Classifications

• • 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
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
• • 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
  • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt 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
  • C08G18/08—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
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
  • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
• • 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
  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/2815—Monohydroxy compounds
  • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
• • 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
  • C08G18/28—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
  • C08G18/44—Polycarbonates
• • 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
  • C08G18/48—Polyethers
  • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
• • 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
  • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
  • C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
  • C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
  • C08L1/08—Cellulose derivatives
  • C08L1/16—Esters of inorganic acids
  • C08L1/18—Cellulose nitrate, i.e. nitrocellulose
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
  • C09D101/08—Cellulose derivatives
  • C09D101/16—Esters of inorganic acids
  • C09D101/18—Cellulose nitrate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J101/00—Adhesives based on cellulose, modified cellulose, or cellulose derivatives
  • C09J101/08—Cellulose derivatives
  • C09J101/16—Esters of inorganic acids
  • C09J101/18—Cellulose nitrate
• • 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
  • A61K2800/413—Nanosized, i.e. having sizes below 100 nm
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
  • C08J2301/02—Cellulose; Modified cellulose
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
  • C08J2375/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
  • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
  • C08L2666/20—Macromolecular compounds having nitrogen in the main chain according to C08L75/00 - C08L79/00; Derivatives thereof

Definitions

• the invention relates to aqueous dispersions comprising nitrocellulose-polyurethane-polyurea particles, a process for their preparation and their use.
• Nitrocellulose or cellulose nitrate or cellulose nitric acid ester is used in a wide variety of applications due to its versatile, conductive and end-use properties
• solvent-borne nitrocellulose compositions e.g. disclosed as furniture coatings, printing inks or overprint varnishes. These paints are exclusively organic solvent-containing systems.
• nail varnishes often have substantially a nitrocellulose base in the binder.
• predominantly organic solvents such as e.g. Ethyl acetate or butyl acetate.
• Emulsions produced to which complex emulsification steps are necessary.
• they also have solvents or plasticizers.
• the emulsions are then combined with other polymers to form an aqueous system.
• mixtures of independently produced nitrocellulose arise on the one hand, with polymer dispersions on the other hand.
• nitrocellulose emulsions and other aqueous systems are sequentially coated on a substrate, such as e.g. Leather are applied, which always results in several process steps.
• Solvent-containing systems based on nitrocellulose and polyurethane are known from the prior art, for example JP-A 03 294 370, JP-A 03 247 624 or JP-A 58-83 001. These described nitrocellulose compositions are used as dispersing media for magnetic powders.
• JP-A 63-14735 discloses aqueous resin emulsions based on water-dispersible, urethane-modified vinyl polymers and nitrocellulose.
• the vinyl polymer has an ionic group and a polyurethane side chain which serves as a dispersing medium for the nitrocellulose.
• the compositions described there are used as coating agents.
• the resin emulsion is prepared by dissolving both the vinyl polymer and the nitrocellulose in an organic solvent, then adding water and dispersing the polymer using a neutralizing agent. The organic solvent can be removed before or after the dispersion.
• a disadvantage of these systems is their lack of storage stability, when the amount of solvent is significantly reduced by distillation.
• the object of the present invention was therefore to provide stable and sedimentation-free aqueous dispersions based on a polyurethane polymer and nitrocellulose, which have residual organic solvent amounts of less than or equal to 1% by weight with respect to the dispersion and, moreover, do not contain any additional external emulsifiers or external plasticizers capable of migrating ,
• the coating compositions prepared from the dispersions of the invention should be sufficiently film-forming and (mechanically) stable during drying, so that coatings, coatings, sizes, paints, adhesives, binders, printing inks, cosmetics and personal care articles and the like for a variety of substrates formulated so can be.
• dispersions which have both polyurethane polymer proportions and nitrocellulose fractions and an average particle size of 20 nm to 700 nm, meet the above requirements. It is possible with these polyurethane-nitrocellulose particles to produce stable, aqueous dispersions, without additionally adding plasticizers,
• the invention therefore relates to aqueous dispersions containing polyurethane-nitrocellulose particles having a particle size of from 20 to 700 nm, preferably from 30 to 550 nm, especially preferably from 50 to 400 nm and very particularly preferably from 100 to 330 nm, which comprises a polyurethane fraction which, as constituent components, compounds selected from the group
• the polyols having number-average molecular weights of from 400 to 8000 g / mol, preferably from 400 to 6000 g / mol and more preferably from 600 to 3000 g / mol and having an OH functionality of from 1.5 to 6, preferably 1, 8 to 3, and more preferably from 1.9 to 2.1,
• the polyols having number-average molecular weights of from 400 to 8000 g / mol, preferably from 400 to 6000 g / mol and more preferably from 600 to 3000 g / mol and having an OH functionality of from 1.5 to 6, preferably 1, 8 to 3, and more preferably from 1.9 to 2.1, c) the low molecular weight compounds of the molecular weight 62 to 400 g / mol, preferably 62 to 240 g / mol, particularly preferably 88 to 140 g / mol, which have two or more hydroxyl and / or amino groups,
• Butanone after preparation of the prepolymer (i) or after the chain extension (ii) but before the dispersion or after the dispersion (iii) is added before the distillation.
• polyisocyanates having an NCO functionality of greater than 2 include 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, for example 4-isocyanatomethyl-1,8 octane diisocyanate (nonane triisocyanate) or triphenylmethane-4,4 ', 4 "-triisocyanate.
• polyisocyanates or polyisocyanate mixtures of the abovementioned type having exclusively aliphatically and / or cycloaliphatically bonded isocyanate groups having an average functionality of from 2 to 4, preferably from 2 to 2.6 and more preferably from 2 to
• Polymeric polyols which can be used as compounds b) have a molecular weight Mn of from 400 to 8000 g / mol, preferably from 400 to 6000 g / mol and more preferably from 600 to 3000 g / mol.
• Their hydroxyl number is 22 to 400 mg KOH / g, preferably 30 to 200 mg KOH / g and more preferably 40 to 160 mg KOH / g and have an OH functionality of 1.5 to 6, preferably from 1.8 to 3 and more preferably from 1.9 to 2.1.
• polyols are the organic polyhydroxyl compounds known in polyurethane coating technology, such as the customary polyester polyols, polyacrylate polyols, polyurethane polyols, polycarbonate polyols, polyether polyols, polyester polyacrylate polyols and polyurethane polyacrylate polyols, polyurethane polyester polyols, polyurethane polyether polyols, polyurethane polycarbonate polyols, polyester polycarbonate polyols, alone or in mixtures.
• polyester polyols such as the customary polyester polyols, polyacrylate polyols, polyurethane polyols, polycarbonate polyols, polyether polyols, polyester polyacrylate polyols and polyurethane polyacrylate polyols, polyurethane polyester polyols, polyurethane polyether polyols, polyurethane polycarbonate polyols, polyester polycarbonate polyols, alone or in mixtures.
• suitable diols are 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, the latter three compounds being preferred.
• suitable polyols to be used here are trimethylolpropane, glycerol, erythritol, pentaerythritol or trishydroxyethyl isocyanurate.
• Suitable dicarboxylic acids are, for example: phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, adipic acid,
• anhydrides are included in the invention by the term "acid”.
• Monocarboxylic acids such as benzoic acid and hexanecarboxylic acid may also be used, provided that the average OH functionality of the polyol is> 2.
• Saturated aliphatic or aromatic acids are preferred, such as adipic acid or isophthalic acid.
• trimellitic acid may be mentioned here.
• Hydroxycarboxylic acids which can be used as reactants in the preparation of a polyester polyol having terminal hydroxyl groups are, for example, hydroxycaproic acid or hydroxybutyric acid.
• Suitable lactones are e.g. Caprolactone, butyrolactone and their homologues.
• polyester polyols are hexanediol adipic acid ester, butanediol adipic acid ester, hexanediol neopentyl glycol adipic acid ester and hexanediol phthalic acid ester.
• hydroxyl group-containing polycarbonates having a molecular weight Mn of 400 to 6000 g / mol, preferably of 600 to 3000 g / mol, which are e.g. by reaction of carbonic acid derivatives, such as diphenyl carbonate, dimethyl carbonate or phosgene with polyols, preferably diols are obtainable.
• diols come e.g. 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-1, 3-propanediol, 2,2,4-trimethylpentanediol-l, 3, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenol A, tetrabromobisphenol A but also lactone-modified diols in question.
• Ethylene glycol 1,2- and 1,3-propanediol, 1,3- and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glyco
• the diol component contains from 40 to 100% by weight of 1,6-hexanediol.
• hexanediol derivatives can also be used, preferably those which, in addition to terminal OH groups, contain ether or ester groups, e.g. Products which can be obtained by reacting 1 mole of hexanediol with at least 1 mole, preferably 1 to 2 moles of caprolactone or by etherification of hexanediol with itself to di- or trihexylenglycol.
• Polyether-polycarbonate diols can also be used.
• the hydroxyl polycarbonates should be substantially linear. However, they may optionally be easily branched by the incorporation of polyfunctional components, especially low molecular weight polyols.
• Polyol components b) furthermore include polyether polyols, for example the polyaddition products of styrene oxides, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin, and their mixed addition and grafting products, as well as by condensation of polyhydric alcohols or mixtures thereof and by alkoxylation of polyhydric alcohols, amines and amino alcohols obtained polyether polyols. ?
• polyether polyols for example the polyaddition products of styrene oxides, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin, and their mixed addition and grafting products, as well as by condensation of polyhydric alcohols or mixtures thereof and by alkoxylation of polyhydric alcohols, amines and amino alcohols obtained polyether polyols.
• the low molecular weight polyols c) used to build up the polyurethane resins generally cause stiffening and / or branching of the polymer chain and are preferably used during the prepolymer synthesis.
• the molecular weight is preferably between 62 and 400 g / mol, more preferably between 62 and 200 g / mol.
• Suitable polyols c) may contain aliphatic, alicyclic or aromatic groups. Mention may be made, for example, of the low molecular weight polyols having up to about 20 carbon atoms per molecule, such as e.g.
• Ethylene glycol diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, neopentyl glycol, bisphenol A (2,2 Bis (4-hydroxyphenyl) propane), hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane), and trimethylolpropane, glycerol or pentaerythritol and mixtures of these and optionally other low molecular weight polyols c).
• Preference is given to 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and trimethylolpropane.
• di- or polyamines and hydrazides can be used as component c), e.g. Ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, isophoronediamine, isomer mixture of 2,2,4- and 2,4,4-
• component c) are in principle also compounds into consideration, containing active hydrogen with respect to isocyanate groups of different reactivity, such as compounds which have not only a primary amino group but also secondary amino groups or in addition to an amino group (primary or secondary) OH groups.
• Examples of these are primary / secondary amines, such as 3-amino-1-methylaminopropane, 3-amino-1-ethylaminopropane, 3-amino-1-cyclohexylaminopropane, 3-amino-1-methylaminobutane, furthermore alkanolamines, such as N-aminoethyl- ethanolamine, ethanolamine, 3-aminopropanol, neopentanolamine and more preferably diethanolamine, N- (2-hydroxyethyl) ethylenediamine, N, N'-bis (2-hydroxyethyl) ethylenediamine.
• These can be used in the preparation of the dispersion according to the invention as chain extenders and / or as chain terminators.
• the dispersions according to the invention may optionally contain building blocks d), which are located respectively at the chain ends and terminate them.
• building blocks are derived, on the one hand, from monofunctional compounds reactive with NCO groups, such as monoamines, in particular mono-secondary amines or monoalcohols.
• monoamines in particular mono-secondary amines or monoalcohols.
• Preferred are ethanol, n-butanol, 2-ethylhexanol, propylamine, butylamine, stearylamine or dibutylamine.
• Preferred isocyanate-reactive groups are hydroxyl or amino groups.
• Suitable anionic or potentially anionic hydrophilic compounds are e.g. Mono- and dihydroxycarboxylic acids, mono- and diaminocarboxylic acids, mono- and dihydroxysulfonic acids, mono- and diaminosulfonic acids and also mono- and dihydroxyphosphonic acids or mono- and diaminophosphonic acids and their salts, such as
• Preferred compounds e) are those which have carboxy or carboxylate and / or sulfonate groups.
• Particularly preferred ionic compounds 5) are those which contain carboxyl and / or sulfonate groups as ionic or potentially ionic groups, such as the salts of N- (2-aminoethyl) - ⁇ -alanine, of 2- (2-aminoethylamino) -ethanesulfonic acid or the addition product of IPDI and acrylic acid (EP-A 0 916 647, Example 1) and dimethylolpropionic acid.
• Suitable nonionic hydrophilic compounds according to the definition of component f) are e.g. Polyoxyalkylene ethers containing at least one hydroxy or amino group. These polyethers contain from 30% to 100% by weight of building blocks derived from ethylene oxide.
• Nonionically hydrophilicizing compounds f) are, for example, also monohydric, 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.
• the polyalkylene oxide polyether alcohols are either pure polyethylene oxide polyethers or mixed polyalkylene oxide polyethers whose alkylene oxide units consist of at least 30 mol%, preferably at least 40 mol%, of ethylene oxide units.
• Particularly preferred nonionic compounds are monofunctional mixed polyalkylene oxide polyethers which have at least 40 mol% of ethylene oxide and not more than 60 mol% of propylene oxide units.
• Suitable starter molecules are e.g. Diethylene glycol monobutyl ether or n-butanol.
• 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.
• Particularly preferred are 5 to 35 wt .-% of component a), 60 to 90 wt .-% of component b),
• component a 10 to 30% by weight of component a), 65 to 85% by weight of component b), 0.5 to 14% by weight of the sum of compounds c) and d), 0.1 up to 3.5% by weight of component e), 0 to 10% by weight of component f), the sum of e) and f) being 0.1 to 13.5% by weight and the sum of all Components added to 100 wt .-%.
• 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 Cellulosesalpeter- are klareester Walsroder ® nitrocellulose A types (Wolff Cellulosics GmbH & Co. KG,
• Medium-viscosity cellulose nitric 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, corresponding 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.
• the process for preparing the dispersions of the invention may be in one or more
• Stage / -n be carried out in homogeneous or multistage reaction, partially in disperse phase. After complete or partial polyaddition from a) -f), a dispersion, emulsification or dissolution step takes place. This is followed, if appropriate, by a further polyaddition or modification in disperse phase.
• the components b) to f) which may have no primary or secondary amino groups and the polyisocyanate components a) for the preparation of an isocyanate-functional polyurethane prepolymer completely or partially and optionally with a with Water-miscible but diluted with isocyanate-inert solvents and diluted to room temperature. heated in the range of 50 to 120 0 C.
• the catalysts known in polyurethane chemistry can be used.
• the alkyl radicals may, for example, also carry hydroxyl groups, as in the case of the dialkylmonoalkanol, alkyldialkanol and trialkanolamines.
• As a neutralizing agent also inorganic bases, such as aqueous ammonia solution or sodium or potassium hydroxide can be used. Preference is given to ammonia, triethylamine, triethanolamine, dimethylethanolamine, diisopropylethylamine, sodium hydroxide or potassium hydroxide.
• the molar amount of the bases is between 50 and 125%, preferably between 70 and 100%, 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 chain extension of the prepolymers preferably takes place before the dispersion.
• the degree of chain extension ie the equivalent ratio of NCO-reactive groups of the compounds used for chain extension to free NCO groups of the prepolymer, is between 40 and 150%, preferably between 50 and 120%, particularly preferably between 60 and 120%.
• the amine components [c), d), f)] 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.
• the diluent content is preferably 70 to 95% by weight.
• the preparation of the dispersion according to the invention from the prepolymers takes place after the chain extension.
• the dissolved and chain-extended polyurethane polymer may be subjected to high shear, such as, e.g. vigorous stirring, either added to the dispersing water or, conversely, the dispersing water is stirred into the prepolymer solutions.
• the water is added to the dissolved prepolymer.
• the solvent still present in the dispersions after the dispersion step is then usually removed by distillation. A removal already during the dispersion is also possible.
• the dispersions according to the invention generally have one
• the nitrocellulose is preferably dissolved in ketofunctional organic solvents such as acetone or 2-butanone prior to addition to the prepolymer (i). Most preferably, the nitrocellulose is dissolved in acetone.
• the content of nitrocellulose in the acetone solution is 5 to 95 wt .-%, preferably 5 to 70 wt .-% and particularly preferably 5 to 50 wt .-%.
• the addition of the acetone nitrocellulose solution may take place during the dissolution step after preparation of the prepolymer before (i) or after (ii) chain extension but before dispersion or after dispersion prior to distillation (iii).
• the addition of the dissolved nitrocellulose occurs after preparation of the prepolymer (i), i. before or after the chain extension step (ii), but before the dispersion (iii).
• the addition of the dissolved nitrocellulose after the chain extension step (ii) takes place before dispersion (iii).
• the content of nitrocellulose in the resulting inventive dispersion, based on total solids, is 0.5% by weight to 85% by weight, preferably 5% by weight to 75% by weight, particularly preferably 10 to 60% by weight. %.
• the solids content of the dispersion according to the invention is between 10 to 70 wt .-%, preferably between 20 to 65 wt .-% and particularly preferably between 30 to 63 wt .-%.
• the polyurethane-nitrocellulose particles containing in the dispersions of the invention have an average particle size between 20 and 700 nm, preferably between 30 and 550 nm, more preferably between 50 and 400 nm and most preferably between 100 and
• the dispersions of the invention may additionally contain antioxidants and / or light stabilizers and / or other auxiliaries and additives such as defoamers and thickeners.
• antioxidants and / or light stabilizers and / or other auxiliaries and additives such as defoamers and thickeners.
• fillers, non-migratory plasticizers, pigments, silica sols, aluminum, clay dispersions, leveling agents or thixotropic agents may also be present.
• up to 70%, based on the total dry substance, of such fillers may be present in the end product.
• the preparation of the coating can be carried out by the different spraying methods such as air pressure, airless or electrostatic spraying using single or optionally two-component spray systems.
• the paints and coating compositions containing the dispersions of the invention can also by other methods, for example by brushing, rolling, pouring, knife coating, dipping, printing or further the
• PolyTHF ® 1000 Polytetramethylenglykolpolyol, OH number 112 mg KOH / g, number-average number average molecular weight 1000 g / mol (BASF AG, Ludwigshafen, DE)
• the mean particle sizes of the dispersions were determined by means of laser correlation spectroscopy measurements (Zetasizer 1000, Malvern Instruments, Malvern, UK).
• the stated nitrogen contents of the nitrocellulose in wt .-% refer to the dry matter of nitrocellulose.
• Example 1 10% Walsroder® ® nitrocellulose E330 / IPA 30%
• the finished prepolymer was dissolved with 503.8 g of acetone at 5O 0 C and then added a solution of 20.6 g diaminosulphonate, 3.2 g of ethylenediamine and 102.7 g of water min within 5 s. The stirring time was 15 min. Was then added over 5 minutes a solution of 59.9 g Walsroder® ® nitrocellulose E330 / IPA 30% and 145.3 g of acetone. The dispersion was carried out by adding 515.3 g of water within 10 min.
• IPA 30 and 307.7 g of acetone were added within 5 minutes a solution of 59.9 g Walsroder® ® nitrocellulose El 160 /.
• the dispersion was carried out by adding 515.3 g of water within 10 min.
• the removal of the solvents was carried out in vacuo and there was obtained a storage-stable PUR dispersion having a solids content of 38.0% and an average particle size of 314 nm.
• the stirring time was 15 min. Subsequently, IPA 30% and 900.7 g of acetone were added within 5 minutes a solution of 175.5 g Walsroder® ® nitrocellulose E 1 160 /. The dispersion was carried out by adding 525.6 g of water within 10 min. In a subsequent distillation Lation 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 38.0% and an average particle size of 523 nm.
• Example 9 40% Walsroder® ® nitrocellulose E560 / IPA 30%
• Example 10 50% Walsroder ® Nitrocellulose E560 / IPA 30%
• the dispersion was carried out by adding 380.5 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 42.9% and an average particle size of 172 nm.
• Example 11 60% Walsroder ® Nitrocellulose E560 / IPA 30%
• the stirring time was 15 min. 30%, and 1391.1 g of acetone was then added over 5 minutes a solution of 350.7 g Walsroder® ® nitrocellulose E560 / IPA.
• the dispersion was carried out by adding 560.5 g of water within 10 min. In a subsequent distillation step, the solvents were removed in vacuo and a storage-stable PUR dispersion having a solids content of 39.0% and an average particle size of 222 nm was obtained.
• Example 12 10% Walsroder® ® nitrocellulose E560 / IPA 30% (addition of the nitrocellulose before the chain extension)
• Example 13 20% Walsroder® ® nitrocellulose E560 / IPA 30% (addition of the nitrocellulose before the chain extension)
• Example 14 30% Walsroder® ® nitrocellulose E560 / IPA 30%
• Example 15 10% Walsroder® ® nitrocellulose E560 / EPA 30% (addition of the nitrocellulose after dispersion)
• Distillation step carried out the removal of the solvents in vacuo and there was obtained a storage-stable PUR dispersion having a solids content of 38.0% and an average particle size of 260 nm.
• Example 16 30% Walsroder® ® E nitrocellulose E560 / IPA 30% (addition of the nitrocellulose after dispersion)
• the stirring time was 15 min ..
• the dispersion was carried out by adding 523.7 g of water within 10 min. Then a solution of 174.2 g Walsroder® ® nitrocellulose E560 / IPA 30% and 690.9 g of acetone was added over 5 min. In a subsequent distillation step, the solvents were removed in vacuo and a storage-stable PUR dispersion having a solids content of 38.0% and an average particle size of 376 nm was obtained.
• Example 17 30% Walsroder® ® nitrocellulose E560 / IPA 30
• the dispersion was carried out by adding 529.4 g of water within 10 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 40.0%, a particle size of 313 nm and an OH content of 0.16 wt .-% was obtained with respect to solid resin.
• Example 18 30% Walsroder® ® nitrocellulose E560 / EPA 30%
• Example 19 10% Walsroder® ® nitrocellulose E560 / EPA 30%
• Example 21 10% Walsroder® ® nitrocellulose E560 / IPA 30%
• the finished prepolymer was dissolved with 6.5 g of triethylamine and 434.9 g of acetone at 5O 0 C and then lentriamin a solution of 2.7 g diethylenetriamine, 2.9 g of hydrazine hydrate and 17.2 g of water within 10 min metered , The stirring time was 5 min. The mixture was then added within 5 min harvester, a solution of 59.4 g WAIS ® nitrocellulose E560 / EPA 30% and 235.7 g of acetone. The dispersion was carried out by adding 605.6 g of water within 15 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 38.0% and an average particle size of 130 nm.
• Example 22 30% Walsroder® ® nitrocellulose E560 / EPA 30%
• the finished prepolymer was dissolved with 6.1 g of triethylamine and 450.9 g of acetone at 50 0 C and then added a solution of 2.1 g diethylenetriamine, 2.2 g of hydrazine hydrate and 13.4 g of water within 10 min , The stirring time was 5 min. Subsequently, within 5 min, a solution of 181.2 g
• Example 23 20% Walsroder® ® nitrocellulose E560 / EPA 30%
• NCO value of 1.18% was reached.
• the finished prepolymer was dissolved with 300.0 g of acetone at 50 0 C and then added a solution of 1.7 g of diethanolamine, 8.5 g of diaminosulfonate and 51.0 g of water within 10 min.
• the stirring time was 60 min. 30% and 468.4 g of acetone was then added over 5 minutes a solution of 118.1 g Walsroder® ® nitrocellulose E560 / IPA.
• the dispersion was carried out by adding 564.3 g of water within

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• 2006
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