STORAGE-STABLE PIGMENTED ISOCYANATE GROUP-CONTAINING FORMULATIONS WITH ISOCYANATE GROUP-CONTAINING GRINDING RESIN AND USE THEREOF

Abstract

The invention relates to storage-stable pigmented formulations containing isocyanate groups, comprising at least one pigment a., at least one component b. containing isocyanate groups, at least one wetting agent and/or dispersant c., at least one isocyanate group-containing grinding resin d. and optionally solvents, wherein the formulation has a viscosity increase of less than 500% after storage at 50° C. over a period of at least 3 days. The invention also relates to the preparation of such formulations and to the use thereof

Claims

1. A storage-stable, isocyanate group-containing formulation comprising the components: a. at least one pigment; b. optionally at least one isocyanate group-containing component which has free isocyanate groups; c. at least one wetting agent and/or dispersant; d. at least one isocyanate group-containing grinding resin comprising free isocyanate groups; and e. optionally solvents, wherein 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 a starting viscosity of the formulation which is determined as of 1 hour after combining all of the components, wherein the viscosity determination is carried out in each case at 20° C. at a shear rate of 500 [1/s], wherein the a molar ratio of the sum of all isocyanate groups of the isocyanate group-containing formulation to the sum of all isocyanate-reactive groups which are not isocyanate groups in the formulation is at least 8:1.

2. The isocyanate group-containing formulation as claimed in claim 1, wherein the isocyanate group-containing grinding resin d. has a viscosity in a range from 100 to 5000 mPas.

3. The formulation as claimed in claim 1, comprising: a. 0.01% to 45% by weight of the at least one pigment; b. 0% to 99% by weight of the at least one isocyanate group-containing component which has free isocyanate groups; c. 0.01% to 20% by weight of the at least one wetting agent and/or dispersant; d. 0.1° A to 35% by weight of the at least one isocyanate group-containing grinding resin comprising free isocyanate groups; e. 0% to 80% by weight of the solvents; in each case based on a total amount of the formulation, with the sum of all constituents in the formulation not exceeding 100% by weight.

4. The formulation as claimed in 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/or 2,4,4-trimethyl-1 ,6-diisocyanatohexane,1,10-diisocyanatodecane, 1,3- and/or 1,4-bis(isocyanatomethyl)benzene (XDI), 1,3- and/or 1,4-bis(1-isocyanato-1-methylethyl)benzene (TMXDI), 2,4- and/or 2,6-diisocyanatotoluene (TDI), 2,4′- and/or 4,4′-diisocyanatodiphenylmethane (MDI), 1-1,5-diisocyanatonaphthalene, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 1-isocyanato-1-methyl4(3)-isocyanatomethylcyclohexane, 2,4′- and/or 4,4′-diisocyanatodicyclohexylmethane (H12MDI), era mixture of at least two of these, and optionally oligomers and reaction products of these.

5. The formulation as claimed in claim 1, 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/or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1-1,10-diisocyanatodecane, 1,3- and/or 1,4-bis(isocyanatomethyl)benzene (XDI), 1,3- and/or 1,4-bis(1-isocyanato-1-methylethyl)benzene (TMXDI), 2,4- and/or 2,6-diisocyanatotoluene (TDI), 2,4′- and/or 4,4′-diisocyanatodiphenylmethane (MDI), 1,5-diisocyanatonaphthalene, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 1-isocyanato-1-methyl-4(3)-isocyanatomethylcyclohexane, 2,4′- and/or 4,4′-diisocyanatodicyclohexylmethane (H12MDI), a mixture of at least two of these, and optionally oligomers and reaction products of these.

6. The formulation as claimed in claim 1, wherein the isocyanate group-containing component b. and the isocyanate group-containing grinding resin d. comprise aliphatic or cycloaliphatic isocyanates or mixtures of these.

7. The formulation as claimed in claim 1, 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 greater than 3%, based on a total amount of the formulation, wherein the formulation has one of the properties selected from (A) to (D) in combination with property (E).

8. The formulation as claimed in claim 1, wherein the formulation exhibits a rise in particle size on storage at 50° C. and standard pressure over a period of 3 days of less than 500%, based on an original particle size of the formulation, based on the intensity-weighted harmonic mean of the hydrodynamic diameter (Z-average) measured by dynamic light scattering.

9. A process for preparing an isocyanate group-containing formulation comprising: i. dispersing at least one pigment a. in at least one isocyanate group-containing grinding resin d. which has free isocyanate groups in the presence of at least one wetting agent and/or dispersant c., to obtain a pigment dispersion, ii. optionally diluting the pigment dispersion obtained from step i. with solvent e., iii. optionally mixing the pigment dispersion from step i. or step ii. with an isocyanate group-containing component b. to obtain the isocyanate group-containing formulation, wherein a molar ratio of the sum of the isocyanate groups to the sum of all isocyanate-reactive groups which are not isocyanate groups in the formulation is at least 8:1.

10. The process for preparing an isocyanate group-containing formulation as claimed in claim 9, wherein the further processing of the initially prepared pigment dispersion i. obtained to form the isocyanate group-containing formulation iii. occurs within 60 minutes.

11. A method of coating a substrate surfaces to obtain a coated objects, comprising applying the storage-stable, isocyanate group-containing formulation of claim 1 to at least a portion of the substrate surface.

12. A coated object obtained as claimed in claim 11.

13. The object as claimed in claim 11, wherein the material of the object comprises textile, wood, plastic, glass, ceramic, carbon, metal, or a combination of at least two of these.

14. An ink, comprising the storage-stable, isocyanate group-containing formulation of claim 1.

15. A method of preparing storage-stable, isocyanate group-containing formulations, comprising preparing the formulation with a grinding resin comprising at least one isocyanate group-containing resin comprising free isocyanate groups.

Description

EXAMPLES

[0270] Agglomerated pigment particles were comminuted during the production of pigment pastes. A high input of energy into the material to be ground was necessary for this. The energy can be input, for example, by means of ultrasound, rotor-stator systems or roller mills. A further method known to those skilled in the art is the grinding of the particle agglomerates in the medium in which they are to be dispersed, for example in ball or bead mills. The production of pigmented pastes was produced using a Dispermat LC30 (VMA-Getzmann GmbH) in a 125 ml double-walled temperature-controlled vessel made from stainless steel. 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 added. Subsequently, the mixture was predispersed using a dispersing disk (diameter 30 mm) for 10 minutes at 10 000 rpm until a homogeneous material (material to be ground) was formed. The dispersing tool was then replaced by a single grinding disk made from polyamide (diameter 32 mm). Zirconium oxide beads (yttrium-stabilized) having an average diameter of 0.6 to 0.8 mm were subsequently added to the material to be ground. The material to be ground was finely ground for 90 minutes at a rotational speed of 14 000 rpm with continuous cooling. After dispersion, the grinding beads were removed by filtration.

[0271] The pigmented isocyanate group-containing formulations were prepared using an isocyanate group-containing grinding resin as follows:

[0272] The pigmented paste was initially charged in a 30 ml glass vessel within at most 60 minutes following its preparation. The solvent (if present in the formulation) was subsequently added gradually with stirring. In a final step, the isocyanate component was added gradually with stirring until a homogeneous mixture was obtained.

[0273] Materials

[0274] Organic pigments were obtained from Clariant SE, inorganic titanium dioxide was obtained from Kronos Worldwide Inc. and black carbon black pigments were obtained from Orion Engineered Carbons GmbH. The precise product designations can be seen in Table 1.

TABLE-US-00001 TABLE 1 Pigments (component a.) Primary Pigment Pigment class Density particle No. Name Manufacturer color Color Index (chemical) (g/cm.sup.3) size (nm) 1 Hostaperm ® Blue Clariant SE Cyan P.B 15:4 Phthalocyanine 1.62 65 BT-617-D 2 Inkjet Magenta Clariant SE Magenta P.V. 19 Quinacridone 1.5 70 5EB02 3 Inkjet Yellow 4GC Clariant SE Yellow P.Y. 155 Disazo 1.5 90 4 Kronos ® 2310 Kronos White P.W. 6 Titanium dioxide 4 n.s.* Worldwide Inc. 5 NIPex ® 35 Orion Black P. Bk. 7 Furnace carbon n.s. 31 Engineered black Carbons GmbH *n.s. = not specified

[0275] Solvents are available from a large number of manufacturers. Solvents from Sigma-Aldrich and Fluka were used for the patent examples.

TABLE-US-00002 TABLE 2 Solvent (component d.) CAS No. Solvent number Manufacturer 1 Butyl acetate (BuAc) ACS reagent, 123-86-4 Sigma-Aldrich ≥99.5% (GC) 2 Butyl glycol acetate (BGA) 99% 112-07-2 Sigma-Aldrich 3 p-Xylene, puriss. p.a. ≥99.0% (GC) 106-42-3 Fluka

[0276] Wetting and dispersing auxiliaries (also called dispersing additives) can be obtained from various manufacturers. Products from Byk Additives & Instruments GmbH were used for the patent examples.

TABLE-US-00003 TABLE 3 Wetting and dispersing additive (component c.) Sum of hydroxyl, amine and acid numbers Content based on of non- the additive volatile Dispersing as supplied matter No. additive Manufacturer Structure (mg KOH/g) (%) 1 Bykjet ® Byk Additives & Solution of a structured 144 40 9131 Instruments GmbH copolymer with groups having pigment affinity 3 Disperbyk ® Byk Additives & High molecular weight 30.7 100 2200 Instruments GmbH copolymer with groups having pigment affinity

[0277] Isocyanate group-containing compounds were obtained from Covestro AG.

TABLE-US-00004 TABLE 4 Isocyanate group-containing compounds (component b.) No. Isocyanate Manufacturer NCO content (%) 1 Desmodur ® Covestro AG Hexamethylene diisocyanate (HDI), monomeric aliphatic diisocyanate having H a molar mass 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 ® Covestro AG Aliphatic polyisocyanate (HDI uretdione) with an NCO content of 21.8 ± 0.7% N3400 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 content of monomeric HDI ≤0.3% according to DIN EN ISO 10283 3 Desmodur ® Covestro AG Aliphatic polyisocyanate (low-viscosity HDI trimer) with an NCO content of N3600 23.0 ± 0.5% according to M105-ISO 11909, a viscosity at 23° C. of 1200 ± 300 mPas according to M014-ISO 3219/A.3 and a content of monomeric HDI ≤0.25% according to M106-ISO 10283.

TABLE-US-00005 TABLE 5 Isocyanate group-containing grinding resin (component d.) No. Isocyanate Manufacturer NCO content (%) 1 Desmodur ® Covestro AG Aliphatic polyisocyanate (low-viscosity HDI trimer) N3600 with an NCO content of 23.0 ± 0.5% according to M105-ISO 11909, a viscosity at 23° C. of 1200 ± 300 mPas according to M014-ISO 3219/A.3 and a content of monomeric HDI ≤0.25% according to M106-ISO 10283.

TABLE-US-00006 TABLE 6 Formulations 1-12 with various NCO/NCO-reactive group ratios. 1 Example/initial weight [g] (comparative) 2 3 4 5 6 7 Paste Isocyanate group-containing grinding resin d. (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 agent and/or dispersant 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.sup.x) Paste composed of 4.39 1.58 2.36 1.65 0.71 0.71 0.71 components a.-d. 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 Starting viscosity [mPa*s] 110.0 51.4 62.5 53.7 53.6 2.8 72.2 Rel. change in viscosity [%], after Solid.sup.a) 46.3.sup.b) 58.2.sup.b) 53.8.sup.b) 22.0.sup.b) 6.1.sup.b) 27.6.sup.b) a, b days of storage at 50° C. Rel. change in the Z-average [%], n.d..sup.xx) −7.6 −2.4 −5.6 −0.8 36.9 −6.7 after 14 days of storage at 50° C. According to the invention No Yes Yes Yes Yes Yes Yes Stable No Yes Yes Yes Yes Yes Yes Example/initial weight [g] 7 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 agent and/or dispersant c. (from Table 3) Bykjet ® 9131 Disperbyk ® 2200 12.68 12.68 12.68 5.87 5.87 5.87 Solvents d. (from Table 2) BuAc/BGA 1:2 p-Xylene 29.57 29.57 29.57 23.48 23.48 23.48 Formulation.sup.x) Paste from components 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 Starting viscosity [mPa*s] 73.7 4.4 100.5 60.4 3.6 82.9 Rel. change in viscosity [%] after a, b days of 52.0.sup.b) 1.0.sup.b) 37.0.sup.b) 36.0.sup.b) 9.0.sup.b) 42.0.sup.b) storage at 50° C. Rel. change in the Z-average [%] after 14 3.0 −8.1 −1.2 6.6 5.2 23.0 days of storage at 50° C. According to the invention Yes Yes Yes Yes Yes Yes Stable Yes Yes Yes Yes Yes Yes .sup.x)Formulations 1-13 were prepared from pastes 1-13, .sup.xx)could not be determined (solid), a: after 3, b: after 14 days

[0278] Example 1 was solid after three days of storage at 50° C. and a determination of the viscosity was no longer possible. Example 1 is therefore not in accordance with the invention. Examples 2 to 13 exhibit a rise in viscosity of less than 500% within 14 days and are therefore in accordance with the invention.