DE102009049630A1 - N-Methylpyrrolidone-deficit aqueous polymer blend, useful to coat e.g. leather, comprises a polyurethane-dispersion based on polyurethane containing Zerewitinoff-active hydrogen atoms, matting agent, crosslinker and/or crosslinking system - Google Patents

Abstract

N-Methylpyrrolidone (NMP)-deficit aqueous polymer blend (I) comprises 0.00-0.25 wt.% of at least one aqueous polyurethane-dispersion based on polyurethane containing Zerewitinoff-active hydrogen atoms from hydroxyl groups and amino groups, at least one matting agent, at least one crosslinker and/or a crosslinking system.

Description

The present invention relates to polymer blends and their use for coating decorative films and decorative surfaces.

Polymer blends containing polymer resins, matting agents and crosslinking components are used in the automotive industry in the coating of decorative surfaces in the automotive interior.

Often, polymer resins based on polyurethane are used. In many polyurethanes, N-methylpyrrolidone (NMP) is used as a solvent because it is unreactive with respect to isocyanate groups and thus is suitable for reducing the viscosity in the prepolymer structure. In addition, NMP is capable of dissolving the high melting point dimethylol propionic acid widely used in polyurethane dispersion chemistry. The use of NMP ensures that a sufficient number of hydrophilic centers in the form of carboxylate groups are incorporated in the polyurethane framework in an economically acceptable reaction time.

However, NMP is classified as a volatile substance. In addition, it has been found that NMP and other cosolvents from coatings of decorative surfaces in automotive interiors evaporate over time. These emissions lead to an increased concentration of NMP and other harmful cosolvents in the automotive interior and thus to a health burden on the occupants.

It was therefore an object of the present invention to provide polymer blends whose use for coating decorative surfaces in automotive interiors results in little or no emission of NMP so that decorative surfaces coated with these polymer blends meet OEM-specific standards comply with.

It was a further object of the present invention to provide polymer blends whose use for coating decorative surfaces in automotive interiors results in little or no emission of NMP while allowing retention of the good properties of decorative surfaces based on conventional polymer blends, such as high dullness with constant high transparency.

The above objects are achieved by the objects of the present invention.

An object of the present invention are NMP-poor aqueous polymer mixtures, which are characterized in that they contain at least one aqueous polyurethane dispersion based on polyurethane containing Zerewitinoff-active hydrogen atoms from OH groups and NH groups in the range of 0, 00 to 0.25 wt .-% based on the total amount of the polyurethane and at least one matting agent and at least one crosslinker and / or a crosslinking system.

Preferably, the polyurethane dispersion has a content of Zerewitinoff-active hydrogen atoms from OH groups and NH groups in the range of 0.00 to 0.22 wt .-%, particularly preferably in the range of 0.00 to 0.20 wt. %, based on the total amount of polyurethane.

Hydrogen bonded to N or O is referred to as Zerewitinoff-active hydrogen (sometimes referred to as "active hydrogen") when it reacts with methyl magnesium iodide to yield methane by a method discovered by Zerewitinoff.

The polyurethane dispersion contains as structural components at least one monoalcohol (f) having an average molecular weight M _n of 32 to 145 g / mol and / or at least one monoamine (g) having an average molecular weight M _n of 17 to 147 g / mol.

The proportion of monoalcohols (f) and monoamines (g) is preferably from 0.1% by weight to 1.5% by weight, particularly preferably from 0.1% by weight to 1.3% by weight, based on all Building components of the polyurethane dispersion.

Preferably, the content of NMP from 0.0 to 0.5 wt .-%, particularly preferably 0.0 to 0.3 wt .-%, most preferably 0.0 to 0.1 wt .-%, based on the total amount of polymer blend. Even more preferably, the polymer mixture according to the invention is free of NMP.

For the purposes of the present invention, free of NMP means that the content of NMP in the polymer mixture is less than or equal to the detection limit (ie ≦ 1 ppm) in a gas chromatographic measurement.

The use of the polymer mixtures according to the invention for the coating of decorative surfaces in the automotive interior leads to a low or no emission of NMP and also leads to a low or no emission of other cosolvents.

The polyurethane dispersions used according to the invention are low in co-solvent. The polyurethane dispersions used according to the invention preferably contain from 0.0 to 0.9% by weight, particularly preferably from 0.0 to 0.5% by weight, very particularly preferably from 0.0 to 0.4% by weight of cosolvents , based on the total amount of the polyurethane dispersion.

The polymer mixtures according to the invention are low in coagents. The polyurethane dispersions used according to the invention preferably contain from 0.0 to 0.9% by weight, particularly preferably from 0.0 to 0.5% by weight, very particularly preferably from 0.0 to 0.4% by weight of cosolvents , based on the total amount of the polyurethane dispersion.

Cosolvents in the context of the present invention are polar organic solvents. Preferably, cosolvents are organic solvents having a Hansen parameter in the range of 7.2 to 16.0 (cal / cm ³ ) ^0.5 , as described in U.S. Pat "Polymer Handbooks", Eds. Brandrup, J .; Immergut, EH; Grulke, EA, 4th Edition, John Wiley, New York, 1999, VII / Page 675-711 are published.

Preferred cosolvents for the purposes of the present invention are polar organic solvents selected from the group consisting of acetone, methyl ethyl ketone, butyl diglycol, dimethyl sulfoxide, N-ethylpyrrolidone, dimethylformamide, dimethylacetamide and dipropylene glycol dimethyl ether.

The cosolvents are on the one hand to be solvents that have already been used in the synthesis of the polyurethane polymer, and on the other to solvents that have been added to the polyurethane dispersion subsequently to adjust the desired properties.

• a) wenigstens ein Polyisocyanat,
• b) wenigstens ein Polyol mit mittlerem Molgewicht M_n von 500 bis 6000 g/mol,
• c) wenigstens ein Polyol mit mittlerem Molgewicht M_n von 62 bis 500 g/mol,
• d) wenigstens eine Verbindung, die eine ionische Gruppe oder eine zur Ausbildung einer ionischen Gruppe befähigte Gruppe enthält und
• e) wenigstens ein Polyamin mit mittlerem Molekulargewicht M_n von 32 bis 500 g/mol.

The aqueous polyurethane dispersion contains as further structural components

• a) at least one polyisocyanate,
• b) at least one polyol having an average molecular weight M _{n of} from 500 to 6000 g / mol,
• c) at least one polyol having an average molecular weight M _{n of} from 62 to 500 g / mol,
• d) at least one compound which contains an ionic group or a group capable of forming an ionic group and
• e) at least one polyamine having an average molecular weight M _{n of} from 32 to 500 g / mol.

The resin of the polyurethane dispersion according to the invention preferably contains a content of component c) of 1.5 to 23% by weight and particularly preferably of 3.0 to 17% by weight and a hard segment content (HS) of 28 to 85% by weight. , preferably from 30 to 80 wt .-% and particularly preferably from 32 to 75 wt .-%, wherein the amount of isocyanate, based on the amount of solids from 22 to 55 wt .-%, preferably 22 and 50 wt .-%, particularly preferably 22 to 48 wt .-% is. The acid number of the solid resin is between 11 and 30 mg KOH / g of solid resin, preferably between 13 and 28 mg KOH / g of solid resin and more preferably between 13 and 27 mg KOH / g of solid resin.

The hard segment content is calculated as follows:

As component a) are the polyisocyanates commonly used in polyurethane chemistry, such as diisocyanates of the formula R ¹ (NCO) ₂ , wherein R ^{1 is} an aliphatic hydrocarbon radical having 4 to 12 carbon atoms, a cycloaliphatic hydrocarbon radical having 6 to 15 carbon atoms, an aromatic Hydrocarbon radical having 6 to 15 carbon atoms or an araliphatic hydrocarbon radical having 7 to 15 carbon atoms. Examples of preferred diisocyanates are tetramethylene diisocyanate, hexamethylene diisocyanate, 4,4'-diisocyanatodiphenylmethane, 2,4'- Diisocyanatodiphenylmethane, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene or α, α, α ', α', '- tetra-methyl-m- or p-xylylene diisocyanate and mixtures of said diisocyanates. Particularly preferred diisocyanates are 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate) and 4,4'-diisocyanatodicyclohexylmethane. Optionally, small amounts of z. B. trihydric and / or higher isocyanates are used, thus to ensure a certain degree of branching or crosslinking of the polyurethane. The amount of polyisocyanate to be used depends on its functionality and should be such that the NCO prepolymer still remains stirrable and dispersible. Such isocyanates are z. B. obtained by divalent isocyanates are reacted together such that a portion of their isocyanate groups are derivatized to isocyanurate, biuret, allophanate or uretdione groups. Such polyisocyanates hydrophilized via ionic groups, such as are commonly used as crosslinkers in aqueous two-component (2K) PU paints, are also suitable. Examples of such isocyanates are in the EP-A 510 438 described in which polyisocyanates are reacted with OH-functional carboxyl compounds. Hydrophilic polyisocyanates are further obtained by reacting polyisocyanates with isocyanate-reactive compounds bearing sulfuric acid groups. Such polyisocyanates have functionalities, eg. B. of more than 2.2, on.

Suitable polymeric polyols b) have a molecular weight range (M _n ) of from 500 to 6000 g / mol, preferably from 500 to 3000 g / mol and more preferably from 650 to 2500 g / mol. The OH functionality is at least 1.8 to 3, preferably 1.9 to 2.2, and particularly preferably 1.92 to 2.0. The polyols are, for example, polyesters, polyethers based on propylene oxide and / or tetrahydrofuran, polycarbonates, polyestercarbonates, polyacetals, polyolefins, polyacrylates and polysiloxanes. Preference is given to using polyesters, polyethers, polyestercarbonates and polycarbonates. Particular preference is given to polyesters, polyethers, polyestercarbonates and polycarbonates having OH functionalities of between 1.92 and 2.0. Mixtures of the described polymeric polyols b) are also suitable.

In addition, in admixture with said polyols b) fatty acid-containing polyesters b1) can be used, which are obtained by Ver- or transesterification product (s) of drying and / or non-drying fatty acids or oils with at least bifunctional polyol compounds, such as. B. in the EP-A 0 017 199 (P.10, Z. 27 to p. 11, Z. 31). As polyol compounds are preferably tetrafunctional hydroxyl components such. As used pentaerythritol.

As polyol b1) is also suitable partially dehydrated castor oil, which is obtained by thermal loading of castor oil under acidic catalysis and in the EP-A 0 709 414 (P.2, Z. 37-40).

Also suitable as polyols b1) are those which are described in the DE-A 199 30 961 (P.2, Z. 46-54, p.2, Z.67 to p.3, Z. 3). There are aliphatic and cycloaliphatic monocarboxylic acids having 8 to 30 carbon atoms such. As oleic acid, lauric acid, linoleic acid or linolenic acid with castor oil fatty acid in the presence of glycerol implemented.

Furthermore, suitable polyols b1) are transesterification products of castor oil with one or more other triglycerides. The molar composition of the mixture is calculated so that the average OH functionality of the final product is in the range of 1.8 to 2.2.

Particularly preferred as component b1) are, as a statistical average with respect to the OH groups, bisfunctional, fatty acid-containing components which contain glycerol or trimethylolpropane units. Very particular preference is given to transesterification products having average OH functionalities of 2 from castor oil with a further oil other than castor oil. The fatty acid-containing polyesters b1) are preferably used with polyols b) which have a M _n of 650 to 2500 g / mol and OH functionalities of 1.9 to 2. The fatty acid-containing polyesters b1) are particularly preferably selected from polyols b) which have an M _{n of} from 650 to 2500 g / mol, OH functionalities of from 1.92 to 2 and are selected from the group consisting of esters, ethers, carbonates or carbonate esters, used.

Preferably, the polyurethane dispersion according to the invention contains as the polyol only component b) in amounts of 15 to 72 wt .-%, preferably from 20 to 70 wt .-% and particularly preferably from 25 to 68 wt .-% based on the total amount of resin.

In a further embodiment of the present invention, the polyurethane dispersion according to the invention contains components b) and b1), the total amount thereof being at most 65% by weight, based on the total amount of resin from components a) to g) and the amount of component b1) , based on the total amount of resin of the polyurethane dispersion from 0 to 30 wt .-%, preferably 0 to 25 wt .-%.

Low molecular weight polyols c) having a molecular weight range (M _n ) of 62 to 500 g / mol, preferably 62 to 400 g / mol and particularly preferably 90 to 300 g / mol are the bifunctional alcohols commonly used in polyurethane chemistry, such as. Etandiol, 1,2- and 1,3-propanediol, 1,2-, 1,3- and 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1.6 Hexanediol, neopentyl glycol, cyclohexane-1,4-dimethanol, 1,2- and 1,4-cyclohexanediol, 2-ethyl-3-propylpentanediol, 2,4-dimethylpentanediol, 2-ethyl-2-butylpropanediol, ether oxygen-containing Diols, such as. As diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene, polypropylene or polybutylene glycols, N-substituted ethanolamines and mixtures of these products. Preferred polyols c) are 1,4-butanediol, 1,5-pentanediol, 3-methylpentanediol-1,5, 1,6-hexanediol, neopentyl glycol, cyclohexane-1,4-dimethanol, 1,2- and 1, 4-cyclohexanediol. Very particularly preferred polyols c) are 1,4-butanediol, 1,6-hexanediol and neopentyl glycol.

Tri- and higher-functional alcohols of the stated molecular weight range can be used proportionally in the amount that the polymer solution remains stirrable. Such components include trimethylolpropane, trimethylolethane, glycerol, and pentaerythritol.

In addition, in admixture with the stated polyols c) fatty acid-containing polyester c1) with molecular weights <500 g / mol can be used by Ver- or transesterification product (s) of drying and / or non-drying fatty acids or oils with at least bifunctional polyol compounds be obtained as they are z. B. in the EP-A 0 017 199 (P.10, Z. 27 to p. 11, Z. 31). As polyol compounds are preferably tri- and tetrafunctional hydroxyl components such. As trimethylolethane, trimethlyolpropane, glycerol or pentaerythritol used. Likewise suitable are fatty acid amides of fatty acids / fatty acid chlorides and dialkanolamines, preferably diethanolamine.

The amounts of components c) and c1) are so dimensioned that their sum measured on the resin of the polyurethane dispersion 1.5 to 23 wt .-%, preferably 1.5 to 10 wt .-% and particularly preferably 1.0 to 8 wt .-% is. The weight ratio of c) to c1) ranges from 100: 0 to 20:80, preferably from 100: 0 to 30:70 and particularly preferably from 100: 0 to 40:60.

In a preferred embodiment, only the component c) in amounts of 1.5 to 23 wt .-%, preferably 1.5 to 10 wt .-% and particularly preferably 1.0 to 8 wt .-%, measured on the resin of Polyurethane dispersion used.

As component d) are low molecular weight OH group and / or NH group-containing compounds which contain ionic groups or capable of forming an ionic group, suitable, such as. Dimethylolpropionic acid, dimethylolbutyric acid, hydroxypivalic acid, reaction products of (meth) acrylic acid and polyamines (eg. DE-A-19 750 186 , P. 2, Z. 52-57) or sulfonate-containing polyol components such as. B. the propoxylated adduct of sodium hydrogen sulfite to 2-butenediol or in the EP-A 0 364 331 (P. 6, Z. 1-6) described, composed of salts of sulfoisophthalic polyester. Preference is given to components containing carboxylic acid groups. Particularly preferred is dimethylolpropionic acid.

Suitable neutralization components for the anionic dispersions are the tertiary amines known to those skilled in the art, ammonia and alkali metal hydroxides.

The NCO prepolymer preferably contains no nonionic hydrophilicizing agents.

As a chain extender e) polyamines having a molecular weight M _n of 32 to 500 g / mol in question, such as. As ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, 2-methyl-pentanediamine-1,5, isophoronediamine, 4,4'-diaminodicyclohexylmethane, piperazine, N ² -methyl-diethylenetriamine or diethylenetriamine. Also suitable is hydrazine. The diamines are preferably ethylenediamine, 2-methylpentanediamine-1,5 or isophoronediamine.

Suitable components f) are monofunctional alcohols having 1 to 18, preferably 1 to 12, particularly preferably 1 to 8 carbon atoms. These include, for example, methanol, ethanol, 1-propanol, 2-propanol, primary butanol, secondary butanol, n-hexanol and its Isomers, 2-ethylhexyl alcohol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, 1-octanol, 1-dodecanol, 1-hexadecanol, lauryl alcohol and stearyl alcohol. Preferred components f) are ethanol, 1-propanol, 2-propanol, primary butanol, secondary butanol, n-hexanol and its isomers, 2-ethylhexyl alcohol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol monobutyl ether and diethylene glycol monobutyl ether. Particularly preferred components f) are n-butanol, n-hexanol, 2-ethylhexyl alcohol, ethylene glycol monobutyl ether or ethylene glycol monomethyl ether.

As monoamine g) are those in question, which have a molecular weight of 17 to 147 g / mol, such as. Ammonia, methylamine, ethylamine, diethylamine, propylamine, n-butylamine, dibutylamine, 2-aminobutane, 1-aminopentane, 2-aminopentane, ethanolamine, diethanolamine, 1-amino-2-propanol, 3-amino-1-propanol, 2-amino-1-butanol, 5-amino-1-pentanol. The preferred monoamines g) include n-butylamine, 2-aminobutane, 1-aminopentane, 2-aminopentane, ethanolamine or diethanolamine. Very particularly preferred components g) are n-butylamine or diethanolamine.

Suitable solvents for the preparation of the polyurethane dispersion are those which boil at atmospheric pressure below 100 ° C, have no isocyanate-reactive groups and, moreover, are water-soluble. In addition, the solvent from the prepared dispersion must be removed by distillation. Examples of such solvents are acetone, methyl ethyl ketone, tert-butyl methyl ether or tetrahydrofuran. Preferably, methyl ethyl ketone or acetone is used as solvent, acetone is particularly preferred.

Furthermore, the polymer mixture contains at least one matting agent. The skilled artisan distinguishes between inorganic (for example, Acematt ^® from Fa. Evonik Degussa / Frankfurt am Main or Syloid ^® from Fa. Grace / Worms) and polymer organic matting agents (for example Polymatte ^® from Messrs. Stahl Europe / Waalwijk or Novomatt ^® from Fa. BASF / Ludwigshafen). The polymer blend according to the invention may also contain combinations of inorganic and organic matting agents. Inorganic matting agents are preferably used in amounts of 0.1-6 wt .-%, more preferably 0.5-5 wt .-%, most preferably 1-4 wt .-%, based on the polymer mixture. Polymer-organic matting agents, based on an aqueous polyurethane dispersion and / or on the basis of organometallic compounds, are particularly preferred in amounts of 0.1-75 wt .-%, particularly preferably 0.5-60 wt .-%, most preferably 10-55 wt .-% used, based on the polymer mixture.

For crosslinking, all types of crosslinking known to those skilled in the art come into question. Examples of chemical and / or physical types of crosslinking, such as amine crosslinking, arizidine crosslinking, carbodiimide crosslinking, enamine crosslinking, epoxy crosslinking, epoxy silane crosslinking, urea crosslinking, hydrazide crosslinking, melamine crosslinking or oxidative drying, are mentioned here by way of example , Even self-crosslinking systems, such as azomethine crosslinking, a carbonyl-amine reaction, which takes place by evaporation of the neutralizing agent and the water, auto-oxidation or UV-aqueous are conceivable. Further possible types of crosslinking are silane crosslinking and / or radiation crosslinking, eg. B. by UV radiation. Likewise, dual-cure networking, i. H. a combination of polyurethane and UV crosslinking chemistry possible. The types of crosslinking mentioned can be carried out individually or in any desired combination.

As polycarbodiimides also those modified according to patent EP0507407 be used.

The polymer mixture preferably contains 0.1-50% by weight of at least one crosslinker or of a crosslinker system, particularly preferably 0.1-25% by weight, very particularly preferably 0.2-15% by weight, based on the polymer mixture ,

The crosslinker or crosslinking system of the polymer mixture is preferably based on a compound selected from the group consisting of polyisocyanate, polyepoxide, epoxysilane, alkoxymethylmelamine, urea resin, polycarbodiimide and polyaziridine. Particular preference is given to using a crosslinker system based on at least one polyisocyanate and / or at least one polycarbodiimide.

If the polyisocyanate is the basis of the crosslinker or of the crosslinker system, the polyisocyanate preferably has an NCO content of between 5 and 30% by weight, particularly preferably between 7 and 25% by weight.

The polyisocyanate may be a polyisocyanate selected from the group consisting of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (H ₁₂ MDI) and hexahydrotoluylene diisocyanate (H ₆ TDI), each of these polyisocyanates being biuret or uretdione or Allophanate or isocyanurate or Iminooxadiazindion can be present.

The NCO content of the polymer mixture crosslinked by the crosslinker or by the crosslinker system, before crosslinking, is preferably between 0.1 and 9.0% by weight, particularly preferably between 0.1 and 8.0% by weight, very particularly preferably between 0.1 and 5.0 wt .-%.

In the polymer mixture are preferably 0 to 75 wt .-%, more preferably 1 to 70 wt .-%, most preferably 5 wt .-% to 65 wt .-% diluent. The diluent is water and / or low molecular weight alcohols or mixtures thereof in varying proportions by weight. Preferred low molecular weight alcohols are selected from the group consisting of ethanol, propanol, isopropanol, n-butanol and isobutanol. Particular preference is given to using a mixture of water and isopropanol as diluent.

The polymer mixture furthermore preferably contains 0-40% by weight, particularly preferably 0-30% by weight, very particularly preferably 0-20% by weight, of at least one slip additive.

The slip additive is one and / or more compounds selected from the group consisting of polydialkylsiloxane, polydimethylsiloxane (PDMS), modified polysiloxanes, branched polyorganosiloxanes, polyolefinic waxes, polyamide waxes, polytetrafluoroethylene (PTFE), alternating ethylene-chlorotrifluoroethylene copolymers (ECTFE), perfluorinated alkoxy resins (PFA) and natural waxes such. B. carnauba wax. It is particularly preferred, however, that the non-functionalized slip additive is a polydimethylsiloxane and has between 10 and 14,000 D silicone building blocks.

Sliding additives are described in detail, for example W. Büchner et al "Industrial Inorganic Chemistry", Verlag Chemie, Weiheim, 1986. Chap. 4 ff. ;
textbook "Lackharze", edited by Dieter Stoye and Werner Freitag, Carl Hanser Verlag, Munich, Vienna 1996. Chap. 9ff .; tego journal, published by Tego Chemie Service GmbH / Essen, 3rd edition 2007 ;
surface additives (Technical Information L-SI1), published by Byk-Chemie / Wesel, issue 09/2005 ; Wax Additives (Technical Information L-CI1), published by Byk-Chemie / Wesel, issue 09/2005 ; Karsten lacquer raw material tables, edited by Olaf Lückert, 10th edition. Vincentz Verlag, Hannover 2000 ; Anthony Bogacki: Are anti-friction varnishes a bluff - sold well? - In: Conference "High quality materials for the vehicle interior", SKZ Würzburg 29./30.06.2005 ,

Likewise, alternatively or in combination, also functionalized slip additives can be used, wherein at least one functionalized and modified polysiloxane slip additive is preferred. The functionalized slip additive is modified with primary and / or secondary and / or tertiary amino groups and / or OH groups.

The functionalized slip additive preferably has an amine number between 0.1 and 3.0 mg KOH / g and / or an OH content between 0.3 and 5.0 wt .-%.

Other additives are present in amounts of preferably 0-50 wt .-%, more preferably in amounts of 0.1-45 wt .-%, most preferably in amounts of 0.1-35 wt .-%, in the polymer mixture , The additives here are selected from the group consisting of light protection agents, such as UV absorbers and reversible radical scavengers, antioxidants, wetting agents, substrate wetting agents, emulsifiers, leveling agents, film-forming aids, rheology aids, flame retardants, biocides, neutralizing agents, defoamers, thickeners, inorganic fillers, organic fillers and pigments.

It is preferred if 0-25 wt .-% of organic fillers and / or inorganic fillers and / or pigments are included.

In addition, other additives known to those skilled in the art can be used. These additives are described, inter alia, in:
- Textbook "Lackadditive" by Johann Bielemann, Wiley-VCH, Weinheim, New York 1998
- Textbook of Paints and Coatings, Volume 4 (Solvents, Plasticizers, Additives), edited by Martina Oertelt, 2nd edition, S. Hirzel Verlag, Stuttgart 2007
- Additives for Aqueous Lacquer Systems, by Wernfried Heilen, Vincentz Netzwork, Hannover 2009
- Plastic coating. Up to date, compact, practical, by Guido Wilke and Jürgen Ortmeier, Vincentz Netzwork, Hannover 2009

Another object of the present invention is the use of the polymer mixture according to the invention for the coating of decorative surfaces, preferably for the coating of decorative surfaces in the automotive interior.

Decorative surfaces for moldings made of a plastic material provided with a foil are widely known. Preferably, a plastic material is used as the base material, which consists of a polymer mixture based on polyvinyl chloride (PVC), in particular soft PVC, polyurethane (PUR), polyolefin, polyester (PES), acrylonitrile-butadiene-styrene copolymer (ABS ), Polymethylmethacrylate, polycarbonate, polyacrylate or copolymers. Here is an example for further literature "Jahnke, Manfred; Mielke, Dirk; Van Well, Michael: Decorative surfaces made of PVC pastes for automotive interiors. - In: SKZ symposium "PVC pastes" on 19./20.09.2007. South German Plastics Center, Würzburg, 2007 " directed.

The polymer mixture is preferably used on the decorative surface as a cover and / or lacquer layer for the decorative surface, wherein the lacquer layer may also consist of one or more identical or different polymer blends. To adjust the technical properties, for example of the friction behavior, the feel, especially the tactile feel, the rheology, the Mattierungsverhaltens, and the light and heat resistance of the polymer mixture, various crosslinker components, matting agents and additives, also referred to as other additives added. The additives are added to each other according to OEM specifications in different parts by weight. This procedure is known to the person skilled in the art.

The polymer mixture according to the invention is used as a coating of decorative films for molded parts or of molded parts. Preferred applications for these decorative films are dashboards or door panels or interior trim parts or seat covering material in a vehicle.

Furthermore, the polymer mixture can be used as a coating material, and it can be used both as a single-layered and as a multilayer coating material. In another application, the coating of a molded part can take place in the production tool (so-called in-mold coating, IMC) (see, for example, "Rompp Online": http://www.roempp.com , Keyword IMC and cited literature). The resulting total dry film thickness over all layers is between 0.5 and 50 g / m ² , preferably between 1 and 35 g / m ² .

The order of the polymer mixture can in a known manner, for. B. by brushing, pouring, knife coating, spraying, spraying, spinning, rolling or dipping done.

Examples

Method for the determination of NMP and other cosolvents in a polymer mixture

10 mg or 10 μl of the sample to be examined are weighed into a 20 ml headspace vial and sealed with PTFE-coated butyl septa. Furthermore, 5 calibrations of the used Colöser in different compositions, but which should be in the range of the desired concentration of the substances to be examined, are used.

The samples are processed in a gas chromatograph (eg GC Clarus 500 with headspace device HS 40 from PerkinElmer / Jüggesheim):
GC conditions:
Column: 60 m capillary column HP-5, ID = 0.25 mm, film thickness = 1 mm
Detector: FID (flame ionization detector)
Detector range: low
Detector temperature: 250 ° C
Injector temperature: 210 ° C
Carrier gas: helium
Carrier gas flow: 1 ml / min
Split: splitless GC temperature program: 1 2 Oven temperature [° C] 55 200 Residence time [min] 0 15 Heating rate [K / min] 15 HS 40 conditions:
Mode: constant
Sample temperature: 210 ° C
Tempering time: 30 min
Pressure build-up time: 1.0 min
Injector time: 0.08 min
Bleeding time: 0.2 min
Cycletime: 30 min
Inject: 1

Evaluation: For each cosolver, the slope is calculated from the calibrations. With the appropriate slope, the amount is calculated for each solvent and then converted to the percentage composition.

The polymer mixture will now be explained in more detail with reference to an embodiment A, consisting of a rear coat and a final coat, and corresponding test results.

Method for determining the gloss level of a polymer mixture

The finish test film is placed smoothly on the vacuum plate of the Coatmaster and the vacuum is switched on. The polymer mixture is applied as a wet film of defined thickness on the finish test film by means of Lackschichtausstreicher and the Coatmaster. Subsequently, the film is dried for 3 minutes in a convection oven at 130 ° C. After drying and cooling to room temperature, the degree of gloss measurement of the film is carried out by means of a reflectometer.

Equipment:

• 1. Erichsen Coatmaster 509 MC with vacuum suction plate (Erichsen / Hemer),
• 2. Rotary vane vacuum pump,
• 3. Erichsen Lackschichtausstreicher (Erichsen / Hemer), System WASAG, Model 288, gap height 40 microns and 100 microns,
• 4. Finish test film Benecke-Kaliko article number VV050472A0265A (Benecke-Kaliko / Hannover),
• 5. Convection oven (Binder / Tuttlingen),
• 6. Reflectometer Dr. Long Refo 3D (Dr. Bruno Lange / Dusseldorf), 60 ° -Meßgeometrie, 300 scale parts (Skt.), After DIN EN ISO 2813 ,

Production of the Polyurethane Dispersion Type 1

Preparation of the fatty acid-containing polyester: In a 51 reactor with a distillation head, 3200 g of castor oil and 1600 g of soybean oil and 2.0 g of dibutyltin oxide were weighed. A stream of nitrogen (5 l / h) was passed through the reactants. Within 140 min. Was heated to 240 ° C and cooled after 6 h at 240 ° C. The OH number was 108 mg KOH / g, the acid number 2.5 mg KOH / g.

119.4 g of the fatty acid-containing polyester, 40.7 g of polyether (polypropylene oxide, OH number 112), 29.9 g of dimethylolpropionic acid, 11.9 g of coconut oil fatty acid diethanolamide and 12.8 g of 1,6-hexanediol were mixed. and heated to 55 ° C. Successively the mixture with 150 g of acetone and 231.7 g Desmodur ^® W was added and boiled under reflux until an NCO content had reached 5.1 wt .-%. It was again adjusted to 55 ° C and the clear solution was treated with 16.9 g of triethylamine, which was stirred well. The entire neutralized prepolymer solution (55 ° C) was dispersed with vigorous stirring in 776.6 g of water, which was at a temperature of 30 ° C, dispersed. After the dispersion was stirred for 5 min. Before within 5 min. A solution of 11.8 g of ethylenediamine, 0.5 g Diethylentriamiin and 7.8 g of diethanolamine dissolved in 73 g of water was added. Subsequently, the acetone was removed by distillation at 40 ° C. in vacuo (120 mbar). To the reaction of the remaining isocyanate groups was stirred at 40 ° C until IR spectroscopy no NCO was detectable. After cooling to 30 ° C was filtered through a 240 micron filter. Characteristics of the polyurethane dispersion: Solids content: 35% Hard segment content: 64% Acid value (based on solid resin): 28.0 mg KOH / g

Production of the polyurethane dispersion type 2

152.1 g Desmodur ^® W and 348.7 g of Desmodur ^® were heated to 55 ° C and stirred. Then, 62.2 g of dimethylolpropionic acid was added. A solution of 470.4 g of Desmophen ^® C 1200, 96.3 g neopentyl glycol, 2.8 g of butyl glycol and 377.5 g of acetone After 5 min, heated within 20 min and added to 68 ° C. At this temperature was stirred until an NCO content of 2.8% was reached. It was then cooled to 60 ° C and 46.9 g of triethylamine were added. 450 g of this solution were dispersed with vigorous stirring in 545.9 g of water, which was initially charged at a temperature of 35 ° C. After dispersion was stirred for 5 min. Then, within 10 minutes, a solution of 2.0 g of diethylenetriamine, 1.1 g of n-butylamine and 3.5 g of ethylenediamine in 60.7 g of water was added. After complete addition, the mixture was stirred for 20 min at 40 ° C before the acetone was distilled off under reduced pressure at this temperature. For complete reaction of the isocyanate groups was stirred at 40 ° C until IR spectroscopy no NCO was detectable. After cooling to <30 ° C., the filter was filtered through a 240 μm fast filter from Erich Drehkopf. Characteristics of the polyurethane dispersion: Mean particle size (LKS): 25 nm pH (solids diluted to 10% by weight): 7.9 Solids content: 35.9% Acid value (based on solid resin): 22.5 mg KOH / g Hard segment content: 59.3%

Production of Polyurethane Dispersion Type 3

62.0 g Desmodur ^® W and 142.0 g of Desmodur ^® I were heated to 55 ° C and stirred. Then, 37.7 g of dimethylolpropionic acid was added. A solution of 470.5 g of Desmophen ^® C 1200, 15.6 g neopentyl glycol, 1.1 g of butyl glycol and 243 g of acetone After 5 min, heated within 20 min and added to 68 ° C. At this temperature was stirred until an NCO content of 1.8% was reached. It was then cooled to 60 ° C and 27.2 g of ethyldiisopropylamine were added. The solution was dispersed with vigorous stirring in 807 g of water, which was initially introduced at a temperature of 35 ° C. After dispersion was stirred for 5 min. Then, within 10 minutes, a solution of 1.8 g of diethylenetriamine, 1.0 g of n-butylamine and 3.3 g of ethylenediamine in 72 g of water was added. After complete addition, the mixture was stirred for 20 min at 40 ° C before the acetone was distilled off under reduced pressure at this temperature. For complete reaction of the isocyanate groups was stirred at 40 ° C until IR spectroscopy no NCO was detectable.

After cooling to <30 ° C., the filter was filtered through a 240 μm fast filter from Erich Drehkopf. Characteristics of the polyurethane dispersion: Mean particle size (LKS): 32 nm pH (solids diluted to 10% by weight): 7.9 Solids content: 35.9% Acid value (based on solid resin): 21.4 mg KOH / g Hard segment content: 36.3% Embodiment A: Weighing [g] 1. Fondlack aqueous polyurethane dispersion type 3 33.6 Matting agent (silica) 3.9 Dilution (2-propanol / water 50/50) 40.5 Demineralised water 19.5 dimethylaminoethanol 0.3 Defoamer (poly (ether siloxane) copolymer) 0.4 Substrate wetting agent (silicone surfactant) 0.4 Thickener (polyacrylic acid) 0.9 Crosslinker (polyisocyanate, HDI trimer) 0.6 Characteristics of the Fondlack: Finish (40 μm, 60 °, 300 sec.): 1.4 ± 0.0 sec. Finish (100 μm, 60 °, 300 sec.): 1.7 ± 0.1 sec. PH value ( DIN ISO 976 ): 8.3 Viscosity (4 mm, based on DIN 53211 ): 42 s 2nd final coat aqueous polyurethane dispersion type 3 24.9 Aqueous polyurethane dispersion Type 1 12.4 Matting agent (silica) 2.9 Dilution (2-propanol / water 50/50) 28.0 Demineralised water 28.8 dimethylaminoethanol 0.3 Substrate wetting agent (silicone surfactant) 0.3 Thickener (polyacrylic acid) 1.3 Crosslinker (polycarbodiimide) 1.1 Characteristics of the final coat: Finish (40 μm, 60 °, 3:00 Ski): 2.3 ± 0.1 sec. Finish (100 μm, 60 °, 300 sec.): 3.5 ± 0.2 sec. PH value ( DIN ISO 976 ): 8.4 Viscosity (4 mm, based on DIN 53211 ): 42 s

The basecoat was applied in an amount of 7 g / m ² and the final coat in an amount of 3 g / m ² on a synthetic leather (definition according to DIN 16922 ) applied by rotogravure.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• EP 510438 A [0024]
• EP 0017199A [0026, 0035]
• EP 0709414 A [0027]
• DE 19930961 A [0028]
• DE 19750186 A [0038]
• EP 0364331 A [0038]
• EP 0507407 [0047]

Cited non-patent literature

• "Polymer Handbooks", Eds. Brandrup, J .; Immergut, EH; Grulke, EA, 4th Edition, John Wiley, New York, 1999, VII / pages 675-711. [0018]
• W. Büchner et al "Industrial Inorganic Chemistry", Verlag Chemie, Weiheim, 1986. Chap. 4 ff. [0056]
• "Lackharze", edited by Dieter Stoye and Werner Freitag, Carl Hanser Verlag, Munich, Vienna 1996. Chap. 9ff .; tego journal, edited by Tego Chemie Service GmbH / Essen, 3rd edition 2007 [0056]
• (Technical Information L-SI1), published by Byk-Chemie / Wesel, Edition 09/2005 [0056]
• Wax Additives (Technical Information L-CI1), published by Byk-Chemie / Wesel, Edition 09/2005 [0056]
• Karsten lacquer raw material tables, edited by Olaf Lückert, 10th edition. Vincentz Verlag, Hannover 2000 [0056]
• Anthony Bogacki: Are anti-friction varnishes a bluff - sold well? - In: Symposium "High quality materials for vehicle interiors", SKZ Würzburg 29./30.06.2005 [0056]
• Textbook "Paint Additives" by Johann Bielemann, Wiley-VCH, Weinheim, New York 1998 [0061]
• Textbook of Paints and Coatings, Volume 4 (Solvents, Plasticizers, Additives), edited by Martina Oertelt, 2nd edition, S. Hirzel Verlag, Stuttgart 2007 [0061]
• Additives for aqueous coating systems, by Wernfried Heilen, Vincentz Netzwork, Hannover 2009 [0061]
• Plastic coating. Up-to-date, compact, practical, by Guido Wilke and Jürgen Ortmeier, Vincentz Netzwork, Hannover 2009 [0061]
• "Jahnke, Manfred; Mielke, Dirk; Van Well, Michael: Decorative surfaces made of PVC pastes for automotive interiors. - In: SKZ symposium "PVC pastes" on 19./20.09.2007. South German Plastics Center, Würzburg, 2007 " [0063]
• http://www.roempp.com [0066]
• DIN EN ISO 2813 [0072]
• DIN ISO 976 [0077]
• DIN 53211 [0077]
• DIN ISO 976 [0077]
• DIN 53211 [0077]
• DIN 16922 [0078]

Claims (15)

NMP-poor aqueous polymer mixture, characterized in that it comprises at least one aqueous polyurethane dispersion based on polyurethane containing Zerewitinoff-active hydrogen atoms from OH groups and NH groups in the range of 0.00 to 0.25 wt. % based on. the total amount of the polyurethane and at least one matting agent and at least one crosslinker and / or a crosslinker system contains. NMP-poor aqueous polymer mixture according to claim 1, characterized in that the polyurethane dispersion as structural components at least one monoalcohol (f) having an average molecular weight M _n of 32 to 145 g / mol and / or at least one monoamine (g) with an average Molecular weight M _n of 17 to 147 g / mol. NMP-poor aqueous polymer mixture according to claim 1 or 2, characterized in that the aqueous polyurethane dispersion as further structural components a) at least one polyisocyanate, b) at least one polyol having an average molecular weight M _n of 500 to 6000 g / mol, c) at least one polyol having an average molecular weight M _n of 62 to 500 g / mol, d) at least one compound containing an ionic group or a group capable of forming an ionic group, and e) at least one polyamine having an average molecular weight M _n of 32 to 500 g / mol. NMP-poor aqueous polymer mixture according to claim 3, characterized in that the polyurethane dispersion contains the component c) in amounts of 1.5 to 23 wt .-% based on all structural components. NMP-poor aqueous polymer mixture according to one of claims 1 to 4, characterized in that the polyurethane dispersion has a hard segment content of 28 to 85 wt .-%. NMP-poor aqueous polymer mixture according to claim 3, characterized in that the polyurethane dispersion contains component b) in amounts of 10 to 65 wt .-% based on all structural components. NMP-poor aqueous polymer mixture according to one of claims 1 to 6, characterized in that the crosslinker and / or the crosslinking system is based on at least one polyisocyanate and / or at least one polycarbodiimide. NMP-poor aqueous polymer mixture according to one of claims 1 to 7, characterized in that the content of NMP from 0.0 to 0.5 wt .-% based on the polymer mixture. NMP-poor aqueous polymer mixture according to one of claims 1 to 8, characterized in that it is free of NMP. Use of a NMP-poor aqueous polymer mixture according to any one of claims 1 to 9 for the coating of decorative surfaces. Use of a NMP-poor aqueous polymer mixture according to one of claims 1 to 9 for coating decorative films. Use of a NMP-poor aqueous polymer mixture according to one of claims 1 to 9 for coating leather. Use of a low-NMP aqueous polymer mixture according to any one of claims 1 to 9 as a coating material. Decorative film having a surface of a NMP-poor aqueous polymer mixture according to any one of claims 1 to 9. Use of a decorative sheet according to claim 14 in the form of a dashboard or a door trim or an interior trim part or a seat covering material.