METHOD FOR THE PRODUCTION OF STOCK-STABLE, PIGMENTED ISOCYANAT GROUP-CONTAINING FORMULAS

Description

[0001] The invention relates to a method for producing an isocyanate group-containing formulation.

[0002] Formulations that can be used as printing inks have been known for a long time and represent the current state of the art. These formulations are predominantly non-reactive, consisting of finely dispersed pigments or dissolved dyes in conventional solvents, water, or oil. To fix the pigments, the formulations often contain a small amount of a binder.

[0003] The treatment of pigments with isocyanates is also known in the literature. For example, US 3,156,576 from 1964 already describes the modification of pigments such as carbon black, silicate, titanium dioxide, and similar compounds with isocyanates. In this procedure, 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 pigment is then immediately incorporated into a silicone under exclusion of moisture, which is subsequently cured.

[0004] US patent 4,075,152 describes a method for preventing pigment flocculation in two-component polyurethane (2K) coatings. This involves first preparing an isocyanate / pigment slurry and then directly mixing this slurry into a polyol. The resulting colored polyols showed no pigment flocculation.

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

[0006] In contrast, US patent 6,341,856 describes the production of a reactive ink for digital printing. This patent describes the processing of compounds with at least one CH-active group, compounds with blocked CH-reactive groups (which prevents the reaction of the active hydrogen with the CH-reactive group), emulsifiers, and pigments or dyes into a room-temperature stable inkjet ink. Polyols and isocyanates are specifically mentioned. The blocking can be achieved either chemically or by encapsulation.

[0007] A disadvantage of the theory from US 6,341,856 is the blocking. Firstly, the blocking is complex and therefore expensive; secondly, the isocyanate group must first be unblocked in order to allow a reaction to proceed with the unblocked isocyanate groups.

[0008] The task was therefore to overcome at least one disadvantage of the state of the art, at least in part.

[0009] Another objective of the invention was to produce a pigment-containing formulation that contains reactive isocyanate groups during its processing.

[0010] Furthermore, an object of the invention was to produce a pigment-containing formulation which has reactive isocyanate groups over the longest possible processing period, preferably over several minutes or preferably over several hours.

[0011] It was also an objective of the invention to provide a method that makes it possible to generate a storage-stable isocyanate group-containing formulation.

[0012] Another objective of the invention was to produce an isocyanate group-containing formulation as an ink, particularly for digital printing.

[0013] The invention therefore relates to a process for producing an isocyanate group-containing formulation comprising at least the following steps: i. Grinding at least one pigment in at least one grinding resin in the presence of at least one wetting agent and / or dispersing agent to obtain a pigment mixture, ii. optionally diluting the pigment mixture obtained from step i. with solvent, iii. mixing the pigment mixture from step i. or step ii. with an isocyanate-containing component 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 is at least 8:1.

[0014] Another object of the invention is a process for producing storage-stable isocyanate group-containing formulations, comprising at least the following steps: i. Grinding at least one pigment in at least one grinding resin in the presence of at least one wetting agent and / or dispersing agent to obtain a pigment mixture, wherein the usual dispersing apparatus known to those skilled in the art may be used until the desired particle size of the at least one pigment is achieved, ii. optionally diluting the pigment mixture obtained from step i. with solvent, iii. mixing the pigment mixture from step i. or step ii. with an isocyanate-containing component to obtain the isocyanate-containing formulation, wherein the ratio of the sum of the isocyanate groups to the sum of all isocyanate-reactive groups in the formulation is at least 6:1, or preferably 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.

[0015] The procedure preferably involves carrying out the steps in the following order: first i., then if necessary ii., and only afterwards iii.

[0016] Stable, and in particular storage-stable, isocyanate-containing formulations according to 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, exhibits a viscosity increase of only ≤ 500%, preferably ≤ 300%, or preferably ≤ 200%, or preferably ≤ 100%, or preferably ≤ 50%. In particular, a viscosity increase of ≤ 100% of the initial viscosity during 3 days of storage at 50 °C is preferred.Furthermore, preferably the increase in particle size in the isocyanate-containing formulation, measured by dynamic light scattering after redispersion of any soft sediments formed, relative to Z-average, is a maximum of 500%, preferably a maximum of 200%, preferably a maximum of 100%, and preferably a maximum of 50%. For the purposes of this invention, "soft sediments" means sediments that redisperse upon shaking.

[0017] Preferably, storage-stable formulations containing isocyanate groups are characterized by the fact that they do not form hard sediments during storage. In the context of the invention, hard sediments are defined as sediments that cannot be redispersed by shaking. Shaking preferably refers to shaking by hand or using conventional laboratory shakers. An IKA® VORTEX 2 shaker was used at a speed of 2000 rpm, with the shaking time preferably in the range of 10 to 60 seconds, or more preferably in the range of 15 to 40 seconds.

[0018] Preferably, the pigment is homogeneously distributed in the formulation produced according to the inventive method. Homogeneous is understood to mean that the percentage of the pigment in the formulation at different locations does not deviate by more than 10 wt%, preferably not more than 5 wt%, and particularly preferably not more than 1 wt% from the average percentage of pigment in the formulation.

[0019] Not the subject of the invention is a storage-stable isocyanate-group-containing formulation comprising the components: a. at least one pigment, b. at least one component containing isocyanate groups, c. at least one wetting agent and / or dispersing agent, d. at least one grinding resin, and e. optionally solvents, characterized in that the formulation, 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, exhibits a viscosity increase of 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. 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.

[0020] A preferred embodiment of the formulation contains at least one component with at least one isocyanate-reactive group, wherein the molar ratio of the isocyanate groups of component b. to the sum of all isocyanate-reactive groups in the formulation is at least 6:1, or preferably 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.

[0021] In a preferred embodiment of the formulation, the formulation contains a. 0.01 to 45 wt.%, preferably 0.1 to 15 wt.%, or preferably 0.1 to 10 wt.%, or preferably 0.2 to 8 wt.%, or preferably 0.5 to 5 wt.% of the at least one pigment; b. 1 to 99 wt.%, preferably 5 to 95 wt.%, or preferably 10 to 93 wt.%, or preferably 20 to 93 wt.%, or preferably 40 to 93 wt.% of the at least one isocyanate-containing component; c. 0.01 to 20 wt.%, preferably 0.05 to 15 wt.%, or preferably 0.1 to 10 wt.% of the at least one wetting agent and / or dispersing agent; d. 0.1 to 30 wt.%, preferably 0.5 to 25 wt.%, or preferably 1 to 15 wt.% of the at least one grinding resin; e. 0 to 80 wt.%, preferably 0 to 75 wt.%, or preferably 0 to 50 wt.%, or preferably 0 to 20 wt.%, or preferably 0 to 10 wt.%, or preferably 0.1 to 30 wt.% solvent; each in relation to the total quantity of the formulation, whereby the sum of all components of the formulation does not exceed 100% by weight.

[0022] Preferably the wording includes 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; c. 0.1 to 10 wt.% of the at least one wetting agent and / or dispersing agent; d. 1 to 15 wt.% of the at least one grinding resin; e. 0 to 30 wt.% solvent, each based on the total amount of the formulation, wherein the sum of all components of the formulation does not exceed 100 wt.%, wherein the molar ratio of the isocyanate groups of component b. to the sum of all isocyanate-reactive groups in the formulation is at least 6:1, or preferably at least 8:1, more preferably at least 11:1, particularly preferably at least 20:1.

[0023] Stable, and in particular storage-stable, isocyanate-containing formulations are preferably characterized by the fact 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, exhibits a viscosity increase of only ≤ 500%, preferably ≤ 300%, or preferably ≤ 200%, or preferably ≤ 100%, or preferably ≤ 50%. In particular, a viscosity increase of ≤ 100% of the initial viscosity during 3 days of storage at 50 °C is preferred. Furthermore, preferably the increase in particle size in the isocyanate group-containing formulation, measured by dynamic light scattering after redispersion of any soft sediments formed, based on Z-average, is a maximum of 500%, preferably a maximum of 200%, preferably a maximum of 100%, preferably a maximum of 50%.Soft sediments are defined as sediments that redisperse upon shaking. The Z-average is the measured intensity-weighted harmonic mean of the hydrodynamic diameter of the particles.

[0024] Furthermore, the formulation preferably has, at the time of determining the initial viscosity or after storage for at least 3 days, or preferably for at least 10 days, or preferably for at least 14 days, an isocyanate group content in the range of 2 to 60 wt.%, or preferably in the range of 3 to 50 wt.%, or preferably in the range of 4 to 35 wt.%, or preferably in the range of 5 to 20 wt.%, based on the total amount of the formulation.

[0025] It is preferred that the isocyanate-containing formulation preferably does not contain hard sediments. Hard sediments are defined as sediments that cannot be redispersed by shaking. Shaking preferably refers to shaking by hand or using conventional laboratory shakers. A conventional laboratory shaker such as an IKA® VORTEX 2 at a speed of 2000 rpm can be used, with the shaking time preferably in the range of 10 to 60 seconds, or more preferably in the range of 15 to 40 seconds. pigments

[0026] Any pigments that a person skilled in the art would use for a stable formulation can be used. Pigments preferably used as component a. can be divided into several classes: organic or inorganic pigments dispersed as a solid dispersion in particle form, 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.

[0027] The at least one pigment can be selected from a wide variety of pigment classes. If the application involves printing techniques, particularly 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.

[0028] Preferably, the pigment is homogeneously distributed in the formulation. Homogeneous means that the percentage of the pigment in the formulation does not deviate by more than 10 wt%, preferably not more than 5 wt%, and particularly preferably not more than 1 wt% from the average percentage of pigment in the formulation at different locations.

[0029] 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; .

[0030] 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 of these.

[0031] Examples of suitable inorganic pigments: White pigments: Titanium dioxide (CI Pigment White 6), zinc white, 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); molybda 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); chrome 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 platelets; Pearlescent Pigments based on metal oxide-coated mica platelets; Liquid Crystal Pigments.

[0032] 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.

[0033] 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. Preferably, component b. contains a polyisocyanate.

[0034] The term "polyisocyanate," as used here, is a collective term for compounds that contain two or more isocyanate groups -N=C=O in their molecule. Diisocyanates are the preferred representatives of these polyisocyanates. These have the general structure O=C=NRN=C=O, where R usually represents aliphatic, alicyclic, araliphatic, and / or aromatic residues.

[0035] When the term "isocyanates" is used here in general, it refers to monoisocyanates as well as monomeric and / or oligomeric polyisocyanates. However, to understand many aspects, it is important to distinguish between monomeric diisocyanates and oligomeric polyisocyanates. When "oligomeric polyisocyanates" are mentioned here, they are polyisocyanates composed of at least two monomeric diisocyanate molecules; that is, they are compounds that represent or contain a reaction product of at least two monomeric diisocyanate molecules.

[0036] Preferably, at least one of the monomeric or oligomeric polyisocyanates contained in the isocyanate group-containing component b. has a (mean) NCO functionality of 2.0 to 6.0, or preferably of 2.3 to 4.5.

[0037] Suitable monomeric polyisocyanates for use in the isocyanate component are preferably those with a molecular weight in the range of 140 to 400 g / mol, containing aliphatic, cycloaliphatic, araliphatic, and / or aromatically bonded isocyanate groups. These polyisocyanates can be obtained by various means, for example, by phosgenation in the liquid or gas phase, or by phosgene-free methods such as thermal urethane cleavage.

[0038] Preferred monomeric isocyanates with aliphatic 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.

[0039] 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- and 2,4,4-trimethyl-1,6-diisocyanatohexane and 1,10-diisocyanatodecane, 1,3- and 1,4-bis(isocyanatomethyl)benzene (xylene diisocyanate; XDI), 1,3- and 1,4-bis(1-isocyanato-1-methyl-ethyl)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-isocyanatomethyl-cyclohexane (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 reaction products thereof.

[0040] The isocyanate group-containing component preferably includes b. Monomeric isocyanates with cycloaliphatic 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.

[0041] Preferred monomeric isocyanates with araliphatic isocyanate groups are 1,3- and 1,4-bis-(isocyanatomethyl)benzene (Xyxlylene diisocyanate; XDI), 1,3- and 1,4-bis(1-isocyanato-1-methylethyl)benzene (TMXDI).

[0042] Preferred monomeric isocyanates with aromatically bonded isocyanate groups are 2,4- and 2,6-diisocyanatotoluene (TDI), 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI) and 1,5-diisocyanatonaphthalene.

[0043] Further suitable diisocyanates can also be found, for example, in Justus Liebig's Annalen der Chemie, Volume 562 (1949), pp. 75-136.

[0044] Preferably, the isocyanate group-containing component b. contains at least 40 wt.%, preferably at least 50 wt.%, or preferably at least 60 wt.%, or preferably at least 70 wt.%, or preferably at least 80 wt.%, or preferably at least 90 wt.% of aliphatic or cyclo-aliphatic isocyanates, based on the total amount of the isocyanate group-containing component b.

[0045] In a preferred embodiment, the isocyanate group-containing component b. comprises aliphatic or cyclo-aliphatic isocyanates.

[0046] Preferably, at least one polyisocyanate can be used as the isocyanate-containing component. Preferably, oligomeric polyisocyanates can be obtained from the monomeric polyisocyanates described above by the "modification" process of 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 monomeric polyisocyanates mentioned above, so that oligomeric polyisocyanates are obtained that are composed of at least two different monomers.

[0047] The production of oligomeric polyisocyanates from monomeric diisocyanates is also referred to here as the modification of monomeric diisocyanates. This "modification," as used here, means the reaction of monomeric diisocyanates to form oligomeric polyisocyanates with uretdione, isocyanurate, allophane, biuret, iminooxadiazindione, and / or oxadiazinetrione structures.

[0048] 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:

[0049] In contrast, reaction products consisting of at least two HDI molecules, which still possess at least two isocyanate groups, are "oligomeric polyisocyanates" within the meaning of the invention. Examples of such "oligomeric polyisocyanates," starting from monomeric HDI, are HDI-isocyanurate and HDI-biuret, each composed of three monomeric HDI building blocks:

[0050] According to the invention, the oligomeric polyisocyanates can, in particular, have uretdione, isocyanurate, allophane, biuret, iminooxadiazindione, 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:

[0051] It is advantageous to use oligomeric polyisocyanates that represent a mixture of at least two oligomeric polyisocyanates, wherein the at least two oligomeric polyisocyanates differ in their structure. This structure is preferably selected from the group consisting of uretdione, isocyanurate, allophanate, biuret, iminooxadiazindione, and oxadiazinetrione structures and mixtures thereof. Such starting mixtures can, in particular, influence the Tg value compared to crosslinking reactions with oligomeric polyisocyanates of only one defined structure, which is advantageous for many applications.

[0052] Preferably, in the process according to the invention, an isocyanate group-containing component b. is used, which contains at least one oligomeric polyisocyanate with biuret, allophane, isocyanurate, and / or iminooxadiazinde ion structure and mixtures thereof.

[0053] Preferably, the oligomeric polyisocyanate contained in the isocyanate-containing component b. is one that contains only a single defined oligomeric structure, for example, exclusively or predominantly an isocyanurate structure. However, due to the manufacturing process, the oligomeric polyisocyanates used according to the invention generally contain several different oligomeric structures side by side.

[0054] Within the scope 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, iminooxadiazindione and / or oxadiazinetrione structures is present to at least 50 mol%, preferably 60 mol%, preferably 70 mol%, particularly preferably 80 mol%, and 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, iminooxadiazine and oxadiazinetrione structures in the oligomeric polyisocyanate.

[0055] Preferably, an oligomeric polyisocyanate of a single defined oligomeric structure is used, wherein the oligomeric structure is selected from uretdione, isocyanurate, allophanate, biuret, iminooxadiazindione and / or oxadiazinetrione structures and is present to at least 50 mol%, preferably 60 mol%, preferably 70 mol%, particularly preferably 80 mol%, and 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, iminooxadiazine and oxadiazinetrione structures in the oligomeric polyisocyanate.

[0056] Preferably, the oligomeric polyisocyanates are those that mainly have an isocyanurate structure and may only contain the aforementioned uretdione, allophanate, biuret, iminooxadiazindione, and / or oxadiazinetrione structures as byproducts. One embodiment of the invention provides for the use of an oligomeric polyisocyanate of a single defined oligomeric structure, wherein the oligomeric structure is an isocyanurate structure and is present at least 50 mol%, preferably 60 mol%, preferably 70 mol%, particularly preferably 80 mol%, and especially 90 mol%, in each case based on the sum of the oligomeric structures present from the group consisting of uretdione, isocyanurate, allophanate, biuret, iminooxadiazine, and oxadiazinetrione structures in the polyisocyanate.

[0057] It is still possible to use oligomeric polyisocyanates that largely lack an isocyanurate structure and mainly contain at least one of the above-mentioned uretdione, allophane, biuret, iminooxadiazindione and / or oxadiazintrione structure types. According to a particular embodiment of the invention, the oligomeric polyisocyanate used comprises at least 50 mol%, preferably 60 mol%, preferably 70 mol%, particularly preferably 80 mol%, and 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, iminooxadiazindione and oxadiazinetrione structures in the polyisocyanate, and from oligomeric polyisocyanates having a structure type selected from the group consisting of uretdione, allophanate, biuret, iminooxadiazine and / or oxadiazinetrione structures.

[0058] Preferably, a low-isocyanurate polyisocyanate is used which, based on the sum of the oligomeric structures present from the group consisting of uretdione, isocyanurate, allophane, biuret, iminooxadiazindione and oxadiazintrione structures in the polyisocyanate, has at most 50 mol%, preferably at most 40 mol%, preferably at most 30 mol%, particularly preferably at most 20 mol%, 10 mol% or 5 mol% isocyanurate structures.

[0059] The use of an oligomeric polyisocyanate of a single defined oligomeric structure type is preferred, wherein the oligomeric structure type is selected from the group consisting of uretdione, allophanate, biuret, iminooxadiazindione and / or oxadiazinetrione structures and this structure type is present to at least 50 mol%, preferably 60 mol%, preferably 70 mol%, particularly preferably 80 mol%, and in particular 90 mol%, based on the sum of the oligomeric structures present from the group consisting of uretdione, isocyanurate, allophanate, biuret, iminooxadiazine and oxadiazinetrione structures in the polyisocyanate.

[0060] The proportions of uretdione, isocyanurate, allophane, biuret, iminooxadiazindione, and / or oxadiazinetrione structures in the isocyanate-containing component b. can be determined, for example, by NMR spectroscopy. Preferably, 13C-NMR spectroscopy, preferably proton-decoupled, can be used, since the aforementioned oligomeric structures give characteristic signals.

[0061] Manufacturing processes for the oligomeric polyisocyanates with uretdione, isocyanurate, allophane, biuret, iminooxadiazindione and / or oxadiazintrione structure to be preferably used in 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.

[0062] A usable oligomeric polyisocyanate is preferably defined as 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%, and particularly preferably 15 to 30%. "Degree of oligomerization" here refers to the percentage of isocyanate groups originally present in the starting mixture that are consumed during the manufacturing process to form uretdione, isocyanurate, allophanate, biuret, iminooxadiazindione, and / or oxadiazinetrione structures.

[0063] The use of an isocyanate-terminated prepolymer as an 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.

[0064] Within the scope of the present invention, isocyanate-reactive groups are understood to be 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. Preferably, isocyanate-reactive groups are understood to be OH, NH, and / or SH.

[0065] Examples of compounds with isocyanate-reactive groups are monohydric, dihydric, and polyhydric alcohols with primary, secondary, and tertiary OH groups, analogous thiols, polyols (e.g., polyether, polyester, polyacrylate, and polycarbonate polyols), analogous polythiols, sulfur-containing hydroxy compounds, amines (e.g., primary, secondary, aliphatic, cycloaliphatic, aromatic, and sterically hindered), polyamines, and aspartic acid esters.

[0066] 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.

[0067] Polyether polyols can be accessed in a known manner by alkoxylation of suitable starter molecules under base catalysis or using double metal cyanide compounds (DMC compounds). Suitable starter molecules for the preparation 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 according to the DMC process, are especially simple polyols such as ethylene glycol, 1,3-propylene glycol and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 2-ethylhexanediol, glycerol, trimethylolpropane, pentaerythritol, as well as low-molecular-weight esters of such polyols containing hydroxyl groups with dicarboxylic acids of the type listed below as examples, or low-molecular-weight ethoxylation or propoxylation products of such simple polyols, or any mixtures of such modified or unmodified alcohols. Suitable alkylene oxides for alkoxylation are especially ethylene oxide and / or propylene oxide, which can be used in any order or mixture during the alkoxylation.

[0068] Polyester polyols can be produced in a known manner by polycondensation of low-molecular-weight polycarboxylic acid derivatives, such as succinic acid, adipic acid, cortic 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 form polyester polyols. Polyester polyols of oleochemical origin can also be used. Such polyester polyols can be prepared, for example, by complete ring opening of epoxidized triglycerides of a fat mixture containing at least partially olefinically unsaturated fatty acids with one or more alcohols with 1 to 12 carbon atoms, followed by partial transesterification of the triglyceride derivatives to alkyl ester polyols with 1 to 12 carbon atoms in the alkyl group.

[0069] The production of suitable polyacrylate polyols is known to those 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 the addition of propylene oxide to acrylic acid, and the hydroxypropyl methacrylate isomer mixture obtainable by the 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.

[0070] Amines can be any mono- or polyhydric 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 as. b.2-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 with 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).

[0071] Furthermore, polyamines, such as the polyaspartic acid derivatives known from EP-B 0 403 921, or polyamines whose amino groups are in a blocked form, such as polyketimines, polyaldimines, or oxazolanes, can also be used. Under the influence of moisture, these blocked amino groups become free amino groups, and in the case of oxazolanes, free hydroxyl groups also form, which can react by crosslinking with isocyanate groups.

[0072] Suitable amino-functional components are in particular polyaspartic acid esters, such as those obtainable according to the process of EP-B 0 403 921 by reacting diamines with fumaric acid or maleic acid esters.

[0073] Preferred amino-functional compounds are polyether polyamines with 2 to 4, preferably 2 to 3, and particularly preferably 2 aliphatic primary amino groups and a number-average molecular weight Mn of 148 to 12200, preferably 148 to 8200, particularly preferably 148 to 4000, and most preferably 148 to 2000 g / mol. Particularly suitable thiols are compounds having at least two thiol groups per molecule.

[0074] Preferred polythiols are selected, for example, from the group consisting of simple alkanethiols, such as methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol or 2-methylcyclohexane-2,3-dithiol, and polythiols containing thioether groups, such as... 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 mixture with each other.

[0075] Sulfur-containing hydroxy compounds are also suitable. Such compounds preferably contain at least one sulfur atom in the form of thio groups, thioether groups, thioesterurethane groups, esterthiourethane groups and / or polythioesterthiourethane groups, as well as at least one OH group.

[0076] Preferred sulfur-containing hydroxy compounds may 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 structures of the type specified in EP-A 1 640 394. Such sulfur-containing hydroxy compounds may be used individually or in any mixtures with one another.

[0077] Particularly preferred sulfur-containing compounds are polyether and polyester thiols of the type mentioned. Most particularly preferred compounds may 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).

[0078] Carboxylic acids, carboxylic anhydrides and epoxides are also suitable as compounds with isocyanate-reactive groups.

[0079] It is also possible that the isocyanate-reactive component comprises mixtures of different compounds with isocyanate-reactive groups.

[0080] In principle, the isocyanate-containing component b can contain any mixture of different polyisocyanates. These can be the mixtures of oligomeric and monomeric polyisocyanates already described above. They can also be mixtures of different isocyanate-terminated prepolymers. By freely combining all suitable polyisocyanates, it is possible to tailor the properties of the formulation and the coatings produced from it as desired.

[0081] It is also preferred for component b. containing isocyanate groups to be mixed with isocyanate-terminated prepolymers containing isocyanate groups and 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 to each other and to the isocyanate-terminated prepolymer by their isocyanate groups, they are bound in the formulation at the end of their preparation. They thus act as reactive diluents.

[0082] In a preferred embodiment of the formulation, the formulation exhibits at least one of the following properties at room temperature: (A) an initial viscosity in the range of 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 the range of 30 to 1000 mPas, preferably from 50 to 500 mPas, or preferably from 100 to 500 mPas; (C) an initial viscosity in the range of 50 to 2000 mPas, or preferably from 100 to 1500 mPas, or preferably from 150 to 1000 mPas; (D) a starting viscosity in the range of 1000 to 100000 mPas, preferably from 2000 to 90000 mPas, or preferably from 2500 to 50000 mPas; (E) an isocyanate group content of less than 60 wt.%, preferably less than 50 wt.%, or preferably less than 30 wt.%, or preferably less than 10 wt.%, or preferably less than 5 wt.%, based on the total amount of the formulation; where the formulation has one of the properties selected from (A) to (D) in combination with property (E).

[0083] Furthermore, the formulation preferably has an isocyanate group content in the range of 2 to 60 wt.%, or preferably in the range of 3 to 50 wt.%, or preferably in the range of 4 to 35 wt.%, or preferably in the range of 5 to 20 wt.%, based on the total amount of the formulation.

[0084] Preferably, the formulation has at least one of the following properties at room temperature: (A) an initial viscosity in the range of 5 to 20 mPas; or (B) an initial viscosity in the range of 100 to 500 mPas; or (C) an initial viscosity in the range of 150 to 1000 mPas; or (D) an initial viscosity in the range of 2500 to 50000 mPas; and / or (E) an isocyanate group content of less than 60% by weight, based on the total amount of the formulation; where the formulation has one of the properties selected from (A) to (D) in combination with property (E).

[0085] Furthermore, the formulation preferably has an isocyanate group content in the range of 5 to 20 wt.%, based on the total amount of the formulation.

[0086] Viscosity determinations (A) to (D) were performed using a Physica MCR 301 (Anton Paar GmbH) with a plate-to-plate (40 mm diameter) measuring geometry at a measuring temperature of 20 °C. All viscosity values ​​refer to a shear rate of 500 1 / s.

[0087] Preferably, the dispersed pigments in the formulation have a mean 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. It is also preferred that the distribution be monomodal. Furthermore, it is preferred that the distribution, as indicated by the polydispersity index (PDI), is less than 0.6, or preferably less than 0.45, or preferably less than 0.35, or preferably less than 0.2.

[0088] In a preferred embodiment of the formulation, the particle size increases by less than 500% when stored at 50 °C and atmospheric pressure for 3 days, relative to the initial particle size of the formulation, as measured by dynamic light scattering. The 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 are always based on the intensity signal (Z-average). The polydispersity index is also determined using the Zetasizer Nano ZS.

[0089] Component c. may contain either a wetting agent or a dispersing agent, or optionally both. Component c. may contain compounds that function as both wetting agents and dispersing agents. Any compound suitable for wetting pigments, as understood by a person skilled in the art, may be used as wetting agent c.

[0090] 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. These dispersants support the breaking up of agglomerates, wet and coat the surface of the particles to be dispersed as surface-active materials, and stabilize them against unwanted reagglomeration. Pigment stabilization is of great importance in the coatings industry, for example, because pigments, as key formulation components, determine the optical appearance and physicochemical properties of a coating. To ensure they can exert their optimal effect within the coating, they should be evenly and finely dispersed throughout the coating during the dispersion process.The preferably finely dispersed pigments should be stabilized to maintain this state during production, storage, processing, and subsequent application, such as film formation. Re-co-assemblage of the primary particles and aggregates can lead to sediment formation in the form of hard and / or soft deposits, increased viscosity, loss of gloss, insufficient color depth, low opacity, pigment floating and sedimentation, and poorly reproducible color tones, as already described in Goldschmidt, Streitberger; BASF Handbook of Coating Technology, BASF Münster and Vincentz Verlag Hannover 2002, pp. 205 ff.

[0091] Preferably, Bykjet ®< 9131, Efka ®< PX 4701, Disperbyk ®< 2200, or a mixture of at least two of these are used.

[0092] Experts know that many pigments, for example those used in printing inks, varnishes, or related applications, are difficult to disperse in formulations. To reduce the energy input required to disperse pigment particles in a liquid medium, wetting and dispersing agents are often used. A wide variety of substances are currently used as dispersing agents for pigments and fillers.

[0093] The dispersing agent 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 acid 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.

[0094] The dispersing agents preferably selected are those compounds as described in the following documents: EP 0 154 678 B1, EP 0 270 126 B1, EP 031899981, EP 041749081, EP 0879860 B1, EP 0893155 B1, EP 1081 169 B1, EP 1416019 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 are described.

[0095] Any compound that a person skilled in the art would select for a formulation as a grinding resin can be used as the grinding resin. Compounds with a defined number of isocyanate-reactive groups are preferably used as the grinding resin to ensure the formulation's storage stability. Preferably, the grinding resin is selected such that the desired ratio of isocyanate groups to isocyanate-reactive groups in the formulation can be maintained. Preferably, the grinding resin contains less than 15 wt.%, or more preferably less than 8 wt.%, or more preferably less than 5 wt.%, or more preferably less than 2 wt.%, based on the total amount of the grinding resin.

[0096] Examples of preferred compounds of the grinding resin d. are monohydric, dihydric, and polyhydric alcohols with primary, secondary, and / or tertiary OH groups, analogous thiols, polyols, e.g., polyether, polyester, polyacrylate, and polycarbonate polyols, analogous polythiols, sulfur-containing hydroxy compounds, amines (e.g., primary, secondary, aliphatic, cycloaliphatic, aromatic, sterically hindered), polyamines, aspartic acid esters, and condensation resins.

[0097] In a preferred embodiment of the formulation, the grinding resin d. is selected from the group consisting of (poly)alcohols, (poly)thiols, (poly)amines, condensation resins starting from a polyaldol reaction or a mixture of at least two thereof.

[0098] The condensation resins are preferably aldehyde resins. These can consist, for example, of urea and butyraldehyde. Such condensation resins are described, for example, in DE 102205060158 A1. Furthermore, condensation products of urea or its derivatives with formaldehyde and CH-acidic aldehydes are known from patent literature. For example, according to DE 1272284, ureidopropionaldehyde is obtained by reacting formaldehyde, urea, and CH-acidic aldehydes in stoichiometric proportions. Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2000 Electronic Release, describes the properties of various condensation resins based on isobutyraldehyde, urea, and formaldehyde in the chapter "Synthetic Resins," subchapter "Ketones and Aldehyde Resins," specifically in the section "Aldehyde Resins."For polyols, predominantly higher molecular weight polyhydroxy compounds such as polyether polyols, polyester polyols, polycarbonate polyols, polysiloxane polyols, and polybutadiene polyols are suitable.

[0099] Preferably, a non-yellowing condensation product of urea and aliphatic aldehydes (e.g., Laropal® < A 81) is used as the grinding resin. Alternatively, a weakly branched, hydroxyl-containing polyester (e.g., Desmophen® < 670) is preferably used as the non-yellowing grinding resin.

[0100] Polyether polyols can be accessed in a known manner by alkoxylation of suitable starter molecules under base catalysis or using double metal cyanide compounds (DMC compounds). Suitable starter molecules for the preparation 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 according to the DMC process, are especially simple polyols such as ethylene glycol, 1,3-propylene glycol and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 2-ethylhexanediol, glycerol, trimethylolpropane, pentaerythritol, as well as low-molecular-weight esters of such polyols containing hydroxyl groups with dicarboxylic acids of the type listed below as examples, or low-molecular-weight ethoxylation or propoxylation products of such simple polyols, or any mixtures of such modified or unmodified alcohols. Suitable alkylene oxides for alkoxylation are especially ethylene oxide and / or propylene oxide, which can be used in any order or mixture during the alkoxylation.

[0101] Polyester polyols can be produced in a known manner by polycondensation of low-molecular-weight polycarboxylic acid derivatives, such as succinic acid, adipic acid, cortic 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 form polyester polyols. Polyester polyols of oleochemical origin can also be used. Such polyester polyols can be prepared, for example, by complete ring opening of epoxidized triglycerides of a fat mixture containing at least partially olefinically unsaturated fatty acids with one or more alcohols with 1 to 12 carbon atoms, followed by partial transesterification of the triglyceride derivatives to alkyl ester polyols with 1 to 12 carbon atoms in the alkyl group.

[0102] The production of suitable polyacrylate polyols is known to those 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 the addition of propylene oxide to acrylic acid, and the hydroxypropyl methacrylate isomer mixture obtainable by the 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.

[0103] Furthermore, polyamines, such as the polyaspartic acid derivatives known from EP-B 0 403 921, or polyamines whose amino groups are in a blocked form, such as polyketimines, polyaldimines, or oxazolanes, can also be used. Under the influence of moisture, these blocked amino groups become free amino groups, and in the case of oxazolanes, free hydroxyl groups also form, which can react by crosslinking with isocyanate groups.

[0104] Sulfur-containing hydroxy compounds are also suitable. Such compounds preferably contain at least one sulfur atom in the form of thio groups, thioether groups, thioesterurethane groups, esterthiourethane groups and / or polythioesterthiourethane groups, as well as at least one OH group.

[0105] Particularly preferred sulfur-containing compounds are polyether and polyester thiols of the type mentioned.

[0106] The abrasive resin can also consist of any mixture of the various compounds described for component d.

[0107] Suitable solvents are all solvents that preferably dissolve the isocyanate-containing component completely. Solvents that do not react or react only slowly with isocyanates and preferably dissolve them completely, and that have a boiling point > 30°C and ≤ 300°C, are preferred. Solvents with a low water content are also preferred, preferably less than 1 wt%, preferably less than 0.5 wt%, or preferably less than 0.1 wt%, or preferably less than 0.01 wt%, based on the total amount of solvent.

[0108] Examples of solvent-containing structural elements selected from ketones, esters, ethers, alicyclic rings, heterocyclic rings, aromatics, chlorine and any mixtures thereof are mentioned, such as ethyl acetate, butyl acetate, methoxypropyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, solvent naphtha ®< 100 and their mixtures.

[0109] Preferred solvents are methyl ethyl ketone, ethyl acetate, butyl acetate, butyl glycol acetate and 2-ethylhexyl acetate.

[0110] The solvent e. can either be a single solvent or any mixture of at least 2 preferably aforementioned solvents.

[0111] If the solvent 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. Preferably, the content of isocyanate-reactive groups in the solvent is less than 20 wt.%, or more preferably less than 10 wt.%, or more preferably less than 5 wt.%, or more preferably less than 3 wt.%, based on the total amount of solvent. Examples

[0112] All percentages that refer to weight always refer to weight percent, unless otherwise stated.

[0113] All viscosity determinations were performed using a Physica MCR 301 (Anton Paar GmbH) with a plate-to-plate (40 mm diameter) measuring geometry at a measuring temperature of 20 °C. All viscosity values ​​refer to a shear rate of 500 1 / s unless otherwise specified. The initial viscosity is defined according to the invention as the viscosity after 1 hour following the combination of all desired components, in particular the selected components a. to e.

[0114] 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 measured values ​​refer to the intensity signal (Z-average).

[0115] Agglomerated pigment particles were broken down during the production of pigment pastes. This required a high energy input into the material being ground. This energy input can be achieved, for example, through 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. Subsequently, pre-dispersion was performed for 10 minutes at 10,000 rpm using a dispersing disc (30 mm diameter) until a homogeneous mass (ground material) was obtained. The dispersing tool was then replaced with a single polyamide grinding disc (32 mm diameter).Zirconium oxide beads (yttrium-stabilized) with a mean diameter of 0.6 to 0.8 mm were then added to the material being ground. Under continuous cooling, the material was finely ground for 90 minutes at a rotational speed of 14,000 rpm. After dispersion, the grinding beads were removed by filtration.

[0116] The preparation of the pigmented isocyanate-containing formulations was carried out as follows: The pigmented paste was placed in a 30 mL glass container. The solvent (if included in the formulation) was then added stepwise while stirring. Finally, the isocyanate component was added stepwise while stirring. The mixture was shaken and homogenized for 30 minutes on a roller mixer (KG TRM50, IDL GmbH & Co. KG). materials

[0117] Organic pigments can be obtained, for example, from Clariant SE. Inorganic titanium dioxide can be obtained, for example, from Kronos Worldwide Inc. Black carbon black pigments can be obtained, for example, from Orion Engineered Carbons GmbH, as was the case for the test results listed below. Table 1: Pigments Nr. name Manufacturer Pigment color Color Index Pigment class (chemical) Density (g / cm³< ) Primary particle size (nm) 1 Hostaperm® Blue BT-617-D Clariant SE Cyan PB 15:4 Phthalocyanin 1,62 65 2 Inkjet Magenta 5EB02 Clariant SE magenta PV 19 Quinacridone 1,5 70 3 Inkjet Yellow 4GC Clariant SE Yellow PY 155 Disazo 1,5 90 4 Kronos ®< 2310 Kronos Worldwide Inc. White PW 6 titanium dioxide 4 *kA 5 NIPex® < 35 Orion Engineered Carbons GmbH Black P. Bk. 7 Furnace soot *kA 31 * kA = no information

[0118] Grinding resins are available from a wide variety of manufacturers. Suitable grinding resins can be obtained from BASF SE or Covestro AG, among others, as was the case for the test results listed below. Table 2: Grinding resins Nr. name Manufacturer Class (chemical) OH number (mg KOH / g) Acid value (mg KOH / g) 1 Laropal A81 BASF SE Condensation resin made from urea and aliphatic aldehydes 40 ≤ 3 2 Desmophen 670 Covestro AG Hydroxyl-containing polyester 141,9 2 ± 1

[0119] Both grinding resins from Table 2 were always used diluted to 70 wt% in butyl acetate.

[0120] Solvents are available from a wide variety of manufacturers. Suitable solvents can be obtained from Sigma-Aldrich, among others, as was the case for the test results listed below. Table 3: Solvents Nr. solvents CAS number Manufacturer 1 Butyl acetate (BuAc) ACS reagent, ≥99.5% (GC) 123-86-4 Sigma-Aldrich 2 Butyl glycol acetate (BGA) 99% 112-07-2 Sigma-Aldrich

[0121] Wetting and dispersing agents (also called dispersing additives) can be obtained from various manufacturers. Among others, Byk Additives & Instruments GmbH and BASF SE offer such additives, as was the case for the test results listed below. Table 4: Web and dispersing additive (component c.) Nr. Dispersing additive Manufacturer structure Sum of hydroxyl, amine and acid values ​​based on the additive's delivery form (mg KOH / g) nfA (%) 1 Bykjet ®< 9131 Byk Additives & Instruments GmbH Solution of a structured copolymer with pigment-affine groups 144 40 2 Efka ®< PX 4701 BASF SE Acrylate block copolymer 40 100 3 Disperbyk ®< 2200 Byk Additives & Instruments GmbH High molecular weight copolymer with pigment-affine groups n / a 100

[0122] Isocyanates corresponding to component b. can be obtained from various manufacturers. Among others, Covestro AG offers such isocyanates, as was the case for the test results listed below. Table 5: Isocyanates (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 ≤ 0.3% according to DIN EN ISO 10283 3 Desmodur ®< N3600 Covestro AG Aliphatic polyisocyanate (low viscosity HDI trimerisate) 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 content of monomeric HDI ≤ 0.25 % according to M106-ISO 10283. Table 6: Examples at different NCO / OH ratios. Example / Weight [g] paste 1 (Comparison) 2 3 4 5 6 7 8 Grinding resin d. Laropal ®< A81 (70% in BuAc) 6,71 6,71 6,71 Desmophen ® < 670 (70% in BuAc) 7,49 7,49 7,49 7,49 7,49 Pigments a. Cyan 41,15 41,15 37,26 41,15 37,26 41,15 41,15 37,26 Additive (wetting and / or dispersing agent) c. Bykjet ®< 9131 44,03 44,03 40,1 44,03 40,1 44,03 44,03 40,1 solvents e. BuAc / BGA 1:2 7,33 7,33 15,93 7,33 15,93 7,33 7,33 15,93 Formulation* 1 (Comparison) 2 3 3 4 5 6 7 Paste made from components a. + c. - e. 1,75 2,9 3 2 1,5 1 1 1 BuAc / BGA 1:2 component e. 0,85 2,26 2,46 1,95 2,46 2,44 3,39 3,44 Desmodur ®< N3600 component b. 2,00 5,28 5,73 4,55 5,74 5,69 7,91 8,04 NCO / NCO reactive groups 5:1 8:1 10:1 10:1 20:1 25:1 35:1 42:1 Initial viscosity [mPa*s] 127 113 74 71 69,4 67 58,4 56 Relative change in viscosity [%] after a, b days of storage at 50 °C 1168 a< 369 a< 320 b< 323 b< 148 b< 100 b< 75 b< 71 b< Relative change in Z-average [%] after 14 days of storage at 50 °C nb** nb** nb** nb** -17,0 -12,9 -15,0 -12,6 According to the invention No Yes Yes Yes Yes Yes Yes Yes Stable No Yes Yes Yes Yes Yes Yes Yes * Formulations 1 to 8 were each prepared from pastes 1 to 8, ** not determined, a: after 3 days, b: after 14 days Table 7: further examples of the invention Example / Weight [g] 9 10 11 12 13 14 15 16 17 18 paste Grinding resin d. (from Table 2) Laropal ®< A81 (70% in BuAc) 6,71 54,83 6,79 50,06 29,66 6,71 6,79 6,71 6,79 45,87 Pigments a. (from Table 1) Cyan 1 37,26 37,26 37,26 Magenta 2 21,70 Yellow 3 37,77 37,77 37,77 White 4 36,70 35,7 Black 5 23,63 Wetting and dispersing agents c. (from Table 4) Bykjet ®< 9131 40,10 40,58 40,10 40,58 40,10 40,58 Efka ®< PX 4701 13,01 3,58 Disperbyk ®< 2200 5,03 1,65 Solvents e.g. (from Table 3) BuAc / BGA 1:2 15,93 18,45 14,85 11,59 33,7 15,93 14,85 15,93 14,85 14,85 Formulation* 9 10 11 12 13 14 15 16 17 18 paste 1,61 1,40 1,59 0,82 1,27 0,81 0,79 0,81 0,79 0,84 BuAc / BGA 1:2 5,52 2,58 5,52 2,75 2,62 0,92 0,92 2,75 Isocyanate b. (from Table 5) Desmodur® < H 9,19 9,21 Desmodur® < N3400 8,28 8,29 Desmodur® < N3600 12,87 6,02 12,89 6,43 6,11 6,41 NCO / NCO-reactive groups 42:1 87:1 42:1 172:1 110:1 128:1 130:1 51:1 51:1 166:1 Initial viscosity [mPa*s] 53,4 68,2 62,9 60 55 3,2 3,0 105 103 55,1 Relative change in Z-average [%] after 14 days of storage at 50 °C -11,6 5,5 -16,8 3,2 -5,4 -13,7 51,21 -13,4 -14 8,2 Relative change in viscosity [%] after 14 days of storage at 50 °C 35,6 45 23,1 29 50 22 33 51 83 34,8 According to the invention Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Stable Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes * Formulations 9 to 18 were each prepared from pastes 9 to 18.

[0123] Example 1 shows a viscosity increase of more than 500% after three days of storage at 50°C and is therefore not according to the invention. All other examples are according to the invention.

Claims

1. Process for preparing an isocyanate group-containing formulation at least comprising the steps: i. dispersing at least one pigment in at least one grinding resin in the presence of at least one wetting agent and / or dispersant, to obtain a pigment dispersion, ii. optionally diluting the pigment dispersion obtained from step i. with solvent, iii. mixing the pigment dispersion from step i. or step ii. with an isocyanate group-containing component to obtain the isocyanate group-containing formulation, wherein the molar ratio of the sum of the isocyanate groups to the sum of all isocyanate-reactive groups in the formulation is at least 8:1.

2. Process according to Claim 1, wherein the formulation is storage stable and contains: a. 0.01% to 45% by weight of at least one pigment; b. 1% to 99% by weight of at least one isocyanate group-containing component; c. 0.01% to 20% by weight of at least one wetting agent and / or dispersant; d. 0.1% to 30% by weight of at least one grinding resin; e. 0% to 80% by weight of solvents; based in each case on the total amount of the formulation, with the sum of all constituents in the formulation not exceeding 100% by weight, and wherein furthermore the formulation after storage at 50°C over a period of at least 3 days exhibits a rise in viscosity of less than 500%, based on the starting viscosity of the formulation, measured in accordance with the description.

3. Process according to Claim 1 or 2, wherein the isocyanate group-containing component 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 reaction products of these.

4. Process according to any of the preceding claims, wherein the isocyanate group-containing component consists of aliphatic or cycloaliphatic isocyanates.

5. Process according to any of the preceding claims, wherein the grinding resin is selected from the group consisting of (poly)alcohols, (poly)thiols, (poly)amines, condensation resins originating from a polyaldol reaction or a mixture of at least two of these.