 4 carbon atoms (such as propane, n-butane, isobutane), and mixtures thereof.
  • a second subject of the invention is the use of a cosmetic agent of the first subject of the invention for temporary deformation and/or shape fixing of keratinic fibers, particularly human hair.
  • a third subject of the invention is a method for temporary deformation of keratinic fibers, particularly human hair, wherein a cosmetic agent of the first subject of the invention is applied onto the keratinic fibers.
  • the keratinic fibers after application of the cosmetic agents of the first subject of the invention, are not rinsed and are left on the fibers.
  • Raw material I1 (wt %) Hydagen HCMF 1 0.50 Lactic acid 0.28 Luviskol 60/40 W NP 2 10.70 Nonionic starch modified by means of propylene oxide 3 2.70 Sodium benzoate 0.30 D-Panthenol 0.15 Dow Corning 939 4 0.20 Dehyquart A CA 5 1.00 Propane/butane 8.00 Water to 100 1 Chitosan (80% deacetylated), molecular weight 50,000 to 1,000,000 g/mol, Cognis) 2 Copolymer of N-vinylpyrrolidone and vinyl acetate 3 Potato starch, propylene oxide content: 10 wt % propylene oxide, viscosity: 64,000 mPa ⁇ s, average molecular weight (weight average): 800 kDa 4 Approx.
  • Formulation I1 was applied onto a test subject as an aerosol foam in order to fix the hairstyle as to shape.
  • the hair achieved a natural shine, a strong hairstyle hold, and durable volume.

Abstract

Cosmetic agents for the temporary deformation of keratinic fibers which contain, in a cosmetic carrier, a combination of at least one chitosan compound and at least one nonionic starch modified by means of propylene oxide, produce a hairstyle with a high degree of hold, excellent flexibility, and good hair care.

Description

    CROSS REFERENCE TO RELATED APPLICATIONS
  • The present application is a continuation of International Application No. PCT/EP2010/065860 filed 21 Oct. 2010, which claims priority to German Patent Application Nos. 10 2009 045 925.1 and 10 2009 045 933.2, both filed 22 Oct. 2009, each of which are incorporated herein by reference.
  • The present invention relates to cosmetic agents for temporary deformation of keratinic fibers containing, in a cosmetic carrier, a combination of at least one chitosan compound and at least one nonionic starch modified with propylene oxide.
  • Styling agents for deformation of keratinic fibers have been known for some time and are used in various embodiments to build up, refresh, and fix in place hairstyles that, for many types of hair, can be obtained only using setting active substances. An important role is played by hair treatment agents used for permanent shaping and those used for temporary shaping of the hair. Temporary shaping operations intended to yield good hold without impairing the healthy appearance of the hair such as its shine can be achieved, for example, using hair sprays, hair waxes, hair gels, blow-dry waves, etc.
  • Corresponding agents for temporary shaping usually contain synthetic polymers as a shaping component. Preparations having a dissolved or dispersed polymer can be applied onto hair using propellant gases or a pump mechanism. Hair gels and hair waxes, however, are not applied directly onto the hair but instead distributed in the hair using a comb or one's hands.
  • Synthetic polymers usually used in agents for temporary shaping are manufactured from corresponding synthetically accessible monomers. These monomers are obtained from fossil substances such as petroleum by conversion to the corresponding polymer modules, in some cases with expenditure of energy.
  • In a more sustainable approach to nature as living space and to resources, it is still desirable to use for cosmetic products only those cosmetic raw materials that are accessible, with as little energy use as possible, from renewable raw materials. A reduction in the amount or even a replacement of synthetic polymers can be undertaken, however, only when the substitute polymers exhibit the properties desired for the intended application and ensure that the keratin-containing fibers (e.g., hairstyle) are held in sufficiently stable fashion in the shape imparted to them.
  • In addition, nature-based substitute polymers should impart volume to the fiber collective and retain the elasticity and smoothness of the keratin-containing fibers that are fixed as to shape. Formation on keratin-containing fibers of polymer particles visible to the naked eye should be avoided. In addition, the keratin-containing fibers must not give a dull impression, but should have a natural shine.
  • The present invention therefore provides a cosmetic composition that brings about very strong and durable shape retention, has a high volume effect, provides good fiber care, and does not exhibit the above disadvantages. A further intention is to be able to dispense, predominantly or as entirely as possible, with use of synthetic polymers based on fossil raw materials.
  • A first subject of the invention is therefore a cosmetic agent for temporary deformation of keratinic fibers, particularly human hair, containing, in a cosmetic carrier
      • at least one chitosan or derivative thereof, and
      • at least one nonionic starch modified by means of propylene oxide.
  • “Keratinic fibers” according to the present invention refer to furs, wool, feathers, and particularly human hair.
  • Chitosans represent biopolymers and are hydrocolloids. In chemical terms, they are partially deacetylated chitins of various molecular weights.
  • Manufacture of chitosans proceeds from chitin, preferably crustacean shell residues, which are available in large quantities as cheap raw materials. The chitin is usually first deproteinated by addition of bases, demineralized by adding mineral acids, and lastly deacetylated by adding strong bases. Molecular weights can be distributed over a broad spectrum. It is preferable to use those grades having an average molecular weight (weight average) from 800,000 to 1,200,000 Dalton, a viscosity per Brookfield (1-wt % in glycolic acid) 5000 mPa·s or less, a degree of deacetylation from 80 to 88%, and an ash content of 0.3 wt % or less.
  • Also appropriate as typical cationic biopolymers as chitosan derivatives are cationically derivatized chitosans (e.g., quaternization products) or alkoxylated chitosans.
  • Preferred agents include as a chitosan at least one neutralization product of chitosan with at least one organic carboxylic acid, such as in particular formic acid, acetic acid, citric acid, lactic acid, pyrrolidonecarboxylic acid, tartaric acid, glycolic acid, nicotinic acid, hydroxyisobutyric acid, hydroxyisovaleric acid, or mixtures of these acids. Preferably, the organic carboxylic acid are chosen from lactic acid, formic acid, pyrrolidonecarboxylic acid, nicotinic acid, hydroxyisobutyric acid, hydroxyisovaleric acid, or mixtures of these acids. This neutralization product can be manufactured, for example, in an aqueous medium by adding chitosan and the corresponding organic carboxylic acid.
  • Suitable chitosans are readily commercially available, for example, under the commercial designations Hydagen® CMF (1 wt % active substance in aqueous solution with 0.4 wt % glycolic acid, molecular weight 500,000 to 5,000,000 g/mol, Cognis), Hydagen® HCMF (chitosan (80% deacetylated), molecular weight 50,000 to 1,000,000 g/mol, Cognis), Kytamer® PC (80 wt % active substance as chitosan pyrrolidone carboxylate (INCI name: Chitosan PCA), Amerchol), and Chitolam® NB/101.
  • The chitosans orderivatives thereof are present in agents according to the present invention preferably in an amount from 0.01 wt % to 5 wt %, more preferably 0.05 wt % to 2.0 wt %, very preferably 0.1 wt % to 1 wt %, based on weight of the agent according to the invention.
  • Starch is a reserve carbohydrate that is stored by many plants in the form of large starch grains (granules), usually 1 to 200 μm in size, in various parts of the plant, for example, in tubers or roots, cereal seeds, fruits and in the pith. A nonionic starch modified with propylene oxide that can be used according to the invention can be obtained from the starch of potatoes, corn, rice, peas, acorns, chestnuts, barley, wheat, bananas, sago, millet, sorghum, oats, barley, rye, beans, yams, arrowroot or cassava. Particularly pronounced effects according to the present invention are achieved with nonionic tapioca starch modified with propylene oxide or nonionic potato starch modified with propylene oxide or with mixtures of these two starches. Very particularly preferably, the agent contains at least one nonionic potato starch modified with propylene oxide.
  • Starch belongs to the homoglycan family and is a polycondensation product of D-glucose. Starch is made up of three structurally different polymers of d-glucopyranose, namely amylose, amylopectin, and an intermediate fraction. Higher plants contain 0 to 45 wt % amylose, based on dry substance.
  • The intermediate fraction, also referred to as “anomalous amylopectin,” is structurally intermediate between amylose and amylopectin. The quantitative indications defined in this Application for amylopectin include the intermediate fraction.
  • It is preferred if the nonionic starch modified with propylene oxide has an amylose content of 25 wt % or less, particularly 20 wt % or less, based on weight of the modified starch. It has become apparent that a starch having 17 to 22 wt % amylose and 78 to 83 wt % amylopectin is particularly suitable for achieving the effect according to the present invention.
  • Amylose is made up of predominantly linear α-1,4-glycosidically linked d-glucose, Mr 50,000 to 150,000. The resulting chains form double helices in the starch.
  • Amylopectin also contains, in addition to the α-1,4 links described for amylose, α-1,6 bonds (in an amount from 4 to 6%) as branching points. The average spacing between the branching points is equal to approximately 12 to 17 glucose units. The molar mass of 107 to 7* 105 corresponds to approx. 105 glucose units, making amylopectin one of the largest biopolymers. The branching points are distributed over the molecule in such a way that a bundle structure, with relatively short side chains, develops. Each double helix is formed by two of these side chains. As a result of the many branching points, amylopectin is relatively easily soluble in water.
  • “Nonionic starch modified with propylene oxide” according to the present invention is a reaction product of a starch with propylene oxide. A reaction product of this kind includes at least one structural unit of formula (PS)
  • Figure US20120213724A1-20120823-C00001
  • wherein at least one of R, R′, or R″ is a group of the formula
  • Figure US20120213724A1-20120823-C00002
  • wherein n is greater than or equal to zero, and at most two of R, R′, and R″ is a hydrogen atom. In formulae of the Application, a bond identified with the “*” symbol is a free valence of the corresponding structural unit. Nonionic starches modified with propylene oxide are provided, for example, by reacting a natural starch with propylene oxide. Before modification with propylene oxide, the starch can have been exposed to a variety of physical or chemical processes such as heat treatment, shear, a thermal, acid-hydrolytic, oxidizing, or enzymatic cleavage, etc.
  • Preferably, the nonionic starch modified with propylene oxide is not present in the agent according to the present invention as individual starch grains (granules). Accordingly, the starch grains are disintegrated, for example, by heat or shear and the corresponding polysaccharide molecules are released from the composite material. The released polysaccharide molecules can be modified with propylene oxide after or before release.
  • In a preferred embodiment, the nonionic starch modified with propylene oxide is gelatinized. When an aqueous suspension of starch is heated or compressed, a tangential swelling of the bodies is then observed at a critical temperature or pressure, with loss of birefringence, a change in X-ray structure, and an abrupt rise in the viscosity of the solution. This phenomenon is called “gelatinization.”
  • Nonionic starches according to the present invention modified with propylene oxide are present in the agent in a molecular weight distribution. Preferred nonionic starches modified with propylene oxide have an average molecular weight from 50 to 2500 kDa (weight average). The molecular weight distribution is determined experimentally by gel filtration chromatography against dextran. The weight average is an average molecular weight that takes into account the total weight of the molecules of various molecular weights, and not simply the number of molecules.
  • For statistical calculation of the weight average, firstly the “weight break” is defined:

  • w i≦(n i M i)/[Σ(N i M i)].
  • This indicates the weight proportion, in the sample, of macromolecules that are made up of i segments (e.g. monomer modules) of mass Mi and that occur Ali times in the sample. The weight average of the molecular weight Mw=Σwi Mi is thus given by

  • M w=[Σ(N iM2 i)/[Σ(N i M i)].
  • Particularly preferred agents contain nonionic starches modified with propylene oxide having an average molecular weight (weight average) from 100 to 2000 kDa, particularly 500 to 1800 kDa, very preferably from 700 to 1000 kDa.
  • In order to adjust the molecular weight, the starch is subjected to a mechanical and/or chemical treatment before or after modification with propylene oxide. To elevate the molecular weight, the aforesaid starch can be crosslinked. Crosslinking of the nonionic starch modified by means of propylene oxide exists when the linear or branched polysaccharide macromolecules of the starch are linked covalently by means of a crosslinking agent, forming a three-dimensional, insoluble, and still swellable polymeric network. Natural starch is generally considered uncrosslinked, and, if crosslinking were desirable, requires artificial crosslinking by means of synthesis chemistry. Artificial crosslinking of this kind can be carried out using crosslinking agents. (Nonionic) starches (modified with propylene oxide) that do not exhibit such crosslinking are uncrosslinked.
  • Crosslinking occurs, for example, using the crosslinking agent epichlorohydrin. Here, a mixture (42-wt % in water) of starch modified with propylene oxide is produced, into which mixture the desired amount of epichlorohydrin is stirred at room temperature. Once the target viscosity is reached after a stirring time of 1 to 5 hours with viscosity monitoring, the crosslinked starch is isolated using ordinary methods.
  • It is particularly preferred if agents according to the present invention contain at least one uncrosslinked nonionic starch modified with propylene oxide as a modified nonionic starch.
  • To achieve a lower molecular weight from 100 to 400 kDa, the starches are preferably exposed to mechanical cleavage, enzymatic cleavage (particularly using α-amylase, β-amylase, glucoamylase, or debranching enzymes), acid-hydrolytic cleavage (particularly using hydrochloric acid, sulfuric acid, or phosphoric acid), thermal cleavage, or reaction with oxidizing agents (such as periodate, hypochlorite, chromic acid, permanganate, nitrogen dioxide, hydrogen peroxide, or organic percarboxylic acid, preferably with hydrogen peroxide). Kneaders, extruders, stator/rotor machines, and/or agitators are suitable for mechanical cleavage of the starch.
  • Oxidative cleavage using hydrogen peroxide is preferred. Here, for example, nonionic starch modified with propylene oxide is added to water, heated to 50 to 70° C., hydrogen peroxide is added, and stirring occurs at 70 to 85° C. for 2 to 5 hours.
  • Propylene oxide content of the starch affects the fine-tuning of the hairstyle hold and hairstyle flexibility, as well as stability of the cosmetic agents. The parameters can be further optimized if the nonionic starch modified with propylene oxide has, based on weight of the modified starch, a propylene oxide content from 1 to 20 wt %, more preferably from 4 to 12 wt %, very preferably from 9.5 to 10.5 wt % or from 4.0 to 6.0 wt %. Propylene oxide content can be determined, for example, by carrying out a Hodges cleavage using the method according to DIN EN 13268.
  • Cosmetic agents containing nonionic starches modified with propylene oxide having, in a 43-wt % aqueous solution, a preferred viscosity from 150 to 1,500,000 mP·s (Brookfield viscosimeter, spindle 7 at 20° C. and 20 rpm) are outstandingly suitable for the invention. Particularly suitable starches modified with propylene oxide have viscosities from 10,000 to 200,000 mPa·s, more preferably from 25,000 to 180,000 mPa·s (measured under the conditions recited above).
  • It is preferred if the cosmetic agent contains the nonionic starch modified with propylene oxide in an amount from 0.1 wt % to 10 wt %, more preferably from 0.2 wt % to 5.0 wt %, very preferably from 1.0 to 3.0 wt %, based on weight of the agent.
  • Agents according to the present invention contain their active substances in a cosmetic carrier, preferably in a water-containing cosmetic carrier, an alcoholic cosmetic carrier, or an aqueous alcoholic cosmetic carrier. For temporary hair deformation, such carriers include lotions, water-in-oil emulsions, oil-in-water emulsions, creams, gels, foams, pomades, waxes, or other preparations that are suitable for use on the hair. It is preferred if the carrier is a water-containing cosmetic carrier or an aqueous alcoholic cosmetic carrier. It is if the cosmetic carrier of the agent according to the present invention contains at least 50 wt % water, based on the weight of the entire agent.
  • “Aqueous alcoholic” carriers for purposes of the present invention are aqueous compositions containing 3 to 70 wt % of a C1 to C4 alcohol, particularly ethanol or isopropanol. Agents according to the present invention can additionally contain further organic solvents such as methoxybutanol, benzyl alcohol, ethyl diglycol, 1,2-propylene glycol, or 1,3-propylene glycol. All water-soluble organic solvents are preferred in this context.
  • It is preferred if the agent according to the present invention additionally contains at least one film-forming and/or setting polymer. Additional film-forming and/or setting polymers of this embodiment are different from the chitosan(s) (derivatives) and the nonionic starch modified with propylene oxide. Film-forming and/or setting polymers can be nonionically, anionically, amphoterically, or cationically charged, preferably nonionically or cationically charged.
  • “Polymers” according to the present invention are compounds constructed from a plurality of molecules wherein one type or several types of atoms or atom groupings (“constituent units,” “basic modules,” or “repeating units”) are repeatedly serially arranged, and that have a molecular weight of at least 10,000 g/mol. The polymers are obtained by polyreaction, which can occur artificially (i.e., synthetically) or naturally.
  • “Film-forming polymers” are those polymers that, upon drying, leave behind a continuous film on the skin, hair, or nails. Film-formers of this kind can be used in a very wide variety of cosmetic products such as face masks, make-up, hair setting agents, hair sprays, hair gels, hair waxes, hair therapies, shampoos, or nail polishes. Those polymers having sufficient solubility in water, alcohol or in water/alcohol mixtures are particularly preferred. It is possible in this way to produce corresponding solutions that can easily be utilized or further processed.
  • “Film-forming polymers” are also those polymers that, when applied in a 0.01- to 20-wt % aqueous, alcoholic, or aqueous alcoholic solution, are capable of depositing a transparent polymer film on the hair.
  • Setting polymers contribute to hold and/or buildup of hair volume and hair fullness of the overall hairstyle. These polymers are at the same time also film-forming polymers and are therefore generally typical substances for shape-imparting hair-treatment agents such as hair setting agents, hair foams, hair waxes, and hair sprays. It is certainly possible for film formation to be localized, and for only a few fibers to be connected to one another.
  • The additional film-forming and/or setting polymers are present preferably in an amount from 0.1 wt % to 10 wt %, particularly 1.0 wt % to 8.0 wt %, very preferably from 2.0 to 6.0 wt %, based on weight of the agent.
  • In a particularly preferred embodiment, agents according to the present invention contain at least one nonionic film-forming and/or nonionic setting polymer as an additional film-forming and/or setting polymer.
  • The additional nonionic film-forming and/or nonionic setting polymers are present in the agent preferably in an amount from 0.1 wt % to 10 wt %, more preferably from 1.0 wt % to 8.0 wt %, very preferably from 2.0 to 6.0 wt %, based on weight of the agent.
  • Nonionic film-forming and/or nonionic setting polymers are preferably chosen from at least one polymer of
      • homopolymers and nonionic copolymers of N-vinylpyrrolidone,
      • nonionic copolymers of isobutene,
      • nonionic copolymers of maleic acid anhydride.
  • Suitable polyvinylpyrrolidones include commercial products such as Luviskol® K 90 or Luviskol® K 85 of the BASF SE company.
  • Suitable polyvinyl acetate is marketed, for example, as an emulsion under the trade name Vinac® by the Air Products company.
  • Agents having as a nonionic film-forming and/or nonionic setting polymer at least one polymer chosen from
      • copolymers of maleic acid anhydride and methyl vinyl ether,
      • polyvinylpyrrolidone,
      • copolymers of N-vinylpyrrolidone and vinyl esters of carboxylic acids having 2 to 18 carbon atoms, particularly N-vinylpyrrolidone and vinyl acetate, or mixtures of these polymers, are very particularly preferred according to the present invention.
  • Those agents according to the present invention having as a nonionic film-forming and/or nonionic setting polymer at least one polymer chosen from
      • polyvinylpyrrolidone,
      • copolymers of N-vinylpyrrolidone and vinyl esters of carboxylic acids having 2 to 18 carbon atoms, particularly N-vinylpyrrolidone and vinyl acetate,
        or mixtures of these polymers, are in turn very particularly preferred according to the present invention.
  • If copolymers of N-vinylpyrrolidone and vinyl esters of carboxylic acids having 2 to 18 carbon atoms, particularly N-vinylpyrrolidone and vinyl acetate, are used, it is preferred if the molar ratio of the structural units of the polymer based on the N-vinylpyrrolidone monomer to the structural units of the polymer based on the monomer that is vinyl esters of carboxylic acids having 2 to 18 carbon atoms (particularly vinyl acetate), is from 20:80 to 80:20, particularly 30:70 to 60:40.
  • Suitable copolymers of vinylpyrrolidone and vinyl acetate are obtainable, for example, under the trademark Luviskol® VA 37, Luviskol® VA 55, Luviskol® VA 64, and Luviskol® VA 73 from the BASF SE Company.
  • Agents according to the present invention preferably contain as an additional film-forming and/or setting polymer, at least one cationic film-forming and/or cationic setting polymer. It is preferred according to the present invention if at least a combination of
      • at least one nonionic film-forming and/or nonionic setting polymer and/or
      • at least one cationic film-forming and/or cationic setting polymer
        is present in the agent as an additional film forming and/or setting polymer.
  • “Cationic polymers” are polymers having in the main chain and/or side chain a group that can be “temporarily” or “permanently” cationic. According to the present invention, those polymers having a cationic group regardless of the pH of the agent are referred to as “permanently cationic.” These are polymers having a quaternary nitrogen atom, for example, in the form of an ammonium group. Preferred cationic groups are quaternary ammonium groups. Those polymers in which the quaternary ammonium group is bonded via a C1-4 hydrocarbon group to a main polymer chain constructed from acrylic acid, methacrylic acid, or derivatives thereof have proven particularly suitable.
  • A cationic film-forming and/or cationic setting polymer preferably suitable according to the present invention is at least one cationic film-forming and/or cationic setting polymer that contains at least one structural element of formula (M9) and additionally at least one structural element of formula (M10)
  • Figure US20120213724A1-20120823-C00003
  • wherein
    • R is a hydrogen atom or a methyl group,
    • R′, R″ and R′″ are, mutually independently, a (C1 to C30) alkyl group,
    • X is an oxygen atom or an NH group,
    • A is an ethane-1,2-diyl group or a propane-1,3-diyl group,
    • n is 1 or 3.
  • All possible physiologically acceptable anions such as chloride, bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate, or p-toluenesulfonate, triflate, serve to compensate for the positive polymer charge.
  • Such compounds are available, for example, as
      • copolymers of dimethylaminoethyl methacrylate, quaternized with diethyl sulfate, with vinylpyrrolidone, having the INCI name Polyquaternium-11, under the designations Gafquat® 440, Gafquat® 734, Gafquat® 755 (each ISP company) and Luviquat PQ 11 PN (BASF SE),
      • copolymers of N-vinylpyrrolidone, N-(3-dimethylaminopropyl)methacrylamide, and 3-(methacryloylamino)propyllauryldimethylammonium chloride (INCI name: Polyquaternium-55), which is marketed e.g. under the commercial name Styleze W 10 or Styleze W 20 (10 resp. 20 wt % active substance in ethanol/water mixture) by the ISP company,
      • copolymers of N-vinylpyrrolidone, N-vinylcaprolactam, N-(3-dimethylaminopropyl)methacrylamide, and 3-(methacryloylamino)propyllauryldimethylammonium chloride (INCI name: Polyquaternium-69), which is marketed, for example, under the commercial name AquaStyle® 300 (28 to 32 wt % active substance in ethanol/water mixture) by the ISP company.
  • Cationic film-forming and/or cationic setting polymers are further selected from cationic quaternized cellulose derivatives.
  • Cationic quaternized cellulose derivatives are further suitable as film-forming and/or setting polymers.
  • Those cationic quaternized celluloses having more than one permanent cationic charge in a side chain are particularly advantageous for purposes of the invention. Among these cationic celluloses, those having the INCI name Polyquaternium-4, marketed, for example, under the designations Celquat® H 100, Celquat® L 200 by the National Starch Company are particularly suitable.
  • Further cationic polymers particularly preferred for use for the invention are those cationic film-forming and/or cationic setting copolymers having at least one structural element of formula (M11)
  • Figure US20120213724A1-20120823-C00004
  • wherein R″ is a (C1 to C4) alkyl group, particularly a methyl group, and additionally at least one further cationic and/or nonionic structural element.
  • All possible physiologically acceptable anions such as chloride, bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate, or p-toluenesulfonate, triflate, serve to compensate for the positive polymer charge.
  • It is preferred if at least one copolymer (c1), having besides at least one structural element of formula (M11) and additionally a structural element of formula (M6)
  • Figure US20120213724A1-20120823-C00005
  • wherein R″ is a (C1 to C4) alkyl group, particularly a methyl group, is present as an additional cationic film-forming and/or cationic setting polymer.
  • All possible physiologically acceptable anions such as chloride, bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate, or p-toluenesulfonate, triflate, serve to compensate for the positive polymer charge of copolymers (c1).
  • Very particularly preferred cationic film-forming and/or cationic setting polymers as copolymers (c1) contain 10 to 30 mol %, preferably 15 to 25 mol %, and particularly 20 mol % structural units according to formula (M11), and 70 to 90 mol %, preferably 75 to 85 mol % and particularly 80 mol % structural units according to formula (M6).
  • It is particularly preferred if copolymers (c1), in addition to polymer units resulting from incorporation of structural units according to formulae (M11) and (M6) into the copolymer, a maximum of 5 wt %, preferably a maximum of 1 wt %, contain polymer units based on the incorporation of other monomers. Copolymers (c1) are preferably constructed exclusively from structural units of formula (M11), where R″ =methyl, and (M6).
  • If a chloride ion is used to compensate for the positive charge of the polymer, such N-methylvinylimidazole/vinylpyrrolidone copolymers are then referred to according to INCI nomenclature as Polyquaternium-16 and are obtainable e.g. from BASF under the trade names Luviquat® Style, Luviquat® FC 370, Luviquat® FC 550, Luviquat® FC 905, and Luviquat® HM 552.
  • If a methosulfate is used to compensate for the positive charge of the polymer, such N-methylvinylimidazole/vinylpyrrolidone copolymers are then referred to according to INCI nomenclature as Polyquaternium-44 and are obtainable e.g. from BASF under the trade names Luviquat® UltraCare.
  • In addition to or instead of copolymer or copolymers (c1), agents according to the present invention can also contain copolymers (c2) that, proceeding from copolymer (c1), contain structural units of formula (M7) as additional structural units:
  • Figure US20120213724A1-20120823-C00006
  • Further particularly preferred agents according to the present invention contain, as a cationic film-forming and/or cationic setting polymer, at least one copolymer (c2) having at least one structural unit according to formula (M11-a), at least one structural unit according to formula (M6), and at least one structural unit according to formula (M7)
  • Figure US20120213724A1-20120823-C00007
  • Here as well, it is particularly preferred if copolymers (c2), in addition to polymer units resulting from incorporation of structural units according to formulae (M11-a), (M6), and (M7) into the copolymer, a maximum of 5 wt %, preferably a maximum of 1 wt %, contain polymer units based on the incorporation of other monomers. Copolymers (c2) are preferably constructed exclusively from structural units of formulae (M11-a), (M6), and (M7).
  • All possible physiologically acceptable anions such as chloride, bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate, or p-toluenesulfonate, triflate, serve to compensate for the positive polymer charge of copolymers (c2).
  • If a methosulfate is used to compensate for the positive charge of the polymer, such N-methylvinylimidazole/vinylpyrrolidone/vinylcaprolactam copolymers are then referred to according to INCI nomenclature as Polyquaternium-46 and are obtainable, for example, from BASF under the trade name Luviquat® Hold.
  • Very particularly preferred copolymers (c2) contain 1 to 20 mol %, preferably 5 to 15 mol %, and particularly 10 mol % structural units according to formula (M-11 a), and 30 to 50 mol %, preferably 35 to 45 mol %, and particularly 40 mol % structural units according to formula (M6), and 40 to 60 mol %, preferably 45 to 55 mol %, and particularly 60 mol % structural units according to formula (M7).
  • In addition to or instead of copolymer or copolymers (c1) and/or (c2), agents according to the present invention can also contain as a cationic film-forming and/or cationic setting polymer, copolymers (c3) having as structural units structural units of formulas (M11-a) and (M6), as well as further structural units from the group of the vinylimidazole units and from the group of the acrylamide and/or methacrylamide units.
  • Further particularly preferred agents according to the present invention contain, as an additional cationic film-forming and/or cationic setting polymer, at least one copolymer (c3) that contains at least one structural unit according to formula (M-11a), at least one structural unit according to formula (M6), at least one structural unit according to formula (M10) and at least one structural unit according to formula (M12)
  • Figure US20120213724A1-20120823-C00008
  • Here, it is particularly preferred if copolymers (c3) contain, besides polymer units that result from incorporation of the aforesaid structural units in accordance with formulas (M11-a), (M6), (M8), and (M12) into the copolymer, a maximum of 5 wt %, preferably a maximum of 1 wt %, polymer units based on incorporation of other monomers. Copolymers (c3) are preferably constructed exclusively from structural units of formulae (M11-a), (M6), (M8), and (M12).
  • All possible physiologically acceptable anions such as chloride, bromide, hydrogen sulfate, methyl sulfate, ethyl sulfate, tetrafluoroborate, phosphate, hydrogen phosphate, dihydrogen phosphate, or p-toluenesulfonate, triflate, serve to compensate for the positive polymer charge of component (c3).
  • If a methosulfate is used to compensate for the positive charge of the polymer, such N-methylvinylimidazole/vinylpyrrolidone/vinylimidazole/methacrylamide copolymers are referred to according to INCI nomenclature as Polyquaternium-68 and are obtainable, for example, from BASF under the trade name Luviquat® Supreme.
  • Very particularly preferred copolymers (c3) contain 1 to 12 mol %, preferably 3 to 9 mol %, and particularly 6 mol % structural units according to formula (M-11 a), and 45 to 65 mol %, preferably 50 to 60 mol %, and particularly 55 mol % structural units according to formula (M6), and 1 to 20 mol %, preferably 5 to 15 mol %, and particularly 10 mol % structural units according to formula (M8), and 20 to 40 mol %, preferably 25 to 35 mol %, and particularly 29 mol % structural units according to formula (M12).
  • Among the additional cationic film-forming and/or setting polymers chosen from cationic polymers having at least one structural element of formula (M11-a), those considered preferred are:
      • vinylpyrrolidone/1-vinyl-3-methyl-1H-imidazolium chloride copolymers (such as the one having the INCI name Polyquaternium-16 with the commercial designations Luviquat® Style, Luviquat® FC 370, Luviquat® FC 550, Luviquat® FC 905, and Luviquat® HM 552 (BASF SE)),
      • vinylpyrrolidone/1-vinyl-3-methyl-1H-imidazolium methyl sulfate copolymers (such as the one having the INCI name Polyquaternium-44 with the commercial designations Luviquat® Care (BASF SE)),
      • vinylpyrrolidone/vinylcaprolactam/1-vinyl-3-methyl-1H-imidazolium terpolymers (such as the one having the INCI name Polyquaternium-46 with the commercial designations Luviquat® Care or Luviquat® Hold (BASF SE)),
      • vinylpyrrolidone/methacrylamide/vinylimidazole/1-vinyl-3-methyl-1H-imidazolium methyl sulfate copolymers (such as the one having the INCI name Polyquaternium-68 with the commercial designation Luviquat® Supreme (BASF SE)),
        as well as mixtures of those polymers.
  • Further cationic polymers preferably usable in agents according to the present invention are “temporarily cationic” polymers. These polymers usually contain an amino group that is present at certain pH values as a quaternary ammonium group and therefore cationically.
  • Likewise considered preferably suitable as temporarily cationic polymers for purposes of the invention are those having at least one structural unit of formulae (M1-1) to (M1-8)
  • Figure US20120213724A1-20120823-C00009
    Figure US20120213724A1-20120823-C00010
  • Those copolymers having at least one structural unit of formulae (M1-1) to (M1-8) and additionally at least one structural unit of formula (M10)
  • Figure US20120213724A1-20120823-C00011
  • where n is 1 or 3 are preferred in this context.
  • The group of polymers
      • vinylcaprolactam/vinylpyrrolidone/dimethylaminoethyl methacrylate copolymer (for example, INCI name: Vinyl Caprolactam/PVP/Di-methylaminoethyl Methacrylate Copolymer, under the trade name Gaffix® VC 713 (ISP)),
      • vinylpyrrolidone/vinylcaprolactam/dimethylaminopropyl methacrylamide copolymer (e.g. INCI name: VP/Vinyl Caprolactam/DMAPA Acrylates Copolymer, under the trade name Aquaflex® SF 40 (ISP)),
      • vinylcaprolactam/vinylpyrrolidone/dimethylaminoethyl methacrylate copolymer (for example, as 35 to 39% solids in ethanol in the form of the commercial product Advantage LC E having the INCI name: Vinyl Caprolactam/VP/Dimethylaminoethyl Methacrylate Copolymer, Alcohol, Laurylpyrrolidone (ISP)),vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymer (for example, INCI name: VP/DMAPA Acrylates Copolymer, with the trade name Styleze CC-10 (ISP)),
        is considered a preferred list for selection therefrom of at least one or more polymers.
  • Cosmetic agents very particularly preferred according to the present invention conform to at least one of the following embodiments A) to O):
  • A): A cosmetic agent for the temporary deformation of keratinic fibers, particularly human hair, containing, in a cosmetic carrier,
      • at least one neutralization product of chitosan with at least one organic carboxylic acid, and
      • at least one nonionic starch modified by means of propylene oxide.
  • B): A cosmetic agent for the temporary deformation of keratinic fibers, particularly human hair, containing, in a cosmetic carrier,
      • at least one neutralization product of chitosan with at least one organic carboxylic acid,
      • at least one nonionic starch modified by means of propylene oxide, and
      • at least one nonionic film-forming and/or nonionic setting polymer.
  • C): A cosmetic agent for the temporary deformation of keratinic fibers, particularly human hair, containing, in a cosmetic carrier,
      • at least one neutralization product of chitosan with at least one organic carboxylic acid,
      • at least one nonionic starch modified by means of propylene oxide, and
      • at least one nonionic film-forming and/or nonionic setting polymer selected from the group that is constituted from
        • copolymers of maleic acid anhydride and methyl vinyl ether,
        • polyvinylpyrrolidone,
        • copolymers of N-vinylpyrrolidone and vinyl esters of carboxylic acids having 2 to 18 carbon atoms, particularly N-vinylpyrrolidone and vinyl acetate,
          or mixtures of those polymers.
  • D): A cosmetic agent for the temporary deformation of keratinic fibers, particularly human hair, containing, in a cosmetic carrier,
      • at least one neutralization product of chitosan with at least one organic carboxylic acid, and
      • at least one nonionic starch, modified by means of propylene oxide and having a molecular weight (weight average) from 50 to 2500 kDa.
  • E): A cosmetic agent for the temporary deformation of keratinic fibers, particularly human hair, containing, in a cosmetic carrier,
      • at least one neutralization product of chitosan with at least one organic carboxylic acid,
      • at least one nonionic starch, modified by means of propylene oxide and having a molecular weight (weight average) from 50 to 2500 kDa, and
      • at least one nonionic film-forming and/or nonionic setting polymer.
  • F): A cosmetic agent for the temporary deformation of keratinic fibers, particularly human hair, containing, in a cosmetic carrier,
      • at least one neutralization product of chitosan with at least one organic carboxylic acid,
      • at least one nonionic starch, modified by means of propylene oxide and having a molecular weight (weight average) from 50 to 2500 kDa, and
      • at least one nonionic film-forming and/or nonionic setting polymer chosen
        • copolymers of maleic acid anhydride and methyl vinyl ether,
        • polyvinylpyrrolidone,
        • copolymers of N-vinylpyrrolidone and vinyl esters of carboxylic acids having 2 to 18 carbon atoms, particularly N-vinylpyrrolidone and vinyl acetate,
          or mixtures of those polymers.
  • G): A cosmetic agent for the temporary deformation of keratinic fibers, particularly human hair, containing, in a cosmetic carrier,
      • at least one neutralization product of chitosan with at least one organic carboxylic acid, and
      • at least one nonionic starch modified with propylene oxide and having a viscosity in the range from 150 to 1,500,000 mPa·s, preferably 10,000 to 200,000 mPa·s, more preferably from 25,000 to 180,000 mPa·s (based on a 43-wt % aqueous solution, Brookfield viscosimeter, spindle 7 at 20° C. and 20 rpm).
  • H): A cosmetic agent for the temporary deformation of keratinic fibers, particularly human hair, containing, in a cosmetic carrier,
      • at least one neutralization product of chitosan with at least one organic carboxylic acid,
      • at least one nonionic starch modified with propylene oxide and having a viscosity in the range from 150 to 1,500,000 mPa·s, preferably 10,000 to 200,000 mPa·s, particularly preferably from 25,000 to 180,000 mPa·s (based on a 43-wt % aqueous solution, Brookfield viscosimeter, spindle 7 at 20° C. and 20 rpm), and
      • at least one nonionic film-forming and/or nonionic setting polymer.
  • I): A cosmetic agent for the temporary deformation of keratinic fibers, particularly human hair, containing, in a cosmetic carrier,
      • at least one neutralization product of chitosan with at least one organic carboxylic acid,
      • at least one nonionic starch modified with propylene oxide and having a viscosity from 150 to 1,500,000 mPa·s, preferably 10,000 to 200,000 mPa·s, particularly preferably from 25,000 to 180,000 mPa·s (based on a 43-wt % aqueous solution, Brookfield viscosimeter, spindle 7 at 20° C. and 20 rpm), and
      • at least one nonionic film-forming and/or nonionic setting polymer chosen from
        • copolymers of maleic acid anhydride and methyl vinyl ether,
        • polyvinylpyrrolidone,
        • copolymers of N-vinylpyrrolidone and vinyl esters of carboxylic acids having 2 to 18 carbon atoms, particularly N-vinylpyrrolidone and vinyl acetate,
          or mixtures of said polymers.
  • J): A cosmetic agent for the temporary deformation of keratinic fibers, particularly human hair, containing, in a cosmetic carrier,
      • at least one neutralization product of chitosan with at least one organic carboxylic acid, and
      • at least one nonionic starch modified with propylene oxide and having a molecular weight (weight average) from 50 to 2500 kDa and a viscosity from 150 to 1,500,000 mPa·s, preferably 10,000 to 200,000 mPa·s, particularly preferably from 25,000 to 180,000 mPa·s (based on a 43-wt % aqueous solution, Brookfield viscosimeter, spindle 7 at 20° C. and 20 rpm).
  • K): A cosmetic agent for the temporary deformation of keratinic fibers, particularly human hair, containing, in a cosmetic carrier,
      • at least one neutralization product of chitosan with at least one organic carboxylic acid,
      • at least one nonionic starch modified with propylene oxide and having a molecular weight (weight average) from 50 to 2500 kDa and a viscosity from 150 to 1,500,000 mPa·s, preferably 10,000 to 200,000 mPa·s, particularly preferably from 25,000 to 180,000 mPa·s (based on a 43-wt % aqueous solution, Brookfield viscosimeter, spindle 7 at 20° C. and 20 rpm), and
      • at least one nonionic film-forming and/or nonionic setting polymer.
  • L): A cosmetic agent for the temporary deformation of keratinic fibers, particularly human hair, containing, in a cosmetic carrier,
      • at least one neutralization product of chitosan with at least one organic carboxylic acid,
      • at least one nonionic starch modified with propylene oxide and having a molecular weight (weight average) from 50 to 2500 kDa and a viscosity from 150 to 1,500,000 mPa·s, preferably 10,000 to 200,000 mPa·s, particularly preferably from 25,000 to 180,000 mPa·s (based on a 43-wt % aqueous solution, Brookfield viscosimeter, spindle 7 at 20° C. and 20 rpm), and
      • at least one nonionic film-forming and/or nonionic setting polymer chosen from
        • copolymers of maleic acid anhydride and methyl vinyl ether,
        • polyvinylpyrrolidone,
        • copolymers of N-vinylpyrrolidone and vinyl esters of carboxylic acids having 2 to 18 carbon atoms, particularly N-vinylpyrrolidone and vinyl acetate,
          or mixtures of those polymers.
  • M): A cosmetic agent for the temporary deformation of keratinic fibers, particularly human hair, containing, in a cosmetic carrier,
      • at least one neutralization product of chitosan with at least one organic carboxylic acid, and
      • at least one nonionic starch modified with propylene oxide and having a viscosity from 150 to 1,500,000 mPa·s, preferably 10,000 to 200,000 mPa·s, particularly preferably from 25,000 to 180,000 mPa·s (based on a 43-wt % aqueous solution, Brookfield viscosimeter, spindle 7 at 20° C. and 20 rpm), and a propylene oxide content from 1 to 20 wt %, preferably 4 to 12 wt %, particularly preferably from 9.5 to 10.5 wt % or from 4.0 to 6.0 wt %, based on the weight of the modified starch.
  • N): A cosmetic agent for the temporary deformation of keratinic fibers, particularly human hair, containing, in a cosmetic carrier,
      • at least one neutralization product of chitosan with at least one organic carboxylic acid,
      • at least one nonionic starch modified with propylene oxide and having a viscosity from 150 to 1,500,000 mPa·s, preferably 10,000 to 200,000 mPa·s, particularly preferably from 25,000 to 180,000 mPa·s (based on a 43-wt % aqueous solution, Brookfield viscosimeter, spindle 7 at 20° C. and 20 rpm), and a propylene oxide content from 1 to 20 wt %, preferably 4 to 12 wt %, particularly preferably from 9.5 to 10.5 wt % or from 4.0 to 6.0 wt %, based on the weight of the modified starch, and
      • at least one nonionic film-forming and/or nonionic setting polymer.
  • 0): A cosmetic agent for the temporary deformation of keratinic fibers, particularly human hair, containing, in a cosmetic carrier,
      • at least one neutralization product of chitosan with at least one organic carboxylic acid,
      • at least one nonionic starch modified with propylene oxide and having a viscosity from 150 to 1,500,000 mPa·s, preferably 10,000 to 200,000 mPa·s, particularly preferably from 25,000 to 180,000 mPa·s (based on a 43-wt % aqueous solution, Brookfield viscosimeter, spindle 7 at 20° C. and 20 rpm), and a propylene oxide content from 1 to 20 wt %, preferably 4 to 12 wt %, particularly preferably from 9.5 to 10.5 wt % or from 4.0 to 6.0 wt %, based on the weight of the modified starch, and
      • at least one nonionic film-forming and/or nonionic setting polymer chosen from
        • copolymers of maleic acid anhydride and methyl vinyl ether,
        • polyvinylpyrrolidone,
        • copolymers of N-vinylpyrrolidone and vinyl esters of carboxylic acids having 2 to 18 carbon atoms, particularly N-vinylpyrrolidone and vinyl acetate,
          or mixtures of said polymers.
  • Preferred additional nonionic film-forming and/or nonionic setting polymers of embodiments A) to O)—when listed—are polyvinylpyrrolidone, copolymers of N-vinylpyrrolidone and vinyl acetate, or mixtures thereof.
  • Preferred organic carboxylic acids of the neutralization product of chitosan in accordance with embodiments A) to O) are chosen from lactic acid, formic acid, pyrrolidonecarboxylic acid, nicotinic acid, hydroxyisobutyric acid, hydroxyisovaleric acid, or mixtures of said acids.
  • Preferred utilization quantities of the ingredients according to embodiments A) to O) are those recited previously (see above).
  • It is preferred to additionally use at least one nonionic surfactant. These surfactants can already, according to the present invention, have an emulsifying effect.
  • Nonionic surfactants contain as a hydrophilic group, for example, a polyol group, a polyalkylene glycol ether group, or a combination of a polyol and polyglycol ether group. Such compounds include:
      • addition products of 2 to 100 mol ethylene oxide and/or 1 to 5 mol propylene oxide with linear and branched fatty alcohols having 8 to 30 carbon atoms, with fatty acids having 8 to 30 carbon atoms, and with alkylphenols having 8 to 15 carbon atoms in the alkyl group,
      • addition products of 2 to 20 units of glycerol with linear or branched fatty alcohols having 8 to 30 carbon atoms in the alkyl group, with linear or branched fatty acids having 8 to 30 carbon atoms in the alkyl group such as, the grades obtainable under the marketing designations Dermofeel® G 10 LW (Straetmans Chemical Products),
      • addition products, end-capped with a methyl or C2 to C6 alkyl residue, of 2 to 50 mol ethylene oxide and/or 1 to 5 mol propylene oxide with linear and branched fatty alcohols having 8 to 30 carbon atoms, with fatty acids having 8 to 30 carbon atoms, and with alkylphenols having 8 to 15 carbon atoms in the alkyl group, such as, for example, the grades obtainable under the marketing designations Dehydol® LS, Dehydol® LT (Cognis),
      • C12 to C30 fatty acid mono- and diesters of addition products of 1 to 30 mol ethylene oxide with glycerol,
      • addition products of 5 to 60 mol ethylene oxide with castor oil and hardened castor oil,
      • polyol fatty acid esters such as the commercial product Hydagen® HSP (Cognis), or Sovermol® grades (Cognis),
      • alkoxylated triglycerides,
      • alkoxylated fatty acid alkyl esters of formula (E4-I)

  • R1CO—(OCH2CHR2)wOR3   (E4-I),
  • wherein R1CO is a linear or branched, saturated and/or unsaturated acyl residue having 6 to 22 carbon atoms, R2 is hydrogen or methyl, R3 is linear or branched alkyl residues having 1 to 4 carbon atoms, and w is a number from 1 to 20,
      • amine oxides,
      • hydroxy mixed ethers such as those described, for example, in German Application 19738866,
      • sorbitan fatty acid esters and addition products of ethylene oxide with sorbitan fatty acid esters, for example the polysorbates,
      • sugar fatty acid esters and addition products of ethylene oxide with sugar fatty acid esters,
      • addition products of ethylene oxide with fatty acid alkanolamides and fatty amines,
      • sugar surfactants of the alkyl and alkenyl oligoglycoside types, in accordance with formula (E4-II)

  • R4O-[G]p   (E4-II),
      • wherein R4 is an alkyl or alkenyl residue having 4 to 22 carbon atoms, G is a sugar residue having 5 or 6 carbon atoms, and p is a number from 1 to 10. They can be obtained according to relevant methods of preparative organic chemistry.
  • Particularly preferred for use in the agent according to the present invention are those nonionic surfactants chosen from
      • addition products of 2 to 20 units of glycerol with linear or branched fatty alcohols having 8 to 30 carbon atoms in the alkyl group,
      • addition products of 2 to 20 units of glycerol with linear or branched fatty acids having 8 to 30 carbon atoms in the alkyl group,
      • addition products of 5 to 60 mol ethylene oxide with castor oil and hardened castor oil, and mixtures of the aforesaid surfactants.
  • Nonionic surfactants are present in the agent preferably in an amount from 0.005 wt % to 10 wt %, particularly from 0.01 wt % to 2 wt %, based on the weight of the agent according to the present invention.
  • The agent according to the present invention has acceptable hair-care properties even without further care-providing substances. To enhance the hair-care effect, the agent can additionally contain at least one cationic surfactant. Examples of cationic surfactants usable in the agents include quaternary ammonium compounds. Ammonium halides are preferred, particularly chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides, and trialkylmethylammonium chlorides (e.g., cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, and tricetylmethylammonium chloride). The highly biodegradable quaternary ester compounds called “esterquats,” such as the methylhydroxyalkyldialkoyloxyalkylammonium methosulfates marketed under the trade names Dehyquart® and Stepantex®, can also be used.
  • Agents according to the present invention are preferably present as foam. For that purpose, the agents are packaged in a delivery apparatus that is either a pressurized-gas container additionally filled with a propellant (“aerosol container”) or a non-aerosol container. Pressurized-gas containers from which a product is distributed through a valve due to the internal gas pressure of the container are referred to as “aerosol containers.” A “non-aerosol container” is defined, conversely to the “aerosol” definition, as a vessel under standard pressure from which a product is distributed by mechanical action by way of a pump system.
  • Agents according to the present invention are present particularly preferably as aerosol hair foam in an aerosol container. The agent therefore preferably additionally contains at least one propellant. In this connection, embodiments A) to O) are likewise considered, in particular, as preferably suitable compositions packaged in an aerosol container with at least one propellant for providing aerosol foam.
  • Agents according to the present invention that are present in the form of an aerosol product can be manufactured in usual fashion. All constituents of the agent except for the propellant are introduced into a suitable pressure-tight container. The latter is then sealed with a valve. Lastly, the desired quantity of propellant is introduced using conventional techniques.
  • As aerosol foam, propellants suitable according to the present invention include N2O, dimethyl ether, CO2, air, alkanes having 3 to 5 carbon atoms such as propane, n-butane, isobutane, n-pentane, and isopentane, and mixtures thereof. In the embodiment as aerosol foam, the aforesaid alkanes, mixtures of the aforesaid alkanes, or mixtures of the aforesaid alkanes with dimethyl ether are used as the only propellant. The invention also expressly includes, however, the concurrent use of fluorochlorocarbon propellants, particularly fluorocarbons.
  • Dimethyl ether, propane, n-butane, isobutane, and mixtures thereof are preferred. Very particularly preferably, mixtures of propane and butane are used as the only propellant at a weight ratio of propane to butane from 70:30 to 15:85. These mixtures are used in the agents preferably in an amount from 3 to 15 wt %, based on total weight of the agent. “Butane” according to the present invention is n-butane, isobutane, and mixtures of n-butane and isobutane. For a given spray apparatus, the sizes of the foam bubbles and the respective size distribution can be adjusted by the quantitative ratio between the propellant and the other constituents of the preparations.
  • When conventional aerosol containers are used, aerosol foam products contain the propellant preferably in amounts from 1 to 35 wt %, based on total product. Quantities from 2 to 30 wt %, particularly 3 to 15 wt %, are particularly preferred.
  • Isopentane is preferably suitable as a propellant for foaming gel-type agents in a two-chamber aerosol container, said propellant being is incorporated into the agents according to the present invention and being packaged in the first chamber of the two-chamber aerosol container. Packaged in the second chamber of the two-chamber aerosol container is at least one further propellant different from isopentane that builds up in the two-chamber aerosol container a higher pressure than isopentane. Propellants of the second chamber are preferably chosen from N2O, dimethyl ether, CO2, air, alkanes having 3 or 4 carbon atoms (such as propane, n-butane, isobutane), and mixtures thereof.
  • A second subject of the invention is the use of a cosmetic agent of the first subject of the invention for temporary deformation and/or shape fixing of keratinic fibers, particularly human hair.
  • A third subject of the invention is a method for temporary deformation of keratinic fibers, particularly human hair, wherein a cosmetic agent of the first subject of the invention is applied onto the keratinic fibers.
  • Preferably, the keratinic fibers, after application of the cosmetic agents of the first subject of the invention, are not rinsed and are left on the fibers.
  • The Examples that follow are intended to explain the subject matter of the present invention without in any way limiting them.
  • EXAMPLES
  • The following formulation according to the present invention was manufactured in an aerosol container as an aerosol foam product:
  • Raw material I1 (wt %)
    Hydagen HCMF1 0.50
    Lactic acid 0.28
    Luviskol 60/40 W NP2 10.70
    Nonionic starch modified by means of propylene oxide3 2.70
    Sodium benzoate 0.30
    D-Panthenol 0.15
    Dow Corning 9394 0.20
    Dehyquart A CA5 1.00
    Propane/butane 8.00
    Water to 100
    1Chitosan (80% deacetylated), molecular weight 50,000 to 1,000,000 g/mol, Cognis)
    2Copolymer of N-vinylpyrrolidone and vinyl acetate
    3Potato starch, propylene oxide content: 10 wt % propylene oxide, viscosity: 64,000 mPa · s, average molecular weight (weight average): 800 kDa
    4Approx. 32 to 26% active substance, INCI name: Amodimethicone, Trideceth-12, Cetrimonium Chloride (Dow Corning)
    5Trimethylhexadecylammonium chloride (approx. 24 to 26% active substance, INCI name: Aqua (Water), Cetrimonium Chloride) (Cognis)
  • Formulation I1 was applied onto a test subject as an aerosol foam in order to fix the hairstyle as to shape. The hair achieved a natural shine, a strong hairstyle hold, and durable volume.

Claims (14)

1. Cosmetic agent for temporary deformation of keratinic fibers comprising, in a cosmetic carrier:
at least one chitosan or derivative thereof, and
at least one nonionic starch modified with propylene oxide.
2. Cosmetic agent according to claim 1, wherein the at least one chitosan or derivative thereof is a neutralization product of chitosan with at least one organic carboxylic acid.
3. Cosmetic agent according to claim 2, wherein the organic carboxylic acid is chosen from lactic acid, formic acid, pyrrolidonecarboxylic acid, nicotinic acid, hydroxyisobutyric acid, hydroxyisovaleric acid, and mixtures thereof.
4. Cosmetic agent according to claim 1, wherein the chitosan or derivative thereof is present in an amount from 0.01 wt % to 5 wt %, based on total weight of the agent.
5. Cosmetic agent according to claim 1, wherein the modified nonionic starch is a modified nonionic tapioca starch, a modified nonionic potato starch or a mixture thereof.
6. Cosmetic agent according to claim 1, wherein the modified nonionic starch has an average molecular weight (weight average) from 50 to 2500 kDa.
7. Cosmetic agent according to claim 1, wherein the modified nonionic starch has a propylene oxide content from 1 to 20 wt %, based on weight of the modified nonionic starch.
8. Cosmetic agent according to claim 1, wherein the modified nonionic starch has, in a 43-wt % aqueous solution, a viscosity from 150 to 1,500,000 mPa·s, based on Brookfield viscosimeter, spindle 7 at 20° C. and 20 rpm.
9. Cosmetic agent according to claim 1, wherein the modified nonionic starch is present in an amount from 0.1 wt % to 10 wt %, based on total weight of the agent.
10. Cosmetic agent according to claim 1, wherein the modified nonionic starch is at least one uncrosslinked nonionic starch modified with propylene oxide.
11. Foam comprising the cosmetic agent according to claim 1.
12. Cosmetic agent according to claim 1 further comprising at least one film-forming and/or setting polymer.
13. Cosmetic agent according to claim 1 wherein the cosmetic carrier further comprises at least 50 wt % water, based on total weight of the agent.
14. Method for temporary deformation of keratinic fibers comprising applying a cosmetic agent according to claim 1 onto the keratinic fibers.
US13/453,393 2009-10-22 2012-04-23 Agent for temporarily styling keratin-containing fibres containing a non-ionic starch modified by propylene oxide and a chitosane Abandoned US20120213724A1 (en)

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DE102009045925A DE102009045925A1 (en) 2009-10-22 2009-10-22 Compositions for shaping keratinic fibers
DE102009045925.1 2009-10-22
DE102009045933A DE102009045933A1 (en) 2009-10-22 2009-10-22 Composition for shaping keratinic fibers
DE102009045933.2 2009-10-22
PCT/EP2010/065860 WO2011048177A1 (en) 2009-10-22 2010-10-21 Agent for temporarily styling keratin-containing fibres, containing a non-ionic starch modified by propylene oxide and a chitosane

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US13/453,291 Abandoned US20120207694A1 (en) 2009-10-22 2012-04-23 Agent for treating keratin-containing fibers, containing a non-ionic starch modified by propylene oxide and an anionic polymer
US13/453,015 Active US8603447B2 (en) 2009-10-22 2012-04-23 Agent for treating keratin-containing fibers, containing a non-ionic starch modified by propylene oxide and an additional film-forming and/or stabilizing nonionic polymer
US13/453,393 Abandoned US20120213724A1 (en) 2009-10-22 2012-04-23 Agent for temporarily styling keratin-containing fibres containing a non-ionic starch modified by propylene oxide and a chitosane
US13/453,194 Abandoned US20120207693A1 (en) 2009-10-22 2012-04-23 Agent for keratin-containing fibers, comprising at least one non-ionic starch modified by propylene oxide and at least one additional film-forming cationic and/or stabilizing polymer
US13/453,530 Abandoned US20120328532A1 (en) 2009-10-22 2012-04-23 Composition for shaping keratin fibers containing starches modified with propylene oxide

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US13/453,015 Active US8603447B2 (en) 2009-10-22 2012-04-23 Agent for treating keratin-containing fibers, containing a non-ionic starch modified by propylene oxide and an additional film-forming and/or stabilizing nonionic polymer

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US13/453,530 Abandoned US20120328532A1 (en) 2009-10-22 2012-04-23 Composition for shaping keratin fibers containing starches modified with propylene oxide

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US8603447B2 (en) 2013-12-10
EP2490659B1 (en) 2017-03-01
EP2490656B1 (en) 2017-01-18
US20120328532A1 (en) 2012-12-27
WO2011048172A2 (en) 2011-04-28
EP2490656A1 (en) 2012-08-29
EP2490659A1 (en) 2012-08-29
EP2490657A1 (en) 2012-08-29
EP2490658A1 (en) 2012-08-29
WO2011048175A1 (en) 2011-04-28
WO2011048178A1 (en) 2011-04-28
EP2490657B1 (en) 2017-01-18
US20120207694A1 (en) 2012-08-16
EP2490653A2 (en) 2012-08-29
WO2011048176A1 (en) 2011-04-28
WO2011048172A3 (en) 2011-06-16
WO2011048177A1 (en) 2011-04-28
US20120207692A1 (en) 2012-08-16
EP2490653B1 (en) 2017-01-11

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