STOCK-STABLE PIGMENTED ISOCYANAT GROUP-CONTAINING FORMULAS WITH ISOCYANAT GROUP-CONTAINING GRINDING RESIN AND THEIR USE

Description

[0001] The invention relates to storage-stable pigmented formulations containing isocyanate groups, comprising at least one pigment a., at least one component containing isocyanate groups b., at least one wetting agent and / or dispersant c., at least one grinding resin containing isocyanate groups d., and optionally solvent e., wherein the formulation exhibits a viscosity increase of less than 500% after storage at 50°C for a period of at least 3 days. Furthermore, the invention relates to the use of such formulations.

[0002] Pigmented ink formulations containing polyurethanes for use in digital printing applications have been known for a long time. These formulations are predominantly non-reactive. Finely dispersed pigments or dyes dissolved in conventional solvents, water, or oil, are used. To fix the pigments, the formulations often contain a small amount of a binder; in special cases, this binder is a polyurethane. For example, WO 11152353 describes the modification of a pigment with polyurethane. This modification leads to particularly stable prints.

[0003] The treatment of pigments with isocyanates is also known in the literature. For example, US Pat. No. 3,156,576 from 1964 describes the modification of pigments such as carbon black, silicate, titanium dioxide, and similar compounds with isocyanates. The dry pigment is incorporated into a dry toluene / TDI mixture with a TDI content of 10%, and the excess liquid is then evaporated at 75°C. The modified, dry pigment is immediately incorporated into a silicone under exclusion of moisture, which is then cured.

[0004] US Pat. No. 4,075,152 describes a process for preventing pigment flocculation in two-component polyurethane coatings. For this purpose, an isocyanate / pigment slurry is first prepared and then directly mixed into a polyol. The resulting colored OH-functional polyurethane pastes exhibited no pigment flocculation.

[0005] Although the examples cited indicate that pretreatment of pigments with isocyanates can be advantageous, they do not provide any teaching on how to produce a storage-stable, pigmented formulation containing isocyanate groups.

[0006] US Pat. No. 6,341,856 describes the production of a reactive ink for digital printing. Compounds containing at least one CH-active group, compounds with blocked CH-reactive groups (which prevent the reaction of the active hydrogen with the CH-reactive group), emulsifiers, and pigments or dyes are processed into an inkjet ink that is stable at room temperature. Polyols and isocyanates are also explicitly mentioned as reactive components.

[0007] DE 198 58 817 A1 discloses aqueous reactive 2-component binder combinations for aqueous reactive filler compounds, processes for producing aqueous reactive filler compounds based on aqueous reactive 2-component binder combinations and the use of such filler compounds.

[0008] US 2006 014857 A1 relates to an aqueous, color and / or effect coating material free of rheology aids based on layered silicates, comprising (A) at least one water-soluble, water-dilutable and / or water-dispersible polyurethane selected from the group consisting of ionically or ionically and non-ionically stabilized polyurethanes grafted with olefinically unsaturated compounds and based on polyisocyanates selected from the group consisting of aliphatic, cycloaliphatic, aliphatic-cycloaliphatic, aromatic, aliphatic-aromatic and cycloaliphatic-aromatic polyisocyanates; (B) at least one color and / or effect pigment;(C) at least one dispersing agent for the color and / or effect pigments, selected from the group consisting of the reaction products of (c1) at least one functionalized copolymer containing (c11) at least one polymerized olefinically unsaturated monomer selected from the group consisting of olefinically unsaturated monomers containing at least one reactive functional group selected from the group consisting of isocyanate groups, anhydride groups, and epoxy groups; and (c12) at least one polymerized olefinically unsaturated monomer that is free of isocyanate-, anhydride-, and epoxy-reactive functional groups;(c 2) at least one homopolymeric polyalkylene glycol and (c 3) at least one compound of the general formula 1: NR 2 -C(O)-NR 2 (1), wherein the variables R are selected from the group consisting of hydrogen atoms and organic, saturated and unsaturated, substituted and unsubstituted, aliphatic, cycloaliphatic, aliphatic-cycloaliphatic, aromatic, aliphatic-aromatic and cycloaliphatic-aromatic radicals which contain at least one amino group -NH-, at least one oxygen atom -O- and / or at least one sulfur atom -S- and / or can be cyclically linked to one another, wherein at least one organic radical R is present and the radical R or at least one of the radicals R contains at least one reactive functional group selected from the group consisting of isocyanate-, anhydride- and epoxy-reactive groups; and (D) at least one rheology aid based on (meth)acrylate copolymers.;

[0009] DE 19858817 A1 discloses aqueous reactive fillers.

[0010] US 2006 / 014857 A1 discloses aqueous chromophores and / or effect-producing coating materials.

[0011] EP 2578646 A1 discloses polyurethane adhesive resin pigments, pigment dispersion compositions and inkjet ink compositions.

[0012] DE 60029067 T2 discloses inkjet processes using reactive dyes.

[0013] The blocking of the isocyanate component before mixing with the polyol component can be done either chemically or by encapsulation.

[0014] The disadvantage of this design is the blocking process. It is complex and therefore expensive. Furthermore, the isocyanate groups must first be unblocked, for example, by heating, before they are available for reaction.

[0015] The task was therefore to at least partially overcome at least one disadvantage of the state of the art.

[0016] A further object of the invention was to provide a pigment-containing formulation that contains reactive isocyanate groups during processing. These can then react with reactants directly after application without the need for complex deblocking.

[0017] Furthermore, it was an object of the invention to provide a pigment-containing formulation which has reactive isocyanate groups over the longest possible processing period, preferably over several weeks or preferably over several months.

[0018] Also disclosed is a process which makes it possible to generate a storage-stable formulation containing isocyanate groups.

[0019] A further object of the invention was to provide a formulation containing isocyanate groups as a color paste, preferably as an ink, in particular as an ink for digital printing.

[0020] A first aspect of the invention relates to a storage-stable formulation containing isocyanate groups comprising the components: a. 0.01 to 45% by weight of at least one pigment, b. 1 to 98% by weight of at least one component containing isocyanate groups and having free isocyanate groups, c. 0.01 to 20% by weight of at least one wetting agent and / or dispersant, d. 0.1 to 35% by weight of at least one grinding resin containing isocyanate groups and containing free isocyanate groups, and e. 0 to 80% by weight of solvent, in each case based on the total amount of the formulation, the sum of all constituents of the formulation not exceeding 100% by weight, characterized in that the formulation has a viscosity increase of less than 500% after storage at 50°C for a period of at least 3 days, based on the initial viscosity of the formulation, which after 1 hour after combining all the desired components, in particular components a. to e., wherein the viscosity determination is carried out in each case at 20 °C at a shear rate of 500 [l / s], wherein the molar ratio of the sum of all isocyanate groups of the isocyanate-containing formulation to the sum of all isocyanate-reactive groups which are not isocyanate groups in the formulation is at least 8:1. and wherein the isocyanate group-containing grinding resin d. has a viscosity in a range of 100 to 5,000 mPas and wherein the isocyanate group-containing grinding resin d. is selected from the group consisting of 1,4-diisocyanatobutane (BDI), 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 and 1,10-diisocyanatodecane, 1,3- and 1,4-bis-(isocyanatomethyl)benzene (xylylene diisocyanate; XDI), 1,3- and 1,4-bis(1-isocyanato-1-methylethyl)benzene (TMXDI), 2,4- and 2,6-diisocyanatotoluene (TDI), 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI) and 1,5-diisocyanatonaphthalene, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate; IPDI), 1-isocyanato-1-methyl-4(3)-isocyanatomethylcyclohexane, 2,4'- and 4,4'-diisocyanatodicyclohexylmethane (H12MDI), or a mixture of at least two of these and optionally oligomers and / or reaction products thereof.

[0021] The viscosity determination is preferably carried out using a Physica MCR 301 (Anton Paar GmbH) with a plate-on-plate (diameter 40 mm) measuring geometry at a measuring temperature of 20°C. It is preferred that, after storage at 50°C for a period of at least 3 days, or preferably at least 5 days, or preferably at least 7 days, or preferably at least 10 days, or preferably at least 14 days, the viscosity increase is less than 500%, preferably less than 300%, or preferably less than 200%, or preferably less than 100%, or preferably less than 50%, based on the initial viscosity of the formulation. According to the invention, the initial viscosity is defined as the viscosity after 1 hour following the combination of all desired components, in particular the selected components a. to e.

[0022] Preferably, the molar ratio of the sum of all isocyanate groups of the isocyanate-containing formulation, in particular the sum of all isocyanate groups of components b. and d., to the sum of all isocyanate-reactive groups in the isocyanate-containing formulation that are not isocyanate groups, is at least 11:1, or preferably at least 15:1, or preferably at least 20:1, or preferably at least 50:1, or preferably at least 100:1.

[0023] In a preferred embodiment of the formulation, the grinding resin d. containing isocyanate groups has a viscosity in a range from 200 to 2,000 mPas, particularly preferably in a range from 350 to 1,000 mPas.

[0024] In a preferred embodiment of the formulation, the formulation contains a. 0.1 to 15% by weight, or preferably 0.1 to 10% by weight, or preferably 0.2 to 8% by weight, or preferably 0.5 to 5% by weight of the at least one pigment; b. preferably 5 to 95% by weight, or preferably 10 to 93% by weight, or preferably 20 to 93% by weight, or preferably 40 to 93% by weight of the at least one isocyanate-containing component which has free isocyanate groups; c. 0.05 to 15% by weight, or preferably 0.1 to 10% by weight of the at least one wetting agent and / or dispersant; d. 0.5 to 25% by weight, or preferably 1 to 15% by weight of the at least one isocyanate-containing grinding resin containing free isocyanate groups; e. preferably 0 to 75% by weight, or preferably 0 to 50% by weight, or preferably 0 to 20% by weight, or preferably 0 to 10% by weight, or preferably 0.1 to 30% by weight of solvent; each based on the total amount of the formulation, whereby the sum of all components of the formulation does not exceed 100% by weight.

[0025] The invention preferably relates to a storage-stable isocyanate group-containing formulation comprising the components: a. 0.1 to 15% by weight, or preferably 0.1 to 10% by weight, or preferably 0.2 to 8% by weight, or preferably 0.5 to 5% by weight of the at least one pigment; b. preferably 5 to 95% by weight, or preferably 10 to 93% by weight, or preferably 20 to 93% by weight, or preferably 40 to 93% by weight of the at least one isocyanate-containing component which has free isocyanate groups; c. 0.05 to 15% by weight, or preferably 0.1 to 10% by weight of the at least one wetting agent and / or dispersant; d. 0.5 to 25% by weight, or preferably 1 to 15% by weight of the at least one isocyanate-containing grinding resin containing free isocyanate groups; e. 0 to 75% by weight, or preferably 0 to 50% by weight, or preferably 0 to 20% by weight, or preferably 0 to 10% by weight, or preferably 0.1 to 30% by weight of solvent; in each case based on the total amount of the formulation, wherein the sum of all components of the formulation does not exceed 100% by weight and wherein the molar ratio of the sum of all isocyanate groups of the isocyanate-containing formulation to the sum of all isocyanate-reactive groups which are not isocyanate groups in the formulation is at least 8:1.

[0026] Preferably, the formulation contains a. 0.5 to 5 wt.% of the at least one pigment; b. 40 to 93 wt.% of the at least one isocyanate-containing component having free isocyanate groups; c. 0.1 to 10 wt.% of the at least one wetting agent and / or dispersant; d. 1 to 15 wt.% of the at least one isocyanate-containing grinding resin containing free isocyanate groups; e. 0 to 30 wt.% solvent, in each case based on the total amount of the formulation, wherein the sum of all components of the formulation does not exceed 100% by weight, wherein the molar ratio of the sum of the isocyanate groups of components b and d to the sum of all isocyanate-reactive groups in the formulation which are not isocyanate groups is at least 8:1, more preferably at least 11:1, particularly preferably at least 20:1.

[0027] Stable, in particular storage-stable, formulations containing isocyanate groups within the meaning of the invention are characterized in that the viscosity during storage at 50°C for at least 3 days, or preferably at least 5 days, or preferably at least 7 days, or preferably at least 10 days, or preferably at least 14 days only exhibits a viscosity increase of ≤ 500%, preferably of ≤ 300%, or preferably of ≤ 200%, or preferably of ≤ 100%, or preferably of ≤ 50%. Particularly preferably, the viscosity increase during storage of the formulation at 50°C for 3 days is ≤ 100%, based on the initial viscosity.Furthermore, the increase in particle size in the isocyanate-containing formulation, measured by dynamic light scattering after redispersion of any soft sediments formed, based on Z-average, is preferably at most 500%, preferably at most 200%, preferably at most 100%, preferably at most 50%. For the purposes of the invention, soft sediments are understood to mean that the sediments redisperse upon shaking.

[0028] Further preferably, at the time of determining the initial viscosity or after storage of at least 3 days, or preferably of at least 10 days, or preferably of at least 14 days, the formulation has a content of isocyanate groups in a range from 2 to 60% by weight, or preferably in a range from 3 to 50% by weight, or preferably in a range from 4 to 35% by weight, or preferably in a range from 5 to 20% by weight, based on the total amount of the formulation.

[0029] It is preferred that the isocyanate-containing formulation preferably does not contain any hard sediments. For the purposes of the invention, hard sediments mean sediments that cannot be redispersed by shaking. Shaking is preferably understood to mean shaking by hand or using conventional laboratory shakers. An IKA® VORTEX 2 operating at a speed of 2000 rpm can be used as a conventional laboratory shaker, with the shaking time preferably being in a range of 10 to 60 seconds, or more preferably in a range of 15 to 40 seconds. Pigments

[0030] Any pigments that a person skilled in the art would use for a stable formulation can be used as pigments. Pigments that are preferably used as component a. can be divided into several classes: organic or inorganic pigments that are dispersed as a solid dispersion in the form of particles, if necessary with the aid of a suitable wetting and / or dispersing agent. The pigments are used either individually or as a mixture of at least two of them.

[0031] The at least one pigment can be selected from a wide variety of pigment classes. If the application involves printing techniques, in particular inkjet printing, pigment particles with a diameter of less than or equal to 100 µm, preferably less than or equal to 10 µm, or preferably less than or equal to 5 µm, are advantageous.

[0032] Examples of suitable organic pigments are: Monoazopigmente: C.I. Pigment Brown 25;C.I. Pigment Orange 5, 13, 36 und 67; C.I. Pigment Red 1, 2, 3, 5, 8, 9, 12, 17, 22, 23, 31, 48 : 1, 48 : 2, 48 : 3, 48 : 4, 49, 49 : 1, 52 : 1, 52 : 2, 53, 53 : 1, 53 : 3, 57 : 1, 251, 112, 146, 170, 184, 210 und 245; C.I. Pigment Yellow 1, 3, 73, 74, 65, 97, 151 und 183; Naphthol AS Pigmente: C.I. Pigment Brown 1; C.I. Pigment Orange 22, 24, 38; C.I. Pigment Red 2, 5, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 21, 22, 23, 31, 32, 95, 112, 114, 119, 136, 146,147, 148, 150, 151, 164, 170, 184, 187, 188, 210, 212, 213, 222, 223, 237, 239, 240, 243, 245, 247, 253, 256, 258, 261, 266, 267, 268, 269; C.I. Pigment Violet 13, 25, 44, 50; Disazopigmente: C.I. Pigment Brown 23; C.I. Pigment Orange 15, 16, 34 und 44; C.I. Pigment Red 144, 166, 214, 220, 221 242 und 248; C.I. Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 90, 106, 113, 114, 121, 126, 127, 152, 155, 170, 171, 172, 174, 176 und 188; Benzimidazolonpigmente: C.I. Pigment Brown 25 C.I.Orange 36, 60, 62, 72 C.I. Pigment Red 171, 175, 176, 185, 208 C.I. Yellow 120, 151, 154, 175, 180, 181, 194 C.I. Violet 32; Anthanthronpigmente: C.I. Pigment Orange 77; C.I. Pigment Red 168 (C.I. Vat Orange 3); Anthrachinonpigmente: C.I. Pigment Yellow 147, 193, 199, und 202;; C.I. Pigment Violet 31; Anthrapyrimidinpigmente: C.I. Pigment Yellow 108 (C.I. Vat Yellow 20); Chinacridonpigmente: C.I. Pigment Red 122, 202 und 206; C.I. Pigment Violet 19; Chinophthalonpigmente: C.I. Pigment Yellow 138; Diketopyrrolopyrrol-Pigmente C.I. Pigment Orange 71 und 73; C.I. Pigment Red 254, 255,264, und 272 Dioxazinpigmente: C.I. Pigment Violet 23 und 37; Flavanthronpigmente: C.I. Pigment Yellow 24 (C.I. Vat Yellow 1); Indanthronpigmente: C.I. Pigment Blue 60 (C.I. Vat Blue 4) und 64 (C.I. Vat Blue 6); Isoindolinpigmente: C.I. Pigment Brown 38; C.I. Pigment Orange 66 und 69; C.I. Pigment Red 260; C.I. Pigment Yellow 139 und 185; Isoindolinonpigmente: C.I. Pigment Orange 61; C.I.Pigment Red 257 und 260; C.I. Pigment Yellow 109, 110, 173 und 185; Isoviolanthronpigmente: C.I. Pigment Violet 31 (C.I. Vat Violet 1); Metallkomplexpigmente: C.I. Pigment Green 8 und 10; C.I. Pigment Red 257 C.I. Pigment Yellow 117, 129, 150 und 153; Perinonpigmente: C.I. Pigment Orange 43 (C.I. Vat Orange 7); C.I. Pigment Red 194 (C.I. Vat Red 15); Perylenpigmente: C.I. Pigment Black 31 und 32; C.I. Pigment Red 123, 149, 178, 179 (C.I. Vat Red 23), 190 (C.I. Vat Red 29) und 224; C.I. Pigment Violet 29; Phthalocyaninpigmente: C.I. Pigment Blue 15, 15 : 1, 15 : 2, 15 : 3, 15 : 4, 15 : 6 und 16; C.I. Pigment Green 7 und 36; Pyranthronpigmente: C.I. Pigment Orange 40 und 51; C.I. Pigment Red 216 (C.I. Vat Orange 4), 226; Thioindigopigmente: C.I. Pigment Red 88 und 181 (C.I. Vat Red 1); C.I. Pigment Violet 38 (C.I. Vat Violet 3); Triarylcarboniumpigmente: C.I. Pigment Blue 1, 2, 9, 10, 14, 61 und 62; C.I. Pigment Green 1 und 4; C.I. Pigment Red 81, 81 : 1 und 169; C.I.Pigment Violet 1, 2, 3, 27 and 39; CI Pigment Black 1 (aniline black); CI Pigment Yellow 101 (aldazine yellow); CI Pigment Brown 22; .

[0033] The at least one pigment is preferably selected from the group consisting of PB 15:4 (e.g. Hostaperm ®< Blue BT-617-D), PV 19 (e.g. Inkjet Magenta 5EB02), PY 155 (e.g. Inkjet Yellow 4GC) or a mixture of at least two thereof.

[0034] Examples of suitable inorganic pigments: White pigments: titanium dioxide (CI Pigment White 6), zinc white, pigment zinc oxide; zinc sulfide, lithopone; lead white; black pigments: iron oxide black (CI Pigment Black 11), iron manganese black, spinel black (CI Pigment Black 27); carbon black (CI Pigment Black 7); colored pigments: chromium oxide, chromium oxide hydrate green; chrome green (CI Pigment Green 48); cobalt green (CI Pigment Green 50); ultramarine green; cobalt blue (CI Pigment Blue 28 and 36); ultramarine blue; iron blue (CI Pigment Blue 27); manganese blue; ultramarine violet; cobalt and manganese violet; iron oxide red (CI Pigment Red 101); cadmium sulfoselenide (CI Pigment Red 108); molybdate red (CI Pigment Red 104); ultramarine red; Iron oxide brown, mixed brown, spinel and corundum phases (CI Pigment Brown 24, 29 and 31), chrome orange; iron oxide yellow (CI Pigment Yellow 42); nickel titanium yellow (CI Pigment Yellow 53; CI Pigment Yellow 157 and 164); chromium titanium yellow; cadmium sulfide and cadmium zinc sulfide (CI Pigment Yellow 37 and 35); chrome yellow (CIPigment Yellow 34), zinc yellow, alkaline earth chromates; Naples yellow; bismuth vanadate (CI Pigment Yellow 184); interference pigments: metallic effect pigments based on coated metal flakes; pearlescent pigments based on metal oxide-coated mica flakes; liquid crystal pigments.

[0035] The at least one pigment is preferably selected from the group consisting of PW 6 (e.g. Kronos ®< 2310), Pigment Black 6 or 7 (e.g. NIPex ®< 35) or a mixture thereof.

[0036] The isocyanate-containing component b. can be any component that contains at least one isocyanate group and would be selected by a person skilled in the art for the storage-stable formulation. Component b. preferably contains a polyisocyanate.

[0037] The term "polyisocyanate," as used here, is a collective term for compounds containing two or more isocyanate groups -N=C=O in the molecule. Preferred representatives of these polyisocyanates are diisocyanates. These have the general structure O=C=NRN=C=O, where R typically represents aliphatic, alicyclic, araliphatic, and / or aromatic radicals.

[0038] When "isocyanates" are referred to generally here, this refers equally to monoisocyanates and monomeric and / or oligomeric polyisocyanates. However, to understand many aspects of the invention, it is important to distinguish between monomeric diisocyanates and oligomeric polyisocyanates. When "oligomeric polyisocyanates" are referred to here, this refers to polyisocyanates composed of at least two monomeric diisocyanate molecules, i.e., compounds that represent or contain a reaction product of at least two monomeric diisocyanate molecules.

[0039] Preferably, at least one of the monomeric or oligomeric polyisocyanates contained in the isocyanate group-containing component b. has an (average) NCO functionality of 2.0 to 6.0, or preferably of 2.3 to 4.5.

[0040] Preferred monomeric polyisocyanates for use in the isocyanate component are those monomeric polyisocyanates with a molecular weight in the range of 140 to 400 g / mol that contain aliphatically, cycloaliphatically, araliphatically, and / or aromatically bound isocyanate groups. These polyisocyanates can be obtained in various ways, for example by phosgenation in the liquid or gas phase or by a phosgene-free route, such as thermal urethane cleavage.

[0041] Preferred monomeric isocyanates with aliphatically bound isocyanate groups are 1,4-diisocyanatobutane (BDI), 1,5-diisocyanatopentane (PDI), 1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane and 1,10-diisocyanatodecane.

[0042] In a preferred embodiment of the formulation, the isocyanate group-containing component b. selected from the group consisting of 1,4-diisocyanatobutane (BDI), 1,5-diisocyanatopentane (PDI), 1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane and 1,10-diisocyanatodecane, 1,3- and 1,4-bis-(isocyanatomethyl)benzene (xylylene diisocyanate; XDI), 1,3- and 1,4-bis(1-isocyanato-1-methylethyl)benzene (TMXDI), 2,4- and 2,6-diisocyanatotoluene (TDI), 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI) and 1,5-diisocyanatonaphthalene 1-Isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate; IPDI), 1-isocyanato-1-methyl-4(3)-isocyanatomethylcyclohexane, 2,4'- and 4,4'-diisocyanatodicyclohexylmethane (H12MDI) or a mixture of at least two thereof, and optionally oligomers and reaction products thereof.

[0043] The formulation contains the grinding resin containing isocyanate groups. selected from the group consisting of 1,4-diisocyanatobutane (BDI), 1,5-diisocyanatopentane (PDI), 1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane and 1,10-diisocyanatodecane, 1,3- and 1,4-bis-(isocyanatomethyl)benzene (xylylene diisocyanate; XDI), 1,3- and 1,4-bis(1-isocyanato-1-methylethyl)benzene (TMXDI), 2,4- and 2,6-diisocyanatotoluene (TDI), 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI) and 1,5-diisocyanatonaphthalene 1-Isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate; IPDI), 1-isocyanato-1-methyl-4(3)-isocyanatomethylcyclohexane, 2,4'- and 4,4'-diisocyanatodicyclohexylmethane (H12MDI) or a mixture of at least two thereof, and optionally oligomers and reaction products thereof.

[0044] The isocyanate-containing grinding resin d. and the isocyanate-containing component b. can be identical or different. Preferably, component b. and component d. are different.

[0045] Preferably, the isocyanate group-containing component b. comprises monomeric isocyanates with cycloaliphatically bound isocyanate groups selected from the group consisting of 1,3- and 1,4-diisocyanatocyclohexane, 1,4-diisocyanato-3,3,5-trimethylcyclohexane, 1,3-diisocyanato-2-methylcyclohexane, 1,3-diisocyanato-4-methylcyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate; IPDI), 1-isocyanato-1-methyl-4(3)-isocyanatomethylcyclohexane, 2,4'- and 4,4'-diisocyanatodicyclohexylmethane (H12MDI), 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane, bis(isocyanatomethyl)norbornane (NBDI), 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-Diisocyanato-adamantane and 1,3-Dimethyl-5,7-diisocyanatoadamantane.

[0046] Preferred monomeric isocyanates with araliphatically bound isocyanate groups are 1,3- and 1,4-bis-(isoisocyanatomethyl)benzene (xylylene diisocyanate; XDI), 1,3- and 1,4-bis(1-isocyanato-1-methylethyl)benzene (TMXDI).

[0047] Preferred monomeric isocyanates with aromatically bound isocyanate groups are 2,4- and 2,6-diisocyanatotoluene (TDI), 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI) and 1,5-diisocyanatonaphthalene.

[0048] Other suitable diisocyanates can also be found, for example, in Justus Liebig's Annalen der Chemie Volume 562 (1949), pp. 75 - 136.

[0049] Preferably, the isocyanate-containing component b contains at least 40% by weight, preferably at least 50% by weight, or preferably at least 60% by weight, or preferably at least 70% by weight, or preferably at least 80% by weight, or preferably at least 90% by weight of aliphatic or cycloaliphatic isocyanates, based on the total amount of the isocyanate-containing component b.

[0050] In a preferred embodiment of the formulation, the formulation comprises the isocyanate group-containing component b., wherein the isocyanate group-containing component b. consists of aliphatic or cycloaliphatic isocyanates.

[0051] Preferably, at least one polyisocyanate can be used as component b containing isocyanate groups. Preferably usable oligomeric polyisocyanates are obtainable from the above-described monomeric polyisocyanates by the process of "modifying" monomeric polyisocyanates described in the following section. Oligomeric polyisocyanates can be obtained by modifying individual monomeric polyisocyanates mentioned above. However, it is also possible to modify mixtures of at least two of the above-mentioned monomeric polyisocyanates to obtain oligomeric polyisocyanates composed of at least two different monomers.

[0052] The production of oligomeric polyisocyanates from monomeric diisocyanates is also referred to here as the modification of monomeric diisocyanates. This "modification," as used here, refers to the reaction of monomeric diisocyanates to form oligomeric polyisocyanates with uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione, and / or oxadiazinetrione structures.

[0053] For example, hexamethylene diisocyanate (HDI) is a "monomeric diisocyanate" because it contains two isocyanate groups and is not a reaction product of at least two polyisocyanate molecules:

[0054] Reaction products of at least two HDI molecules that still contain at least two isocyanate groups are, in contrast, "oligomeric polyisocyanates" within the meaning of the invention. Examples of such "oligomeric polyisocyanates" based on monomeric HDI include HDI isocyanurate and HDI biuret, each of which is composed of three monomeric HDI building blocks:

[0055] According to the invention, the oligomeric polyisocyanates may, in particular, have uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione, and / or oxadiazinetrione structures. According to one embodiment of the invention, the oligomeric polyisocyanates have at least one of the following oligomeric structure types or mixtures thereof:

[0056] It is advantageous to use oligomeric polyisocyanates, which are a mixture of at least two oligomeric polyisocyanates, where the at least two oligomeric polyisocyanates differ in their structure. This structure is preferably selected from the group consisting of uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione, and oxadiazinetrione structures, and mixtures thereof. Such starting mixtures can influence the Tg value, particularly compared to crosslinking reactions with oligomeric polyisocyanates of only one defined structure, which is advantageous for many applications.

[0057] Preferably, in the disclosed process, an isocyanate group-containing component b. is used which contains at least one oligomeric polyisocyanate with biuret, allophanate, isocyanurate, and / or iminooxadiazinedione structure and optionally mixtures thereof.

[0058] The oligomeric polyisocyanate contained in the isocyanate-containing component b. is preferably one that contains only a single, defined oligomeric structure, for example, exclusively or predominantly an isocyanurate structure. However, due to the manufacturing process, several different oligomeric structures are generally present side by side in the oligomeric polyisocyanates used according to the invention.

[0059] In the context of the present invention, oligomeric polyisocyanate is considered to be composed of a single defined oligomeric structure if an oligomeric structure selected from uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure is present to at least 50 mol%, preferably 60 mol%, more preferably 70 mol%, particularly preferably 80 mol%, in particular 90 mol%, in each case based on the sum of the oligomeric structures present from the group consisting of uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and oxadiazinetrione structure in the oligomeric polyisocyanate.

[0060] Preferably, an oligomeric polyisocyanate of a single defined oligomeric structure is used, wherein the oligomeric structure is selected from uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure and is present to an extent of at least 50 mol%, preferably 60 mol%, more preferably 70 mol%, particularly preferably 80 mol%, in particular 90 mol%, in each case based on the sum of the oligomeric structures present from the group consisting of uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and oxadiazinetrione structure in the oligomeric polyisocyanate.

[0061] The oligomeric polyisocyanates are preferably those that primarily have an isocyanurate structure and may contain the above-mentioned uretdione, allophanate, biuret, iminooxadiazinedione, and / or oxadiazinetrione structures only as by-products. Thus, one embodiment of the invention provides for the use of an oligomeric polyisocyanate with a single, defined oligomeric structure, wherein the oligomeric structure is an isocyanurate structure and is present in the polyisocyanate to an extent of at least 50 mol%, preferably 60 mol%, more preferably 70 mol%, particularly preferably 80 mol%, and in particular 90 mol%, based in each case on the sum of the oligomeric structures present from the group consisting of uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione, and oxadiazinetrione structures.

[0062] It is also possible to use oligomeric polyisocyanates which largely do not have an isocyanurate structure and mainly contain at least one of the above-mentioned uretdione, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure types. According to a particular embodiment of the invention, the oligomeric polyisocyanate used consists of at least 50 mol%, preferably 60 mol%, more preferably 70 mol%, particularly preferably 80 mol%, in particular 90 mol%, in each case based on the sum of the oligomeric structures present from the group consisting of uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and oxadiazinetrione structure in the polyisocyanate, of oligomeric polyisocyanates which have a structure type selected from the group consisting of uretdione, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure.

[0063] Preference is given to using a low-isocyanurate polyisocyanate which, based on the sum of the oligomeric structures present from the group consisting of uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and oxadiazinetrione structure in the polyisocyanate, has at most 50 mol%, preferably at most 40 mol%, more preferably at most 30 mol%, particularly preferably at most 20 mol%, 10 mol% or 5 mol% of isocyanurate structures.

[0064] Preference is given to using an oligomeric polyisocyanate of a single defined oligomeric structure type, wherein the oligomeric structure type is selected from the group consisting of uretdione, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure and this structure type is present to at least 50 mol%, preferably 60 mol%, preferably 70 mol%, particularly preferably 80 mol%, in particular 90 mol%, based on the sum of the oligomeric structures present from the group consisting of uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and oxadiazinetrione structure in the polyisocyanate.

[0065] The proportions of uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione, and / or oxadiazinetrione structures in the isocyanate-containing component b can be determined, for example, by NMR spectroscopy. 13C NMR spectroscopy, preferably proton-decoupled, is preferred, since the aforementioned oligomeric structures yield characteristic signals.

[0066] Manufacturing processes for the oligomeric polyisocyanates with uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure preferably used in the isocyanate group-containing component b. are 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 and EP-A 0 798 299.

[0067] A usable oligomeric polyisocyanate is preferably defined by containing oligomeric polyisocyanates obtained from monomeric diisocyanates, regardless of the type of modification reaction used, while maintaining a degree of oligomerization of 5 to 45%, preferably 10 to 40%, particularly preferably 15 to 30%. "Degree of oligomerization" is understood to mean the percentage of the isocyanate groups originally present in the starting mixture that is consumed during the production process to form uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione, and / or oxadiazinetrione structures.

[0068] The use of an isocyanate-terminated prepolymer as the oligomeric polyisocyanate is preferred. These prepolymers are known to those skilled in the art and can be obtained by reacting an excess of a suitable monomeric isocyanate, as described above, with a suitable compound bearing isocyanate-reactive groups.

[0069] For the purposes of the present invention, isocyanate-reactive groups are understood to mean amine, amide, urethane, alcohol, thiol, epoxide, carboxylic acid, carboxylic anhydride groups, or groups containing Zerewitinoff-active hydrogen. For the definition of Zerewitinoff-active hydrogen, reference is made to Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart. Isocyanate-reactive groups are preferably understood to be OH, NH, and / or SH. Although isocyanate groups can also react with themselves, these are expressly not included here.

[0070] Examples of compounds with isocyanate-reactive groups are mono-, di- and polyhydric alcohols with primary, secondary and tertiary OH groups, analogous thiols, polyols, e.g. polyether, polyester, polyacrylate, polycarbonate polyols, analogous polythiols, sulfur-containing hydroxy compounds, amines (e.g. primary, secondary, aliphatic, cycloaliphatic, aromatic, sterically hindered), polyamines and aspartic acid esters.

[0071] Alcohols can be, for example, low molecular weight diols (e.g. 1,2-ethanediol, 1,3- or 1,2-propanediol, 1,4-butanediol), triols (e.g. glycerol, trimethylolpropane) and tetraols (e.g. pentaerythritol), but also higher molecular weight polyhydroxy compounds such as polyether polyols, polyester polyols, polycarbonate polyols, polysiloxane polyols, and polybutadiene polyols.

[0072] Polyether polyols can be prepared in a conventional manner by alkoxylation of suitable starter molecules under base catalysis or using double metal cyanide compounds (DMC compounds). Suitable starter molecules for the production of polyether polyols include, for example, simple, low-molecular-weight polyols, water, organic polyamines with at least two NH bonds, or any mixtures of such starter molecules.Preferred starter molecules for the preparation of polyether polyols by alkoxylation, particularly by the DMC process, are, in particular, simple polyols such as ethylene glycol, 1,3-propylene glycol and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, glycerol, trimethylolpropane, pentaerythritol, as well as low-molecular-weight, hydroxyl-containing esters of such polyols with dicarboxylic acids of the type exemplified below, or low-molecular-weight ethoxylation or propoxylation products of such simple polyols, or any mixtures of such modified or unmodified alcohols. Alkylene oxides suitable for alkoxylation are, in particular, ethylene oxide and / or propylene oxide, which can be used in any order or as a mixture during the alkoxylation.

[0073] Polyester polyols can be prepared in a known manner by polycondensation of low molecular weight polycarboxylic acid derivatives, such as succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, succinic acid, dimer fatty acid, trimer fatty acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, citric acid or trimellitic acid, with low molecular weight polyols, such as ethylene glycol, diethylene glycol, neopentyl glycol, hexanediol, butanediol, propylene glycol, glycerol, trimethylolpropane, 1,4-hydroxymethylcyclohexane, 2-methyl-1,3-propanediol, butanetriol-1,2,4, triethylene glycol, Tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycol,or by ring-opening polymerization of cyclic carboxylic acid esters, such as ε-caprolactone. Furthermore, hydroxycarboxylic acid derivatives, such as lactic acid, cinnamic acid, or ω-hydroxycaproic acid, can also be polycondensed to polyester polyols. However, polyester polyols of oleochemical origin can also be used. Such polyester polyols can be produced, for example, by complete ring opening of epoxidized triglycerides of an at least partially olefinically unsaturated fatty acid-containing fat mixture with one or more alcohols having 1 to 12 carbon atoms, followed by partial transesterification of the triglyceride derivatives to alkyl ester polyols having 1 to 12 carbon atoms in the alkyl radical.

[0074] The preparation of suitable polyacrylate polyols is known per se to the person skilled in the art. They are obtained by radical polymerization of olefinically unsaturated monomers containing hydroxyl groups or by radical copolymerization of olefinically unsaturated monomers containing hydroxyl groups with, optionally, other olefinically unsaturated monomers, such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, styrene, acrylic acid, acrylonitrile, and / or methacrylonitrile. Suitable olefinically unsaturated monomers containing hydroxyl groups are in particular 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, the hydroxypropyl acrylate isomer mixture obtainable by addition of propylene oxide to acrylic acid and the hydroxypropyl methacrylate isomer mixture obtainable by addition of propylene oxide to methacrylic acid.Suitable radical initiators are those from the group of azo compounds, such as azoisobutyronitrile (AIBN), or from the group of peroxides, such as di-tert-butyl peroxide.

[0075] Amines can be any mono- or polyvalent amines, such as: B. methylamine, ethylamine, n-propylamine, isopropylamine, the isomeric butylamines, pentylamines, hexylamines and octylamines, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine, cyclohexylamine, the isomeric methylcyclohexylamine, aminomethylcyclohexane, dimethylamine, diethylamine, Dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, bis-(2-ethylhexyl)amine, N-methyl- and N-ethylcyclohexylamine, dicyclohexylamine, hydrazine, ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 2-methyl-pentamethylenediamine, 1,6-diaminohexane, 2,2,4- or 2,4,4-trimethylhexamethylenediamine, 1,2-diaminocyclohexane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane (isophoronediamine, IPDA), 4,4'-diaminodicyclohexyl-methane, pyrrolidine, piperidine, piperazine, (3-aminopropyl)-trimethoxysilane, (3-aminopropyl)-triethoxysilane and (3-Methylamino)propyl-trimethoxysilane, amino alcohols, such as2-aminoethanol, 2-methylaminoethanol, 2-(dimethylamino)-ethanol, 2-(diethylamino)-ethanol, 2-(dibutyl-amino)-ethanol, diethanolamine, N-methyl-diethanolamine, triethanolamine, 3-amino-1-propanol, 3-dimethylamino-1-propanol, 1-amino-2-propanol, 1-Dimethylamino-2-propanol, 1-diethylamino-2-propanol, bis-(2-hydroxypropyl)-amine, bis-(2-hydroxypropyl)-methylamine, 2-(hydroxyethyl)-bis-(2-hydroxypropyl)-amine, tris-(2-hydroxypropyl)-amine, 4-amino-2-butanol, 2-amino-2-methylpropanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-hydroxypropyl-1,3-propanediol and N-(2-hydroxyethyl)-piperidine, etheramines, such as 2-methoxyethylamine, 3-methoxypropylamine, 2-(2-dimethylaminoethoxy)-ethanol and 1,4-bis-(3-aminopropoxy)-butane or aromatic di- and triamines with at least one alkyl substituent having 1 to 3 carbon atoms on the aromatic ring, such as2,4-toluenediamine, 2,6-toluenediamine, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1,3-diethyl,2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3,5-triethyl-2,6-diaminobenzene, 3,5,3',5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 1-ethyl-2,4-diaminobenzene, 1-ethyl-2,6-diaminobenzene, 2,6-diethylnaphthylene-1,5-diamine, 4,4'-Methylenebis-(2,6-Diisopropylaniline).

[0076] Furthermore, polyamines, such as the polyaspartic acid derivatives known from EP-B 0 403 921, or polyamines whose amino groups are in blocked form, such as polyketimines, polyaldimines, or oxazolanes, can also be used. Under the influence of moisture, these blocked amino groups form free amino groups and, in the case of oxazolanes, also free hydroxyl groups, which can react with isocyanate groups by crosslinking.

[0077] Suitable amino-functional components are, in particular, polyaspartic acid esters, such as those obtainable, for example, by the process of EP-B 0 403 921 by reacting diamines with fumaric acid or maleic acid esters.

[0078] Preferred amino-functional compounds are polyetherpolyamines having 2 to 4, preferably 2 to 3, and particularly preferably 2 aliphatically bonded primary amino groups and a number-average molecular weight Mn of 148 to 12,200, preferably 148 to 8,200, particularly preferably 148 to 4,000, and most preferably 148 to 2,000 g / mol. Particularly suitable thiols are compounds that have at least two thiol groups per molecule.

[0079] Preferred polythiols are, for example, selected from the group consisting of simple alkanethiols, such as methanedithiol, 1,2-ethanedithiol, 1,1-propaneedithiol, 1,2-propaneedithiol, 1,3-propaneedithiol, 2,2-propaneedithiol, 1,4-butaneedithiol, 2,3-butaneedithiol, 1,5-pentaneedithiol, 1,6-hexaneedithiol, 1,2,3-propanetrithiol, 1,1-cyclohexaneedithiol, 1,2-cyclohexaneedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol or 2-methylcyclohexane-2,3-dithiol, polythiols containing thioether groups, such as e.g. B. 2,4-dimercaptomethyl-1,5-dimercapto-3-thiapentane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimer-capto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,6-bis-(mercaptoethylthio)-1,10-di-mercapto-3,8-dithiadecane, 4,5-bis-(mercaptoethylthio)-1,10-dimercapto-3,8-dithiadecane, tetrakis-(mercaptomethyl)methane, 1,1,3,3-Tetrakis(mercaptomethylthio)propane, 1,1,5,5-Tetrakis(mercapto-methylthio)-3-thiapentan, 1,1,6,6-Tetrakis(mercaptomethylthio)-3,4-dithiahexan, 2-Mercaptoethylthio-1,3-dimercaptopropan, 2,3-Bis(mercaptoethylthio)-1-mercaptopropan, 2,2-Bis(mercaptomethyl)-1,3-dimercaptopropan, Bis-(mercaptomethyl)sulfid, Bis(mercaptomethyl)disulfid, Bis(mercaptoethyl)-sulfid, Bis(mercapto-ethyl)disulfid, Bis(mercaptopropyl)sulfid, Bis(mercaptopropyl)disulfid, Bis(mercaptomethyl-thio)methan, Tris(mercaptomethylthio)methan, Bis(mercaptoethylthio)methan, Tris(mercapto-ethylthio)methan, Bis(mercaptopropylthio)methan, 1,2-Bis(mercaptomethylthio)ethan, 1,2-Bis-(mercaptoethylthio)ethan, 2-Mercaptoethylthio)ethan, 1,3-Bis(mercaptomethylthio)propan, 1,3-Bis(mercaptopropylthio)propan, 1,2,3-Tris(mercaptomethylthio)propan, 1,2,3-Tris(mercapto-ethylthio)propan, 1,2,3-Tris(mercaptopropylthio)propan, Tetrakis(mercaptomethylthio)methan, Tetrakis(mercaptoethylthiomethyl)methan, Tetrakis(mercaptopropylthiomethyl)methan, 2,5-Dimercapto-1,4-dithian, 2,5-Bis(mercaptomethyl)-1,4-dithian und dessen gemäß JP-A 07118263 erhältliche Oligomere, 1,5-Bis(mercaptopropyl)-1,4-dithian, 1,5-Bis(2-mercaptoethylthiomethyl)-1,4-dithian, 2-Mercaptomethyl-6-mercapto-1,4-dithiacycloheptan, 2,4,6-Trimercapto-1,3,5-trithian, 2,4,6-Trimercaptomethyl-1,3,5-trithian oder 2-(3-Bis(mercaptomethyl)-2-thiapropyl)-1,3-dithiolan, Polyesterthiolen, wie z. B. Ethylenglycol-bis(2-mercaptoacetat), Ethylenglycol-bis(3-mercaptopropionat), Diethylenglycol(2-mercaptoacetat), Diethylenglycol(3-mercaptopropionat), 2,3-Dimercapto-1-propanol(3-mercaptopropionat), 3-Mercapto-1,2-propandiol-bis(2-mercapto-acetat), 3-Mercapto-1,2-propandiol-bis(3-mercaptopropionat), Trimethylolpropan-tris(2-mercapto-acetat), Trimethylolpropan-tris(3-mercaptopropionat), Trimethylolethan-tris(2-mercaptoacetat), Trimethylolethan-tris(3-mercaptopropionat), Pentaerythrit-tetrakis(2-mercaptoacetat), Pentaerythrit-tetrakis(3-mercaptopropionat), Glycerin-tris(2-mercaptoacetat),Glycerin-tris(3-mercaptopropionat), 1,4-Cyclohexandiol-bis(2-mercaptoacetat), 1,4-Cyclohexandiol-bis(3-mercaptopropionat), Hydroxy-methylsulfid-bis(2-mercaptoacetat), Hydroxymethylsulfid-bis(3-mercaptopropionat), Hydroxyethyl-sulfid(2-mercaptoacetat), Hydroxyethylsulfid(3-mercaptopropionat), Hydroxymethyldisulfid(2-mercaptoacetat), Hydroxymethyldisulfid(3-mercaptopropionat), (2-Mercaptoethylester)thioglycolat oder Bis(2-mercaptoethylester)thiodipropionat und aromatischen Thioverbindungen, wie z. B. 1,2-Dimercaptobenzol, 1,3-Dimercaptobenzol, 1,4-Dimercaptobenzol, 1,2-Bis(mercaptomethyl)benzol, 1,4-Bis(mercaptomethyl)benzol, 1,2-Bis(mercaptoethyl)benzol, 1,4-Bis(mercaptoethyl)benzol, 1,2,3-Trimercaptobenzol, 1,2,4-Trimercaptobenzol, 1,3,5-Trimercaptobenzol, 1,2,3-Tris-(mercaptomethyl)benzol, 1,2,4-Tris(mercaptomethyl)benzol, 1,3,5-Tris(mercaptomethyl)benzol, 1,2,3-Tris-(mercaptoethyl)benzol, 1,3,5-Tris(mercaptoethyl)benzol, 1,2,4-Tris(mercaptoethyl)-benzol, 2,5-Toluoldithiol, 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 1,2,3,4-tetramercaptobenzene, 1,2,3,5-tetramercapto-benzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis(mercaptomethyl)benzene, 1,2,3,5-tetrakis(mercaptomethyl)benzene, 1,2,4,5-tetrakis(mercaptomethyl)benzene, 1,2,3,4-tetrakis(mercapto-ethyl)benzene, 1,2,3,5-tetrakis(mercaptoethyl)benzene, 1,2,4,5-Tetrakis(mercaptoethyl)benzene, 2,2'-Dimercaptobiphenyl, or 4,4'-Dimercaptobiphenyl. Such polythiols can be used individually or in any mixtures.

[0080] Sulfur-containing hydroxy compounds are also suitable. Such compounds preferably contain at least one sulfur atom in the form of thio groups, thioether groups, thioester urethane groups, ester thiourethane groups, and / or polythioester thiourethane groups, as well as at least one OH group.

[0081] Preferred sulfur-containing hydroxy compounds can be selected from the group consisting of simple mercapto alcohols, such as 2-mercaptoethanol, 3-mercaptopropanol, 1,3-dimercapto-2-propanol, 2,3-dimercaptopropanol or dithioerythritol, alcohols containing thioether structures, such as di(2-hydroxyethyl) sulfide, 1,2-bis(2-hydroxyethylmercapto)ethane, bis(2-hydroxyethyl) disulfide or 1,4-dithiane-2,5-diol, and sulfur-containing diols with polyesterurethane, polythioesterurethane, polyesterthiourethane or polythioesterthiourethane structure of the type mentioned in EP-A 1 640 394. Such sulfur-containing hydroxy compounds can be used individually or in the form of any desired mixtures with one another.

[0082] Particularly preferred sulfur-containing compounds are polyether and polyester thiols of the type mentioned. Very particularly preferred compounds can be selected from the group consisting of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate) and Pentaerythritol tetrakis(3-mercaptopropionate).

[0083] Carboxylic acids, carboxylic anhydrides and epoxides are also suitable as compounds with isocyanate-reactive groups.

[0084] It is also possible that the isocyanate-reactive component comprises mixtures of different compounds with isocyanate-reactive groups.

[0085] In principle, the isocyanate-containing component b can contain any mixture of different polyisocyanates. These can be the mixtures of oligomeric and monomeric polyisocyanates described above. They can also be mixtures of various isocyanate-terminated prepolymers. By freely combining all suitable polyisocyanates, it is possible to adjust the properties of the formulation and the resulting coatings as desired.

[0086] It is also preferred for the isocyanate-containing component b. to mix isocyanate-terminated prepolymers with monomeric or oligomeric polyisocyanates. This embodiment of the invention has the advantage that monomeric and / or oligomeric polyisocyanates can be used to reduce the viscosity of an isocyanate-terminated prepolymer. Since the monomeric / oligomeric polyisocyanates can be crosslinked with each other and with the isocyanate-terminated prepolymer through their isocyanate groups, they are bound in the formulation at the end of their preparation. They thus act as reactive diluents.

[0087] In a preferred embodiment of the formulation, the formulation has at least one of the following properties at room temperature (23°C): (A) an initial viscosity in a range from 1 to 200 mPas, preferably from 1 to 100 mPas, or preferably from 5 to 50 mPas, or preferably from 5 to 20 mPas; (B) an initial viscosity in a range from 30 to 1000 mPas, preferably from 50 to 500 mPas, or preferably from 100 to 500 mPas; (C) an initial viscosity in a range from 50 to 2000 mPas, or preferably from 100 to 1500 mPas, or preferably from 150 to 1000 mPas; (D) an initial viscosity in a range from 1,000 to 100,000 mPas, preferably from 2,000 to 90,000 mPas, or preferably from 2,500 to 50,000 mPas; (E) a content of isocyanate groups of less than 60% by weight, preferably less than 50% by weight, or preferably less than 30% by weight, or preferably less than 10% by weight, or preferably less than 5% by weight, or based on the total amount of the formulation; wherein the formulation has one of the properties selected from (A) to (D) in combination with property (E). Viscosities are measured according to the procedure described under "Measurement Methods."

[0088] Furthermore, the formulation preferably has a content of isocyanate groups in a range from 2 to 60% by weight, or preferably in a range from 3 to 50% by weight, or preferably in a range from 4 to 35% by weight, or preferably in a range from 5 to 20% by weight, based on the total amount of the formulation.

[0089] In a preferred embodiment of the formulation, the formulation has at least one of the following properties at room temperature: (A) an initial viscosity in a range from 5 to 20 mPas; or (B) an initial viscosity in a range from 100 to 500 mPas; or (C) an initial viscosity in a range from 150 to 1000 mPas; or (D) an initial viscosity in a range from 2500 to 50000 mPas; and / or (E) an isocyanate group content of 2 to 60 wt.%, based on the total amount of the formulation; wherein the formulation has one of the properties selected from (A) to (D) in combination with property (E).

[0090] The invention preferably relates to a storage-stable isocyanate group-containing formulation comprising the components: a. at least one pigment, b. optionally at least one isocyanate-containing component which has free isocyanate groups, c. at least one wetting agent and / or dispersant, d. at least one isocyanate-containing grinding resin containing free isocyanate groups, and e. optionally solvent, wherein the molar ratio of the sum of all isocyanate groups in the isocyanate-containing formulation to the sum of all isocyanate-reactive groups that are not isocyanate groups in the formulation is at least 8:1, wherein the formulation has at least one of the following properties at room temperature: (A) an initial viscosity in a range from 5 to 20 mPas; or (B) an initial viscosity in a range from 100 to 500 mPas; or (C) an initial viscosity in a range from 150 to 1000 mPas; or (D) an initial viscosity in a range from 2500 to 50000 mPas; and / or (E) an isocyanate group content of 2 to 60 wt. %, based on the total amount of the formulation; and wherein the formulation has one of the properties selected from (A) to (D) in combination with property (E).

[0091] Furthermore, the formulation preferably has a content of isocyanate groups in a range of 5 to 20 wt.%, based on the total amount of the formulation.

[0092] The viscosity determinations for (A) to (D) were carried out using a Physica MCR 301 (Anton Paar GmbH) with a plate-on-plate (40 mm diameter) measurement geometry at a temperature of 20 °C. All viscosity data refer to a shear rate of 500 [1 / s].

[0093] The dispersed pigments in the formulation are preferably present with an average particle size (Z-average) of less than 20 µm, or preferably less than 5 µm, or preferably less than 1 µm, or preferably less than 0.5 µm, or preferably less than 0.2 µm. Furthermore, it is preferred that the distribution be monomodal. It is further preferred that the distribution, indicated by the polydispersity index (PDI), be less than 0.6, or preferably less than 0.45, or preferably less than 0.35, or preferably less than 0.2.

[0094] In a preferred embodiment of the formulation, the formulation exhibits a particle size increase of less than 500%, based on the Z-average, which indicates the intensity-weighted harmonic mean of the hydrodynamic diameter, measured by dynamic light scattering upon storage at 50°C and atmospheric pressure for a period of 3 days. The particle size measurements were performed using dynamic light scattering with a Zetasizer Nano ZS (Malvern Instruments Ltd.) at a temperature of 20°C. The polydispersity index is also determined using the Zetasizer Nano ZS.

[0095] Component c. can contain either a wetting agent or a dispersing agent, or optionally both a wetting agent and a dispersing agent. Component c. can contain compounds that act as both a wetting agent and a dispersing agent. Wetting agents c. can be any compounds known to the person skilled in the art to be suitable for wetting pigments.

[0096] For the reliable dispersion and stabilization of pigments in coating systems, dispersants are generally used to reduce the mechanical shear forces required for effective dispersion of the solids while simultaneously achieving the highest possible filler levels. Dispersants assist in breaking up agglomerates, act as surface-active materials, wetting and coating the surface of the particles to be dispersed, and stabilizing them against unwanted re-agglomeration. Pigment stabilization is of great importance, for example, in the coatings industry, because pigments, as an important formulation component, determine the visual appearance and physicochemical properties of a coating. To ensure their optimal effectiveness in the coating, they should be evenly and finely distributed throughout the coating during the dispersion process.The preferably finely dispersed pigments should be stabilized to ensure this state is maintained during production, storage, processing, and subsequent applications such as film formation. Reaggregation of primary particles and aggregates can lead to sedimentation in the form of hard and / or soft sediments, increased viscosity, loss of gloss, insufficient color depth, poor hiding power, floating of the pigments, and poorly reproducible color shades, as already described in Goldschmidt, Streitberger; BASF Handbook of Coating Technology, BASF Münster and Vincentz Verlag Hannover 2002, p. 205 ff.

[0097] Bykjet ®< 9131 or Disperbyk ®< 2200, or a mixture thereof, are preferably used.

[0098] Those skilled in the art are aware that many pigments, for example, for use in printing inks, coatings, or related applications, are difficult to disperse in formulations. Wetting and dispersing agents are therefore often used to reduce the energy input required to disperse pigment particles in a liquid medium. A variety of different substances are known that are currently used as dispersants for pigments and fillers.

[0099] The dispersant c is preferred. selected from the group consisting of polymers and copolymers with functional and / or pigment-affine groups, alkylammonium salts of polymers and copolymers, polymers and copolymers with acidic groups, comb and block copolymers, such as block copolymers with basic pigment-affine groups, modified acrylate block copolymers, modified polyurethanes, modified and / or salted polyamines, epoxy-amine adducts, phosphoric acid esters of polyethers, polyesters and polyether esters, basic or acidic ethoxylates such as alkoxylated mono- or polyamines or acidic 1,2-dicarboxylic anhydride half-esters of alkoxylated monoalcohols, reaction products of unsaturated fatty acids with mono-, di- and polyamines, amino alcohols, and unsaturated 1,2-dicarboxylic acids and their anhydrides and their salts and reaction products with alcohols and / or amines;Polymers and copolymers with fatty acid residues, modified polyacrylates, such as transesterified polyacrylates, modified polyesters, such as acid-functional and / or amino-functional polyesters, polyphosphates and mixtures of at least two thereof;

[0100] As dispersants, preference is given to selecting compounds such as those described in the publications EP 0 154 678 B1, EP 0 270 126 B1, EP 031899981, EP 041749081, EP 0879860 B1, EP 0893155 B1, EP 1081 169 B1, EP1416019 A1, EP 1486 524 A1, EP 1593 700 B1, EP 1640 389 A1, EP 1650 246 A1, EP 1742 990, EP 1803 753, EP 1837 355, DE 102006048144, DE 102006062439 , DE 102006062440 , DE 102006062441 and DE 102007005720.

[0101] As the isocyanate-containing grinding resin d. containing free isocyanate groups, all compounds that a person skilled in the art would select as an isocyanate-containing grinding resin for a formulation according to the invention can be used. These compounds are preferably also selected from the group of isocyanate-containing compounds already described for the isocyanate-containing component b.

[0102] Preferably, the isocyanate-containing component b. and the isocyanate-containing grinding resin d. differ in at least one property. Preferably, the viscosity of component b. differs from the viscosity of the grinding resin d., preferably in a range from 20 to 10,000 mPas, more preferably in a range from 30 to 5,000 mPas. Furthermore, the isocyanate-containing grinding resin d. has a higher viscosity, preferably at least 20 mPas, more preferably 50 mPas higher than the isocyanate-containing component b. The grinding resin is preferably selected such that it is ideally suited for grinding the pigments, while the isocyanate-containing component b. is selected such that the desired viscosity or the desired functionality of the formulation is obtained.

[0103] Furthermore, the isocyanate-containing grinding resin d. preferably has a higher viscosity than the isocyanate-containing component b.

[0104] The grinding resin containing isocyanate groups can also consist of any mixture of the various compounds described for component d.

[0105] Suitable solvents are all those solvents e. that preferably completely dissolve the isocyanate-containing component b. Preference is given to using solvents that do not react or react only slowly with isocyanates and preferably completely dissolve them, as well as having a boiling point of > 30°C and < 300°C. Also preferred are those solvents e. that have a low water content, preferably less than 1% by weight, preferably less than 0.5% by weight, or preferably less than 0.1% by weight, or preferably less than 0.01% by weight, based on the total amount of solvent e.

[0106] Examples of solvents include structural elements selected from ketone, ester, ether, alicyclic rings, heterocyclic rings, aromatics, chlorine, and any mixtures thereof, such as ethyl acetate, butyl acetate, methoxypropyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, DMSO, DMF, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ethylene glycol dimethyl ether, bis(2-methoxyethyl) ether, Solventnaphtha ®< 100, and mixtures thereof. Preferred solvents are methyl ethyl ketone, ethyl acetate, butyl acetate, butylglycol acetate, and 2-ethylhexyl acetate.

[0107] The solvent e. can either be a single solvent or any mixture of at least two of the above-mentioned solvents.

[0108] If the solvent e. contains isocyanate-reactive groups, these groups are taken into account when determining the ratio of isocyanate groups to isocyanate-reactive groups during the preparation of the formulation. The content of isocyanate-reactive groups in the solvent e. is preferably less than 20 wt. %, or preferably less than 10 wt. %, or preferably less than 5 wt. %, or preferably less than 3 wt. %, based on the total amount of solvent e.

[0109] Also disclosed is a process for producing storage-stable formulations containing isocyanate groups, comprising at least the steps: i. Grinding at least one pigment a. in at least one isocyanate-containing grinding resin d. which has free isocyanate groups, in the presence of at least one wetting agent and / or dispersant c. and optionally a solvent e. or a solvent mixture to obtain a pigment grinding, it being possible to use the customary dispersing apparatus known to the person skilled in the art, until the desired particle size of the at least one pigment is achieved, ii. Optionally diluting the resulting pigment grinding from step i. with solvent e., iii. Optionally mixing the pigment grinding from step i. or step ii. with an isocyanate-containing component b. which contains free isocyanate groups, to obtain the isocyanate-containing formulation, wherein the molar ratio of the sum of the isocyanate groups to the sum of all isocyanate-reactive groups in the formulation which are not isocyanate groups is at least 8:1, or preferably at least 11:1, or preferably at least 15:1, or preferably at least 20:1, or preferably at least 50:1, or preferably at least 100:1.

[0110] In the process, steps i. are preferably carried out first, then, if necessary, ii., and only then, if necessary, iii.

[0111] In a preferred embodiment of the process, the time between steps i. and iii. is not more than 60 minutes, more preferably ≤ 45 minutes, particularly preferably ≤ 30 minutes, most particularly preferably ≤ 15 minutes.

[0112] Stable, in particular storage-stable, formulations containing isocyanate groups within the meaning of the invention are preferably characterized in that the viscosity during storage at 50°C for at least 3 days, or preferably at least 5 days, or preferably at least 7 days, or preferably at least 10 days, or preferably at least 14 days only exhibits a viscosity increase of ≤ 500%, preferably of ≤ 300%, or preferably of ≤ 200%, or preferably of ≤ 100%, or preferably of ≤ 50%. Particularly preferably, the viscosity increase during storage of the formulation at 50°C for 3 days is ≤ 100%, based on the initial viscosity.Furthermore, the increase in particle size in the isocyanate-containing formulation, measured by dynamic light scattering after redispersion of any soft sediments formed, based on Z-average, is preferably at most 500%, preferably at most 200%, preferably at most 100%, preferably at most 50%. For the purposes of the invention, soft sediments are understood to mean that the sediments redisperse upon shaking.

[0113] Storage-stable formulations containing isocyanate groups are preferably characterized by the fact that they do not form hard sediments during storage. For the purposes of the invention, hard sediments are understood to mean those that cannot be redispersed by shaking. Shaking is preferably understood to mean shaking by hand or using conventional laboratory shakers. An IKA ® VORTEX 2 was used as the laboratory shaker at a speed of 2000 rpm, with the shaking time preferably in a range of 10 to 60 seconds, or more preferably in a range of 15 to 40 seconds.

[0114] The invention further provides for the use of the formulation according to the invention for coating or printing substrate surfaces to obtain coated objects. To obtain coated objects, the formulation according to the invention is preferably applied to the object.

[0115] The invention further relates to an object coated or printed according to the inventive use. The coating or printing is preferably applied over the entire surface of the substrate, but can alternatively also be applied to only a portion of the surface.

[0116] In a preferred embodiment of the object, the substrate is selected from the group consisting of textile, wood, plastic, glass, ceramic, carbon, metal, or a combination of at least two thereof. The coating is preferably applied as a continuous layer on at least part of the surface.

[0117] Coating is preferably carried out using a method that a person skilled in the art would select for this purpose. The coating is preferably selected from the group consisting of brushing, pouring, knife coating, spraying, dipping, flow coating, rolling, or a combination of at least two of these. All process variants known in the art can be used for this purpose.

[0118] Printing can be any printing process that a person skilled in the art would use. Preferably, the printing process is selected from letterpress, intaglio, planographic, stencil, pad printing, stamp printing, frottage printing, embossed printing, offset printing, screen printing, digital printing, or a combination of at least two of these. Preferred digital printing processes are inkjet and valvejet processes and processes based on similar functionality.

[0119] The invention further relates to the use of the formulation according to the invention as an ink. To obtain objects printed with the ink, the formulation according to the invention is preferably printed onto the object.

[0120] A preferred embodiment of the inventive use of the inventive formulation as an ink is the formulation as an ink for digital printing. As an ink for digital printing, the formulation preferably has a viscosity in a range from 1 to 200 mPas, or preferably in a range from 1 to 100 mPas, or preferably in a range from 3 to 50 mPas, or preferably in a range from 3 to 20 mPas.

[0121] A further subject matter of the invention relates to a printed object obtainable using the formulation according to the invention as ink, in particular as ink for digital printing processes.

[0122] In a preferred embodiment, the material of the object is selected from the group consisting of textile, wood, plastic, glass, ceramic, carbon, metal or a combination of at least two thereof.

[0123] A further object of the invention relates to the use of a polyisocyanate as grinding resin d. for the storage-stable isocyanate group-containing formulations according to the invention

[0124] In a preferred embodiment of the use of the polyisocyanate as grinding resin d., the grinding resin d. has a viscosity in a range from 100 to 5,000 mPas, or preferably in a range from 200 to 2,000 mPas, or preferably in a range from 350 to 1,000 mPas. Measurement methods:

[0125] All percentages that are weight specifications always refer to percentages by weight unless otherwise stated.

[0126] All viscosity determinations were performed using a Physica MCR 301 (Anton Paar GmbH) with a plate-on-plate (40 mm diameter) measurement geometry at a temperature of 20 °C. All viscosity data refer to a shear rate of 500 [1 / s], unless otherwise stated. The initial viscosity is defined according to the invention as the viscosity after 1 hour after combining all desired components, in particular the selected components a. to d.

[0127] All particle size measurements were performed using dynamic light scattering with a Zetasizer Nano ZS (Malvern Instruments Ltd.) at a temperature of 20 °C. All measurements always refer to the intensity-weighted harmonic mean of the hydrodynamic diameter (Z-average). Examples

[0128] Agglomerated pigment particles were ground during the production of pigment pastes. This required a high energy input into the millbase. The energy input can be achieved, for example, by ultrasound, rotor-stator systems, or roller mills. Another method known to those skilled in the art is grinding the particle agglomerates in the medium in which they are to be dispersed, e.g., in ball or bead mills. The production of pigmented pastes was carried out using a Dispermat LC30 (VMA-Getzmann GmbH) in a 125 ml double-walled stainless steel temperature control vessel. In a first step, all materials were weighed into this vessel and mixed by hand. In the case of Disperbyk ®< 2200, this was dissolved in the solvent p-xylene 30 minutes before all components were combined. Subsequently, pre-dispersion was carried out using a dispersing disk (diameter 30 mm) for 10 minutes at 10,000 rpm until a homogeneous mass (ground material) was obtained.The dispersing tool was then replaced with a single-disk polyamide grinding disc (32 mm diameter). Zirconia beads (yttrium-stabilized) with an average diameter of 0.6 to 0.8 mm were then added to the millbase. The millbase was finely ground for 90 minutes at a rotation speed of 14,000 rpm while continuously cooling. After dispersion, the grinding beads were removed by filtration.

[0129] The preparation of the pigmented formulations containing isocyanate groups using an isocyanate-containing grinding resin was carried out as follows: The pigmented paste was placed in a 30 mL glass vessel within a maximum of 60 minutes of its preparation. The solvent (if included in the formulation) was then added gradually while stirring. In a final step, the isocyanate component was added gradually while stirring until a homogeneous mixture was obtained. Materials

[0130] Organic pigments were purchased from Clariant SE, inorganic titanium dioxide from Kronos Worldwide Inc., and black carbon black pigments from Orion Engineered Carbons GmbH. The exact product names can be found in Table 1. Table 1: Pigments (component a.) Nr. name Manufacturer Pigment color Color Index Pigment class (chemical) Density (g / cm 3 ) Primary particle size (nm) 1 Hostaperm ®< Blue BT-617-D Clariant SE Cyan PB 15:4 Phthalocyanine 1,62 65 2 Inkjet Magenta 5EB02 Clariant SE magenta PV19 Quinacridone 1,5 70 3 Inkjet Yellow 4GC Clariant SE Yellow PY 155 Disazo 1,5 90 4 Kronos ®< 2310 Kronos Worldwide Inc. White PW6 Titanium dioxide 4 n / a *< 5 NIPex ®< 35 Orion Engineered Carbons GmbH Black P. Bk. 7 Furnace soot n / a 31 * n / a = not specified

[0131] Solvents are available from a variety of manufacturers. Solvents from Sigma-Aldrich and Fluka were used for the patent examples. Table 2: Solvent (component d.) Nr. Solvent CAS number Manufacturer 1 Butyl acetate (BuAc) ACS reagent, ≥99.5% (GC) 123-86-4 Sigma-Aldrich 2 Butylglycol acetate (BGA) 99% 112-07-2 Sigma-Aldrich 3 p-Xylene, puriss .pa ≥99.0% (GC) 106-42-3 Fluka

[0132] Wetting and dispersing agents (also called dispersing additives) can be obtained from various manufacturers. Products from Byk Additives & Instruments GmbH were used for the patent examples. Table 3: Wetting and dispersing additive (component c.) Nr. Dispersing additive Manufacturer structure Sum of hydroxyl, amine and acid number based on delivery form additive (mg KOH / g) non-renewable energy (%) 1 Bykjet ®< 9131 Byk Additives & Instruments GmbH Solution of a structured 144 40 Copolymers with pigment-affinic groups 3 Disperbyk ®< 2200 Byk Additives & Instruments GmbH High molecular 30,7 100 Copolymer with pigment-affinic groups

[0133] Compounds containing isocyanate groups were purchased from Covestro AG. Table 4: Compounds containing isocyanate groups (component b.) Nr. Isocyanate Manufacturer NCO content (%) 1 Desmodur ®< H Covestro AG Hexamethylene diisocyanate (HDI), monomeric aliphatic diisocyanate with a molecular weight of 168, an equivalent weight of 84, an NCO content ≥ 49.7% according to DIN EN ISO 11909 and a purity of ≥ 99.5% (GC). 2 Desmodur ®< N3400 Covestro AG Aliphatic polyisocyanate (HDI uretdione) with an NCO content of 21.8 ± 0.7 % according to DIN EN ISO 11909, a viscosity at 23 °C of 175 ± 75 mPas according to DIN EN ISO 3219 / A.3 and a monomeric HDI content of ≤ 0.3 % according to DIN EN ISO 10283 3 Desmodur ®< N3600 Covestro AG Aliphatic polyisocyanate (low-viscosity HDI trimer) with an NCO content of 23.0 ± 0.5% according to M105-ISO 11909, a viscosity at 23 °C of 1,200 ± 300 mPas according to M014-ISO 3219 / A.3 and a monomeric HDI content of ≤ 0.25% according to M106-ISO 10283. Table 5: Grinding resin containing isocyanate groups (component d.) Nr. Isocyanate Manufacturer NCO content (%) 1 Desmodur ®< N3600 Covestro AG Aliphatic polyisocyanate (low-viscosity HDI trimer) with an NCO content of 23.0 ± 0.5% according to M105-ISO 11909, a viscosity at 23 °C of 1,200 ± 300 mPas according to M014-ISO 3219 / A.3 and a monomeric HDI content of ≤ 0.25% according to M106-ISO 10283. Table 6: Formulations 1 - 12 with different NCO / NCO-reactive group ratios. Example / Sample weight [g] 1 (Comparison) 2 3 4 5 6 7a paste Grinding resin containing isocyanate groups (from Table 5) Desmodur ®< N3600 4,73 4,73 37,00 4,53 40,33 40,33 40,33 Pigments a. (from Table 1) Cyan 1 37,90 37,90 Magenta 2 25,38 Yellow 3 36,36 Black 4 White 5 42,45 42,45 42,45 Wetting and / or dispersing agent c. (from Table 3) Bykjet ®< 9131 40,79 40,79 23,56 39,06 Disperbyk ®< 2200 2,12 2,12 2,12 Solvent e. (from Table 2) BuAc / BGA 1:2 16,58 16,58 14,06 20,05 6,61 6,61 6,61 p-xylene 8,49 8,49 8,49 Formulation x)< Paste from component a.-d. 4,39 1,58 2,36 1,65 0,71 0,71 0,71 BuAc / BGA 1:2 1,69 5,52 5,29 5,50 2,79 1,39 Isocyanate group-containing compound b. (from Table 4) Desmodur ®< N3600 3,92 12,89 12,34 12,84 6,51 Desmodur ®< H 9,29 Desmodur ®< N3400 7,90 NCO / NCO reactive group 5 44 51 43 4804 14628 5485 Initial viscosity [mPa*s] 110,0 51,4 62,5 53,7 53,6 2,8 72,2 Relative change in viscosity [%], after a, b days storage at 50 °C Festival a)< 46,3 b)< 58,2 b)< 53,8 b)< 22,0 b)< 6,1 b)< 27,6 b)< Relative change in Z-Average [%] after 14 days of storage at 50 °C nb xx)< -7,6 -2,4 -5,6 -0,8 36,9 -6,7 According to the invention No Yes Yes Yes Yes Yes Yes Stable No Yes Yes Yes Yes Yes Yes x)< Formulations 1-13 were prepared from pastes 1-13. xx)< not determinable (solid), a: after 3, b: after 14 days Example / Sample weight [g] 7b 8 9 10 11 12 paste Isocyanate group-containing compound b. (from Table 4) Desmodur ®< N3600 34,31 34,31 34,31 45,13 45,13 45,13 Pigments a. (from Table 1) Cyan 1 Magenta 2 25,52 25,52 25,52 Yellow 3 Black 4 23,44 23,44 23,44 White 5 Wetting and / or dispersing agent c. (from Table 3) Bykjet ®< 9131 Disperbyk ®< 2200 12,68 12,68 12,68 5,87 5,87 5,87 Solvent d. (from Table 2) BuAc / BGA 1:2 p-xylene 29,57 29,57 29,57 23,48 23,48 23,48 Formulation x)< Paste from component a.-d. 1,13 1,13 1,13 1,17 1,17 1,17 BuAc / BGA 1:2 2,66 1,33 2,65 1,32 Isocyanate group-containing compound b. (from Table 4) Desmodur ®< N3600 6,21 6,18 Desmodur ®< H 8,87 8,83 Desmodur ®< N3400 7,54 7,51 NCO / NCO reactive group 490 1486 558 1039 3133 1180 Initial viscosity [mPa*s] 73,7 4,4 100,5 60,4 3,6 82,9 Relative change in viscosity [%], after a, b days storage at 50 °C 52,0 b)< 1,0 b)< 37,0 b)< 36,0 b)< 9,0 b)< 42,0 b)< Relative change in Z-Average [%] after 14 days of storage at 50 °C 3,0 -8,1 -1,2 6,6 5,2 23,0 According to the invention Yes Yes Yes Yes Yes Yes Stable Yes Yes Yes Yes Yes Yes x)< Formulations 1-13 were prepared from pastes 1-13. xx)< not determinable (solid), a: after 3, b: after 14 days

[0134] Example 1 solidified after three days of storage at 50 °C, and viscosity determination was no longer possible. Example 1 is therefore not in accordance with the invention. Examples 2 to 13 show a viscosity increase of less than 500% within 14 days and are therefore in accordance with the invention.

Claims

1. Storage-stable, isocyanate group-containing formulation comprising the components: a. 0.01% to 45% by weight of at least one pigment, b. 1% to 98% by weight of at least one isocyanate group-containing component comprising free isocyanate groups, c. 0.01% to 20% by weight of at least one wetting agent and / or dispersant, d. 0.1% to 35% by weight of at least one isocyanate group-containing grinding resin containing free isocyanate groups and e. 0% to 80% by weight of solvent, in each case based on the total amount of the formulation, wherein the sum of all constituents of the formulation does not exceed 100% by weight, characterized in that the formulation exhibits a viscosity increase of less than 500% after storage at 50°C over a period of at least 3 days based on the starting viscosity of the formulation which is determined 1 hour after combination of all desired components, especially components a. to e., wherein the viscosity determination is in each case undertaken at 20°C at a shear rate of 500 [l / s], wherein the molar ratio of the sum of all isocyanate groups of the isocyanate-containing formulation to the sum of all isocyanate-reactive groups distinct from isocyanate groups in the formulation is at least 8:1 and wherein the isocyanate group-containing grinding resin d. has a viscosity in a range from 100 to 5000 mPas and wherein the isocyanate group-containing grinding resin d. is selected from the group consisting of 1,4-diisocyanatobutane (BDI), 1,5-diisocyanatopentane (PDI), 1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- and 2,4,4-trimethyl-1,6-diisocyanatohexane and 1,10-diisocyanatodecane, 1,3- and 1,4-bis(isocyanatomethyl)benzene (xylylene diisocyanate; XDI), 1,3- and 1,4-bis(1-isocyanato-1-methylethyl) benzene (TMXDI), 2,4- and 2,6-diisocyanatotoluene (TDI), 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI) and 1,5-diisocyanatonaphthalene, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate; IPDI), 1-isocyanato-1-methyl-4(3)-isocyanatomethylcyclohexane, 2,4'- and 4,4'-diisocyanatodicyclohexylmethane (H12MDI) or a mixture of at least two of these and optionally oligomers and / or reaction products thereof.

2. Formulation according to Claim 1, wherein the isocyanate group-containing component b. is selected from the group consisting of 1,4-diisocyanatobutane (BDI), 1,5-diisocyanatopentane (PDI), 1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- and 2,4,4-trimethyl-1,6-diisocyanatohexane and 1,10-diisocyanatodecane, 1,3- and 1,4-bis(isocyanatomethyl)benzene (xylylene diisocyanate; XDI), 1,3- and 1,4-bis(1-isocyanato-1-methylethyl) benzene (TMXDI), 2,4- and 2,6-diisocyanatotoluene (TDI), 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI) and 1,5-diisocyanatonaphthalene, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate; IPDI), 1-isocyanato-1-methyl-4(3)-isocyanatomethylcyclohexane, 2,4'- and 4,4'-diisocyanatodicyclohexylmethane (H12MDI) or a mixture of at least two of these and optionally oligomers and / or reaction products thereof.

3. Formulation according to any of the preceding claims, wherein the isocyanate group-containing component b. and the isocyanate group-containing grinding resin d. consists of aliphatic or cycloaliphatic isocyanates or mixtures thereof.

4. Formulation according to any of the preceding claims, wherein the formulation has at least one of the following properties at room temperature: (A) a starting viscosity in a range from 1 to 200 mPas; (B) a starting viscosity in a range from 30 to 1000 mPas; (C) a starting viscosity in a range from 50 to 2000 mPas; (D) a starting viscosity in a range from 1000 to 100 000 mPas; (E) a content of isocyanate groups of less than 60% by weight and more than 3% based on the total amount of the formulation, wherein the formulation has any of the properties selected from (A) to (D) in combination with property (E).

5. Formulation according to any of the preceding claims, wherein the formulation exhibits an increase in particle size upon storage at 50°C and standard pressure over a period of 3 days of less than 500% based on the original particle size of the formulation based on the intensity-weighted harmonic mean of the hydrodynamic diameter (Z-average) measured by dynamic light scattering.

6. Use of the formulation according to any of Claims 1 to 5 for coating substrate surfaces to obtain coated objects.

7. Coated object obtainable according to Claim 6.

8. Object according to either of Claims 6 and 7, wherein the material of the object is selected from the group consisting of textile, wood, plastic, glass, ceramic, carbon, metal or a combination of at least two of these.

9. Use of the formulation according to any of Claims 1 to 5 as ink.

10. Use of a polyisocyanate as grinding resin d. for storage-stable isocyanate group-containing formulations according to any of Claims 1 to 5.