Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/04—Dispersions; Emulsions
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/0241—Containing particulates characterized by their shape and/or structure
• • 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
  • A61K8/73—Polysaccharides
• • 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
  • A61K8/73—Polysaccharides
  • A61K8/731—Cellulose; Quaternized cellulose derivatives
• • 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
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q3/00—Manicure or pedicure preparations
  • A61Q3/02—Nail coatings
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/41—Particular ingredients further characterized by their size
  • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/60—Particulates further characterized by their structure or composition
  • A61K2800/65—Characterized by the composition of the particulate/core
  • A61K2800/654—The particulate/core comprising macromolecular material

Definitions

• the present invention relates to a novel aqueous binder system for nail varnishes based on dispersions containing nitrocellulose-polyurethane-polyurea particles.
• Nail varnishes as they are used today, are produced almost exclusively on the basis of solvent-containing, physically drying binders.
• predominantly nitrocellulose is used as the main constituent in the solvent-containing binder.
• Nitrocellulose itself is practically insoluble in water. Only by modification of the polymer backbone such as e.g. the introduction of hydrophilic side groups, a water solubility can be produced. However, by changing the polymer backbone, the previously positive properties of the nitrocellulose, such as e.g. the high gloss adversely affects.
• EP-A 0 391 322 describes aqueous nail varnishes based on aqueous polyurethanes and / or polyurethane-acrylate copolymers as binders.
• WO 2003/039445 teaches the use of aqueous polyurethane dispersions for the preparation of organic low-solvent or nail-free nail varnishes.
• US 6391964 describes the use of water-based acrylate polymer emulsions in combination with water-based polyurethane resins for the preparation of aqueous nail varnishes.
• e.g. US Pat. No. 5,950,063 describes aqueous acrylate binders for the preparation of water-based nail varnishes.
• US Pat. No. 5,637,292 describes the use of aqueous acrylate polymers having a proportion of acrylate monomers which are reacted by means of UV light after formulation of the nail varnish and thus have very rapid drying / curing.
• a disadvantage of these systems is the presence of acrylate monomers, which consists of View of the application hygiene must be classified as questionable. In addition, exposure to UV light can be tissue damaging and should therefore be avoided.
• WO 1999/055290 further describes the use of film-forming polyurethane polymers in combination with nitrocellulose, however, using organic solvents and / or plasticizers. Aqueous systems, however, are not described.
• the invention therefore relates to aqueous nail varnishes at least comprising polyurethane-nitrocellulose particles in the form of an aqueous dispersion (I) with an average particle size of 20 to 700 nm, measured by means of laser correlation spectroscopy (Zetasizer 1000, Malvern Instruments, Malvern, UK).
• aqueous nail varnishes of the present invention contain, based on the total formulation, less than 5% by weight, preferably ⁇ 2% by weight, particularly preferably ⁇ 1% by weight, of organic solvents and / or plasticizers.
• Plasticizers are understood as meaning compounds such as phthalates, castor oil, acetyltributyl citrate or alkylated phosphates.
• polymeric polyols having number average molecular weights of 400 to 8000 g / mol, preferably 400 to 6000 g / mol and particularly preferably from 600 to
• the prepolymers are dispersed in water before or after step B), optionally containing potentially ionic groups being converted into the ionic form by partial or complete reaction with a neutralizing agent,
• Preferred organic solvents for preparing the dispersions essential to the invention are aliphatic ketones, more preferably acetone or 2-butanone.
• Suitable polyisocyanates of component Al) are the aromatic, araliphatic, aliphatic or cycloaliphatic polyisocyanates of an NCO functionality of> 2 known per se to those skilled in the art.
• polystyrene resin examples include 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bisisocyanate.
• HDI 1,6-hexamethylene diisocyanate
• IPDI isophorone diisocyanate
• 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate examples include 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bisisocyanate.
• modified diisocyanates having a uretdione, isocyanurate, urethane, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure and unmodified polyisocyanate having more than 2 NCO groups per molecule, such as Isocyanatomethyl-l, 8-octane diisocyanate (nonane triisocyanate) or triphenylmethane-4,4 ', 4'triisocyanate are used with.
• polyisocyanates or polyisocyanate mixtures of the abovementioned type with exclusively aliphatically and / or cycloaliphatically bonded isocyanate groups and an average NCO functionality of the mixture of 2 to 4, preferably 2 to 2.6 and particularly preferably 2 to 2.4.
• Hexamethylene diisocyanate, isophorone diisocyanate, the isomeric bis (4,4'-isocyanatocyclohexyl) methanes and mixtures thereof are particularly preferably used in Al).
• polymeric polyols having a number average molecular weight M n of 400 to 8000 g / mol, preferably from 400 to 6000 g / mol and particularly preferably from 600 to 3000 g / mol. These preferably have an OH functionality of from 1.5 to 6, particularly preferably from 1.8 to 3, very particularly preferably from 1.9 to 2.1.
• Such polymeric polyols are the polyester polyols known per se in polyurethane lacquer technology, polyacrylate polyols, polyurethane polyols, polycarbonate polyols, polyether polyols, polyester polyacrylate polyols, polyurethane polyacrylate polyols, polyurethane polyester polyols, polyurethane polyether polyols, polyurethane polycarbonate polyols, polyester polycarbonate polyols and phenol / formaldehyde resins. These can be used in A2) individually or in any mixtures with each other.
• polyester polyols are the known polycondensates of di- and optionally tri- and tetraols and di- and optionally tri- and tetracarboxylic acids or hydroxycarboxylic acids or lactones.
• free polycarboxylic acids it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols to prepare 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 iso
• polyols such as trimethy- lolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene or Trishydroxyethylisocyanurat be used.
• 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-dimethyl succinic acid are 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.
• Hydroxycarboxylic acids which may 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 M n 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, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1, 4-bishydroxymethylcyclohexane, 2-methyl-1,3-propanediol, 2,2,4-trimethylpentanediol-1,3,3-methyl-1,5-pentanediol, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenol A, tetrabromide bisphenol A and lactone-modified diols of the abovementioned type.
• the diol component preferably contains from 40 to 100% by weight of hexanediol, preference being given to 1,6-hexanediol and / or hexanediol derivatives.
• hexanediol derivatives are based on hexanediol and have ester or ether groups in addition to terminal OH groups.
• Such derivatives are obtainable by reaction of hexanediol with excess caprolactone or by etherification of hexanediol with itself to di- or trihexylenglykol.
• polyether-polycarbonate diols are preferably of linear construction, but can also be easily obtained by the incorporation of polyfunctional components, in particular low molecular weight polyols.
• polyfunctional components in particular low molecular weight polyols.
• glycerol, trimethylolpropane, hexanetriol-1,2,6, butanetriol-1,2,4, trimethylolpropane, trimethylolethane, pentaerythritol, quinitol, mannitol, sorbitol, methyl glycoside or 1,3,4,6-dianhydrohexitols are suitable for this purpose.
• polyether polyols can be used. 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.
• polyester polyols polytetramethylene glycol polyethers and / or polycarbonate polyols are preferably used.
• polyols with molecular weights of 62 to 399 g / mol and up to 20 carbon atoms can be used. These may be ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 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 and any mixtures thereof among themselves.
• ester diols of the stated molecular weight range, such as ⁇ -hydroxybutyl- ⁇ -hydroxy-caproic acid ester, ⁇ -hydroxyhexyl- ⁇ -hydroxybutyric acid ester, adipic acid ( ⁇ -hydroxyethyl) ester or terephthalic acid bis ( ⁇ -hydroxyethyl) ester.
• monofunctional isocyanate-reactive hydroxyl-containing compounds in A3).
• monofunctional compounds are ethanol, n-butanol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol mono-propyl ether, pylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, 2-ethylhexanol, 1-octanol, 1-dodecanol, 1-hexadecanol.
• 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.
• anionic or potentially anionic hydrophilicizing agents are dimethylolpropionic acid, dimethylolbutyric acid, hydroxypivalic acid, malic acid, citric acid, glycolic acid, lactic acid, and the adduct of sodium bisulfite with butene-2-diol-1, 4, polyethersulfonate and the propoxylated adduct of 2-butenediol and NaHSO 3 , as described in DE-A 2 446 440, pages 5-9, formula I-III.
• Preferred anionic or potentially anionic hydrophilicizing agents of component A4) are those of the abovementioned type which have carboxy or carboxylate and / or sulfonate groups.
• anionic or potentially anionic hydrophilicizing agents are those which contain carboxyl and / or sulfonate groups as ionic or potentially ionic groups, such as the salts of dimethylolpropionic acid or dimethylolbutyric acid.
• Suitable nonionically hydrophilicizing compounds of component A4) are e.g. Polyoxy- alkylene ethers containing at least one hydroxy or amino 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).
• polyethylene oxide ethers or mixed polyalkylene oxide ethers, wherein they contain at least 30 mol%, preferably at least 40 mol%, based on all the alkylene oxide units present of ethylene oxide units.
• Particularly preferred nonionic compounds are monofunctional mixed polyalkylene oxide polyethers having from 40 to 100 mole% of ethylene oxide and from 0 to 60 mole% of propylene oxide units.
• Suitable starter molecules for such nonionic hydrophilicizing agents are saturated monohydric alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomeric pentanols, hexanols, octanols and nonanols, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanols or hydroxymethylcyclohexane, 3-ethyl-3-hydroxymethyloxetane or tetrahydrofurfuryl alcohol, diethylene glycol monoalkyl ethers, such as diethylene glycol monobutyl ether, unsaturated alcohols such as allyl alcohol, 1,1
• Alkylene oxides which are suitable for the alkoxylation reaction are, in particular, ethylene oxide and propylene oxide, which can be used in any desired order or even as a mixture in the alkoxylation reaction.
• component Bl can di- or polyamines such as 1, 2-ethylenediamine, 1,2- and 1,3-diaminopropane, 1, 4-diaminobutane, 1, 6-diaminohexane, isophoronediamine, isomer mixture of 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylenetriamine, 1, 3- and 1, 4-xylylenediamine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-l, 3- and 1,4-xylylenediamine and 4 , 4-diamino-dicyclohexylmethane and / or dimethylethylenediamine can be used. Also possible is the use of hydrazine or hydrazides such as adipic dihydrazide.
• component Bl compounds which, in addition to a primary amino group, also have secondary amino groups or, in addition to an amino group (primary or secondary), also OH groups, can be used.
• primary / secondary amines such as diethanolamine, 3-amino-1-methylaminopropane, 3-amino-1-ethylaminopropane, 3-amino-1-cyclohexylaminopropane, 3-amino-1-methylaminobutane, alkanolamines, such as N-aminoethylethanolamine , Ethanolamine, 3-aminopropanol, neopentanolamine.
• component Bl it is also possible to use monofunctional isocyanate-reactive amine compounds, for example methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methylaminopropylamine, diethyl (methyl) aminopropylamine, Mo ⁇ holin, piperidine, or suitable substituted derivatives thereof, amidamines from diprimary amines and monocarboxylic acids, monoketime of diprimary amines, primary / tertiary amines, such as N, N-dimethyl-aminopropylamine.
• monofunctional isocyanate-reactive amine compounds for example methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, is
• Suitable anionic or potentially anionic hydrophilizing compounds are mono- and diaminocarboxylic acids, mono- and diaminosulfonic acids and mono- and diaminophosphonic acids and their salts.
• anionic or potentially anionic hydrophilicizing agents are N- (2-aminoethyl) - ⁇ -alanine, 2- (2-aminoethylamino) -ethanesulfonic acid, ethylenediamine-propyl- or -butylsulfonic acid, 1,2- or 1,3-propylenediamine- ⁇ -ethylsulfonic acid, glycine,
• cyclohexylaminopropanesulfonic acid from WO-A 01/88006 can be used as anionic or potentially anionic hydrophilicizing agent.
• Preferred anionic or potentially anionic hydrophilicizing agents of component B2) are those of the abovementioned type which have carboxy or carboxylate and / or sulfonate groups.
• Particularly preferred anionic or potentially anionic hydrophilicizing agents B2) are those containing carboxylate and / or sulfonate groups as ionic or potentially ionic groups, such as the salts of N- (2-aminoethyl) - ⁇ -alanine, the 2- (2-amino -ethylamino) ethanesulfonic acid or the addition product of IPDI and acrylic acid (EP-A 0 916 647, Example 1).
• the aminic components B1), B2) can optionally be used individually or in mixtures in water- or solvent-diluted form in the process according to the invention, wherein in principle any order of addition is possible. If water or organic solvents are used as diluents, the diluent content in the chain-extending component used in B) is preferably 70 to 95% by weight.
• the ratio of NCO groups of the compounds of component Al) to NCO-reactive groups such as amino, hydroxy or thiol groups of the compounds of components A2) to A4) is 1.05 to 3.5 in the preparation of the NCO-functional prepolymer , preferably 1.2 to 3.0, particularly preferably 1.3 to 2.5.
• the amino-functional compounds in stage B) are used in such an amount that the equivalent ratio of isocyanate-reactive amino groups of these compounds to the free isocyanate groups of the prepolymer is 40 to 150%, preferably between 50 and 125%, particularly preferably between 60 and 120%.
• the components Al) to A4) and Bl) to B2) are used in the following amounts, the individual amounts always adding up to 100% by weight:
• components A4) and B2) 0.1 to 25 wt .-% of components A4) and B2), wherein based on the total amounts of the components Al) to A4) and Bl) to B2) 0.1 to 5 wt .-% of anionic or potentially anionic hydrophilicizing agents A4) and B2) are used.
• the components Al) to A4) and Bl) to B2) are used in the following amounts, the individual amounts always adding up to 100% by weight:
• components A4) and B2) 0.1 to 15 wt .-% of components A4) and B2), wherein based on the total amounts of the components Al) to A4) and Bl) to B2) 0.2 to 4 wt .-% of anionic or potentially anionic hydrophilicizing agents A4) and B2) are used.
• the components Al) to A4) and Bl) to B2) are used in the following amounts, the individual amounts always adding up to 100% by weight:
• bases such as tertiary amines, e.g. Trialkylamines having 1 to 12, preferably 1 to 6 carbon atoms used in each alkyl radical or alkali metal bases such as the corresponding hydroxides.
• alkyl radicals may, for example, also carry hydroxyl groups, as in the case of the dialkylmonoalkanol, alkyldialkanol and trialkanolamines.
• inorganic bases such as aqueous ammonia solution or sodium or potassium hydroxide can also be used as neutralizing agents.
• ammonia triethylamine, triethanolamine, dimethylethanolamine or diisopropylethylamine and sodium hydroxide.
• the molar amount of the bases is generally 50 and 125 mol%, preferably between 70 and 100 mol% of the molar amount of the acid groups to be neutralized.
• the neutralization can also take place simultaneously with the dispersion in which the dispersing water already contains the neutralizing agent.
• the dispersion in water according to step C) is preferably carried out after the chain extension.
• the dissolved and chain-extended polyurethane polymer is optionally either added to the dispersing water with high shear, such as vigorous stirring, or conversely, the dispersing water is added to the chain-extended polyurethane. stirred polymer solutions.
• the water is added to the dissolved chain-extended polyurethane polymer.
• Suitable nitrocellulose in step D) is water-insoluble nitrocellulose of all nitrogen contents and viscosity stages.
• nitrocelluloses which, for example, have the usual collodium qualities (for the term "collodium” see Römpp's Chemie Lexikon, Thieme Verlag, Stuttgart), ie cellulose nitric acid esters having a nitrogen content of 10 to 12.8% by weight, preferably a nitrogen fraction from 10.7 to 12.3 wt .-% based on dry matter of nitrocellulose.
• cellulose nitric acid esters having a nitrogen content of 10.7 to 12.6 wt .-%, most preferably from 10.7 to 12.3 wt .-%.
• examples of such are the Cellulosesalpeterklareester Walsroder® ® nitrocellulose A types (Wolff Cellulosics GmbH & Co. KG, Bomlitz DE) with a nitrogen content of 10.7 to 11.3 wt .-% or Walsroder® ® nitrocellulose AM-types (Wolff Cellulosics GmbH & Co.
• Bomlitz DE which have a nitrogen content of 11 3 to 11.8 wt .-% or Walsroder® ® nitrocellulose e-types (Wolff Cellulosics GmbH & Co. KG, Bomlitz DE) with a nitrogen content of 11, 8 to 12.3 wt .-%.
• cellulose nitric acid esters of certain nitrogen contents all viscosity stages are suitable in each case.
• Low-viscosity cellulose nitric acid esters of different nitrogen contents are classified according to ISO 14446 into the following groups:> 30A,> 3OM,> 30E.
• Medium-viscosity cellulose nitric acid esters of different nitrogen contents are classified according to ISO 14446 into the following groups: 18 E to 29 E, 18 M to 29 M, 18 A to 29 A.
• Highly viscous cellulose nitric esters of different nitrogen contents, according to ISO 14446 are: ⁇ 17 E, ⁇ 17 M and ⁇ 17 A.
• the nitrocellulose is usually supplied in a phlegmatized form in commercial form.
• Typical phlegmatizers are, for example, alcohols or water.
• the content of phlegmatizing agent is between 5 to 40 wt .-%.
• Nitrocelluloses which have been moistened with alcohols or water are preferably used to prepare the dispersions according to the invention.
• nitrocellulose moistened with 10 to 40% by weight of isopropanol (based on the total mass of the delivery form) is used.
• nitrocellulose E 560 isopropanol 30%
• Walsroder ® nitrocellulose E 560 Water 30% The nitrocellulose is preferably added after step B) and before dispersion in water C).
• the nitrocellulose is dissolved in an organic solvent or solvent mixture, particularly preferably dissolved in an aliphatic ketone and very particularly preferably dissolved in acetone.
• the polyurethane dispersion relevant to the invention contains from 1 to 90% by weight, particularly preferably from 10 to 70% by weight and very particularly preferably from 20 to 60% by weight, of nitrocellulose.
• step E solvent contained in the dispersions is separated by distillation.
• the pH of the dispersions essential to the invention is typically less than 9.0, preferably less than 8.5, more preferably less than 8.0.
• the solids content of the hybrid dispersions essential to the invention is typically from 20 to 65% by weight, preferably from 25 to 60% by weight, particularly preferably from 30 to 50% by weight and very particularly preferably from 35 to 45% by weight.
• the polyurethane nitrocellulose particles present in the dispersions essential to the invention have an average particle size of 20 to 700 nm, preferably 30 to 400 nm.
• nail polishes which are essential to the invention and which usually serve as primary and / or secondary film formers in nail polish formulations
• other nail polishes known to the person skilled in the art (Cosmetics & Toiletries 108, 1988, 70-82) may comprise film-forming polymers (H) such as toluenesulfonamide-formaldehyde resin can be used both as primary and as secondary resin systems.
• the nail varnishes according to the invention may also contain additives (IQ) such as dyes, pigments, antioxidants, light stabilizers, emulsifiers, defoamers, thickeners, fillers, leveling agents, preservatives, moisturizing substances, odorous substances, radical scavengers and thixotropic agents.
• IQ additives
• additives for example, optionally organically modified clays such as bentonite, montmorillonite, hectorite and smectite.
• the dyes and / or color and / or pearlescent pigments known per se to the person skilled in the art as Sudan Red, DC Red 17, DC Green 6, DC Yellow 1 1, DC Violet 2, titanium, iron, chromium can be used as additives. , Ceria, carbon black, with titanium, iron oxide, etc., coated mica.
• up to 80% by weight, based on the total dry matter, of these additives may be present in the end product.
• the nail varnishes according to the invention may e.g. be used as a single-coat or in multi-layer structures.
• nail polish can be done by methods known in the art, such as by brushing, rolling, pouring, knife coating or spraying.
• Another object of the present invention is the use of nail varnishes according to the invention for both the coating of foot and / or fingernails as well as finger and / orplexnagelimitationen (artificial nails).
• the gloss of the nail varnishes according to the invention is 50 to 100 gloss units, preferably 60 to 100 gloss units and particularly preferably 70 to 100 gloss units measured at an angle of 20 ° according to DIN 67530 by means of a gloss meter (micro-haze plus, BYK Gardner, Germany).
• the curing / drying of the nail varnishes of the invention is preferably carried out at room temperature (23 0 C), but can also be carried out at a higher or lower temperature.
• the tack-free state of the paints of the invention is achieved at room temperature ⁇ 10 minutes, preferably ⁇ 8 minutes, more preferably ⁇ 5 minutes.
• the pendulum hardness of the nail varnishes of the invention measured after 12 h drying at 32 0 C for> 50 s, preferably> 100 s, more preferably> 140 s.
• Diaminosulphonate NH 2 -CH 2 CH 2 -NH-CH 2 CH 2 -SO 3 Na (45% in water)
• Desmophen ® C2200 polycarbonate polyol, OH number 56 mg KOH / g, number-average molecular weight 2000 g / mol (Bayer MaterialScience AG, Leverkusen, DE)
• nitrocellulose types used in each case were obtained from Wolff Cellulosics GmbH & Co. KG, Walsrode, Germany.
• the solids contents were determined according to DIN-EN ISO 3251.
• NCO contents were determined volumetrically in accordance with DIN-EN ISO 11909, unless expressly stated otherwise.
• the mean particle sizes of the dispersions were determined by means of laser correlation spectroscopy measurements (Zetasizer 1000, Malvern Instruments, Malvern, UK).
• the pendulum hardness was determined on a pendulum hardness tester "Pendulum Hardness Tester” from BYK Gardner GmbH, Germany in accordance with DIN EN ISO 1522.
• the gloss was determined according to DIN 67530 by means of a glossmeter "microhaze plus” from BYK Gardner GmbH, Germany, after elevation and drying of the respective nail varnish on a black-colored polyamide plastic substrate.
• the determination of the drying time at room temperature after application of a layer on the human fingernail with a brush was determined by the time when no sticking of the nail varnish was observed by touch.
• the finished prepolymer was dissolved in 276.0 g of acetone at 5O 0 C and then added a solution of 17.3 g diaminosulphonate, 2.0 g of ethylenediamine and 66.1 g of water min within 5 s. The stirring time was 15 min. Subsequently, a solution of 233.2 g of Walsroder® nitrocellulose E560 / IPA 30% and 925.1 g of acetone was added within 5 min. The dispersion was carried out by adding 536.6 g of water within 10 min. In a subsequent distillation step, the removal of the solvents was carried out in vacuo and there was obtained a storage-stable PUR dispersion having a solids content of 40.0% and an average particle size of 261 nm.
• the prepolymer was dissolved with 276.0 g of acetone at 50 0 C and then added a solution of 19.9 g of diaminosulfonate, 2.0 g of ethylenediamine and 66.1 g of water within 5 min. The stirring time was 15 min. Subsequently, a solution of 234.4 g of Walsroder® nitrocellulose E560 / IPA 30% and 925.1 g of acetone was added within 5 min. The dispersion was carried out by adding 538.2 g of water within 10 min. In a subsequent distillation step, the removal of the solvent was carried out in vacuo and there was obtained a storage-stable PUR dispersion having a solids content of 41.9% and an average particle size of 154 nm.
• the finished prepolymer was dissolved with 9.3 g of triethylamine and 638.3 g of acetone at 50 0 C and then a solution of 1.0 g diethylenetriamine, 0.9 g of ethylenediamine, 2.1 g of hydrazine hydrate and 8.6 g Water added within 10 min. The stirring time was 5 min. Subsequently, within 5 min, a solution of 174.4 g of Walsroder® nitrocellulose E330 / IPA 30%, and 488.3 g of acetone was added. The dispersion was carried out by adding 601.9 g of water within 15 min. In a subsequent distillation step, the removal of the solvents in vacuo and it was a storage-stable PUR dispersion having a solids content of 39.0% and an average particle size of 260 nm was obtained.
• the finished prepolymer was dissolved with 375 g of acetone at 50 0 C and then added a solution of 20.2 g of diaminosulfonate, 2.2 g of ethylenediamine and 90.0 g of water within 5 min. The stirring time was 15 min. Subsequently, a solution of 268.0 g of Walsroder® nitrocellulose E560 / H2O 30%, a medium-viscosity nitrocellulose with a nitrogen content between 11.8 to 12.3%, ISO 14446: 23 E, and 893.4 g of acetone was added within 5 min added and stirred for 30 minutes. The dispersion was carried out by adding 458.4 g of water within 10 min. In a subsequent distillation step, the removal of the solvents was carried out in vacuo and there was obtained a storage-stable PUR dispersion having a solids content of 41, 0% and an average particle size of 279 nm.
• Example 1 The dispersion obtained in Example 1 was coated on a glass substrate by means of a film-drawing frame in a wet film thickness of 100 ⁇ m and dried at 32 ° C for 12 hours.
• the performance properties of the obtained nail polish according to the invention are shown in Table 1.
• Example 2 The dispersion obtained in Example 2 was coated on a glass substrate by means of a film-drawing frame in a wet film thickness of 100 ⁇ m and dried at 32 ° C for 12 hours.
• the performance properties of the obtained nail polish according to the invention are shown in Table 1.
• Example 3 The dispersion obtained in Example 3 was coated on a glass substrate by means of a film-drawing frame in a wet film thickness of 100 ⁇ m and dried at 32 ° C for 12 hours.
• the performance properties of the obtained nail polish according to the invention are shown in Table 1.
• Example 6 The same procedure as in Example 6, wherein 10 wt .-% of a butyl glycol / water mixture (1: 1 parts by weight) were added to the dispersion of Example 1 as a leveling agent.
• the performance properties of the obtained nail polish according to the invention are shown in Table 1.

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