WO2007003264A2 - Derives d'acide polyaspartique dans des produits de revetement contenant du polysiloxane - Google Patents

Derives d'acide polyaspartique dans des produits de revetement contenant du polysiloxane Download PDF

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WO2007003264A2
WO2007003264A2 PCT/EP2006/005830 EP2006005830W WO2007003264A2 WO 2007003264 A2 WO2007003264 A2 WO 2007003264A2 EP 2006005830 W EP2006005830 W EP 2006005830W WO 2007003264 A2 WO2007003264 A2 WO 2007003264A2
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mol
formula
polyaspartic acid
units
acid
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PCT/EP2006/005830
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German (de)
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WO2007003264A3 (fr
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Josephus Slaats
Jürgen REINERS
Michael Franken
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Lanxess Deutschland Gmbh
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Priority to EP06754426A priority Critical patent/EP1904556A2/fr
Priority to BRPI0613117A priority patent/BRPI0613117A2/pt
Publication of WO2007003264A2 publication Critical patent/WO2007003264A2/fr
Publication of WO2007003264A3 publication Critical patent/WO2007003264A3/fr

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    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3821—Carboxylic acids; Esters thereof with monohydroxyl 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
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5036—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
    • 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
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

Definitions

  • the invention relates to mixtures comprising polyaspartic acid derivatives and polysiloxanes, their preparation and use for reducing the tack in PUR and / or acrylate coatings, corresponding coating dispersions and the substrates coated therewith.
  • polysiloxanes in the coating sector above all as defoamers, deaerators, leveling agents or as a tribological additive (that is to say as lubricants, grip agents or for setting up a specific so-called stick-slip effect).
  • polysiloxanes also have disadvantages in the finish, for example in the top coat of the leather finish: it may happen that the stickiness of the leather directly after the drying channel of a spraying machine is still too high, so that the leathers can not be stacked immediately without the finishing layers stick together and the leather can not later be separated without damaging the finish.
  • the dressing layer after the short heating time in the drying channel due to the not yet completed crosslinking reaction in the polyurethane and / or Polyacrylatf ⁇ lm does not have the excellent fastness properties, which has the leather after complete reaction, so that some stickiness of the Surface even after drying can not be excluded.
  • the object of the invention was to provide polysiloxane-containing mixtures which, especially in polyurethane and / or polyacrylate coating dispersions, can markedly reduce the tackiness of the coatings obtained therewith.
  • the mixture preferably contains as polyaspartic acid derivatives of component A) optionally hydrophobically modified polyaspartic acid, its salts, esters and / or amides, in particular polyaspartic acid salts with counterions from the group lithium, sodium, potassium, ammonium, alkylammonium, dialkylammonium, trialkylammonium, tetralkylammonium , wherein preferably partial esters or partial amides of polyaspartic acid, particularly preferably hydrophobically modified polyaspartic acid derivatives, in particular hydrophobically modified esters or amides of polyaspartic acid are used.
  • Preferred polyaspartic acid derivatives A) are, for example, polyaspartic acid and polyaspartic acid salts with counterions from the group lithium, sodium, potassium, ammonium, alkylammonium, dialkylammonium, trialkylammonium, tetralkylammonium, where the reaction with the counterion-yielding base may be partial or complete.
  • Such products are known per se and are obtainable, for example, by dissolving polysuccinimide in water in the presence of the corresponding base.
  • polyaspartic acid derivatives A) are partial esters or partial amides of polyaspartic acid.
  • hydrophobically modified polyaspartic acid derivatives are preferably understood as meaning those derivatives of polyaspartic acid which have hydrocarbon radicals having 1 to 60 carbon atoms, preferably alkyl radicals having 1 to 60 carbon atoms, in particular alkyl radicals having 8 to 30 carbon atoms as substituents. Preference is given to polyaspartic acid derivatives which are not completely dissolved in water but form a disperse phase in a continuous phase of water.
  • Suitable hydrophobically modified polyaspartic esters are, for example, also those known from EP 0 959 091 A1 and EP-A-959 090, of hydrophobically modified polyaspartic acid Esteramiden derived copolymers containing aspartic acid aspartic acid ester, aspartic acid amide units, other proteinogenic or non-proteinogenic amino acid units and iminodisuccinate units as structural units.
  • Very particularly preferred polyaspartic acid derivatives A) are (co) polymers which
  • W is a trivalent radical from the group
  • Hydrogen optionally substituted alkyl radicals, alkenyl radicals, aralkyl radicals or
  • Cycloalkyl radicals which are represented by O atoms, N atoms, Si atoms or amide, carbonate,
  • Urethane, urea, allophanate, biuret, isocyanurate groups or mixtures thereof may be interrupted and
  • M + represents H + or an alkali ion, an NH 4 -In or a primary, secondary, tertiary or quaternary aliphatic ammonium radical which preferably bears a C 1 -C 22 -alkyl or -hydroxyalkyl group,
  • R ⁇ represents a hydrocarbon radical with Ci-Cgo atoms, preferably a saturated C j -Cö Q alkyl, especially for a Cg-C3 alkyl, and Q regardless of
  • R ⁇ is hydrogen or has the same meaning as R ⁇
  • c) optionally contain polyether units having an average molecular weight of 200- 6000 g / mol.
  • radicals W are derived, for example, from the hydrocarbon skeletons of the polycarboxylic acids from the following group or their anhydrides:
  • Dicarboxylic acids or dicarboxylic acid anhydrides such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, tricarboxylic acids or their anhydrides such as 1,2,3-propanetricarboxylic acid, citric acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,3-cyclohexanetricarboxylic acid, 2,3,5-Norbornantricarbonklare, trimellitic acid, trimellitic anhydride, • and tetracarboxylic acids or their anhydrides or bisanhydrides such as 1,2,3,4-butane tetracarboxylic acid, 1, 2,4,5-cyclohexanetetracarboxylic acid, 2,3,5,6- Norbornanetetracarboxylic acid, 2,3,5,6- Norbomantetracarbonkladhydid, pyromellitic acid, Pyrom
  • Suitable radicals M + are, for example, hydrogen (H +), hydroxyethylammonium, bis (2-hydroxyethyl) ammonium, tris (2-hydroxyethyl) ammonium, triethylammonium, tetraethylammonium, ammonium, butylammonium, N-methyl-N-bis (2-hydroxyethyl ) -ammonium, N-dimethyl-N- (2-hydroxyethyl) -ammonium, N-diethyl-N- (2-hydroxyethyl) -ammonium, benzyltrimethylammonium, morpholinium, hexadecylammonium, oleylammonium, octadecylammonium, as well as alkali ions such as sodium, potassium, lithium , Preference is given to sodium, potassium, hydrogen, ammonium, 2-hydroxyethylammonium, bis (2-hydroxyethyl) ammonium
  • Suitable nitrogen substituents R 1 and R 2 are independently, for example, optionally substituted Ci-C 2 oo-alkyl or C 2 -C 2 o-alkenyl groups such as methyl, ethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, butyl, hexyl , Octyl, 2-ethyl-hexyl, octenyl, decyl, undecyl, undecenyl, dodecyl, tetradecyl, hexadecyl, oleyl, octadecyl, 12-hydroxy-9-octadecenyl, eicosanyl, 3-heptamethyl-trisiloxanyl-propyl, N-2- (e.g.
  • R 7, R 8 is C r C 3 -alkyl, C 2 -C 3 -alkenyl or C 5 -C are 0 cycloalkenyl,
  • n, m is a number from 1 to 100, preferably from 1 to 50, and
  • radicals -NR 1 R 2 are derived by abstraction of an H atom of monofunctional polyethers with primary amino groups based on oxirane, methyl oxirane, tetrahydrofuran or mixtures thereof, the polyether segments random or blockwise can be arranged. Particular preference is given to radicals derived from monofunctional aminopolyethers which have polyoxypropene and / or polyoxyethene units in any desired order.
  • Such products are known per se and, for example, under the name Jeffamine ® M-600, Jeffamine ® M-1000, Jeffamine ® M-2070, Jeffamine® available M-2005 (products of Huntsman).
  • radicals -NR 1 R 2 which are derived by abstraction of an H atom of monofunctional polyethers with primary amino groups, resulting from the reaction of polyisocyanates with monofunctional hydroxyl-terminated polyethers and subsequent hydrolysis. Instead of the hydrolysis, it is also possible to react the remaining isocyanate groups, for example with excess primary diamines, so that a free amino group remains.
  • Suitable polyisocyanates for preparing the monofunctional polyether having primary amino groups are: isophorone diisocyanate, bis (isocyanatocyclohexyl) methane, xylylene diisocyanate, 1,4-bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, toluylene diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane -2,4'-diisocyanate, the isocyanurate, biuret, allophanate, urea, uretdione group-containing oligomers of the aforementioned diisocyanates.
  • monofunctional hydroxyl-functional polyethers As monofunctional hydroxyl-functional polyethers, the alkoxylation products known per se from polyurethane chemistry on the basis of monofunctional starter alcohols obtained by polymerization of ethene oxide or propene oxide onto e.g. Methanol, ethanol or butanol, etc., are known.
  • Suitable diamines are: 1,2-ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1, 4-butylenediamine, 1, 2-dimethyl-1, 2-ethylenediamine 1, 6-hexamethylenediamine, isophoronediamine, bis (aminocyclohexyl) methane, xylylenediamine.
  • the structural unit of the formula I corresponds to the formula II
  • R 3 and R 4 have the abovementioned meaning.
  • the polyaspartic acid derivative of component A) contains ester-group-containing units of the formula
  • W has the above meaning and R is any organic radical in an amount of less than 5 wt .-%, in particular less than 2 wt .-%, preferably less than 1 wt .-%, based on the copolymer.
  • Preferred units of the formula Ia in particular units of the formula Ib, contain as the radical of the formula -NR ⁇ R ⁇ one which is derived from compounds of the formula HNR- ⁇ R ⁇ , as such the following compounds are preferred: secondary, preferably primary amines, such as 2-ethylhexylamine, 1-octylamine, 1-decylamine, 1-undecylamine, 1-dodecylamine, tetradecylamine, perfluorohexyl-1H, 1H, 2H, 2H-ethylamine, perfluorooctyl-1H, 1H, 2H, 2H-ethylamine, perfluorodecyl-1H, 1H, 2H, 2H-ethylamine, N-aminoethyl-N-methyl-perfluorooctylsulfonamide, hexadecylamine, octadecylamine, oc
  • the optionally present polyether units can be incorporated in the main chain of the copolymer or in the side chain or in the main chain and side chain.
  • Suitable polyether units are derived for the side chain of monofunctional amino-polyethers or for the backbone of diamino-polyethers.
  • Surfonamine ML-300 products of Huntsman
  • Further suitable monofunctional amino-polyethers are accessible, for example, by reacting a monofunctional OH-functional polyether with a diisocyanate in a molar ratio of 1: 1 or an excess of diisocyanate, the resulting reaction product optionally freed from excess diisocyanate and the isocyanate groups then to the amine hydrolyzed.
  • Examples are reaction products of propene oxide polyethers or Polyethenoxidpolyethem or Mischpolyethern based on ethene oxide and propene oxide, which were started on monofunctional alcohols such as methanol, ethanol, methoxyethanol, methoxy-diethylene glycol, butanol, butyldiglycol, etc., with diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, bis ( isocyanato-cyclohexyl) -methane, xylylene diisocyanate, tolylene diisocyanate, etc.
  • monofunctional alcohols such as methanol, ethanol, methoxyethanol, methoxy-diethylene glycol, butanol, butyldiglycol, etc.
  • diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, bis ( isocyanato-cyclohexyl)
  • diamino polyethers examples include:
  • diaminopolyethers based on propene oxide and / or ethene oxide having an average molar mass of 200-4000 g / mol.
  • diaminopolyethers which are obtained by reacting diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, bis-isocyanatocyclohexylmethane with hydroxyl-functional polyethers based on ethene oxide, propene oxide or tetrahydrofuran or their copolyethers or mixtures thereof in a molar ratio of NCO: OH greater than 1: 1 and subsequent hydrolysis of terminal isocyanate group are available.
  • diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, bis-isocyanatocyclohexylmethane with hydroxyl-functional polyethers based on ethene oxide, propene oxide or tetrahydrofuran or their copolyethers or mixtures thereof in a molar ratio of NCO: OH greater than 1: 1 and subsequent hydrolysis of terminal isocyanate group are available
  • hydroxy-terminated building blocks such as polycarbonate, polyester, Polyestercarbonatdiole and Polyethercarbonatdiole, for example, by reaction of the aforementioned hydroxyl-functional polyethers and other conventional building blocks such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hexanediol , Caprolactone by polycondensation with diphenyl carbonate or dimethyl carbonate (with elimination of phenol or methanol) and / or by polycondensation with adipic acid, glutaric acid, terephthalic acid, isophthalic acid (with elimination of water) or mixtures derived therefrom as raw materials for the preparation of diamino polyether the synthetic route described above, provided that at least one of the blocks contains incorporated in the polymer chain polyether units.
  • Suitable diisocyanates and diamines for the reaction of these building blocks are the already mentioned diisocyanates and diamines.
  • Particularly preferred reactants for this synthesis are polyethers based on oxirane and methyloxirane having two hydroxyl end groups, diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate and diamines such as ethylenediamine, hexamethylenediamine and isophoronediamine.
  • diaminofunctional polyethers Another possibility for the preparation of suitable diaminofunctional polyethers is the base-catalyzed addition of acrylonitrile to hydroxyl-terminated polyethers and subsequent hydrogenation of the nitrile groups to amino groups.
  • these polyurethanes, polyureas or polyurethane ureas may also be any other polymer diols customary in polyurethane chemistry (C4 polyethers, polyesters, polycarbonates, polyestercarbonates ), low molecular weight diols (butanediol, hexanediol, the adducts of ethylene oxide or propylene oxide with tallow fatty amine hydrogenated tallow fatty amine), hydrophilizing agents (dimethylol propionic acid, the adduct of sodium bisulfite to a 1,4-butenediol-initiated propylene oxide polyether having a molecular weight between 300 and 1000 g / mol), diamines (hydrazine hydrate, ethylenediamine, hexamethylene
  • polyethene oxide and / or polypropene oxide units containing diamines having an average molecular weight of 200 to 6000 g / mol.
  • poly in the abovementioned commodity designations preferably has a value such that the corresponding monoamines or diamines have a preferred number average molecular weight of from 200 to 4000 g / mol, preferably from 400 to 2500 g / mol.
  • Preferred copolymers according to the invention contain structural units of the formulas (IIa) and (Ub)
  • copolymers according to the invention may contain further divalent bridge members V in the main chain which are different from the units a), b) and c).
  • Preferred copolymers contain 0 to 10 mol% of such divalent bridge members V in the main chain, based on the sum of all units of formula I, wherein V is a bivalent radical derived from polycarboxylic acids, polyamines, lactams or aminocarboxylic acids.
  • the bridge members V are preferably derived from polyamines, in particular diamines, or polycarboxylic acids, in particular dicarboxylic acids, and from aminocarboxylic acids or their lactams.
  • These units may be contained in the main chain and then preferably serve to link the units of the formula I, Ia, Ib, II, IIa, IIb with one another in any order. They can also serve to link different polyether units that are incorporated in the main chain. It is also possible for a plurality of divalent radicals from the abovementioned group of polycarboxylic acids, polyamines, lactams and aminocarboxylic acids to be condensed and thus incorporated into longer bridge members.
  • Preferred bridge members V are derived from the following polyamines (VI): ethylenediamine, 1,2- and 1,3-propylenediamine, 1,6-hexamethylenediamine, isophoronediamine, bisaminocyclohexylmethane, diethylenetriamine, triethylenetetramine, bishexamethylenetriamine, diaminocyclohexane, xylylenediamine, Bis-3-aminopropyl ether, bis-aminomethyltricyclo [5.2.1.0 2 ' 6 ] decane.
  • Preference is given to diamines, in particular ethylenediamine and propylenediamine, isophoronediamine, hexamethylenediamine.
  • Preferred bridge members V are derived from the following polycarboxylic acids (V-2): oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, tartaric acid, cyclohexane-1,2-dicarboxylic acid, cyclohexane-l, 3-dicarboxylic acid, cyclohexane-l, 4 dicarboxylic acid, 1-cyclohexene-1,2-dicarboxylic acid anhydride, 4-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic anhydride, 3-cyclohexene-1,2-dicarboxylic anhydride, norbornane-2,3-dicarboxylic acid , Norbornane-2,3-dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic
  • dicarboxylic acids in particular succinic acids, glutaric acid, adipic acid.
  • Preferred bridge members V are derived from the following aminocarboxylic acids (V-3): glycine, alanine, aspartic acid, glutamic acid, other naturally occurring amino acids, aminopropionic acid, aminobutyric acid, aminohexanecarboxylic acid. Glycine, aspartic acid, glutamic acid are preferred.
  • Preferred bridge members V are derived from the following lactams (V-4): butyrolactam, caprolactam, laurolactam. Preference is given to caprolactam.
  • Suitable longer bridge members V can also be obtained by condensation or cocondensation reaction of the aforementioned building blocks V-I to V-4. Due to the terminal amino groups and / or carboxyl groups, these bridge members are incorporated in the main chain during the preparation of the preferred 10 (co) polymers of the component.
  • the preferred (co) polymers of component A) preferably have the following radicals, which can be defined via the starting materials and preferably from the optionally used polycarboxylic acids, dicarboxylic acids, polyamines, diamines, lactams, ammonia, amines, polyethers and for the preparation the monofunctional and difunctional polyether
  • the end groups may be based on the following radicals: alkyl radicals, alkoxy radicals, alkylamino radicals, cycloalkylamino radicals or aliphatic amino-substituted aralkyl radicals, polyetheramino radicals, N-substituted maleimide radicals, OH, COOH, CONH 2 and NH 2 groups, and radicals, which are derived from aspartic acid and its derivatives.
  • Preferred end groups are, for example, hydroxyl, amino, carboxyl and its salts,
  • polyether-modified copolymers having a number average molecular weight of from 500 to 50,000, preferably from 1,500 to 30,000, g / mol, in particular those which are
  • copolymers of component A) which contain from 10 to 90% by weight, in particular from 30 to 80% by weight, of structural units of the formula I, in each case based on the copolymer.
  • the copolymer of component A) consists of more than 95 wt .-%, in particular more than 98 wt .-% of the structural units of the formula I, Ia, optionally the polyether units and optionally divalent bridge members.
  • Al - consists of the copolymer of component A) to more than 95 wt .-%, in particular more than 98 wt .-% of structural units of the formula I and optionally polyether units, wherein
  • polyether units having an average molecular weight of 200 to 6000 g / mol.
  • the radical -NR 3 R 4 in formula Ia in particular Ib, represents radicals which are derived from the following amines HNR 3 R 4 : dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, hexadecenylamine, octadecenylamine, tallow fatty amine, hydrogenated Tallow fatty amine, N-methyl-octadecylamine, perfluorohexyl-1H, 1H, 2H, 2H-ethylamine, perfluorooctyl-1H, 1H, 2H, 2H-ethylamine, perfluoro-decyl-1H, 1H, 2H, 2H-ethylamine, N-aminoethyl- N-methyl-perfluorooctylsulfonamide, branched aliphatic amine, branched aliphatic
  • the copolymer of component A) comprises polyether units of component ii) derived from diamines of the formula
  • A2 - consists of the copolymer of component A) to more than 95 wt .-%, in particular more than 98 wt .-% of structural units of the formula I, of which
  • R ⁇ is a radical containing more than two ether groups, which are derived from Cz-C ⁇ -alkylene oxide units, which is optionally substituted by urethane, carbonate, urea, biuret, allophanate, isocyanate, alkylene, cycloalkylene or aralkylene groups is interrupted and
  • R6 is hydrogen or has the meaning of R ⁇ .
  • radical -NR 3 R 4 in formula Ia, in particular Ib has the same meaning as stated for the embodiment Al above.
  • the radical -NR 5 R 6 is derived from amines of the formulas HNR 5 R 6 which correspond to the abovementioned monofunctional amino-polyethers, in particular primary amino-polyethers.
  • polyether units of components ii) which are derived from the following monoamines:
  • R is H or C 1 -C 4 -alkyl, in particular H or CH 3,
  • R 1 is H or CH 3 and
  • a number from 5 to 50 means, in particular
  • R, R 'and n have the abovementioned meaning
  • R ' is H or CH3.
  • polyaspartic acid derivatives in particular polyaspartic acid amides of component A), which contain no polyether groups.
  • Very particularly preferred components A) are, for example, polyaspartic acid and its salts with sodium, potassium, ammonium and amines and alkanolamines as counterion.
  • Very particularly preferred components A) are hydrophobically modified polyaspartic acid derivatives, in particular the amide derivatives which are obtainable by incorporation of alkyl radicals having 1 to 60 C atoms, in particular alkyl radicals having 8 to 30 C atoms and optionally polyether units, into the polyaspartic acid polymer, as described above in the embodiments Al and A2.
  • Such products are known, for example, from EP-A 842 300 and EP-A 1 518 881.
  • Particularly preferred are hydrophobically modified polyaspartic acid derivatives, in particular hydrophobically modified esters or amides of polyaspartic acid, as described for example in DE-A 195 28 782.
  • polyaspartic acid derivatives of component A can also be prepared in the manner described in EP-A 1 518 881 or in an analogous manner.
  • Preferred polyether-modified polyaspartic acid derivatives of component A) according to embodiment A1 have weight average molecular weights of from 500 to 30,000, preferably from 1,000 to 20,000, in particular from 1,000 to 10,000, g / mol by gel permeation chromatography (calibrated with polystyrene).
  • the structural units are preferably arranged alternately, block-wise or randomly distributed.
  • the polyaspartic acid derivatives of component A) may also contain branching points which, for example, in the case of maleic anhydride by incorporation of iminodisuccinate or by incorporation of Nitrilo trisuccinate or in concomitant use of tri- or tetracarboxylic acids or by Michael addition of polyamines to the double bond of maleimide End groups and further reaction of the resulting secondary amine can arise.
  • branching points which, for example, in the case of maleic anhydride by incorporation of iminodisuccinate or by incorporation of Nitrilo trisuccinate or in concomitant use of tri- or tetracarboxylic acids or by Michael addition of polyamines to the double bond of maleimide End groups and further reaction of the resulting secondary amine can arise.
  • branching points which, for example, in the case of maleic anhydride by incorporation of iminodisuccinate or by incorporation of Nitrilo trisuccinate or in concomitant use of tri
  • Suitable monofunctional compounds for controlling the molecular weights are monocarboxylic acids such as formic acid, acetic acid, propionic acid, benzoic acid, cyclohexanecarboxylic acid, stearic acid, or monoamines such as butylamine, dibutylamine, aminoethanol, hexylamine, dodecylamine, hexadecylamine, octadecylamine, octadecenylamine, and the above monofunctional polyetheramines.
  • monocarboxylic acids such as formic acid, acetic acid, propionic acid, benzoic acid, cyclohexanecarboxylic acid, stearic acid
  • monoamines such as butylamine, dibutylamine, aminoethanol, hexylamine, dodecylamine, hexadecylamine, octadecylamine, octadecenylamine, and the
  • the optionally polyether-modified polyaspartic acid derivatives of component A), in particular polyaspartic acid amides, are preferably self-dispersing.
  • external dispersants As such, in principle cationic, anionic and nonionic dispersants come into question, as they are e.g. in "Methods of Organic Chemistry” (Houben-Weyl), 4th Edition, Volume XTV / 1, Georg Thieme Verlag, Stuttgart 1961, p 190 f. are described.
  • Preferred dispersants include, for example Cg-Cig-n-alkyl sulfates, Cg-Cig-n-alkyl benzene sulphonates, Cs-C i g n-alkyl-trimethyl-ammonium salts, N-di-Cs-C1 8-alkyl-dirnethyl-ammonium- salts, Cg-Qg-n-alkyl-carboxylates, Cg-Qg-n-alkyl-dmethylamine oxides, Cg-Cig-n-alkyl-dimethyl- phosphine oxides and - preferably - oligoethylene glycol mono-Q-cis-alkyl ethers having an average of 2 to 30 ethoxy groups per molecule.
  • n-alkyl radicals may also be replaced by partially unsaturated linear aliphatic radicals.
  • Particularly preferred dispersants are oligoethylene glycol mono-Ci-Ci 4 alkyl ethers having an average of 4 to 12 ethoxy groups per molecule, in particular oligoethylene glycol mono-Cu-alkyl ethers having an average of 8 ethoxy groups per molecule.
  • Preferred dispersants further include oleic acid, oleic acid sarcosides, ricinoleic acid, stearic acid, fatty acid partial esters of polyols such as glycerol, trimethylolpropane or pentaerythritol and their acylation, ethoxylation and propoxylation products, e.g.
  • Glycerol monostearate and monooleate, sorbitan monostearate and monooleate, sorbitan tristearate and trioleate and their reaction products with dicarboxylic acid anhydrides such as succinic anhydride, maleic anhydride, phthalic anhydride or tetrahydrophthalic anhydride, reaction products of bis (hydroxymethyl) tricyclodecane and maleic anhydride or succinic anhydride and derivatives thereof, preferably in the form of their alkali or ammonium salts.
  • Particularly preferred dispersants are salts of long-chain fatty acids, preferably of oleic acid and an aminoalcohol, preferably hydroxyethylamine, bishydroxyethylamine or trishydroxyethylamine.
  • aqueous dispersant For the preparation of an aqueous dispersion, it is generally recommended to meter the dispersant into the reaction mixture before, during or after the dispersion at from 7O 0 C to 140 0 C with stirring. It is also possible to disperse the reaction mixture in an aqueous dispersant solution.
  • the dispersant content is generally not more than 30, preferably 3 to 15 wt .-%, based on the aqueous dispersion of component A).
  • the solids content of the dispersions of component A) is preferably from 5 to 60% by weight, particularly preferably from 10 to 40% by weight.
  • the average particle size of the dispersed polyaspartic acid amides is generally 50 to 1000, preferably 50 to 700 and in particular 80 to 400 nm.
  • the pH during the dispersion is preferably set between 5 and 11, particularly preferably 6 to 10.
  • the particle size of the disperse phase For application in the coating, it may be advantageous to reduce the particle size of the disperse phase.
  • an already obtained pre-emulsion under high shear rate can be aftertreated in known dispersing machines such as jet dispersers with suitable nozzles, high-pressure emulsifying machines or mixers with rotor-stator principle. It is also possible to generate the dispersion in situ in the chambers or nozzles of the mentioned devices.
  • the Dispersion time can be between a few minutes up to 4 hours.
  • the dispersion is preferably carried out in a temperature range between 20 and 75 0 C.
  • the bleaching can be carried out oxidatively or reductively. Preference is given to oxidative bleaching. Suitable oxidizing agents are hydrogen peroxide or alkali metal or ammonium persulfate in aqueous solution.
  • the bleach may be in the temperature range between 20 and 9O 0 C, preferably between 30 and 60 0 C are performed. Unused bleach is then destroyed with a reducing agent.
  • a reducing agent for example, sodium bisulfite solution, or peroxide-decomposing enzyme formulations based on oxidoreductases are as besipiel intercept BAYREDUKT ® EPK (product of LANXESS Germany GmbH).
  • the decomposition of radicals of the oxidizing agent is advantageously carried out at temperatures between 20 and 45 0 C in the pH range between 5 and 8.
  • Suitable polysiloxanes of component B) are known per se and commercially available.
  • Ci-C ⁇ o-alkyl, aryl and aralkyl radicals substituted Si atoms are suitable as components B) contain.
  • the basic skeleton of the siloxanes may contain predominantly D units and optionally M units, but may also have branches through T and Q units, it being possible for the structural elements to be combined as desired.
  • T units are e.g. Polysilsesquioxanes accessible by hydrolysis of trialkoxysilanes.
  • D units are repeat units which lead to a linear polysiloxane chain, for example of the general formula - [Si (CH 3 ) 2 -O] -, in which the 2 valences of the silicon remaining after abstraction of the 2 adjacent O atoms Atoms are saturated by hydrocarbon radicals.
  • M units are repeating units which form the end groups of a linear or branched polysiloxane chain, for example of the general formula Si (CH 3 VO-), in which the 3 valencies of the Si atoms remaining after abstraction of the adjacent O atom are saturated by hydrocarbon radicals are.
  • T units in the case of polysiloxanes are repeat units which lead to a branched polysiloxane chain, for example of the general formula - [O-Si (CH 3 ) O] -, in which the valence of the Si atoms remaining after abstraction of the 3 adjacent O atoms are saturated by hydrocarbon radicals.
  • Q units in the case of polysiloxanes are repeating units which lead to a branching in a polysiloxane chain, the Si atom being coordinated by 4 oxygen atoms.
  • the polysiloxanes may be, for example, simple polydialkylsiloxanes with or without reactive groups on the silicon units (alkoxysilane groups, silanol groups). Also suitable are polysiloxanes with organofunctional substituents, or those which are substituted by polyether units.
  • the organofunctional substituents may be charge neutral or ionic in nature. There may also be several substituents in the polysiloxane chain side by side. It is also possible to use mixtures of the polysiloxanes.
  • Suitable organofunctional substituents bonded to Si atoms are e.g. 3-aminopropyl, N (2-aminoethyl) -aminopropyl, hydroxymethyl, hydroxyethyl, hydropropyl, hydroxybutyl,
  • Spacer groups to which Si atoms may be bonded epoxyalkyl, epoxyalkoxyalkyl,
  • Spacer groups can, for example, alkylene radicals, or by ester, urethane, urea, carbonate, imino or amide interrupted
  • Preferred polysiloxanes are used as aqueous dispersions of the aforementioned Polysüoxan types.
  • polysiloxanes having a molecular weight of 500 to 200,000 g / mol and / or a degree of polymerization of 7 to 2750 (SiO units) (and / or having a viscosity, measured at 25 ° C, from 25 to 500,000 cP at 25 0 C, in particular 100 to 250,000 cP, preferably 1000 to 250,000).
  • Polysiloxanes are suitable in which the valences remaining on the Si atom after abstraction of the O atoms are saturated by hydrocarbon radicals.
  • the hydrocarbon radicals have 1-60 carbon atoms and may be interrupted by heteroatoms such as O, N, S and P or by functional groups such as hydroxy, amino, epoxy, isocyanato, carbamoyl, ureido, alkoxycarbonyl, trimethylsilyloxy, carboxyl, carboxylate, sulfonic acid , Sulphonate, phosphoric acid, phosphate, mercapto.
  • Particularly preferred polysiloxanes are polydimethylsiloxanes which are predominantly composed of M, D, T and Q units and optionally also have reactive chain ends of the silanol group and alkoxysilyl group type or optionally hydroxy, carboxy, amino-functionalized alkyl radicals.
  • Such polysiloxanes which may for example also be present as silicone emulsions, are known to the person skilled in the art and are commercially available.
  • carboxyl-functional polysiloxanes of EP-A 1 108 765 Particular preference is also given to the carboxyl-functional polysiloxanes of EP-A 1 108 765.
  • carboxyl-containing polysiloxanes described in the examples which are obtained by reacting aminopolysiloxane derivatives with polycarboxylic anhydrides and the cyanurea-containing polysiloxanes from EP-A 1 263 992, which are advantageously used because of the reactive groups in the dressing.
  • polysiloxane resins which may also be present in the form of polysiloxane resin emulsions, in particular those polysiloxanes having a viscosity of 100 to 200,000 cSt at 25 ° C., which are commercially available.
  • examples include: Dow Corning Fluid 200 (viscosity 60000 cP), DC 200 with a viscosity of 100, 200 or 500 cP, Dow Corning 3289 Bladder Lubricant (viscosity 200000 cP), Dow Corning Q2-3238 Dispersible Silicone Additives.
  • Preferred mixtures according to the invention contain
  • the pH of the mixture according to the invention is preferably 4.5 to 12, preferably in the pH range from 4.5 to 10, in particular from 5 to 8. Particular preference is given to mixtures according to the invention comprising
  • contents of the components A) and B) refer to the dry residue, and the total dry residue of the mixture 10 to 70 wt .-%, in particular 20 to 70 wt .-%, and the mixture has a viscosity of 50 to 5000 mPas, in particular 100 to 4000 mPas, at 20 0 C and 100 s' 1 has.
  • the dry residue is the concentration that can be detected gravimetrically as the residue after evaporation of the volatiles such as water and solvent.
  • the mixture generally has an average particle size (measured by laser correlation spectroscopy or ultracentrifuge) of from 30 to 1000, preferably from 30 to 700, and particularly preferably from 50 to 400 nm.
  • the mixture according to the invention may also contain conventional additives, such as the already mentioned dispersants, emulsifiers, pH-regulating additives (acids, bases for adjusting a pH of the mixture between 5 and 8), and optionally conventional material protection agents, these additives in one the components A) or B) may be contained or may be added separately.
  • conventional additives such as the already mentioned dispersants, emulsifiers, pH-regulating additives (acids, bases for adjusting a pH of the mixture between 5 and 8), and optionally conventional material protection agents, these additives in one the components A) or B) may be contained or may be added separately.
  • the invention further relates to a process for the preparation of the mixture according to the invention, characterized in that component A) and component B) are mixed, preferably dispersed under shear in component B) and preferably the total dry residue with water to 10 to 70 wt .-% sets.
  • the mixing, in particular the dispersion is generally carried out at 10 0 C to 15O 0 C, optionally under pressure, preferably under pressure at 15 0 C to 100 0 C, more preferably at 15 ° C to 70 0 C with the addition of shear energy.
  • component B) in component A It is also possible to disperse component B) in component A).
  • the addition of water to adjust the total dry residue of the mixture can be made at the beginning, during or at the end of the dispersion.
  • Suitable shear units are stirrers of generally conventional geometry, but also high-speed stirrers or devices with a rotor-stator principle, such as dissolvers, Ultra-Turrax, and nozzle technologies and high-pressure emulsification techniques such as homogenizers, microfluidizers or jet dispersers with nozzle technology. It is also possible to obtain stable dispersions by treatment with ultrasound.
  • the mixture according to the invention can be formulated with other customary additives known to those skilled in the art and auxiliaries for the ready-to-use coating composition.
  • the invention further relates to the use of the mixture according to the invention for reducing the tackiness of coatings of substrates based on aqueous polyurethane and / or polyacrylate dispersions.
  • the invention further relates to a process for the preparation of coating dispersions which are suitable for coating substrates, in particular for leather finishing, characterized in that mixtures according to the invention with at least one polyurethane and / or polyacrylate polymer and optionally pigment pastes and conventional finishing auxiliaries, which are described in preferred form below, mixes.
  • a homogeneous mixture is preferably obtained.
  • the viscosity is preferably adjusted to the proper for the type of application spray viscosity of 15 to 35 seconds (flow time in Ford cup, nozzle 4mm) and stirred the crosslinker.
  • the invention further relates to coating dispersions containing a mixture according to the invention and
  • Preferred components C) are polyurethane dispersions.
  • polyurethane dispersions which are obtainable from the following building blocks:
  • Suitable polyisocyanates 1) are preferably diisocyanates such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate, bis (isocyanatocyclohexyl) methane, and the di- and trimers of the aforementioned diisocyanates having an NCO functionality greater than 2.
  • Suitable polyols 2 are polyethers, such as poly (oxypropylene) diols, poly (oxyethylene) diols having a molecular weight of 500 to 12,000 g / mol, preferably a molecular weight of 500 to 4000 g / mol, particularly preferably having a molecular weight of 500 to 2500 g / mol, poly (tetrahydrofuran) diols having a molecular weight of 200 to 4000 g / mol, mixed polyethers of EO and PO and random or block copolyethers of the type of polytetrahydrofuran-ethylene oxide copolyether, polytetrahydrofuran-propylene oxide copolyether , Polytetrahydrofuran-Ethylöenoxid.Propyklenoxid, wherein the blocks of the monomer units may be arranged differently among each other, that is, an AB structure, ABA structure, BAB structure, A-random (B + C) -
  • Suitable polyols 3) are, for example, polyethers which are obtainable by reacting polyhydric alcohols having a functionality greater than 2, such as trimethylolpropane, pentaerythritol, glycerol, sorbitol, etc., with alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide and mixtures thereof.
  • Suitable polyols 4) are linear or branched monoalcohols such as ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, 2-ethylhexanol, octanol, up to the C30 alcohol.
  • Suitable polyols 4) are furthermore diols, such as ethanediol, propanediol, butanediol, hexanediol, bis (2-hydroxyethoxy) benzene, bis-2,2- [4- (2-hydroxyethoxy) -phenyl] -propane, bis-hydroxymethyltricyclo [5.2.1.0 2 ' 6 ] decane.
  • diols such as ethanediol, propanediol, butanediol, hexanediol, bis (2-hydroxyethoxy) benzene, bis-2,2- [4- (2-hydroxyethoxy) -phenyl] -propane, bis-hydroxymethyltricyclo [5.2.1.0 2 ' 6 ] decane.
  • Suitable polyols 4) are trifunctional alcohols such as trimethylolpropane, glycerol, 1,1,1-tris (2-hydroxyethoxy-methyl) -propane, etc.
  • Suitable polyols 4) having an OH functionality of 4 and higher are, for example, pentaerythritol, sorbitol, Gluconolactone, polyglycerol etc.
  • Suitable ionic group-containing polyols 5) are dimethylolpropionic acid, dihydroxybutyric acid, dimethylolbutyric acid, tartaric acid, sulfo-containing diols, such as adducts of sodium disulfite with propoxylated 1,4-butanediol.
  • Suitable amino-functional compounds 6) are ethylenediamine, isophoronediamine, bis (aminocyclohexyl) methane, N- (2-aminoethyl) 2-aminoethane-1-sulfonic acid and its alkali metal salts, N- (2-aminoethyl) 2-aminoethane-1 carboxylic acid, Michael adducts of acrylic acid with isophoronediamine, cyanamide, diethylenetriamine, aminoethanol, diethanolamine.
  • Suitable blocking agents may be butanone oxime, dimethylpyrazole, pyrazole, caprolactam, sodium bisulfite, acetylacetone, diethyl malonate.
  • Suitable neutralizing agents 8 are, for example, triethylamine, N, N-dimethyl-aminoethanol, tripropylamine, N-methyl-bis (2-hydroxyethyl) amine, diethyl-aminoethanol, tris (2-hydroxyethyl) amine.
  • Particularly suitable film-forming components for use in topcoating formulations are polyurethane dispersions whose films have a Shore A hardness of more than 50, in particular 50-100.
  • the adjustment of the hardness Shore A by changing the reactants and the adjustment of the stoichiometric ratios of the reactants and the reaction parameters for the reaction are known in the art.
  • aqueous polyurethane dispersions for leather finishing are commercially available.
  • polyurethane dispersions which contain no solvents, such as NMP or other co-solvents, which are sometimes used to improve film formation, for example propylene glycol diacetate, methoxypropyl acetate, methoxypropanol, ethoxyethyl acetate, ethoxyethanol, etc.
  • solvents such as NMP or other co-solvents
  • Suitable components B) are also polyacrylate dispersions.
  • the preparation of polyacrylate dispersions is generally carried out by solution or emulsion copolymerization.
  • Preferred polyacrylates have a molecular weight of 10,000 to 1,000,000 g / mol.
  • polyacrylate dispersions which are selected from at least one of the following monomers obtainable by free-radical copolymerization:
  • vinyl esters such as vinyl acetate, vinyl propionate and / or
  • Unsaturated dicarboxylic acids such as crotonic acid, itaconic acid or maleic anhydride.
  • Suitable components C) are also mixtures of polyacrylate and polyurethane dispersions or dispersions obtained by grafting acrylate comonomers onto polyurethane dispersions (PUR-P AC hybrids), provided that they have a hardness sufficient to produce topcoats Shore A and are crosslinkable or crosslinkable with conventional crosslinkers.
  • M + is hydrogen, sodium or potassium and / or the radical of an alkanolamine, particularly ethanolamine, diethanolamine, diethylaminoethanol, dimethylaminoethanol, ethyldiethanolamine, methyldiethanolamine or triethanolamine is, B) at least one polysiloxane having a viscosity of 10,000 to 500,000 mPas at 25 ° C and
  • Crosslinking agents and conventional additives in particular the abovementioned additives, may be contained as further components.
  • the coating dispersions according to the invention preferably contain further customary additives:
  • crosslinking agents For example, crosslinking agents, rheological additives (thickeners), flow control agents, defoamers, deaerators, matting agents, grip agents, antioxidants and / or pigments for shading.
  • thickeners For example, crosslinking agents, rheological additives (thickeners), flow control agents, defoamers, deaerators, matting agents, grip agents, antioxidants and / or pigments for shading.
  • Crosslinkers are, for example, polyisocyanates, polyepoxides, polyaziridines, polycarbodiimides, melamine-formaldehyde condensates, organometallic compounds (eg siccatives) for accelerating oxidatively drying binder systems and mineral crosslinkers (such as ZnO), or in the case of UV-crosslinkable systems, the corresponding polymerization initiators when energy is supplied in the form of visible light or higher energy radiation in the UV range, initiate the polymerization and cause crosslinking of binder systems containing the polymerizable group.
  • Particularly preferred are polyisocyanates which are hydrophilic modified are preferably those which can be easily distributed homogeneously by stirring in the finishing liquor at room temperature.
  • the crosslinking agent-activated coating dispersions generally have a pot life of 1 to 24 hours, preferably between 1 and 12 hours at room temperature, and should be applied to the substrate as soon as possible after activation of the mixture. After one too long waiting time, the mixture can not be used without restrictions regarding the achievable final properties of the coating.
  • crosslinking is based on the combination of different curing mechanisms, e.g. rapid UV curing combined with slower cure via an addition mechanism (epoxide, carbodiimide, aziridine, or isocyanate crosslinking).
  • rapid UV curing combined with slower cure via an addition mechanism (epoxide, carbodiimide, aziridine, or isocyanate crosslinking).
  • Rheological additives include, for example, thickeners to adjust the viscosity of the formulation to the correct peak viscosity. Outlet times of 10-50 seconds in the Ford cup with nozzle 4 mm are preferred. Particularly suitable are polyacrylate thickeners or nonionic, associative polyurethane thickeners.
  • Antioxidants are additives that can be added to the coating dispersion to prevent any heat yellowing or discoloration of the coating due to excessive exposure and weathering during use.
  • Suitable auxiliaries of this type are for example sterically hindered phenols or hindered amine light stabilizers, so-called.
  • HALS amines such as Tinuvin ® 765, Ciba Specialties Company).
  • Pigment masterbatches are preferably concentrates which are used after dilution in the formulation in order to be able to nuance the color of the coated substrate.
  • Flow control agents for example, special polyethermodif ⁇ initiatede polydimethylsiloxanes as Aquaderm ® Fluid H (LANXESS Germany GmbH). Suitable polyether siloxanes are mentioned, for example, in EP-A-0318751 (page 3, line 28 to page 4, line 11). Further polyether siloxanes are known per se to the person skilled in the art and are commercially available.
  • Antifoaming agents can be, for example, various silicone-containing antifoams or component-free antifoams based on component B) or solid defoamers.
  • Matting agents are different from component B), for example silicate-containing or silicate-free formulations based on organic nanoparticles for adjusting the gloss or the degree of matting.
  • Suitable matting agents are, for example, amorphous fumed silicas, spherical particles based on silicates or polysilsesquioxanes.
  • the silica particles may be present as such or modified by a surface treatment with, for example, organosilanes.
  • organic particles such as crosslinked or uncrosslinked commercially available polyacrylate-based microbeads which are monodisperse-accessible, or microbeads based on polyurethane precipitation dispersions, which as a rule have a somewhat broader particle size distribution than the polyacrylates have, are suitable for matting advantageous.
  • aqueous products or matting agents which can be incorporated directly without agglomeration in the coating formulation or can be dispersed in as an aqueous concentrate. Therefore, the matting agents are often already aqueous formulations which are added as a concentrate as needed to the finish formulation (coating dispersion).
  • the matting agents contained therein have, for example, an average particle size of 5 to 50 ⁇ m, preferably 5 to 25 ⁇ m.
  • Gripping means are additives for setting a non-blocking, pleasant silky surface touch or special effects of the finished coated / dressed leather articles. These are wax emulsions, special silicone formulations developed for this purpose or fluorine-containing aqueous dispersions.
  • Particularly preferred coating dispersions preferably for the production of automotive leather finishes, consist of the following components:
  • crosslinker use 100% or optionally diluted up to 50% in solvents not NCO-reactive solvents such as propylene glycol diacetate, butyl acetate, ethoxyethyl acetate, methoxypropyl acetate, propylene carbonate, etc.
  • solvents not NCO-reactive solvents such as propylene glycol diacetate, butyl acetate, ethoxyethyl acetate, methoxypropyl acetate, propylene carbonate, etc.
  • Preferred of these coating dispersions preferably contain more than 85%, in particular more than 90%, preferably more than 95%, particularly preferably more than 98% of the components A), B), C), D), E), F), G), H), I), J), optionally K) and water.
  • component A) according to the invention in combination with other hydrophobically modified polyacrylate dispersions.
  • water repellents based on polyacrylate or silicone active substances or fluorine-containing copolymers or other polyurethane-based fluorocarbon resins based on commercially available building blocks such as OH-containing perfluoroalkyl telomeres.
  • topcoats it is possible to use the coating dispersions according to the invention as base coats (primer) or for top coats. Particularly preferred is the use in topcoats. The use is preferably carried out in topcoats which have the composition described above.
  • the wet application rate of the coating dispersions according to the invention as basecoats is preferably 1 to 10 grams per square foot (sqft).
  • the wet application rate of the coating dispersions according to the invention as a topcoat is preferably 1 to 10 grams per square foot (sqft).
  • the dry application amount is preferably 0.5 to 5 g / sq.
  • application methods are the usual application techniques such as casting, spraying, plushing, or direct and indirect roller application methods such as roll coating, reverse roll coating etc. Particularly preferred is in the leather finishing the job by means of spray guns and sharpening machines.
  • the leather preferably in a drying apparatus such as a dry box or on a conveyor belt in a drying tunnel at temperatures between 50 and 100 0 C (set temperature at the drying device) dried for a period of between 1 minute and 5 minutes and then stacked.
  • a drying apparatus such as a dry box or on a conveyor belt in a drying tunnel at temperatures between 50 and 100 0 C (set temperature at the drying device) dried for a period of between 1 minute and 5 minutes and then stacked.
  • the leathers which have been dressed or coated with topping formulations containing the mixtures or the coating dispersions according to the invention are tack-free and can easily be separated from one another after cooling, while the leathers produced according to the prior art and then hot were stacked, stick to the dressing layer to each other or can be very difficult to separate, which is sometimes possible only with damage of the dressing layers.
  • the leathers produced using the mixtures or coating dispersions according to the invention have a very high level of fastness and are therefore particularly suitable for the production of automotive leather.
  • the invention furthermore relates to leather comprising the agents according to the invention and substrates coated with at least one inventive mixture or a coating dispersion according to the invention.
  • Preferred substrates are leather, textile, non-woven and other flexible and non-flexible materials.
  • the resulting leathers are particularly suitable for the production of automotive leather, which must meet particularly high standards in terms of fastness properties.
  • Polyether 4 ⁇ -methyl- ⁇ - (2-aminopropyl) poly (oxypropylene-co-oxyethylene) as
  • Pigment highly concentrated, finely divided emulsifier-free pigment dispersion with very low binder content; like EUDERM Colors B / C-N; 20-65% depending on the pigment, LANXESS
  • black pigment EUDERM Black B-N, 23% by weight
  • Filler anionic dispersion; soft antikle- and fillers for aqueous
  • Binder primers such as EUDERM Nappa Soft S; about 25% by weight, LANXESS
  • Primer aid anionic dispersion - auxiliary for aqueous primers for drying, such as EUDERM Paste DO; 52Gew .-%; LANXESS
  • Polyurethane binder 1 medium hardness aliphatic anionic polyurethane dispersion such as BAYDERM Bottom 51 UD; 35% by weight; Rohm and Haas
  • Polyacrylate binder (Component C) Polyacrylate dispersion for use in topcoats such as HYDRHOLAC CL-I; about 37% by weight, Rohm and Haas
  • Silicone 1 aqueous silicone emulsion, solids content about 59% by weight, handle
  • Thickener associative polyurethane thickener such as Acrysol RM-1020, solids content 20
  • Matting agent polyurethane formulation with matting components
  • HYDRHOLAC UD-2 solids content. 24% by weight, Rohm and Haas.
  • Polyurethane binder 2 (component C) hard polyurethane dispersion with high light fastness for
  • Topcoats with good physical properties such as BAYDERM Finish 61 UD; Solids content about 40% by weight; Rohm and Haas.
  • Crosslinker water-dispersible polyisocyanate with an NCO content of 8.5
  • Flow control agent silicone-based; 100% by weight: AQUADERM Fluid H, LANXESS. PREPARATIONS
  • the reactor is then gradually evacuated to 200 mbar and further heated with simultaneous distillation of water until a bottom temperature of 130-140 0 C is reached and no more reaction water passes.
  • aqueous defoamer preparation After cooling to 65 ° C., 0.5 g of an aqueous defoamer preparation are added. At reduced stirring speed 100.0 g of hydrogen peroxide 35% within 20 minutes at 60-70 0 C are metered. It is stirred for 4 hours at 65 0 C and then cooled to 30-38 0 C. At 30-38 0 C, 1.0 g defoamer, and then 3.0 g of a reducing agent in 2 portions added. It is stirred for 3 hours at 35 ° C, cooled below 30 0 C and filled through a 100 micron filter.
  • d 50 140 nm (Coulter LS 230) (??) Mw (GPC) 11200 g / mol
  • Sump temperature 140 0 C is reached and no more water distilled off. Then takes place at 140 0 C.
  • 109.45 g of the 2.1. described pre-product (0.5 mol) are initially charged at 140 0 C. Then 175 g (0.175 mol) of a heated to 80 0 C melt of polyether 2 are added. The mixture is stirred for a further 4 hours at 140 0 C and then cooled to 115 ° C. Then 14.25 g of oleic acid are added, stirred for 5 minutes, and starting at 115 ° C.und highest stirrer speed, a solution of 465 g of water and 6.1 g of ethanolamine within 60 minutes, the batch is cooled to 65 ° C. , After addition of 0.5 g of defoamer, 20.0 g of 35% hydrogen peroxide are added at 65 ° C.
  • section 2.2. be 109.45 g of the under Example 2, Section 2.1. described pre-product (0.5 mol) with 45 g (0.075 mol) of polyether 3 at 140 0 C for 4 hours.
  • 65 0 C 8.4 g of oleic acid are added and added a solution of 280 g of water and 3.6 g of ethanolamine within 60 minutes. It is stirred for 10 minutes.
  • 65 ° C 20.0 g of hydrogen peroxide 35% are added within 10 minutes.
  • the mixture is stirred for 3 hours at 65.degree.
  • 0.2 g defoamer are subsequently metered in 1.5 g of a reducing agent in 2 portions within 30 minutes.
  • stirring is continued for 2 hours at 25-35 0 C and the mixture is then filled through 100 micron filter.
  • Solids content 28.4% by weight
  • Viscosity about 80 mPas (100 s ⁇ 2O 0 C)
  • a precursor is prepared, with the modification that 337.0 g (1.25 mol) of hydrogenated tallow fatty amine (Q 6 / Cig-alkylamine mixture with primary amino groups), previously 80 0 C was melted, are used.
  • the reaction time is 3 hours at 14O 0 C. 1229.3 g of red-brown melt are discharged and comminuted after cooling.
  • Section 4.1. precursor 0.5 mol
  • melt of polyether 2 at 140 0 C 75 g (0.075 mol) and reacted for 4 hours at 140 0 C.
  • 115 ° C 8.4 g of oleic acid are added, stirred for 5 minutes and added starting at 115 ° C and the highest agitator 365 g of water and 3.63 g of ethanolamine within 60 minutes, the batch is cooled to 65 0 C.
  • 20.0 g of 35% hydrogen peroxide are added at 65 ° C. within 10 minutes.
  • the mixture is stirred for 4 hours at 65 0 C and the reaction mixture cooled to 35 0 C. At 35 ° C., 0.25 g of defoamer and then 1.5 g of a reducing agent are metered in in 2 portions within 15 minutes. After completion of the addition, the mixture is stirred for 3 hours at 35 ° C and the mixture is then filled through 100 micron filter.
  • Example 5 (component A).
  • Solids content 30.4% by weight
  • Section 4.1. precursor (0.5 mol) described are metered in at 140 0 C 225 g (0.1125 mol) of polyether 4 and reacted for 7 hours at 140 0 C. Then cooled to 120 0 C, added 16.8 g of oleic acid, stirred for 15 minutes and then metered at the highest stirrer speed, a solution of 620 g of water and 7.26 g of ethanolamine within 60 minutes starting at 115 ° C, the approach on 65 ° C is cooled. The mixture is then stirred for 30 minutes and 3 g of 50% sodium hydroxide added in 50 g of water. At 65 ° C 20.0 g of hydrogen peroxide 35% are added within 10 minutes.
  • the reaction vessel is charged with 234.0 g of diethylene glycol and 294.15 g of maleic anhydride (3 mol) and 115.2 g of trimellitic anhydride (0.6 mol) are introduced at room temperature with stirring.
  • the mixture is heated to 65 0 C, wherein an exothermic reaction at 50 0 C starts and the temperature rises to 87 ° C.
  • 306.0 g of ammonia water (25%, 4.5 mol) in 3 hours at 50-60 0 C added.
  • After completion of the addition for 1 hour at 7O 0 C is stirred.
  • In the subsequent vacuum distillation (200 mbar) is heated until the bottom temperature has reached 14O 0 C and no distillate passes more.
  • a stirred reactor 265.0 g of diethylene glycol are introduced. At room temperature, 332.5 g of maleic anhydride (3.39 mol) are added with stirring and the mixture is heated to 55 0 C. Ammonia water are then at 55 0 C with cooling 277.2 g (4.08 mol NH 3) are metered (25%), so that the temperature in the range 50 to 6O 0 C remains. After the addition is stirred at 70 0 C for 1 hour. The reactor is then gradually evacuated to 200 mbar and heated with simultaneous distilling off of water until a bottom temperature of 130-140 0 C is reached and no more reaction water passes.
  • component B 60 parts by weight of a high molecular weight silicone resin (Dow Corning 3289, silicone content: 80%) (component B) are initially charged at room temperature. 32.5 parts by weight of the product of Preparation Example 9, which is present as an aqueous dispersion (component A), are added at room temperature and dispersed with rapid stirring, wherein the temperature rises to about 40 0 C. The mixture is stirred for a further 1 hour after completion of the addition, whereby a homogeneous mixture is obtained. It is then adjusted with 7.5 parts by weight of water to a solids content of 60 wt .-% and cooled to room temperature.
  • component A a high molecular weight silicone resin
  • the starting material used was a crust (made from bovine wet blue) with a thickness of 1.0-1.2 mm.
  • the leather Before applying the primer, the leather is pre-milled in the crust state in the millcass for 6 hours and then placed on a stuffer.
  • the primed leather obtained with an application rate of 3 - 4 g / sqft wet injected 2 times, 2 minutes, were dried after each application at a temperature of 90 0 C.
  • topcoat formulations were prepared according to the table below by stirring the components in the order given.
  • the crosslinker was finally added and the spray viscosity adjusted by adding thickener and water.
  • the mixtures thus obtained have a pot life of about 4 hours and were sprayed immediately after the preparation of the corresponding primed crust (2 crosses, dry application rate: 0.6-0.7 g / qfs (g / sqft) (airless spray gun) and a Temperature of 100 0 C dried for 2 minutes.
  • the tack of the finish immediately after drying was determined and evaluated as follows. After drying, the leather is allowed to cool and tests for temporary stickiness by rubbing the side of the scar on the side of the scar, hearing or feeling how the leather slowly or rapidly unfolds.
  • the resulting leathers were conditioned, blank samples were punched out and evaluated by the following methods:
  • a leather sample 2cm x 2cm is punched out of a leather sample of 5cm x 5cm, so that this serves as a comparison. Place the leather sample (2cm x 2cm) at 120 0 C for 24 hours in a convection oven. After the test, this sample is with. of the larger sample with the gray scale to evaluate the degree of yellowing.
  • the starting material used was an automotive nappa crust with a thickness of 1.0-1.2 mm.
  • the following table shows the formulations for the spray primer and for the two topcoats subsequently applied with a spray gun.
  • Base coat 2x spray 3.0-4.0 g / qfs (wet); millen for 6 hours, galleries
  • the leathers were evaluated for optical and physical properties:
  • the starting material used was an automotive crust with a thickness of 1.0-0.2 mm.
  • the following table shows the formulations of the spray primer applied to the 3 Crust and for the topcoats subsequently applied by means of a spray gun.
  • Base coat 2 x spray 3.0- 4.0 gr / qfs (wet), zero for 6 hours, studs
  • Top coat 2 inject 2 x 0.7 gr / qfs. dry, studs
  • the leathers with a topcoat without test product (Application Example 3), a topcoat with a mixture of test product and silicone, wherein the same product proportions compared to Example 5 were used (Application Example 4), and with a topcoat containing a previously prepared mixture of test product and silicone (Application Example 5) were evaluated for their properties as follows:
  • the leathers of application examples 3 to 5 have approximately the same high level of physical fastness, with the leathers of 3 and 5 getting the best rating. Furthermore, it should be noted that the leather produced according to the invention according to Application Example 5 is significantly less sticky than the leather of Application Example 3 and the leather of Application Example 4 does not stick at all.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un mélange contenant A) au moins un dérivé d'acide polyaspartique et B) au moins un polysiloxane.
PCT/EP2006/005830 2005-07-02 2006-06-17 Derives d'acide polyaspartique dans des produits de revetement contenant du polysiloxane WO2007003264A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP06754426A EP1904556A2 (fr) 2005-07-02 2006-06-17 Derives d'acide polyaspartique dans des produits de revetement contenant du polysiloxane
BRPI0613117A BRPI0613117A2 (pt) 2005-07-02 2006-06-17 mistura, processo para preparação de mistura, emprego da mistura, dispersões de revestimento, processo para preparação de dispersões de revestimento, substrato

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005031043A DE102005031043A1 (de) 2005-07-02 2005-07-02 Polyasparaginsäurederivate in Polysiloxanhaltigen Beschichtungsmitteln
DE102005031043.5 2005-07-02

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WO2007003264A3 WO2007003264A3 (fr) 2007-06-07

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KR (1) KR20080026150A (fr)
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WO (1) WO2007003264A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8591999B2 (en) 2008-05-28 2013-11-26 Dow Corning Corporation Coating compositions
RU2690169C2 (ru) * 2016-12-29 2019-05-31 Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт химии силикатов им. И.В. Гребенщикова Российской академии наук (ИХС РАН) Полимерная защитная композиция

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CN102268223B (zh) * 2011-06-29 2012-11-21 北京碧海舟腐蚀防护工业股份有限公司 防结蜡有机涂料及包括其的有机涂层的制备方法
CN103113820B (zh) * 2013-03-13 2016-10-05 鹿尼德(上海)表面材料技术有限公司 双组份液体保护漆
CN104098994B (zh) * 2013-04-02 2016-12-28 江苏国松特种涂料有限公司 一种防腐涂料底漆和面漆组合物
WO2020129811A1 (fr) * 2018-12-19 2020-06-25 大日精化工業株式会社 Dispersion aqueuse de polyuréthane-urée, matériau de revêtement mat et agent de traitement de surface
CN111944111B (zh) * 2019-04-30 2022-04-22 万华化学集团股份有限公司 一种水性自消光聚氨酯分散体和制备方法及其组合物
CN113354792B (zh) * 2021-04-30 2022-04-01 浙江艾特普科技有限公司 一种低粘度高渗透聚天门冬氨酸酯
CN113243621A (zh) * 2021-05-21 2021-08-13 温州市灰度鞋业有限公司 一种防磨女靴及其制备方法
CN113637398B (zh) * 2021-08-25 2022-03-08 黄山中邦孚而道涂料有限公司 一种底面合一型无溶剂聚天门冬氨酸酯重防腐涂料、制备方法及其应用

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EP0959091A1 (fr) * 1998-05-20 1999-11-24 Th. Goldschmidt AG Copolymère de polyesteramide-succinimide modifié et son utilisation
EP0994136A1 (fr) * 1998-10-16 2000-04-19 Bayer Ag Dispersions aqueuses de polyuréthane
EP1108765A2 (fr) * 1999-12-13 2001-06-20 Bayer Ag Hydrophobisation avec des polysiloxanes ayant des groupes carboxyliques
EP1118682A1 (fr) * 2000-01-19 2001-07-25 Bayer Aktiengesellschaft Préparations d'agents de tannage/ retannage
DE10003322A1 (de) * 2000-01-27 2001-08-02 Bayer Ag Polysiloxane zur Hydrophobierung
GB2391551A (en) * 2002-08-06 2004-02-11 Reckitt Benckiser Nv Carpet cleaning
EP1416057A1 (fr) * 2002-10-28 2004-05-06 Bayer Chemicals AG Cuir sans chrome, imperméable à l'eau
EP1518881A2 (fr) * 2003-09-17 2005-03-30 Bayer Chemicals AG Polymère modifié par un poyether utlisé comme adjuvant dans la fabrication du cuir
WO2005044216A1 (fr) * 2004-10-26 2005-05-19 Shiseido Co., Ltd. Preparation pour la peau a usage externe

Patent Citations (9)

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Publication number Priority date Publication date Assignee Title
EP0959091A1 (fr) * 1998-05-20 1999-11-24 Th. Goldschmidt AG Copolymère de polyesteramide-succinimide modifié et son utilisation
EP0994136A1 (fr) * 1998-10-16 2000-04-19 Bayer Ag Dispersions aqueuses de polyuréthane
EP1108765A2 (fr) * 1999-12-13 2001-06-20 Bayer Ag Hydrophobisation avec des polysiloxanes ayant des groupes carboxyliques
EP1118682A1 (fr) * 2000-01-19 2001-07-25 Bayer Aktiengesellschaft Préparations d'agents de tannage/ retannage
DE10003322A1 (de) * 2000-01-27 2001-08-02 Bayer Ag Polysiloxane zur Hydrophobierung
GB2391551A (en) * 2002-08-06 2004-02-11 Reckitt Benckiser Nv Carpet cleaning
EP1416057A1 (fr) * 2002-10-28 2004-05-06 Bayer Chemicals AG Cuir sans chrome, imperméable à l'eau
EP1518881A2 (fr) * 2003-09-17 2005-03-30 Bayer Chemicals AG Polymère modifié par un poyether utlisé comme adjuvant dans la fabrication du cuir
WO2005044216A1 (fr) * 2004-10-26 2005-05-19 Shiseido Co., Ltd. Preparation pour la peau a usage externe

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8591999B2 (en) 2008-05-28 2013-11-26 Dow Corning Corporation Coating compositions
RU2690169C2 (ru) * 2016-12-29 2019-05-31 Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт химии силикатов им. И.В. Гребенщикова Российской академии наук (ИХС РАН) Полимерная защитная композиция

Also Published As

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EP1904556A2 (fr) 2008-04-02
KR20080026150A (ko) 2008-03-24
DE102005031043A1 (de) 2007-01-25
WO2007003264A3 (fr) 2007-06-07
CN101213266A (zh) 2008-07-02
BRPI0613117A2 (pt) 2016-11-29

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