EP3727598A1 - Spezieller polyurethanharnstoff zur erhöhung der wasserbeständigkeit einer geformten frisur - Google Patents
Spezieller polyurethanharnstoff zur erhöhung der wasserbeständigkeit einer geformten frisurInfo
- Publication number
- EP3727598A1 EP3727598A1 EP18825648.1A EP18825648A EP3727598A1 EP 3727598 A1 EP3727598 A1 EP 3727598A1 EP 18825648 A EP18825648 A EP 18825648A EP 3727598 A1 EP3727598 A1 EP 3727598A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hair
- component
- mol
- water
- use according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/87—Polyurethanes
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- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
- A45D7/00—Processes of waving, straightening or curling hair
- A45D7/04—Processes of waving, straightening or curling hair chemical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3234—Polyamines cycloaliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
Definitions
- the invention relates to the use of a specific polyurethaneurea on hair to improve the water resistance of the hairstyle obtained by shaping the hair, as well as a method for water resistant and / or washable hair shaping using the specific polyurethaneurea and a composition containing the specific polyurethaneurea in particular dosage forms.
- Hair fixatives are usually in the form of mousses or hair sprays, and they hardly differ in their composition. Mousse mousses are applied to damp hair as a tool to model the hairstyle. In contrast, hair sprays, hair creams, hair gels or hair waxes are applied to dry finished styled hair to fix the hairstyle for everyday wear.
- the means for fixing or shaping the hairstyle are usually in the form of preparations which can be sprayed from aerosol containers, squeeze bottles or pumping, spraying or frothing devices and which consist of an alcoholic, aqueous or aqueous-alcoholic solution of film-forming natural substances or synthetic polymers.
- These polymers can be selected from the group of nonionic, cationic, amphoteric or anionic polymers.
- WO 2009/118105 A1 describes hair-setting compositions which obtain a polyurethaneurea which can be obtained by reacting a water-insoluble, non-water-dispersible isocyanate-functional polyurethane prepolymer with an amino-functional compound.
- the hair setting compositions disclosed herein are well-suited for stabilizing hairstyles until the next hair wash. However, hereby no hairstyles can be made sustainable that would outlast a hair wash.
- the object of the present invention was therefore to overcome at least one disadvantage of the prior art, at least in part. Furthermore, it was an object to provide a polyurethaneurea which, when used on hair, is suitable for achieving increased water resistance of the hairstyle formed therewith. In particular, it was an object to achieve a water resistance of the molded polyurethaneurea hairstyle over several washes. Another task was to provide a method that makes it possible to produce a water- and / or wash-resistant hairstyle. Surprisingly, this object has been achieved by using a polyurethaneurea obtainable by reacting at least the following components: a) a polyisocyanate component,
- an amino-functional chain extender component wherein the polyisocyanate component a) comprises> 75 mol% isophorone diisocyanate (IPDI) and the amino-functional chain extender component c)> 75 mol% isophorone diamine (IPDA), on hair to improve the water resistance or the washing resistance of the hairstyle obtained by shaping the hair.
- IPDI isophorone diisocyanate
- IPDA isophorone diamine
- Water resistance is understood according to the invention to mean that the resistance of the hairstyle formed with the polyurethaneurea to water is tested or determined.
- the hair is surrounded in a rinsing treatment at least in part with liquid water, so impregnated or rinsed here.
- the water can be any form of liquid water that comes in contact with hair in everyday life. Examples include drinking water, rainwater, swimming pool water (chlorinated, ozonated or otherwise sanitized), sea water or distilled water.
- Washing resistance is understood according to the invention as meaning that the resistance of the hairstyle formed with the polyurethaneurea to surfactant-containing water is tested or determined, the hair in this washing treatment being completely surrounded by the surfactant-containing water, ie rinsed therein.
- an amino-functional chain extender component is understood as meaning a component which comprises at least one compound having two isocyanate-reactive amino groups and no hydrophilicizing groups.
- the shaping of the hair into a hairstyle is selected from the group consisting of: a. A smoothing of curly hair;
- Smoothing curly hair under a. can be carried out in any manner known to those skilled in the art, in particular by means of a smoothing device.
- the smoothing of curly hair preferably takes place by means of a smoothing iron, a smoothing rod or a similar smoothing device, which is suitable for this purpose.
- the smoothing device is designed so that it is equipped with the help of at least 150 ° C heated elements.
- the smoothing device is preferably suitable for smoothing curls to a degree of smoothness of at least 50%, or preferably at least 80%, or preferably at least 90%.
- the degree of smoothness is determined by determining the width of a strand of hair before and after smoothing by means of a ruler.
- a degree of smoothness of 50%, or 80%, or 90% means that the width of the strand of hair after step a. by 50%, or 80%, or 90% narrower compared to the width before step a. has become.
- Curling in straight hair under b. can be carried out in any manner known to those skilled in the art, in particular by means of a curling device.
- the curling of straight hair by means of a curling iron or similar curling device, which is suitable for this.
- the curling device is designed such that it contains, for example, at temperatures of 40 to 80 ° C by means of curl-generating elements, which preferably can be easily heated.
- the curler is suitable for producing curls to a degree of curl of at least 50%, or preferably at least 80%, or preferably at least 90%.
- the degree of curl is determined by determining the length of a strand of hair before and after curling by means of a ruler.
- a degree of curl of 50%, or 80%, or 90% means that the length of the hair strand after step b. 50%, or 80%, or 90% shorter than before step b ..
- Reinforcing the curls under c. is preferably done in the same way as the introduction of the curls under b.
- the strengthening of the curls under c. by using a polyurethane-containing composition in preferably wet hair in the form of the use according to the invention, wherein the hair is then dried with or without auxiliaries.
- the curler is suitable for creating curls to a curl degree of at least 30%, or preferably at least 40%, or preferably 50%.
- the degree of curl is determined by determining the length of a strand of hair before and after curling by means of a ruler.
- a degree of curl of 30%, or 40%, or 50% means that the length of the hair strand after step b. 30%, 40% or 50% shorter than before step c ..
- the shape of the hairdressed hair remains at least 5%, preferably at least 7%, or preferably at least 10% after contact with water.
- the degree of preservation of the shape of the coiffured hair may preferably vary greatly depending on the type of treatment. So it makes a difference whether the hair prior to the use of the invention polyurethaneurea were smoothed or whether the hair was lured.
- the degree of preservation of the hairstyle is also referred to as "styling retention" in the following.
- the smoothing of the hair remains below a. at least 50%, or preferably at least 60%, or preferably at least at least 70% or at least 80%, or at least 90% after contact with water, or the curling of the hair under b. at least 5%, or preferably at least 7%, or preferably at least 10%, or the curl under c. at least 5%, or preferably at least 7%, or preferably at least 10%.
- the present invention therefore preferably relates to the use according to the invention, wherein the styling retention x for smoothed hair, in particular according to the abovementioned group a., At least 50%, or preferably at least 60%, or preferably at least 70% or at least 80%, or at least 90% after contact with water.
- the styling retention times calculated for smoothed hair are calculated according to:
- the water resistance test is preferably performed by individually dipping smoothed hair tresses individually into a 38 ° C heated 2 liter water bath for 30 seconds, draining for 10 seconds, and allowing to dry completely at room temperature air for 24 hours.
- the present invention relates to the use according to the invention, wherein the curling hair styling retention x, in particular according to the abovementioned group b. and / or c. at least 5%, or preferably at least 7%, or preferably at least 10%.
- the styling retention x curly for curly hair is calculated according to:
- the polyurethaneurea is in the form of a hair-cosmetic composition.
- this is selected from the group consisting of a gel, a cream, an aerosol, a spray, a hair wax or a combination of at least two thereof.
- the polyisocyanate component a) may comprise> 80 mol%, preferably> 85 mol%, more preferably 95 mol% and particularly preferably 100 mol% of IPDI.
- polyisocyanates of component a) which can be used in addition to IPDI in a molar proportion of less than 25 mol% are the aromatic, araliphatic, aliphatic or cycloaliphatic polyisocyanates known per se to the person skilled in the art having an NCO functionality of>
- polyisocyanates examples include 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 2,2,4 and / or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bis (4,4'-isocyanatocyclohexyl) methanes or their mixtures any isomer content, 1,4-cyclohexylene diisocyanate, 1,4-phenylene diisocyanate, 2,4- and / or 2,6-toluene diisocyanate, 1,5-naphthylene diisocyanate, 2,2'- and / or 2,4'- and or 4,4'-diphenylmethane diisocyanate, 1,3- and / or 1,4-bis (2-isocyanato-prop-2-yl) -benzene (TMXDI), 1,3-bis (isocyanatomethyl) benzene (XDI ), Alkyl 2,6-d
- modified diisocyanates or triisocyanates having uretdione, isocyanurate, urethane, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structures.
- polyisocyanates or polyisocyanate mixtures of the abovementioned type having exclusively aliphatically and / or cycloaliphatically bonded isocyanate groups and an average NCO functionality of the mixture of from 2 to 4, preferably from 2 to 2.6 and particularly preferably from 2 to 2.4 ,
- the polymeric polyol component b) has a number-average molecular weight of> 400 and ⁇ 8000 g / mol, particularly preferably from 600 to 3000 g / mol and / or has an average OH functionalities of from 1.5 to 6, preferably from 1.8 to 3 and particularly preferably from 1.9 to 2.1.
- the polymeric polyol component b) comprises or consists of a polyester, preferably a polyester based on adipic acid.
- polyester polyols known per se in polyurethane coating technology, polyacrylate polyols, polyurethane polyols, polycarbonate polyols, polyether polyols, polyester polyacrylate polyols, polyurethane polyacrylate polyols, polyurethane polyester polyols, polyurethane polyether polyols, polyurethane polycarbonate polyols and polyester polycarbonate polyols. These can be used in b) individually or in any mixtures with one another.
- Polyester polyols are, for example, the known polycondensates of di- and optionally tri- and tetraoic and di- and optionally tri- and tetracarboxylic acids or hydroxycarboxylic acids or lactones. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols for the preparation of the polyesters.
- diols examples include ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4), hexanediol (1,6) and isomers, neopentyl glycol or hydroxypivalic acid neopentyl glycol esters, with hexanediol (1,6) and isomers, neopentyl glycol and neopentyl glycol hydroxypivalate being preferred.
- polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4), hexanediol (1,6) and isomers,
- polyols such as trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene or trishydroxyethyl isocyanurate.
- Suitable dicarboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid, maleic acid, fumaric acid, itaconic acid, malonic acid, suberic acid, 2-methylsuccinic acid, 3,3-diethylglutaric acid and / or 2 , 2-Dimethylsuccinic be used.
- the acid source used may also be the corresponding anhydrides.
- monocarboxylic acids such as benzoic acid and hexanecarboxylic acid may additionally be used.
- Preferred acids are aliphatic or aromatic acids of the abovementioned type. Particular preference is given to adipic acid, isophthalic acid and, if appropriate, trimellitic acid, very particular preference to adipic acid.
- Hydroxycarboxylic acids which can be co-used as reactants in the preparation of a hydroxyl-terminated polyester polyol include, for example, hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid, hydroxystearic acid, and the like.
- Suitable lactones are caprolactone, butyrolactone and homologs. Preference is given to caprolactone.
- hydroxyl-containing polycarbonates preferably polycarbonatediols, having number-average molecular weights Mn of from 400 to 8000 g / mol, preferably from 600 to 3000 g / mol.
- carbonic acid derivatives such as diphenyl carbonate, dimethyl carbonate or phosgene
- diols examples include ethylene glycol, 1,2- and 1,3-propanediol, 1,3- and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bis-hydroxymethylcyclohexane, 2- Methyl-l, 3-propanediol, 2,2,4-Trimethylpentandiol-l, 3, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenol A and lactone-modified diols of the aforementioned kind.
- the hydroxyl-containing polycarbonates are preferably linearly constructed.
- polyether polyols can be used in component b).
- Suitable examples are the polytetramethylene glycol polyethers known per se in polyurethane chemistry, such as are obtainable by polymerization of tetrahydrofuran by means of cationic ring opening.
- polyether polyols are the per se known addition products of styrene oxide, ethylene oxide, propylene oxide, butylene oxides and / or epichlorohydrin to di- or polyfunctional starter molecules.
- starter molecules it is possible to use all compounds known from the prior art, for example water, butyldiglycol, glycerol, diethylene glycol, trimethylolpropane, propylene glycol, sorbitol, ethylenediamine, triethanolamine, 1,4-butanediol.
- Preferred starter molecules are water, ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol and butyl diglycol.
- the hydrophilizing component c) is an anionically hydrophilicizing component and preferably a sulphonate.
- Suitable anionic or potentially anionic hydrophilizing compounds of component c) are compounds which have at least one isocyanate-reactive group such as a hydroxyl group or amino group and at least one functionality such as -COO-M + , -SC> 3-M + , - PO (0 -M + ) 2 with M +, for example, the same metal cation, H + , NH 4 + , NHR 3 + , where each R can be a C 1 -C 12 -alkyl radical, C 5 -C 6 -cycloalkyl radical and / or a C 2 -C 4 -hydroxyalkyl radical which undergoes a pH-dependent dissociation equilibrium upon interaction with aqueous media and thus can be negatively or neutrally charged.
- Suitable anionic or potentially anionic hydrophilizing compounds are mono- and dihydroxycarboxylic acids, mono- and dihydroxysulfonic acids, as well as mono- and dihydroxyphosphonic acids and their salts.
- Examples of such anionic or potentially anionic hydrophilicizing agents are dimethylolpropionic acid, dimethylolbutyric acid, hydroxypivalic acid, malic acid, citric acid, glycolic acid, lactic acid and the propoxylated adduct of 2-butenediol and Nal ISO, as described in DE-A 2 446 440, page 5-9, For mel I-III is described.
- Preferred anionic or potentially anionic hydrophilicizing agents of component c) are those of the abovementioned type which have carboxylate or carboxylic acid groups and / or sulfonate groups.
- Suitable nonionically hydrophilicizing compounds of component c) are e.g. Polyoxyalkylene ethers containing at least one hydroxy or amino group, preferably at least one hydroxy group.
- Examples are the monohydroxy-functional, on average 5 to 70, preferably 7 to 55 ethylene oxide units per molecule having Polyalkylenoxidpolyetheralkohole, as they are accessible in a conventional manner by alkoxylation of suitable starter molecules (eg in Ullmann's Encyclopaedia of Industrial Chemistry, 4th Edition, Volume 19 , Verlag Chemie, Weinheim pp. 31-38).
- suitable starter molecules eg in Ullmann's Encyclopaedia of Industrial Chemistry, 4th Edition, Volume 19 , Verlag Chemie, Weinheim pp. 31-38.
- These compounds are either pure polyethylene oxide ethers or mixed polyalkylene oxide ethers, but then they contain at least 30 mol%, preferably at least 40 mol%, based on all alkylene oxide units contained in ethylene oxide units.
- Particularly preferred nonionic compounds are monofunctional, mixed polyalkylene oxide polyethers having from 40 to 100 mole percent ethylene oxide and from 0 to 60 mole percent propylene oxide units.
- hydrophilization it is also possible to use mixtures of anionic or potentially anionic hydrophilicizing agents and nonionic hydrophilicizing agents.
- the amino-functional chain extender component d) can comprise> 85 mol%, preferably> 95 mol% and particularly preferably 100 mol% IPDA.
- amino-functional chain extender d in addition to IPDI, further NH 2 and / or NH-functional compounds can be used.
- the chain extension / termination is preferably carried out in water prior to dispersion, in which case the isocyanate groups react with the chain extender to form urea groups.
- Suitable components - which can be used in addition to IPDA in a molar fraction of less than 25% - are di- or polyamines such as 1,2-ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, 1 , 6-diaminohexane, 2,2,4- and 2,4,4- Trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylenetriamine, triaminononane,
- di- or polyamines such as 1,2-ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, 1 , 6-diaminohexane, 2,2,4- and 2,4,4- Trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylenetriamine, triaminononane,
- 1,3- and 1,4-xylylenediamine a, a, a ', a'-tetramethyl-l, 3- and 1,4-xylylenediamine and 4,4-diaminodicyclohexylmethane and / or dimethylethylenediamine.
- hydrazine or hydrazides such as adipic dihydrazide.
- Examples are hydroxy-functional compounds having molecular weights of from 62 to 399 g / mol such as, for example, polyols of the stated molecular weight range having up to 20 carbon atoms, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol,
- 1,3-butylene glycol 1,3-butylene glycol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, neopentyl glycol, hydroquinone dihydroxyethyl ether, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), hydrogenated bisphenol A, (2,2-bis (4 -hydroxycyclohexyl) propane), trimethylolpropane, glycerol, pentaerythritol.
- monofunctional isocyanate-reactive amine compounds can be used, such as methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methyl-aminopropylamine, diethyl (methyl) aminopropylamine, morpholine, piperidine.
- no further building blocks are preferably used for the preparation of the polyurethaneurea for use according to the invention.
- the preparation of the polyurethaneurea for its use according to the invention can be carried out in one or more stages in homogeneous or multistage reaction by the processes known to the person skilled in the art, and in some cases in disperse phase.
- a dispersing, emulsifying or dissolving step is preferably carried out. This is followed, if appropriate, by a further polyaddition or modification in disperse or dissolved (homogeneous) phase.
- all known from the prior art methods such.
- prepolymer mixing method, acetone method or Schmelzdispergier vide can be used. Preference is given to working by the acetone process.
- Another object of the invention is a method for water-resistant and / or wash-resistant forms of hair to a hairstyle with the steps: i. Treating the hair with a polyurethaneurea, obtainable by reacting at least one polyisocyanate component, a polymeric polyol component, a hydrophilizing component and an amino-functional chain extender component, wherein the polyisocyanate component a)> 75 mol% of isophorone diisocyanate (IPDI) and the amino-functional chain extender component c) comprises> 75 mol% isophoronediamine (IPDA); ii. Shapes the hair to the desired hairstyle;
- a polyurethaneurea obtainable by reacting at least one polyisocyanate component, a polymeric polyol component, a hydrophilizing component and an amino-functional chain extender component, wherein the polyisocyanate component a)> 75 mol% of isophorone diisocyanate (IPDI) and the amino-functional chain extender component
- While bringing the hair into contact with water under point iv. is understood according to the invention that at least a portion of the in step ii. In the form of brought hair is immersed in water. What is meant by water has already been defined above.
- a washing process with surfactant-containing water, also called shampooing is preferably included in the contacting of the hair.
- Another object of the invention is a waterproof hair cosmetic composition
- a polyurethaneurea obtainable by reacting at least b) a polyisocyanate component,
- polyisocyanate component a) comprises> 75 mol% isophorone diisocyanate (IPDI) and the amino-functional chain extender component c)> 75 mol% isophoronediamine (IPDA) and the composition is selected from the group consisting of Group consisting of a gel, a cream, an aerosol, a spray, a hair wax or a combination of at least two thereof is formed.
- IPDI isophorone diisocyanate
- IPDA isophoronediamine
- the hair-cosmetic composition preferably comprises a solvent, a solvent mixture or a dispersant and a polyurethaneurea previously suitable for the use according to the invention, where the solvent, the solvent mixture or the dispersant comprises water or ethanol and water.
- the hair cosmetic composition contains only water as a solvent or dispersant.
- the solvent mixture may optionally contain further cosmetically suitable solvents.
- Preferred solvents are aliphatic alcohols having C 2-4 carbon atoms, such as isopropanol, t-butanol, n-butanol; Polyols such as propylene glycol, glycerin, ethylene glycol and polyol ethers; Acetone; unbranched or branched hydrocarbons such as pentane, hexane, isopentane and cyclic hydrocarbons such as cyclopentane and cyclohexane; and their mixtures.
- the hair-cosmetic composition comprises a solvent mixture
- the solvent mixture > 10 wt .-% and ⁇ 98 wt .-%, preferably> 15 wt .-% and ⁇ 98 wt%, more preferably> 20 Wt .-% and ⁇ 90 wt .-% and particularly preferably> 20 wt .-% and ⁇ 80 wt .-% ethanol.
- the solvent mixture consists of water and ethanol.
- the composition prefferably contains> 0.1% by weight and ⁇ 30% by weight, preferably> 0.1% by weight and ⁇ 20% by weight, more preferably> 0.5% by weight.
- -% and ⁇ 15 wt .-% and particularly preferably> 0.5 wt .-% and ⁇ 10 wt .-% of the polyurethane urea comprises.
- composition which is> 10% by weight and ⁇ 98% by weight, preferably> 20% by weight and ⁇ 98% by weight, more preferably> 30% by weight and ⁇ 98% by weight. % and more preferably> 40 wt .-% and ⁇ 98 wt .-% of the solvent mixture.
- composition according to the invention may contain, in addition to the above-described polyurethane, further suitable fungicidal agents which may in particular also contribute to the pinning and styling of the hair.
- the proportion of one or more further fungicides may be from 0 to 20% by weight and in particular 0 to 10% by weight, based on the total formulation.
- the one or more other fungi are selected from the group of nonionic, anionic, amphoteric and / or cationic polymers and mixtures thereof.
- the composition in Porm is selected from the group consisting of a pump spray, an aerosol, a gel, a foam, a mousse, a lotion, a wax, a pomade, an oil, a milk, an oil in water emulsion, an aqueous solution or a cream.
- the cosmetic composition is preferably in the form of oil-in-water, silicone in-water, water-in-oil, water-in-silicone, oil-in-water-in-oil, water-in-oil-in-water, emulsion.
- O emulsifiers having an HLB value ⁇ 7 and optionally one or more O / W emulsifiers having an HLB value> 10, wherein HLB (according to Griffin) 20 * (1 - Mi / M), where Mi is the molecular weight is the lipophilic portion of a molecule and M is the molecular weight of the entire molecule.
- the silicone emulsifiers may advantageously from the group containing Alkyldimethiconcopolyole such.
- PEG-10 Dimethicone KF-6017 from Shin Etsu
- PEG / PPG 18/18 Dimethicone Dow Corning 5225C from Dow Corning Ltd.
- PEG / PPG-19/19 Dimethicone Dow Corning BY -11,030 from Dow Corning Ltd.
- the W / O emulsifiers having an HLB value ⁇ 7 can advantageously be selected from the group comprising sorbitan stearate, sorbitan oleate, glyceryl isostearate, polyglyceryl-3-oleate, pentaerythrityl isostearate, methyl glucose dioleate, PEG-7-hydrogenated ricinus oil, polyglyceryl-4-isostearate, hexyl laurate, Sorbitan isostearate, polyglyceryl-2-dipolyhydroxystearate, polyglyceryl-3-diisostearate, PEG-30 dipolyhydroxystearate, diisostearoylpolyglyceryl-3-diisostearate, polyglyceryl-3-dipolyhydroxystearate, polyglyceryl-4-dipolyhydroxystearate, polyglyceryl-3-dioleate and wool wax alcohol (Eucerit) ,
- the O / W emulsifiers having an HLB value> 10 can advantageously be chosen from the group comprising lecithin, trilaureth-4-phosphate, polysorbate-20, polysorbate-60, PEG-22-dodecylglycol copolymer, sucrose stearate and sucrose laurate.
- an oil thickener can advantageously be used.
- Particularly advantageous oil thickeners are organo-modified clays such as organically modified bentonite (Bentone ® 34 from Rheox) organomodified Hectorite (Bentone ® 27 and Bentone ® 38 from Rheox) or organo-montmorillonite, hydrophobic fumed Kiesselklare, wherein the silanol groups with trimethylsiloxy groups are substituted (AEROSIL ® R812 from Degussa) or (dimethylsiloxy groups with polydimethylsiloxane or Aerosil ® R972, Aerosil ® R974 by Degussa, CAB-O-SIL ® TS-610, "CAB-O-SIL ® TS-720 from Cabot), magnesium or aluminum stearate, or styrene copolymers such as styrene-butadiene-styrene, styrene-isoprene-styrene, styren
- the aqueous phase may further contain stabilizing agents.
- the stabilizing agent may be, for example, sodium chloride, magnesium chloride or magnesium sulfate and mixtures thereof.
- Oils can be used in W / O, W / Si and O / W emulsions.
- the fat phase of the composition of the invention contains at least one non-volatile oil.
- the fat phase of the composition may also contain volatile oils and waxes.
- the O / W composition advantageously contains 0 to 45% by weight of oils, based on the total weight of the composition, and more preferably 0 to 20% by weight of oils.
- the W / O or W / Si composition advantageously contains at least 20% by weight of oils, based on the total weight of the composition.
- the non-volatile oil is advantageously selected from the group of mineral, animal, vegetable or synthetic origin, polar or nonpolar oils and mixtures thereof.
- Polar oils can be selected from lecithins and fatty acid triglycerides, namely the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 8 to 24, in particular 12 to 18, carbon atoms.
- the fatty acid triglycerides may be selected from the group of cocoglyceride, olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, castor oil, wheat germ oil, grapeseed oil, safflower oil, evening primrose oil, macadamia nut oil, apricot kernel oil, avocado oil and the like.
- polar oils can be selected from the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms and from the group of esters of aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms.
- ester oils may preferably be selected from the group of phenethyl benzoate, octyl palmitate, octyl cocoate, octyl isostearate, octyl dodecyl myristate, octyl dodecanol, cetearyl isononanoate, isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, diisopropyl adipate, isooctyl stearate, isononyl stearate , isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl laurate, 2-hexyl
- the polar oils may be selected from the group of dialkyl ethers and dialkyl carbonates, are, for example, dicaprylyl ether (Cetiol OE ® from BASF) and / or dicaprylyl carbonate (Cetiol ® CC, for example, from BASF).
- dialkyl ethers and dialkyl carbonates are, for example, dicaprylyl ether (Cetiol OE ® from BASF) and / or dicaprylyl carbonate (Cetiol ® CC, for example, from BASF).
- polar oils from the group isoeicosane, neopentyl glycol diheptanoate, propylene glycol dicaprylate / dicaprate, caprylic / capric / diglyceryl succinate, butylene glycol
- Dicaprylate / dicaprate Ci2-i3-alkyl lactate, di-Ci2-i3-alkyl tartrate, 02-15 alkyl benzoate, myristyl myristate, isodecyl neopentanoate, triisostearin, dipentaerythrityl hexacaprylate / hexacaprate,
- the non-volatile oil may also advantageously be a non-polar oil, which is selected from the group of branched and unbranched hydrocarbons, especially mineral oil, Vaselineöl, paraffin oil, squalane and squalene, polyolefins example, polydecenes, hydrogenated polyisobutenes, 03-16 isoparaffin and Isohexadecan ,
- the nonpolar non-volatile oil may be selected from nonvolatile silicone oils.
- the polydimethylsiloxanes PDMS
- phenylated such as the phenyltrimethicone
- functional groups for example hydroxy groups, thiol groups and / or amino groups
- composition of the invention may further contain a wax.
- a wax is defined as lipophilic fatty substance, which is solid at room temperature (25 ° C) and at a melting temperature between 30 ° C and 200 ° C shows a reversible change in state solid / liquid. Above the melting point, the wax becomes low viscous and miscible with oils.
- the wax is advantageously selected from the group of natural waxes such as cotton wax, carnauba wax, candelilla wax, esparto wax, Japan wax, montan wax, sugarcane wax, beeswax, wool wax, shellac, microwaxes, ceresin, ozokerite, ouricuri wax, cork fiber wax, fignite waxes, berry wax, shea butter or synthetic waxes such as paraffin waxes, polyethylene waxes, Fischer-Tropsch synthesis waxes, hydrogenated oils, fatty acid esters and glycerides solid at 25 ° C, silicone waxes and derivatives (alkyl derivatives, alkoxy derivatives and / or esters of polymethylsiloxane) and mixtures thereof.
- the waxes may be in the form of stable dispersions of colloidal wax particles which can be prepared by known methods, for example, according to "Microemulsion Theory and Practice", LM Prince Ed., Academic Press (1977), pp. 21-
- the waxes may be contained in amounts of from 0 to 10% by weight, based on the total weight of the composition, and preferably from 0 to 5% by weight.
- composition of the invention may further comprise a volatile oil selected from the group of volatile hydrocarbon oils, siliconized oils or fluorinated oils.
- the volatile oil may be contained in an amount of 0 to 25% by weight based on the total weight of the emulsion, preferably 0 to 20% by weight, and more preferably 0 to 15% by weight.
- a volatile oil is an oil that dissipates in contact with the skin at room temperature and atmospheric pressure in less than one hour.
- the volatile oil is liquid at room temperature and at room temperature and atmospheric pressure has a vapor pressure of 0.13 to 40,000 Pa (10 3 to 300 mm Hg), preferably 1.3 to 13,000 Pa (0.01 to 100 mm Hg), and especially preferably 1.3 to 1300 Pa (0.01 to 10 mm Hg) and has a boiling point of 150 to 260 ° C and preferably 170 to 250 ° C.
- a hydrocarbon oil is understood as meaning an oil which is essentially formed from carbon atoms and hydrogen atoms and optionally oxygen atoms or nitrogen atoms and contains no silicon atoms or fluorine atoms, and which may also consist of carbon atoms and hydrogen atoms; but it may also contain ester groups, ether groups, amino groups or amide groups.
- a silicone oil is understood to mean an oil which contains at least one silicon atom and in particular Si-O groups, in particular polydiorganosiloxanes.
- a fluorinated oil is meant an oil containing at least one fluorine atom.
- the volatile hydrocarbon oil of the present invention may be selected from hydrocarbon oils having a flash point of 40 to 102 ° C, preferably 40 to 55 ° C, and more preferably 40 to 50 ° C.
- the volatile hydrocarbon oils are those having 8 to 16 carbon atoms and mixtures thereof, in particular branched Cs-6 ö alkanes, such as the isoalkanes (which are also referred to as isoparaffins) with 8 to 16 Kohl enstoffato men, isododecane, isodecane, isohexadecane and
- the oils sold under the trade names Isopars ® or Permetyls ® and the branched Cs-16 esters such as isohexyl neopentanoate and mixtures thereof.
- volatile hydrocarbon oils such as isododecane, isodecane and isohexadecane.
- the volatile siliconized oil is preferably selected from among the siliconized oils having a flash point of from 40 to 102 ° C, preferably a flash point above 55 ° C and at most 95 ° C, and more preferably in the range of 65 to 95 ° C.
- the volatile siliconized oils are called straight-chain or cyclic silicone oils having 2 to 7 silicon atoms, these silicones optionally containing alkyl or alkoxy groups having 1 to 10 carbon atoms.
- volatile siliconized oils such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane and mixtures thereof.
- volatile siliconized oils such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasilox
- the volatile fluorinated oil generally has no flash point.
- the volatile fluorinated oils are nonafluoroethoxybutane, nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane, dodecafluoropentane, and mixtures thereof.
- the preferred cosmetically acceptable medium of the composition of the invention comprises water and optionally a cosmetically acceptable water-miscible, suitable organic solvent.
- the water used in the composition according to the invention may be a floral water, pure demineralized water, mineral water, thermal water and / or seawater.
- the water content in the range of 40 to 95 wt .-%, preferably in the range of 50 to 90 wt .-%, most preferably in the range of 60 to 80 wt .-% based on the total weight of the composition.
- the water content is in the range from 0 to 60% by weight, preferably in the range from 10 to 50% by weight, more preferably in the range from 30 to 50% by weight, based on the total weight of the Composition.
- the composition may further be foamed with a propellant gas.
- the emulsions described above may be stabilized by O / W, W / O or W / Si emulsifier, thickener (such as hydrodispersion) or solids (such as Pickering emulsion).
- the composition may contain one or more emulsifiers or surfactants.
- oil-in-water emulsions preferably contain at least one emulsifier with an HLB value> 7 and optionally a co-emulsifier.
- nonionic emulsifiers are used:
- Derivatives eg glyceryl monostearate, sorbitan stearate, glyceryl stearyl citrate, sucrose stearate
- Particularly advantageous nonionic O / W emulsifiers are ethoxylated fatty alcohols or fatty acids, preferably PEG-100 stearate, PEG-40 stearate, ceteareth-20, ceteth-20, steareth-20, ceteareth-12, ceteth-12, steareth-12 and esters of mono-, oligo- or polysaccharides with fatty acids, preferably cetearyl glucoside, methyl glucose distearate.
- anionic emulsifiers are soaps (eg sodium or triethanolamine salts of stearic or palmitic acid) and esters of citric acid such as glyceryl stearate citrate.
- Suitable coemulsifiers for the novel O / W emulsions fatty alcohols having 8 to 30 carbon atoms monoglycerol esters of saturated or unsaturated, branched or unbranched alkanecarboxylic acids having a chain length of 8 to 24 carbon atoms, in particular 12 to 18 carbon atoms, propylene glycol esters of saturated or unsaturated, branched or unbranched alkanecarboxylic acids having a chain length of 8 to 24 carbon atoms, in particular 12 to 18 carbon atoms, and sorbitan esters of saturated or unsaturated, branched or unbranched alkanecarboxylic acids having a chain length of 8 to 24 carbon atoms, in particular 12 to 18 carbon atoms.
- coemulsifiers are glyceryl monostearate, glyceryl monooleate, diglyceryl monostearate, sorbitan monoisostearate, sucrose distearate, cetyl alcohol, stearyl alcohol, behenyl alcohol, isobehenyl alcohol, and polyethylene glycol (2) stearyl ether (steareth-2).
- emulsifiers are z.
- the above with respect to the retention styling x geg kills the styling retention x ge iockt said applies for the inventive composition to straightened hair and respect for curly hair accordingly.
- the hair tresses Prior to testing, the hair tresses were washed for 1 minute with 0.3 g of a commercial silicone-free shampoo (Syoss "Volume Lift Shampoo") at 38 ° C. The hair tresses were then rinsed for 1 minute at 38 ° C and combed through with a conventional comb (wide side). The hair strands were then dried for 1 minute at about 75 ° C using a hair dryer.
- a commercial silicone-free shampoo Syoss "Volume Lift Shampoo”
- Product B Amphomer (INCI: Ocylacrylamide / Acrylates / Butylaminoethyl Methacrylate Copolymer), 100% adjusted to pH 9.6 with AMP (Amino Methylpropanol), 2% by weight.
- the hair strands were dried again with the hair dryer at 75 ° C for 3 minutes. Then the strands of hair were smoothed for 5 times 3 seconds at 230 ° C with a commercially available flat iron and then completely dried at 56% relative humidity at 23 ° C for 12 hours.
- Example 1A and 1B Treatment with Product A or Product B
- the hair strands were rotated on a cold-rolled winder and secured by means of a rubber.
- the tresses were then dried with the hair dryer for 5 minutes at 75 ° C and then completely dried at 56% relative humidity at 23 ° C for 12 hours.
- step 0 After the preparation of the strands of hair, as described in step 0), in each case 1 g of product A B, C, D, E or F was applied to the respective strand of hair. Each of the three strands of hair was briefly stripped to distribute the product along the length of the respective strand of hair.
- the hair tresses were combed and turned on a cold corrugator and secured by means of a rubber. The tresses were then dried with the hair dryer at 75 ° C. for 5 minutes and then completely dried at 56% relative humidity at 23 ° C. for 12 hours.
- Each of the hair tresses treated in Examples 1 and 2 were individually dipped for 30 seconds in a 2 liter water bath heated to 38 ° C, allowed to drain for 10 seconds and allowed to dry completely at room temperature in air for 24 hours.
- the width or length of the tress was then measured with a ruler (1 mm scale).
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- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
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Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP17208264.6A EP3498338A1 (de) | 2017-12-18 | 2017-12-18 | Spezieller polyurethanharnstoff zur erhöhung der wasserbeständigkeit einer geformten frisur |
| PCT/EP2018/085170 WO2019121495A1 (de) | 2017-12-18 | 2018-12-17 | Spezieller polyurethanharnstoff zur erhöhung der wasserbeständigkeit einer geformten frisur |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP3727598A1 true EP3727598A1 (de) | 2020-10-28 |
Family
ID=60942815
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP17208264.6A Ceased EP3498338A1 (de) | 2017-12-18 | 2017-12-18 | Spezieller polyurethanharnstoff zur erhöhung der wasserbeständigkeit einer geformten frisur |
| EP18825648.1A Withdrawn EP3727598A1 (de) | 2017-12-18 | 2018-12-17 | Spezieller polyurethanharnstoff zur erhöhung der wasserbeständigkeit einer geformten frisur |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP17208264.6A Ceased EP3498338A1 (de) | 2017-12-18 | 2017-12-18 | Spezieller polyurethanharnstoff zur erhöhung der wasserbeständigkeit einer geformten frisur |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20200352847A1 (de) |
| EP (2) | EP3498338A1 (de) |
| JP (1) | JP2021506834A (de) |
| BR (1) | BR112020012093A2 (de) |
| WO (1) | WO2019121495A1 (de) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3888627A1 (de) * | 2020-03-31 | 2021-10-06 | Covestro Deutschland AG | Biobasierte polyurethan-dispersionen für dekorative kosmetische anwendungen |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2446440C3 (de) | 1974-09-28 | 1981-04-30 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von wäßrigen Dispersionen von Sulfonatgruppen aufweisenden Polyurethanen |
| EP2105127A1 (de) | 2008-03-26 | 2009-09-30 | Bayer MaterialScience AG | Haarfestiger-Zusammensetzung |
| EP2712609A1 (de) * | 2012-09-26 | 2014-04-02 | Bayer MaterialScience AG | Polyurethanharnstoff-Mischung für die Haut-, sowie Haarkosmetik |
| EP3020454A1 (de) * | 2014-11-17 | 2016-05-18 | Covestro Deutschland AG | Polyurethanharnstoffe für Haarstyling-Zusammensetzungen |
| DE102015225967A1 (de) * | 2015-12-18 | 2016-09-15 | Henkel Ag & Co. Kgaa | "Aerosolsprays für keratinhaltige Fasern, enthaltend mindestens ein Sulfonat-haltiges Polyurethanpolymer" |
-
2017
- 2017-12-18 EP EP17208264.6A patent/EP3498338A1/de not_active Ceased
-
2018
- 2018-12-17 EP EP18825648.1A patent/EP3727598A1/de not_active Withdrawn
- 2018-12-17 JP JP2020533131A patent/JP2021506834A/ja active Pending
- 2018-12-17 US US16/764,485 patent/US20200352847A1/en not_active Abandoned
- 2018-12-17 WO PCT/EP2018/085170 patent/WO2019121495A1/de not_active Ceased
- 2018-12-17 BR BR112020012093-6A patent/BR112020012093A2/pt not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| US20200352847A1 (en) | 2020-11-12 |
| EP3498338A1 (de) | 2019-06-19 |
| BR112020012093A2 (pt) | 2020-11-17 |
| JP2021506834A (ja) | 2021-02-22 |
| WO2019121495A1 (de) | 2019-06-27 |
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