Polyisocyanate mixture

Abstract

The invention relates to a polyisocyanate mixture, a process for its production and its use as starting component in the production of polyurethane plastics. The invention further relates to coating agents containing the polyisocyanate mixture and to the substrates coated with said coating agents.

Description

[0001] Polyisocyanate chemical

[0002] The invention relates to a polyisocyanate mixture, a process for its preparation, and the use of the polyisocyanate mixture. Further subjects of the invention are a composition containing the polyisocyanate mixture, a process for producing a coating on a substrate, and the coated substrate.

[0003] Two-component polyurethane coatings (2K-PUR) have gained importance in a wide variety of applications due to their outstanding technological properties. Polyisocyanates based on linear aliphatic or cycloaliphatic diisocyanates are typically used as crosslinking components for light-resistant, non-yellowing 2K-PUR coatings and paints.

[0004] 2K-PUR coatings, which are crosslinked with aliphatic polyisocyanates, in particular derivatives of hexamethylene diisocyanate (HDI), optionally in combination with polyisocyanates based on cycloaliphatic isophorone diisocyanate (IPDI), provide coatings with high mechanical and chemical resistance and very good appearance.

[0005] Despite the high quality level already achieved by 2K PUR coatings, there is a constant interest in the market for coating systems with ever-improving properties, particularly improved scratch resistance.

[0006] The trend toward more sustainable products has led to increasing demand for bio-based raw materials in recent years, including in the polyurethane sector. This prompted the development of polyisocyanate crosslinkers based on 1,5-diisocyanatopentane (hereinafter also referred to as pentamethylene diisocyanate or PDI), which is accessible from biomass (see, for example, EP-A 3 271 432 and WO 2016 / 169810). PUR coatings and adhesives produced using bio-based PDI polyisocyanates exhibit a similar level of properties to those crosslinked with comparable petrochemical-based HDI polyisocyanates, and are even superior in some applications.

[0007] A serious disadvantage of PDI polyisocyanates, however, is the fact that they exhibit higher viscosities than corresponding HDI derivatives with a comparable oligomer distribution (M. Widemann et al., ACS Sustainable Chem. Eng. 2018, 6, 9753-9759; DOI: http: / / dx.doi.org / 10.1021 / acssuschemeng.8b00758), and their processing generally requires larger amounts of organic solvents. However, the lowest possible content of volatile organic components is desirable, especially in sustainable coating and adhesive systems.

[0008] Especially for applications such as automotive refinishing, there was a need for sustainable polyisocyanate mixtures with sufficiently low viscosities to enable them to be processed in low-solvent or solvent-free form.

[0009] The object of the present invention was therefore to provide sustainable polyisocyanate mixtures that have sufficiently low viscosities to enable them to be processed in low-solvent or solvent-free form and that lead to coatings with improved scratch resistance. In response to this need, the present invention provides a

[0010] Polyisocyanate mixture containing at least one polyisocyanate M) of the general formula (I) in which

[0011] R represents a linear or branched, saturated or unsaturated aliphatic and / or saturated or unsaturated cycloaliphatic radical having (6 to 22) - p carbon atoms, each of which may optionally be substituted,

[0012] R' and R" independently of one another represent hydrogen or an aliphatic radical having 1 to 10 carbon atoms, where at least one of the radicals R' and R" represents hydrogen, n represents an integer from 1 to 12, m represents an integer from 1 to 10 and p represents 0 or 1 and at least one polyisocyanate N) different from polyisocyanate M) having a uretdione, isocyanurate, iminooxadiazinedione, urethane, allophanate, biuret and / or oxadiazinetrione structure which carries aliphatically, cycloaliphatically, araliphatically and / or aromatically bound isocyanate groups, where the polyisocyanates M) and N) are present in a weight ratio to one another of 50:50 to 20:80.

[0013] The invention also relates to a process for the preparation of the polyisocyanate mixtures according to the invention, characterized in that at least one polyisocyanate M) of the general formula (I) in which

[0014] R represents a linear or branched, saturated or unsaturated aliphatic and / or saturated or unsaturated cycloaliphatic radical having (6 to 22) - p carbon atoms, each of which may optionally be substituted, R' and R“ independently of one another represent hydrogen or an aliphatic radical having 1 to 10

[0015] Carbon atoms, where at least one of the radicals R' and R" is hydrogen, n is an integer from 1 to 12, m is an integer from 1 to 10 and p is 0 or 1 with at least one polyisocyanate N) different from polyisocyanate M) having a uretdione, isocyanurate, iminooxadiazinedione, urethane, allophanate, biuret and / or oxadiazinetrione structure which carries aliphatically, cycloaliphatically, araliphatically and / or aromatically bound isocyanate groups, so that the polyisocyanates M) and N) are mixed in a weight ratio to one another of 50:50 to 20:80, preferably of 50:50 to 25:75 and particularly preferably of 50:50 to 30:70, very particularly preferably of 45:55 to 30:70, are available.

[0016] According to the invention, the terms "comprising" and "containing" preferably mean "consisting essentially of" and particularly preferably "consisting of." The further embodiments mentioned in the claims and in the description can be combined as desired, unless the context clearly indicates otherwise.

[0017] "At least one," as used herein, refers to 1 or more, for example, 2, 3, 4, 5, 6, 7, 8, 9, or more. In the context of components of the compounds described herein, this statement does not refer to the absolute amount of molecules, but rather to the type of component. "At least one polyisocyanate" therefore means, for example, that only one type of polyisocyanate or several different types of polyisocyanates may be present, without specifying the amount of the individual components.

[0018] Numerical values ​​stated without decimal places refer to the full specified value with one decimal place. For example, "99%" stands for "99.0%."

[0019] Numerical ranges specified in the format "in / from x to y" include the specified values. If multiple preferred numerical ranges are specified in this format, it is understood that all ranges resulting from the combination of the different endpoints are also included.

[0020] For the purposes of this document, the term "aliphatic" is defined as non-aromatic hydrocarbon groups that are saturated or unsaturated.

[0021] Here, the term "araliphatic" is defined as aliphatic hydrocarbon radicals that are saturated or unsaturated and have at least one aromatic substituent.

[0022] For the purposes of this document, the term "alicyclic" or "cycloaliphatic" is defined as optionally substituted, carbocyclic, or heterocyclic compounds or moieties that are not aromatic (such as cycloalkanes, cycloalkenes, or oxa-, thia-, aza-, or thiazacycloalkanes). Specific examples include cyclohexyl groups, cyclopentyl groups, and their N- or O-heterocyclic derivatives, such as pyrimidine, pyrazine, tetrahydropyran, or tetrahydrofuran. In the event that the groups or compounds are disclosed as "optionally substituted" or "substituted", suitable substituents are -F, -Cl, -Br, -I, -OH, -OCH3, OCH2CH3, -O-isopropyl or -on-propyl, -OCF3, -CF3, -S-Ci-6-alkyl and / or (optionally via an attached heteroatom) a linear or branched, aliphatic and / or alicyclic structural unit having 1 to 12 carbon atoms, each acting as a replacement for a carbon-bonded hydrogen atom of the molecule in question.Preferred substituents are halogen (especially -F, -CI), C1-6 alkoxy (especially methoxy and ethoxy), hydroxy, trifluoromethyl and trifluoromethoxy, each of which acts as a replacement for a carbon-bonded hydrogen atom of the molecule in question.

[0023] The general term “polyurethanes” is used below as a synonym for the multitude of different polymers with, for example, urethane, urea and / or thiourethane structures, which can be produced from polyisocyanates and H-acidic compounds, such as polyols, polyamines and / or polythiols.

[0024] The polyisocyanate mixture according to the invention represents a physical mixture and thus differs from a polyisocyanate produced purely chemically in a direct way, for example with regard to the oligomer distribution which can be determined by means of gel permeation chromatography according to DIN EN ISO 13885-1:2021-11.

[0025] In a first preferred embodiment of the polyisocyanate mixture according to the invention, the polyisocyanates M) and N) are present in a weight ratio to one another of 50:50 to 25:75, preferably 50:50 to 30:70, particularly preferably 45:55 to 30:70.

[0026] In a further preferred embodiment, the polyisocyanate mixture according to the invention has, in each case based on the solvent-free solid resin, color numbers of less than 100 APHA, preferably of less than 80 APHA, particularly preferably of less than 60 APHA, and / or an NCO content of 6.0 to 24.4 wt.%, preferably 8.0 to 23.2 wt.%, particularly preferably 10.0 to 22.2 wt.%, and / or a residual monomer content measured by gas chromatography with an internal standard according to DIN EN ISO 10283:2007-11 of less than 0.14 wt.%, preferably less than 0.12 wt.% and particularly preferably less than 0.10 wt.%.

[0027] In a further preferred embodiment, the polyisocyanate mixture according to the invention has a shear strength according to DIN EN ISO 3219:1994-10 at a shear rate of 250 s -1 measured viscosity at 23°C of less than 5000 mPas, preferably less than 4000 mPas and particularly preferably less than 3500 mPas.

[0028] The at least one polyisocyanate M) is mixed with the at least one polyisocyanate N) such that the polyisocyanate mixture according to the invention is obtained and the polyisocyanates M) and N) are present in the above-mentioned weight ratio to one another. Properties such as viscosity, NCO content and functionality of the process products according to the invention can be specifically adjusted by suitable choice of the mixing ratios within the stated limits. Mixing is carried out by any desired method and in any desired sequence, at a temperature of 0 to 60°C, preferably 10 to 50°C, particularly preferably 20 to 40°C, optionally under an inert gas atmosphere, preferably with exclusion of moisture. The process according to the invention can be carried out solvent-free. If desired, suitable solvents that are inert towards the reactive groups of the starting polyisocyanates M) and N) can also be used.Suitable for this purpose are solvents made from fossil raw materials or from renewable raw materials, in particular the conventional paint solvents known per se, such as:Ethyl acetate, butyl acetate, ethylene glycol monomethyl or ethyl ether acetate, 1-methoxypropyl-2-acetate, 3-methoxy-n-butyl acetate, ethyl(-)-L-lactate, acetone, 2-butanone, 4-methyl-2-pentanone, cyclohexanone, dihydrolevoglucosenone, toluene, xylene, chlorobenzene, white spirit, higher substituted aromatics, such as those sold under the names Solventnaphtha, Solvesso®, Isopar®, Nappar®, Varsol® (ExxonMobil Chemical Central Europe, Cologne, DE) and Shellsol® (Shell Deutschland Oil GmbH, Hamburg, DE), but also solvents such as dimethylfuran, 2-methyltetrahydrofuran, dimethylisosorbide (DMI), γ-valerolactone, propylene glycol diacetate, diethylene glycol dimethyl ether, Dipropylene glycol dimethyl ether, diethylene glycol ethyl and butyl ether acetate, N-methylpyrrolidone and N-methylcaprolactam, or any mixtures of such solvents.

[0029] In a preferred embodiment of the process according to the invention, 20 to 50 parts by weight, preferably 30 to 50 parts by weight, more preferably 30 to 45 parts by weight of the polyisocyanate M) and 50 to 80 parts by weight, preferably 50 to 70 parts by weight, more preferably 55 to 70 parts by weight of the polyisocyanate N) are mixed, the parts by weight of the polyisocyanates M) and N) adding up to 100 parts by weight. If one or more solvents are used, these can be present either in the at least one polyisocyanate M) and / or in the at least one polyisocyanate N), preferably in the at least one polyisocyanate N) before the start of mixing. In the process according to the invention, however, they can also be added after completion or at any time during the actual mixing process.

[0030] If at all, solvents are used in the process according to the invention in an amount of up to 50 wt.%, preferably 40 wt.%, particularly preferably 30 wt.%, based on the sum of polyisocyanate M), polyisocyanate N) and solvent.

[0031] The polyisocyanates M) and N) are further described below and preferred embodiments are mentioned.

[0032] Polyisocyanate M)

[0033] The polyisocyanate M) is a special PDI allophanate polyisocyanate and is described by the general formula (I). A general formula (I) of the at least one polyisocyanate M) is preferred. in which

[0034] R represents a linear or branched, saturated or unsaturated aliphatic and / or saturated or unsaturated cycloaliphatic radical having (8 to 20) - p, particularly preferably having (10 to 18) - p and very particularly preferably having (12 to 14) - p carbon atoms, which may optionally be substituted,

[0035] R' and R" independently of one another represent hydrogen or an aliphatic radical having 1 to 10 carbon atoms, where at least one of the radicals R' and R" represents hydrogen, n represents an integer from 1 to 12, m represents an integer from 1 to 7, particularly preferably an integer from 2 to 5 and most particularly preferably an integer from 2 to 4, and p represents 0 or 1.

[0036] The 1,5-diisocyanatopentane (here also referred to as pentamethylene diisocyanate or PDI) used to produce the polyisocyanate M) can be produced in various ways, for example by phosgenation in the liquid or gas phase or by a phosgene-free route, such as by thermal urethane cleavage, starting from 1,5-diaminopentane preferably obtained biotechnologically by decarboxylation of the naturally occurring amino acid lysine.

[0037] A further preferred embodiment relates to a process for the preparation of the polyisocyanate M) by reacting 1,5-diisocyanatopentane with at least one alcohol B) of the general formula (II) which

[0038] R represents a linear or branched, saturated or unsaturated aliphatic and / or saturated or unsaturated cycloaliphatic radical having (6 to 22) - p carbon atoms, each of which may optionally be substituted,

[0039] R' and R" independently of one another represent hydrogen or an aliphatic radical having 1 to 10 carbon atoms, where at least one of the radicals R' and R" represents hydrogen, m represents an integer from 1 to 10 and p represents 0 or 1.

[0040] Preferably, 1,5-diisocyanatopentane is reacted with at least one alcohol B) of the general formula (II), which

[0041] R represents a linear or branched, saturated or unsaturated aliphatic and / or saturated or unsaturated cycloaliphatic radical having (6 to 22) - p carbon atoms, each of which may optionally be substituted, R' and R" independently represent hydrogen or an aliphatic radical having 1 to 10 carbon atoms, where at least one of the radicals R' and R" represents hydrogen, m represents an integer from 1 to 10 and p represents 0 or 1.

[0042] As alcoholic component B) in the production of the polyisocyanate M) at least one alcohol of the general formula (II) is used, Use in which

[0043] R represents a linear or branched, saturated or unsaturated aliphatic and / or saturated or unsaturated cycloaliphatic radical having (6 to 22) - p, preferably having (8 to 20) - p, particularly preferably having (10 to 18) - p and very particularly preferably having (12 to 14) - p carbon atoms, which may in each case be optionally substituted,

[0044] R' and R" independently of one another represent hydrogen or an aliphatic radical having 1 to 10 carbon atoms, where at least one of the radicals R' and R" represents hydrogen, and m represents an integer from 1 to 10, preferably an integer from 1 to 7, more preferably an integer from 2 to 5 and most preferably an integer from 2 to 4, and p represents 0 or 1.

[0045] These alcohols are, for example, the known alkoxylation products of fatty alcohols of the general formula (III)

[0046] R 1 -OH (in), in which

[0047] R 1 represents a linear or branched, saturated or unsaturated aliphatic and / or saturated or unsaturated cycloaliphatic radical having 6 to 22, preferably 8 to 20, particularly preferably 10 to 18, very particularly preferably 12 to 14 carbon atoms, each of which may optionally be substituted, and / or fatty acids of the general formula (IV)

[0048] R 2 -COOH (iv), in which

[0049] R 2represents a linear or branched, saturated or unsaturated aliphatic and / or saturated or unsaturated cycloaliphatic radical having 5 to 21, preferably 7 to 19, particularly preferably 9 to 17, very particularly preferably 11 to 13 carbon atoms, which may in each case be optionally substituted.

[0050] In the above-mentioned fatty alcohols of the general formula (III), in the general formula (I) and the general formula (II) p stands for 0 and R 1 for R, including the preferences mentioned for R 1 . Likewise, residues R 1 and also R are examples of suitable, preferred and particularly preferred radicals derived from the fatty alcohols mentioned below as examples of suitable, preferred and particularly preferred.

[0051] For the above-mentioned fatty acids of the general formula (IV), in the general formula (I) and the general formula (II) p stands for 1 and R 2for R, including the preferences mentioned for R 2 . Likewise, residues R 2 and also R are mentioned as examples of suitable, preferred and particularly preferred radicals derived from the fatty acids mentioned below as examples of suitable, preferred and particularly preferred.

[0052] Fatty alcohols suitable for alkoxylation are, for example, 1-hexanol (caproic alcohol), 1-heptanol (enanth alcohol), 1-octanol (caprylic alcohol), 1-nonyl alcohol (pelargon alcohol), 1-decanol (capric alcohol), 1-dodecanol (lauryl alcohol), 1-tetradecanol (myristyl alcohol), 1-hexadecanol (cetyl alcohol), 1-heptadecanol (margaryl alcohol), 1-octadecanol (stearyl alcohol), 1-eicosanol (arachidyl alcohol), 1-docosanol (behenyl alcohol), 1-tetracosanol (lignoceryl alcohol), 1-hexacosanol (ceryl alcohol), 1-octacosanol (montanyl alcohol), 1-triacontanol (melissyl alcohol), c / s-9-hexadecen-1-ol (palmitoleyl alcohol), c / s-9-octadecen-1-ol (oleyl alcohol), f / 'ans-9-octadecen-1-ol (elaidyl alcohol), c / s-11-octadecen-1-ol, c / s,c / s-9,12-octadecadien-1-ol (linoleyl alcohol) and 6,9,12-octadecatrien-1-ol (γ-linolenyl alcohol). Suitable fatty acids include, for example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid),Undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid), pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid (margaric acid), octadecanoic acid (stearic acid), nonadecanoic acid, eicosanoic acid (arachidic acid), heneicosanoic acid and docosanoic acid (behenic acid), c / s-9-octadecenoic acid (oleic acid) and c / s-13-docosenoic acid (erucic acid).

[0053] Preferred fatty alcohols and fatty acids are those produced using vegetable and animal oils and fats.

[0054] Particularly preferred fatty alcohols for preparing the alcoholic component B) are 1-decanol, 1-dodecanol, 1-tetradecanol, and 1-octadecanol, very particularly preferably 1-dodecanol and 1-tetradecanol. Particularly preferred fatty acids are decanoic acid, dodecanoic acid, tetradecanoic acid, and hexadecanoic acid, very particularly preferably dodecanoic acid and tetradecanoic acid. For preparing the alcoholic component B) by alkoxylation of the fatty alcohols and / or fatty acids mentioned, any alkylene oxides having 2 to 12 carbon atoms, such as ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxyhexane, 1,2-epoxyoctane, or 1,2-epoxydodecane, are suitable; these can be used in any order or as a mixture in the alkoxylation reaction. Preferred alkylene oxides are those having 2 to 4 carbon atoms. Particularly preferred alkylene oxides for the preparation of the alcoholic component B) are ethylene oxide and propylene oxide.The number of carbon atoms of the radicals R' or R" in the general formula (I) results from the alkylene oxides mentioned above as examples and with preference. Thus, R' and R" in the general formula (I) and / or formula (II) independently of one another represent hydrogen or an aliphatic radical having preferably 1 to 2 carbon atoms, where at least one of the radicals R' and R" represents hydrogen.

[0055] Suitable alcoholic components B) for preparing the polyisocyanates M) are, in particular, alkoxylation products of the fatty acids and / or fatty alcohols mentioned, which have an average of 1 to 10, preferably 1 to 7, particularly preferably 2 to 5, and most preferably 2 to 4 alkylene oxide units. The numbers and numerical ranges mentioned above as averages result in the inventive and preferred integers m in the general formula (I) and the general formula (II).

[0056] In a further preferred embodiment, alkoxylation products containing an average of 1 to 10, preferably 1 to 7, particularly preferably 2 to 5, and most particularly preferably 2 to 4, alkylene oxide units are used as alcoholic component B), the alkylene oxide units preferably comprising or consisting of ethylene oxide and / or propylene oxide units. The numbers and numerical ranges mentioned above as statistical averages result in the inventive and preferred integers m in general formula (I) and general formula (II).

[0057] The alcoholic components B) preferably have a pH, measured on a 1% solution of the respective alcoholic component B) in water, of 4.0 to 8.0, preferably of 4.5 to 7.5, particularly preferably of 5.0 to 7.0 and / or total contents of alkali cations of at most 100 ppm, preferably of 1 to 70 ppm, particularly preferably of 2 to 50 ppm.

[0058] If necessary, component B) may contain, in addition to the alkoxylation products of fatty alcohols and / or fatty acids mentioned, other alcoholic compounds in minor amounts.

[0059] These include, for example, monoalcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomeric pentanoyl, hexanoyl, octanols and nonanols, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanols, hydroxymethylcyclohexane, 3-methyl-3-hydroxymethyloxetane, benzyl alcohol, phenol, the isomeric cresols, octylphenols, nonylphenols and naphthols, furfuryl alcohol and tetrahydrofurfuryl alcohol, unbranched aliphatic diols such as. B. 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol, cycloaliphatic diols, such as B. 1,2- and 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 4,4'-(1-methylethylidene)-biscyclohexanol, triols such as B. 1,2,3-propanetriol, 1,1,1-trimethylolethane, 1,2,6-hexanetriol, 1,1,1-trimethylolpropane, and 1,3,5-tris(2-hydroxyethyl)isocyanurate, tetrafunctional alcohols, such as B.2,2-bis(hydroxymethyl)-1,3-propanediol or any mixtures of such alcohols.

[0060] If at all, these further alcoholic compounds are used to produce the polyisocyanate M) in amounts of not more than 25% by weight, preferably not more than 20% by weight, particularly preferably not more than 15% by weight, based on the amount of alkoxylation products of fatty alcohols and / or fatty acids used.

[0061] To prepare the polyisocyanate M), 1,5-diisocyanatopentane is reacted with at least one alcoholic component B), preferably at temperatures of 40 to 200 °C, particularly preferably 60 to 180 °C, and / or maintaining an equivalent ratio of isocyanate groups to isocyanate-reactive groups of preferably 4:1 to 50:1, particularly preferably 5:1 to 30:1, very particularly preferably 10:1 to 25:1, to form allophanate polyisocyanates.

[0062] The process for preparing the polyisocyanate M) can be carried out uncatalyzed as a thermally induced allophanatization. However, suitable catalysts are preferably used to accelerate the allophanatization reaction. These catalysts are the customary known allophanatization catalysts, for example metal carboxylates, metal chelates, or tertiary amines of the type described in GB-A-0 994 890 (page 2, lines 73 to 87), alkylating agents of the type described in US-A-3 769 318 (column 6, lines 5 to 49), or strong acids, as described by way of example in EP-A-0 000 194 (page 13, line 27 to page 14, lines 1 to 18).

[0063] Suitable allophanatization catalysts are in particular zinc compounds, such as zinc (II) stearate, zinc (II) n-octanoate, zinc (II) 2-ethyl-1-hexanoate, zinc (II) naphthenate or zinc (II) acetylacetonate, tin compounds, such as tin (II) n-octanoate, tin (II) 2-ethyl-1-hexanoate, tin (II) laurate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dimaleate or dioctyltin diacetate, zirconium compounds, such as. B. Zirconium (IV) 2-ethyl-1-hexanoate, zirconium (IV) neodecanoate, zirconium (IV) naphthenate or zirconium (IV) acetylacetonate, aluminum tri(ethylacetoacetate), iron (III) chloride, potassium octoate, manganese, cobalt or nickel compounds and strong acids, such as B. trifluoroacetic acid, sulfuric acid, hydrogen chloride, hydrogen bromide, phosphoric acid or perchloric acid, or any mixtures of these catalysts.

[0064] Suitable, albeit less preferred, catalysts for the preparation of polyisocyanate M) are also those compounds that, in addition to the allophanatization reaction, also catalyze the trimerization of isocyanate groups to form isocyanurate structures. Such catalysts are described, for example, in EP-A-0 649 866, page 4, line 7 to page 5, line 15.

[0065] Preferred catalysts for preparing the polyisocyanate M) are zinc and / or zirconium compounds of the abovementioned type. Very particular preference is given to using at least zinc(II)n-octanoate, zinc(II)2-ethyl-1-hexanoate and / or zinc(II)stearate, zirconium(IV)n-octanoate, zirconium(IV)2-ethyl-1-hexanoate and / or zirconium(IV)neodecanoate.

[0066] These catalysts are used in the preparation of the polyisocyanate M), if at all, preferably in an amount of 0.001 to 5 wt. %, particularly preferably 0.005 to 1 wt. %, based on the total weight of reactants A) and B), and can be added both before the start of the reaction and at any time during the reaction. Lead octoate is preferably not used as a catalyst in the preparation of the polyisocyanates M), and thus a polyisocyanate mixture according to the invention is preferred which is free of catalytic amounts, particularly preferably free of detectable amounts of lead octoate.

[0067] The polyisocyanate M) is preferably prepared solvent-free. However, suitable solvents that are inert toward the reactive groups of the starting components can also be used if desired. Suitable solvents include, for example, the solvents described above as suitable solvents for the process according to the invention or any desired mixtures of such solvents.

[0068] In one possible embodiment, in the preparation of the polyisocyanate M), the PDI is initially charged at a temperature between 20 and 100°C - optionally under an inert gas, such as nitrogen, and optionally in the presence of a suitable solvent of the type mentioned. The alcoholic component B) is then added in the amount stated above, and the reaction temperature for the urethanization is adjusted, if appropriate by a suitable measure (heating or cooling), to a temperature of 30 to 120°C, preferably 50 to 100°C. Following the urethanization reaction, i.e. when the NCO content theoretically corresponding to complete conversion of isocyanate and hydroxyl groups has been reached, the allophanatization can be started, for example without the addition of a catalyst, by heating the reaction mixture to a temperature of 140 to 200°C.However, suitable catalysts of the above-mentioned type are preferably used to accelerate the allophanatization reaction, temperatures in the range from 60 to 140°C, preferably 80 to 120°C, generally being sufficient, depending on the type and amount of catalyst used.

[0069] In another possible embodiment of the process for preparing the polyisocyanate M), the optionally used catalyst is admixed to the PDI and / or the alcoholic component B) before the start of the actual reaction. In this case, the intermediately formed urethane groups spontaneously react further to form the desired allophanate structure. In this type of single-stage reaction, the PDI, optionally containing the catalyst, is initially introduced - optionally under an inert gas such as nitrogen, and optionally in the presence of a suitable solvent of the type mentioned - generally at temperatures optimal for allophanatization in the range of 60 to 140°C, preferably 80 to 120°C, and reacted with the alcoholic component B), optionally containing the catalyst.

[0070] However, it is also possible to add the catalyst to the reaction mixture at any time during the urethanization reaction. In this embodiment of the process, a temperature in the range of 30 to 120°C, preferably 50 to 100°C, is generally set for the pure urethanization reaction, which takes place before the catalyst addition. After adding a suitable catalyst, the allophanatization reaction is finally carried out at temperatures of generally 60 to 140°C, preferably 80 to 120°C.

[0071] The progress of the reaction in the process for preparing the polyisocyanate M) can be monitored, for example, by titrimetric determination of the NCO content in accordance with DIN EN ISO 1 1909:2007-05. Once the desired NCO content has been reached, preferably when the degree of allophanatization (i.e. the percentage of urethane groups converted to allophanate groups, which form intermediately from the hydroxyl groups of component B), which can be calculated from the NCO content, of the reaction mixture is at least 80%, particularly preferably at least 90%, and very particularly preferably when the NCO content corresponding to complete allophanatization has been reached or fallen below, the reaction is terminated. In the case of a purely thermal reaction, this can be done, for example, by cooling the reaction mixture to room temperature.However, with the preferred use of an allophanatization catalyst of the type mentioned, the reaction is generally stopped by adding suitable catalyst poisons, for example acids such as phosphoric acid or acid chlorides such as benzoyl chloride or isophthaloyl dichloride.

[0072] The reaction mixture is then preferably freed from volatile constituents (excess PDI, any solvents used and, if no catalyst poison is used, any active catalyst) by thin-film distillation in a high vacuum, for example at a pressure of less than 1.0 mbar, preferably less than 0.5 mbar, particularly preferably less than 0.2 mbar, under the gentlest possible conditions, for example at a temperature of 100 to 200 °C, preferably 120 to 180 °C.

[0073] The resulting distillates, which contain, in addition to the unreacted PDI and any solvents used, if no catalyst poison is used, possibly active catalyst, can be used without any problem for further allophanatization in the process for the production of the polyisocyanate M).

[0074] In a further embodiment of the process for preparing the polyisocyanate M), the volatile components mentioned are separated from the oligomerization product by extraction with suitable solvents inert to isocyanate groups, for example aliphatic or cycloaliphatic hydrocarbons such as pentane, hexane, heptane, cyclopentane or cyclohexane.

[0075] Regardless of the type of process for their preparation, the polyisocyanates M) are clear, virtually colorless polyisocyanates which, in each case based on the solvent-free solid resin, have color numbers of less than 100 APHA, preferably of less than 80 APHA, particularly preferably of less than 60 APHA, and / or an NCO content of 6.0 to 18.0 wt.%, preferably 8.0 to 16.0 wt.%, particularly preferably 10.0 to 15.0 wt.%, and / or a residual monomer content of less than 0.14 wt.%, preferably less than 0.12 wt.% and particularly preferably less than 0.10 wt.%, measured by gas chromatography with an internal standard in accordance with DIN EN ISO 10283:2007-11.

[0076] Polyisocyanate N)

[0077] Polyisocyanates N) for the polyisocyanate mixture according to the invention and the process according to the invention are any polyisocyanates having a uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure prepared by modifying simple aliphatic, cycloaliphatic, araliphatic and / or aromatic diisocyanates and / or triisocyanates, as described, for example, in J. Prakt. Chem. 336 (1994) 185 - 200, in DE-A 1 670 666, DE-A 1 954 093, DE-A 2 414 413, DE-A 2 452 532, DE-A 2 641 380, DE-A 3 700 209, DE-A 3 900 053 and DE-A 3 928 503 or in EP-A 0 336 205, EP-A 0 339 396 EP-A 0 798 299, EP-A 0 962 454, EP-A 0 962 455, EP-A 2 785 760, EP-A 2 883 895, EP-A 3 107 922, EP-A 3 107 948 and EP-A 3 337 836 or any mixtures of such polyisocyanates.

[0078] Suitable diisocyanates and triisocyanates A) are any diisocyanates and triisocyanates which can be obtained in various ways, for example by phosgenation of the corresponding diamines or triamines, which can be produced using fossil raw materials or else from renewable raw materials, optionally with a mass balance, in the liquid or gas phase or by a phosgene-free route, such as, for example, by thermal urethane cleavage, preferably those in the molecular weight range 140 to 400 with aliphatically, cycloaliphatically, araliphatically and / or aromatically bound isocyanate groups, such as, for example, 1,4-diisocyanatobutane, 1,5-diisocyanatopentane (PDI), 1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or2,4,4-trimethyl-1,6-diisocyanatohexane, 1,8-diisocyanatooctane, 1,9-diisocyanatononane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and 1,4-bis-(isocyanatomethyl)-cyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane.

[0079] (Isophorone diisocyanate, IPDI), 2,4'- and 4,4'-diisocyanatodicyclohexylmethane (H12-MDI), 4,4'-diisocyanato-3,3'-dimethyldicyclohexylmethane, 4,4'-diisocyanato-3,3',5,5'-tetramethyldicyclohexylmethane, 4,4'-Diisocyanato-1,1'-bi(cyclohexyl), 4,4'-Diisocyanato-3,3'-dimethyl-1,1'-bi(cyclohexyl), 4,4'-Diisocyanato-2,2',5,5'-tetra-methyl-1,1'-bi(cyclohexyl), 1,8-Diisocyanato-p-menthane, 1 ,3-diisocyanatoadamantane, 1,3-dimethyl-5,7-diisocyanatoadamantane, 1-isocyanato-1-methyl-4(3)isocyanato-methylcyclohexane, bis-(isocyanatomethyl)-norbornane (NBDI), 4-isocyanatomethyl-1,8-octane diisocyanate (triisocyanatononane; TIN), 1,3- and 1,4-bis(isocyanatomethyl)benzene

[0080] (xylylene diisocyanate, XDI), 1,3- and 1,4-bis-(2-isocyanato-prop-2-yl)-benzene (TMXDI), 1,3-

[0081] Bis(isocyanatomethyl)-4-methylbenzene, 1,3-Bis(isocyanatomethyl)-4-ethylbenzene, 1,3-

[0082] Bis(isocyanatomethyl)-5-methylbenzene, 1,3-bis(isocyanatomethyl)-4,5-dimethylbenzene, 1,4-

[0083] Bis(isocyanatomethyl)-2,5-dimethylbenzene, 1,4-bis(isocyanatomethyl)-2,3,5,6-tetramethylbenzene, 1,3-

[0084] Bis(isocyanatomethyl)-5-tert-butylbenzene, 1,3-bis(isocyanatomethyl)-4-chlorobenzene, 1,3-

[0085] Bis(isocyanatomethyl)-4,5-dichlorobenzene, 1,3-bis(isocyanatomethyl)-2,4,5,6-tetrachlorobenzene, 1,4-

[0086] Bis(isocyanatomethyl)-2,3,5,6-tetrachlorobenzene, 1,4-bis(isocyanatomethyl)-2,3,5,6-tetrabromobenzene,

[0087] 1,4-bis(2-isocyanatoethyl)benzene and 1,4-bis(isocyanatomethyl)naphthalene, 1,2-, 1,3- and 1,4-diisocyanatobenzene (phenylene diisocyanate), 2,4- and 2,6-diisocyanatotoluene (TDI), 2,3,5,6-tetramethyl-

[0088] 1 .4-diisocyanatobenzene, the isomeric diethylphenylene diisocyanates, diisopropylphenylene diisocyanates,

[0089] Diisododecylphenylene diisocyanates and biphenyl diisocyanates, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 2,2'-, 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI), 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-Diisocyanatodiphenylethane, 1,5-Diisocyanatonaphthalene (naphthylene diisocyanate, NDI), diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate,

[0090] Diethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycol diphenyl ether diisocyanate,

[0091] Benzophenone diisocyanate, triisocyanatobenzene, 2,4,6-triisocyanatotoluene, trimethylbenzene triisocyanate, diphenylmethane 2,4,4'-triisocyanate, 3-methyldiphenylmethane 4,6,4'-triisocyanate, the isomeric naphthalene triisocyanates and methylnaphthalene diisocyanates, triphenylmethane triisocyanate, 2,4-diisocyanato-1-[(5-isocyanato-2-methylphenyl)methyl]benzene or mixtures of at least two such diisocyanates and triisocyanates. If appropriate, when modifying the above-mentioned diisocyanates and / or triisocyanates to polyisocyanates N), minor amounts of monoisocyanates, in particular those with a molecular weight of 99 to 300, such as e.g. B. n-butyl isocyanate, n-amyl isocyanate, n-hexyl isocyanate, n-heptyl isocyanate, n-octyl isocyanate, undecyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate, cetyl isocyanate, stearyl isocyanate, cyclopentyl isocyanate, cyclohexyl isocyanate, 3- or 4-methylcyclohexyl isocyanate, benzyl isocyanate, phenyl isocyanate or naphthyl isocyanate, may also be used.If at all, monoisocyanates are used in amounts of up to 30 wt.%, preferably up to 20 wt.%, particularly preferably up to 10 wt.%, based on the total amount of mono-, di- and triisocyanates.

[0092] In the preparation of polyisocyanates N), the actual modification reaction is generally followed by a further process step for separating the unreacted excess monomeric diisocyanates and / or triisocyanates and, if appropriate, monoisocyanates. This monomer separation is carried out by conventional methods, preferably by thin-film distillation under vacuum or by extraction with suitable solvents inert toward isocyanate groups, for example, aliphatic or cycloaliphatic hydrocarbons such as pentane, hexane, heptane, cyclopentane, or cyclohexane.

[0093] Preferably, polyisocyanates of the type mentioned which have an average isocyanate functionality of 1.8 to 8.0, preferably of 2.0 to 7.0 and particularly preferably of 2.3 to 6.0, and / or a content of isocyanate groups of 6.0 to 26.0 wt. %, preferably of 8.0 to 25.0 wt. %, particularly preferably 10.0 to 24.0 wt. %, and / or a content of monomeric diisocyanates of less than 0.14 wt. %, preferably less than 0.12 wt. %, particularly preferably less than 0.10 wt. % are used as polyisocyanate N) in the polyisocyanate mixture according to the invention. For the alternative, optional case that triisocyanates and / or monoisocyanates were used to prepare the polyisocyanates N), the above-mentioned residual monomer contents of less than 0.14 wt.%, preferably less than 0.12 wt.%, particularly preferably less than 0.10 wt.%, refer to the sum of all residual contents of all diisocyanates, triisocyanates and monoisocyanates used.The NCO contents are determined according to DIN EN ISO 11909:2007-05, the residual monomer contents according to DIN EN ISO 10283:2007-11 using gas chromatography with an internal standard.

[0094] Particularly preferred polyisocyanates N) for the polyisocyanate mixture according to the invention are those of the type mentioned with exclusively aliphatically and / or cycloaliphatically bound isocyanate groups.

[0095] Very particularly preferred polyisocyanates N) are polyisocyanates containing at least isocyanurate structures based on 1,5-diisocyanatopentane, 1,6-diisocyanatohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 1,3-bis(isocyanatomethyl)benzene, bis(isocyanatomethyl)norbornane and / or 4,4'-diisocyanatodicyclohexylmethane, and most preferably polyisocyanates containing at least isocyanurate structures based on 1,5-diisocyanatopentane, 1,6-diisocyanatohexane or isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane. Polyisocyanate mixture and further objects of the invention:

[0096] The polyisocyanate mixtures according to the invention are completely stable to crystallization and remain completely clear and free of turbidity even at 5°C and after four weeks of storage.

[0097] The polyisocyanate mixtures according to the invention represent valuable starting materials for the production of polyurethane plastics by the isocyanate polyaddition process. Therefore, a further subject of the invention is the use of the polyisocyanate mixture according to the invention or of the polyisocyanate mixture obtainable or produced, preferably directly produced, by the process according to the invention as a starting component in the production of polyurethane plastics, preferably for producing a coating on a substrate, wherein the substrate is preferably an optionally pretreated body, in particular of a vehicle, or parts thereof.

[0098] The polyisocyanate mixtures according to the invention are outstandingly suitable as curing agents for plastics. Therefore, a composition comprising either at least one polyisocyanate mixture according to the invention and at least one binder reactive toward isocyanate groups, or comprising at least one polyisocyanate mixture according to the invention, obtainable or prepared by the process according to the invention, and at least one binder reactive toward isocyanate groups, is a further subject of the present invention.

[0099] In a preferred embodiment, the composition according to the invention contains the at least one binder reactive toward isocyanate groups in a component 1) and the at least one polyisocyanate mixture according to the invention in a component 2) or the at least one polyisocyanate mixture obtainable or prepared by the process according to the invention in a component 2). Such a composition is also referred to below as a two-component system.

[0100] Here or alternatively, it is further preferred that the at least one binder reactive towards isocyanate groups is a polyhydroxy compound, preferably a polyether polyol, polyester polyol, polyurethane polyol, polysiloxane polyol, polycarbonate polyol, polyether polyamine, polybutadiene polyol, polyacrylate polyol and / or polymethacrylate polyol and copolymers thereof and particularly preferably a polyester polyol, polyacrylate polyol or any mixtures of the aforementioned.

[0101] It is particularly preferred in the composition according to the invention that the at least one binder reactive towards isocyanate groups comprises at least one hydroxy-functional compound having a hydroxyl group content of > 2.0 wt.%, preferably > 3.0 wt.% and particularly preferably > 3.5 wt.%, based on the solids content of the binder reactive towards isocyanate groups.

[0102] In a further preferred embodiment, the composition according to the invention is a coating composition which optionally contains one or more auxiliaries and additives.

[0103] In a preferred embodiment, the inventive composition of components 1) and 2) is referred to below as a two-component system or as a coating composition or as a coating agent or as a two-component polyurethane varnish, in which the usual polyether polyols, polyester polyols, polycarbonate polyols and / or polyacrylate polyols are present as the hydroxy-functional component as reactants for the polyisocyanates. Preferred hydroxy-functional components are polyacrylate polyols, i.e., polymers or copolymers of (meth)acrylic acid alkyl esters, optionally with styrene or other copolymerizable olefinically unsaturated monomers.

[0104] Although the polyisocyanate mixtures according to the invention can be used solvent-free due to their low viscosity, they can also be diluted without clouding with conventional solvents, for example the aforementioned isocyanate-inert solvents that may optionally be used in the process according to the invention. In general, the coating compositions formulated with the polyisocyanate mixtures according to the invention, to which the auxiliaries and additives customary in the coatings sector, such as flow control agents, color pigments, fillers, or matting agents, may optionally be incorporated, possess good coating properties even when dried at room temperature. However, the compositions according to the invention can of course also be dried under forced conditions at elevated temperatures or by baking at temperatures up to 260°C.

[0105] Examples of suitable auxiliaries and additives are, in particular, light stabilizers such as UV absorbers and sterically hindered amines (HALS), furthermore stabilizers, fillers and anti-settling agents, defoamers, anti-crater and / or wetting agents, leveling agents, film-forming aids, reactive diluents, solvents, substances for rheology control, slip additives and / or components which prevent soiling and / or improve the cleanability of the cured coatings, furthermore matting agents.

[0106] The use of light stabilizers, in particular UV absorbers such as substituted benzotriazoles, S-phenyltriazines or oxalanilides as well as sterically hindered amines, in particular with 2,2,6,6-tetramethylpiperidyl structures - referred to as HALS - is described as an example in A. Valet, Lichtschutzmittel für Lacke, Vincentz Verlag, Hanover, 1996.

[0107] Stabilizers such as radical scavengers and other polymerization inhibitors such as sterically hindered phenols stabilize coating components during storage and are intended to prevent discoloration during curing. Acidic stabilizers such as alkyl-substituted partial phosphoric acid esters can also be considered for component 2).

[0108] The composition according to the invention may further contain pigments, dyes and / or fillers. The pigments used for this purpose, including metallic or other effect pigments, dyes and / or fillers, are known to the person skilled in the art.

[0109] Preferred fillers are those compounds that do not negatively affect the appearance of the coating. Examples include nanoparticles based on silicon dioxide, aluminum oxide, or zirconium oxide. For further information, please refer to the Römpp Encyclopedia "Lacke und Druckfarben" (Lacke and Printing Inks), Georg Thieme Verlag, Stuttgart, 1998, pages 250 to 252.

[0110] If fillers, matting agents, or pigments are present in the composition according to the invention, the addition of anti-settling agents may be useful to prevent the components from separating during storage. Wetting and leveling agents improve the surface wetting and / or leveling of coatings. Examples include fluorosurfactants, silicone surfactants, and special polyacrylates.Rheology-controlling additives are important for controlling the properties of the composition during application and during the flow phase on the substrate and are known, for example, from patents WO 94 / 22968, EP-A-0 276 501, EP-A-0 249 201 or WO 97 / 12945; crosslinked polymeric microparticles, as disclosed, for example, in EP-A-0 008 127; inorganic layered silicates such as aluminum-magnesium silicates, sodium-magnesium and sodium-magnesium-fluoro-lithium layered silicates of the montmorillonite type; silicas such as Aerosil®; or synthetic polymers with ionic and / or associative groups such as polyvinyl alcohol, poly(meth)acrylamide, poly(meth)acrylic acid, polyvinylpyrrolidone, styrene-maleic anhydride or ethylene-maleic anhydride copolymers and their derivatives or hydrophobically modified ethoxylated urethanes or polyacrylates.

[0111] The composition according to the invention can be used solvent-free, but preferably contains at least one solvent, e.g. in component 1) and / or component 2).

[0112] Suitable solvents should be used in a manner known to those skilled in the art, tailored to the composition used and the application method. Solvents should dissolve the components used, promote their mixing, and avoid incompatibilities. Furthermore, they should leave the coating during application and curing in a manner tailored to the ongoing crosslinking reaction, so that a solvent-free coating is created with the best possible appearance and without defects such as popping or pinholes. Solvents used in two-component technology are particularly suitable. Examples are ketones such as acetone, methyl ethyl ketone or hexanone; esters such as ethyl acetate, butyl acetate, methoxypropyl acetate; substituted glycols and other ethers; aromatics such as xylene or solvent naphtha, e.g., from Exxon-Chemie; and mixtures of the aforementioned solvents.

[0113] To control the curing rate, suitable catalysts can be used in the formulation of the coating agents, for example the catalysts commonly used in isocyanate chemistry, such as tertiary amines such as triethylamine, pyridine, methylpyridine, benzyldimethylamine, N,N-endoethylenepiperazine, N-methylpiperidine, pentamethyldiethylenetriamine, N,N-dimethylaminocyclohexane, N,N'-dimethylpiperazine or metal salts such as iron(III) chloride, zinc chloride, zinc 2-ethylcaproate, tin(II) octanoate, tin(II) ethylcaproate, dibutyltin(IV) dilaurate, bismuth(III) 2-ethylhexanoate, bismuth(III) octoate or molybdenum glycolate.

[0114] The polyisocyanate mixtures according to the invention are also suitable as crosslinking components for binders or binder components containing isocyanate-reactive groups, particularly alcoholic hydroxyl groups, dissolved or dispersed in water in the production of aqueous two-component polyurethane systems. Due to their low viscosity, they can be used either as such, i.e., in hydrophobic form, or in hydrophilically modified form by known processes, e.g., according to EP-B 0 540 985, EP-B 0 959 087, or EP-B 1 287 052.

[0115] The polyisocyanate mixtures according to the invention can also be combined with polyamines, such as the polyaspartic acid derivatives known from EP-B 0 403 921, obtainable by reacting diamines with fumaric acid or maleic acid esters, or with polyamines whose amino groups are present in blocked form, such as polyketimines, polyaldimines, or oxazolanes. Under the influence of moisture, these blocked amino groups form free amino groups and, in the case of oxazolanes, also free hydroxyl groups, which react with the isocyanate groups of the polyisocyanate mixtures according to the invention by crosslinking.

[0116] The polyisocyanate mixtures according to the invention can also be combined with compounds which have at least one thiol group.

[0117] These are, for example, the polythiols known from EP-A 3 872 108, such as simple alkanethiols, polythiols containing thioether groups, polyetherthiols, polyesterthiols, aromatic thio compounds and / or mercapto alcohols.

[0118] According to a preferred embodiment, the isocyanate groups of the polyisocyanate mixtures according to the invention can be partially or completely reacted with at least one blocking agent.

[0119] These blocking agents are, in particular, blocking agents known per se from polyurethane chemistry, such as, for example, malonic acid diethyl ester, acetoacetic ester, activated cyclic ketones, such as, for example, cyclopentanone-2-carboxymethyl ester and -carboxyethyl ester, acetone oxime, butanone oxime, e-caprolactam, 3,5-dimethylpyrazole, 1,2,4-triazole, dimethyl-1,2,4-triazole, imidazole, diisopropylamine, benzyl-tert-butylamine or any mixtures of these blocking agents.

[0120] In blocked form, the polyisocyanate mixtures according to the invention can also be used in combination with the above-mentioned paint binders or paint binder components in the sense of one-component PUR stoving systems.

[0121] In all coating combinations, the polyisocyanate mixtures according to the invention and the reactant are present in amounts such that 0.5 to 3, preferably 0.6 to 2.0, particularly preferably 0.8 to 1.6, optionally blocked, isocyanate-reactive groups are present for each optionally blocked isocyanate group. If desired, the allophanate polyisocyanates according to the invention can also be admixed in minor amounts to non-functional coating binders to achieve very specific properties, for example, as an additive to improve adhesion.

[0122] Any substrates can be considered as substrates for the coatings formulated with the aid of the polyisocyanate mixtures according to the invention, such as metal, wood, glass, stone, ceramic materials, concrete, hard and flexible plastics, textiles, leather and paper, which can optionally also be provided with conventional primers before coating.

[0123] The invention further provides a process for producing a coating on a substrate, comprising the following steps: a) providing an optionally pretreated substrate; b) applying at least one composition according to the invention; and c) curing the composition, optionally with the addition of heat. The invention thus further provides coating compositions comprising the polyisocyanate mixtures according to the invention, and a coated substrate obtainable or produced by the process according to the invention, wherein the optionally pretreated substrate is preferably a body, in particular of a vehicle, or parts thereof and / or preferably comprises one or more of the materials selected from metal, plastic, or mixtures thereof.Alternatively or additionally, the coated substrate is at least partially coated with a polyurethane, polyurea, and / or polythiourethane according to the invention and / or at least one polyisocyanate mixture according to the invention and / or at least one coating composition according to the invention. The polyisocyanate mixtures or compositions according to the invention are also very suitable for use in direct coating applications and result in corresponding directly coated substrates.

[0124] The coating compositions according to the invention can be present, for example, as a two-component system comprising a crosslinker component containing at least one polyisocyanate mixture according to the invention and a binder component containing at least one paint binder or a paint binder component with groups reactive toward isocyanate groups, or as a one-component system containing at least one polyisocyanate mixture according to the invention in blocked form. Such systems are also subject of the present invention.

[0125] In addition to the preferred use as crosslinking components for solvent-free, solvent-based or aqueous 2K-PUR coatings, the polyisocyanate mixtures according to the invention are outstandingly suitable as crosslinking agents for solvent-free or solvent-based adhesive binders or aqueous dispersion adhesives, or also as building components for the production of lightfast compact or foamed polyurethane moldings.

[0126] Therefore, a further subject matter of the invention are polyurethanes, polyurea and / or polythiourethanes, obtainable or prepared by reacting at least one polyisocyanate mixture according to the invention with at least one hydroxy-, amino- and / or thiofunctional component.

[0127] The features identified as preferred for the process according to the invention or the polyisocyanate mixture according to the invention are also preferred for the further subject matters of the invention.

[0128] The following examples serve to illustrate the present invention, but should in no way be construed as limiting the scope of protection. Examples

[0129] Unless otherwise stated, all percentages are based on weight.

[0130] The NCO content was determined titrimetrically according to DIN EN ISO 11909:2007-05.

[0131] All viscosity measurements were carried out using a Physica MCR 51 rheometer from Anton Paar Germany GmbH (DE) according to DIN EN ISO 3219:1994-10 at a shear rate of 250 s -1 .

[0132] The residual monomer contents were measured according to DIN EN ISO 10283:2007-11 using gas chromatography with an internal standard.

[0133] The platinum-cobalt color number was measured spectrophotometrically according to DIN EN ISO 6271-2:2005-03 using a LICO 400 spectrophotometer from Lange, Germany.

[0134] The contents (mol-%) of the allophanate, urethane and optionally isocyanurate and / or uretdione structures present in the polyisocyanates according to the invention were determined from the integrals of proton-decoupled 13 C NMR spectra (recorded on a Bruker DPX-400) are calculated and refer to the sum of allophanate, urethane, isocyanurate, and / or uretdione structures present. For PDI and HDI polyisocyanates dissolved in CDCh, the individual structural elements exhibit the following chemical shifts (in ppm): allophanate: 155.7 and 153.8; urethane: 156.3; isocyanurate: 148.4; uretdione: 157.1.

[0135] The drying properties of the coating systems were determined according to DIN 53 150:2002-09.

[0136] The gloss of the resulting coatings was measured reflectometrically according to DIN EN ISO 2813:1999-06 at a 20° angle.

[0137] The determination of pendulum damping according to König was carried out according to DIN EN ISO 1522:2007-04 on glass plates.

[0138] To test the coatings for solvent resistance, small amounts of the solvents xylene, 1-methoxypropyl 2-acetate, ethyl acetate, and acetone were placed in test tubes and a cotton ball was placed over the opening to create a solvent-saturated atmosphere inside the test tubes. The test tubes were then placed with the cotton ball on the surface of the coatings applied to glass and left there for 1 or 5 minutes. After wiping off the solvent, the film was examined for destruction / softening / loss of adhesion and rated (0 = no change, 5 = film completely dissolved). The ratings for the four solvents are given in the following order: xylene, 1-methoxypropyl 2-acetate, ethyl acetate, and acetone as four consecutive numbers. The gasoline resistance test was carried out analogously using premium gasoline E10.

[0139] The wet scratch resistance of the coatings was tested using a laboratory washing system according to DIN EN ISO 20566:2010-08. The gloss loss is expressed in Gloss Units (GU) after scratching (10 cycles). The lower the gloss loss in GU, the more resistant the coating is to wet scratching. Polyisocyanate N1)

[0140] PDI polyisocyanate containing isocyanurate groups, prepared by catalytic trimerization of PDI according to the process described in WO 2016 / 146579 for polyisocyanate component A2). The reaction was deactivated at an NCO content of the crude mixture of 36.7% by adding an equimolar amount of dibutyl phosphate, based on the amount of catalyst used, and stirring for 30 minutes at 80°C. Unreacted PDI was then removed by thin-film distillation at a temperature of 140°C and a pressure of 0.5 mbar.

[0141] NCO content: 21.8% monomeric PDI: 0.09%

[0142] Viscosity (23 °C): 9850 mPas

[0143] Color number (Hazen): 34

[0144] Polyisocyanate N2)

[0145] HDI polyisocyanate containing isocyanurate groups, prepared by catalytic trimerization of HDI based on Example 11 of EP-A 330 966, except that the reaction was stopped at an NCO content of the crude mixture of 40% by adding dibutyl phosphate. Unreacted HDI was then separated by thin-film distillation at a temperature of 130°C and a pressure of 0.2 mbar.

[0146] NCO content: 21.7%

[0147] Monomeric HDI: 0.1%

[0148] Viscosity (23°C): 3080 mPas

[0149] Color number (Hazen): 18

[0150] Polyisocyanate N3)

[0151] HDI polyisocyanate containing isocyanurate groups, prepared by catalytic trimerization of HDI based on Example 11 of EP-A 330 966, with the modification that 2-ethylhexanol was used as the catalyst solvent instead of 2-ethyl-1,3-hexanediol, and the reaction was stopped at an NCO content of the crude mixture of 42.5% by adding dibutyl phosphate. Unreacted HDI was then separated by thin-film distillation at a temperature of 130°C and a pressure of 0.2 mbar. The product had the following characteristics and composition:

[0152] NCO content: 22.9% monomeric HDI: 0.08%

[0153] Viscosity (23°C): 1210 mPas

[0154] Color number (Hazen): 10

[0155] Polyisocyanate M1)

[0156] 1234 g (8.0 mol) of PDI were initially charged at 95°C under dry nitrogen and with stirring, and 0.16 g of zinc(II)-2-ethyl-1-hexanoate was added as a catalyst. Over a period of approximately 45 minutes, 309 g (1.0 mol) of a statistically triethoxylated lauryl alcohol (OH number: 181.8 mg KOH / g, Na content: 28 mg / kg, K content: < 1 mg / kg) were added dropwise, with the temperature of the mixture rising to 100°C due to the exothermic reaction. The reaction mixture was then further stirred at 100°C until the NCO content had dropped to 35.6% after approximately 1 hour. The catalyst was deactivated by adding 0.16 g of orthophosphoric acid, and the unreacted monomeric PDI was separated in a thin-film evaporator at a temperature of 130°C and a pressure of 0.1 mbar. This yielded 723 g of a virtually colorless, clear polyisocyanate mixture with the following characteristics and composition:

[0157] NCO content: 14.1% monomeric PDI: 0.03%

[0158] Viscosity (23°C): 290 mPas

[0159] Color number (APHA): 21 Hazen

[0160] Composition: Allophanate: 70.3 mol-% Urethane: 4.2 mol-% Isocyanurate: 24.9 mol-%

[0161] Uretdione: 0.6 mol%

[0162] (Production of polyisocyanate mixture 1)

[0163] 30 parts by weight of polyisocyanate M1) were homogeneously mixed with 70 parts by weight of polyisocyanate N1) at 50°C by stirring. After cooling to room temperature, a polyisocyanate mixture 1 according to the invention was obtained with the following characteristics:

[0164] NCO content: 19.5% monomeric PDI: 0.07%

[0165] Viscosity (23°C): 3100 mPas

[0166] Color number (Hazen): 29

[0167] The polyisocyanate mixture 1 according to the invention has a viscosity comparable to that of the standard HDI trimer N2).

[0168] (Production of polyisocyanate mixture 2)

[0169] 50 parts by weight of polyisocyanate M1) were mixed homogeneously with 50 parts by weight of polyisocyanate N1) at 50°C by stirring. After cooling to room temperature, a polyisocyanate mixture 2 according to the invention was obtained with the following characteristics:

[0170] NCO content: 18.0% monomeric PDI: 0.06%

[0171] Viscosity (23°C): 1300 mPas

[0172] Color number (Hazen): 28 The polyisocyanate mixture 2 according to the invention has a viscosity comparable to that of the low-viscosity HDI trimer N3).

[0173] Examples 3 - 6 (Coating composition and coating, according to the invention and comparison)

[0174] 166.9 parts by weight of the commercially available polyacrylate polyol Uralac CY240 EF-75 (Covestro AG, Leverkusen, DE) with a solids content of 74 wt.% and an OH content (based on the solids) of 4.0%, corresponding to an equivalent weight of 425 g / eq OH, were mixed with 2.9 parts by weight of a 10% solution of a commercially available leveling additive (BYK 331; BYK-Chemie GmbH, Wesel, DE) in butyl acetate, 5.8 parts by weight of a 1% solution of dibutyltin dilaurate (DBTL) in butyl acetate as catalyst, 1.9 parts by weight of a 50% solution of a commercially available light stabilizer (Tinuvin 123; BASF SE, Ludwigshafen, DE), Tinuvin 384-2 (BASF SE, Ludwigshafen, DE) (used as a 50% solution in butyl acetate) and the commercially available surface additive BYK-358 N (BYK-Chemie GmbH, Wesel, DE; used as supplied) were mixed homogeneously by intensive stirring at room temperature. Subsequently, the mixture was homogenized by adding an equal weight of- parts of a solvent mixture consisting of butyl acetate and xylene and further intensive stirring, a non-volatile content of 68 wt.% was achieved.

[0175] The polyisocyanate mixtures according to the invention or comparative polyisocyanates (component B) were stirred into this base paint component (component A) and the solids content of the finished coating compositions was adjusted with butyl acetate / xylene (1 : 1) to a flow time of approx. 20 s in an ISO cup with a 4 mm nozzle.

[0176] Table 1 : Compositions of the individual formulations To determine the pendulum damping according to König and to test solvent and gasoline resistance, the coating materials were applied to glass plates using a gravity-feed gun in a wet film thickness of 150 μm. After 10 minutes of flash-off at room temperature, they were cured within 30 minutes at 60°C. All glass plates were stored at room temperature for at least 48 hours prior to testing.

[0177] To determine scratch resistance, the coating materials were applied as clear coats using a gravity-feed gun (dry film thickness approx. 50 μm) to e-coated panels that had previously been coated with a commercially available 1-component OEM hydro-filler (dry film thickness approx. 35 μm) and a black 1-component OEM hydro-basecoat (dry film thickness approx. 15 μm). The clear coats were cured within 30 minutes at 60°C. All panels were stored at room temperature for at least 48 hours prior to testing.

[0178] Table 2: Results of the application tests

[0179] Comparison of Example 3 with Comparative Example 5 shows that the inventive polyisocyanate mixture 1 based on PDI as a crosslinker in an automotive refinish clearcoat results in properties comparable to those of the standard HDI trimer N2). Comparison of Example 4 with Comparative Example 6 shows that crosslinking with the inventive polyisocyanate mixture 2 based on PDI, which has a higher proportion of polyisocyanate M than the polyisocyanate mixture 1, significantly increases the scratch resistance of the automotive refinish clearcoat compared to the low-viscosity HDI polyisocyanate N3).

[0180] By appropriately selecting the proportion of polyisocyanate M in the polyisocyanate mixtures according to the invention, the scratch resistance of coatings can be specifically adjusted.

Claims

1 . Polyisocyanate mixture containing at least one polyisocyanate M) of the general formula (I) in which R represents a linear or branched, saturated or unsaturated aliphatic and / or saturated or unsaturated cycloaliphatic radical having (6 to 22) - p carbon atoms, each of which may optionally be substituted, R' and R" independently of one another represent hydrogen or an aliphatic radical having 1 to 10 carbon atoms, where at least one of the radicals R' and R" represents hydrogen, n represents an integer from 1 to 12, m represents an integer from 1 to 10 and p represents 0 or 1 and at least one polyisocyanate N) different from polyisocyanate M) having a uretdione, isocyanurate, iminooxadiazinedione, urethane, allophanate, biuret and / or oxadiazinetrione structure which carries aliphatically, cycloaliphatically, araliphatically and / or aromatically bound isocyanate groups, where the polyisocyanates M) and N) are present in a weight ratio to one another of 50:50 to 20:

80.

2. Polyisocyanate mixture according to claim 1, characterized in that the polyisocyanates M) and N) are present in a weight ratio to one another of 50:50 to 25:75, preferably 45:55 to 30:70 and particularly preferably 50:50 to 30:

70.

3. Polyisocyanate mixture according to claim 1 or 2, characterized in that it has an NCO content determined according to DIN EN ISO 11909:2007-05 of 6 to 24.4 wt.%, preferably of 8 to 23.2 wt.% and particularly preferably of 10 to 22.2 wt.%.

4. Polyisocyanate mixture according to one of claims 1 to 3, characterized in that the polyisocyanate N) contains aliphatically, araliphatically and / or cycloaliphatically bound isocyanate groups, preferably based on 1,5-diisocyanatopentane, 1,6-diisocyanatohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 1,3-bis(isocyanatomethyl)benzene, bis(isocyanatomethyl)norbornane and / or 4,4'-diisocyanatodicyclohexylmethane and particularly preferably at least isocyanurate structures based on 1,5-diisocyanatopentane, Contains 1,6-diisocyanatohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 1,3-bis(isocyanatomethyl)benzene, bis(isocyanatomethyl)norbornane and / or 4,4'-diisocyanatodicyclohexylmethane and very particularly preferably contains isocyanurate structures based on 1,5-diisocyanatopentane, 1,6-diisocyanatohexane and / or 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane.

5. Polyisocyanate mixture according to one of claims 1 to 4 having a shear rate of 250 s according to DIN EN ISO 3219:1994-10 -1 measured viscosity at 23°C of less than 5000 mPas, preferably less than 4000 mPas, particularly preferably less than 3500 mPas.

6. A process for the preparation of a polyisocyanate mixture, characterized in that at least one polyisocyanate M) of the general formula (I) in which R represents a linear or branched, saturated or unsaturated aliphatic and / or saturated or unsaturated cycloaliphatic radical having (6 to 22) - p carbon atoms, each of which may optionally be substituted, R' and R" independently of one another represent hydrogen or an aliphatic radical having 1 to 10 carbon atoms, where at least one of the radicals R' and R" represents hydrogen, n represents an integer from 1 to 12, m represents an integer from 1 to 10 and p represents 0 or 1 with at least one polyisocyanate N) different from polyisocyanate M) having a uretdione, isocyanurate, iminooxadiazinedione, urethane, allophanate, biuret and / or oxadiazinetrione structure which carries aliphatically, cycloaliphatically, araliphatically and / or aromatically bound isocyanate groups, so that the polyisocyanates M) and N) are mixed in a weight ratio to one another of 50:50 to 20:80, preferably of 50:50 to 25:75 and particularly preferably of 50:50 to 30 : 70, are present.

7. Use of the polyisocyanate mixture according to one of claims 1 to 5 or of the polyisocyanate mixture obtainable or prepared, preferably prepared directly, by the process according to claim 6 as a starting component in the production of polyurethane plastics, preferably for producing a coating on a substrate, wherein the substrate is preferably an optionally pretreated body, in particular of a vehicle, or parts thereof.

8. Polyurethane, polyurea and / or polythiourethane, obtainable or prepared by reacting at least one polyisocyanate mixture according to one of claims 1 to 5 with at least one hydroxy-, amino- and / or thiofunctional component.

9. Composition comprising either at least one polyisocyanate mixture according to one of claims 1 to 5 and at least one binder reactive towards isocyanate groups or comprising at least one polyisocyanate mixture obtainable or prepared by a process according to claim 6 and at least one binder reactive towards isocyanate groups.

10. Composition according to claim 9, characterized in that it contains the at least one binder reactive towards isocyanate groups in a component 1) and the at least one polyisocyanate mixture according to one of claims 1 to 5 in a component 2) or the at least one polyisocyanate mixture, obtainable or produced by a process according to claim 6, in a component 2) and / or that the at least one binder reactive towards isocyanate groups is a polyhydroxy compound, preferably a polyether polyol, polyester polyol, polyurethane polyol, polysiloxane polyol, polycarbonate polyol, polyether polyamine, polybutadiene polyol, polyacrylate polyol and / or polymethacrylate polyol and also copolymers thereof and particularly preferably a polyester polyol, polyacrylate polyol or any mixtures of the aforementioned.

11. Composition according to claim 9 or 10, characterized in that the at least one binder reactive towards isocyanate groups comprises at least one hydroxy-functional compound having a hydroxyl group content of > 2.0 wt.%, preferably > 3.0 wt.% and particularly preferably > 3.5 wt.%, based on the solids content of the binder reactive towards isocyanate groups.

12. Composition according to one of claims 9 to 11, characterized in that it is a coating composition which optionally contains one or more auxiliaries and additives.

13. A process for producing a coating on a substrate, comprising the following steps: a) providing an optionally pretreated substrate; b) applying at least one composition according to one of claims 9 to 12; c) curing the composition, optionally with the addition of heat.

14. Coated substrate obtainable or produced by a process according to claim 13, wherein the optionally pretreated substrate is preferably a body, in particular of a vehicle, or parts thereof and / or preferably comprises one or more of the materials selected from metal, plastic or mixtures thereof.

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