Multi component dispersant

Abstract

The invention relates to a composition comprising i) 10-90 wt. % of an ethylenically unsaturated component (A), ii) 10-90 wt. % of a component (B) having urethane and/or urea groups, iii) 0-4 wt. % of an organic component (C) which is different from components (A) and (B), and iv) 0-9 wt. % of other ingredients (D) wherein the wt. % are calculated on the total weight of the composition, wherein the sum of the wt. % of component (A) and the wt. % of component (B) is 91-100 wt. %, component (A) consists of compounds having 1-8 ethylenically unsaturated bonds and a molar mass of 100-1400 g/mol, component (A) contains no amino groups, component (B) contains no primary and no secondary amino groups, component (B) consists of compounds having 2-40 functional groups selected from urethane and urea groups, having 1-40 groups selected from tertiary amino groups, salts thereof, quaternary ammonium groups, and mixtures thereof, component (B) contains not more tertiary amino groups than the sum of urethane and urea groups, and component (B) has a nitrogen content in the range of 1.0 to 12.0 wt. %, component (C) consists of organic compounds having a molar mass of less than 1000 g/mol.

Claims

1. A composition comprising: i) 10-90 wt. % of an ethylenically unsaturated component (A), ii) 10-90 wt. % of a component (B) comprising urethane and/or urea groups, iii) 0-4 wt. % of an organic component (C) which is different from components (A) and (B), and iv) 0-9 wt. % of other ingredients (D), wherein the weight percentages are calculated based on the total weight of the composition, wherein the sum of the wt. % of component (A) and the wt. % of component (B) is 91-100 wt. %, component (A) comprises at least one compound including 1-8 ethylenically unsaturated bonds and a molar mass of 100-1400 g/mol, and component (A) contains no amino groups, component (B) contains no primary and no secondary amino groups, component (B) comprises at least one compound including 2-10 functional groups selected from urethane and urea groups, and including 1-40 groups selected from tertiary amino groups and salts thereof, quaternary ammonium groups, and mixtures thereof, component (B) contains not more tertiary amino groups than the sum of urethane and urea groups, and component (B) has a nitrogen content in the range of 1.0 to 12.0 wt. %, component (C) comprises at least one organic compound having a molar mass of less than 1000 g/mol.

2. The composition according to claim 1 comprising i) 25-75 wt. % of component (A), ii) 25-75 wt. % of component (B), iii) 0-2 wt. % of component (C), and iv) 0-2 wt. % of other ingredients (D), wherein the sum of the wt. % of component (A) and the wt. % of component (B) is 98-100 wt. %.

3. The composition according to claim 1 wherein at least 70 wt. % of component (A) is selected from species comprising (meth)acryl groups.

4. The composition according to claim 1, wherein at least 70 wt. % of component (A) comprises species including 2-4 ethylenically unsaturated bonds.

5. The composition according to claim 1, wherein at least 70 wt. % of component (A) is selected from species having a proportion of carbon atoms to ethylenically unsaturated bonds of from 12:1 to 3:1.

6. The composition according to claim 1, wherein component (B) has a molecular weight distribution and has a number-average molecular weight M.sub.n in the range of 2000-200000 g/mol.

7. The composition according to claim 1, wherein component (B) has a nitrogen content in the range of 4-9 wt. %.

8. The composition according to claim 1, wherein component B has an iodine value in the range of 0.0 to 10.0.

9. The composition according to claim 1, wherein at least 90 wt. % of component (B) comprises one or more adducts which are obtained by reacting one or more polyisocyanates (a) having at least two isocyanate groups per molecule with one or more compounds (b) of the formula (I)
Y—(XH).sub.n  (I) where XH is a group that is reactive towards isocyanates, and Y is a monomeric or polymeric group that is not reactive towards isocyanates, the monomeric or polymeric group contains no tertiary amino groups and no hydrolysable silane groups, and the monomeric or polymeric group comprises one or more aliphatic, cycloaliphatic and/or aromatic groups, and where the one or more compounds (b) of the formula (I) possess a number-average molar mass M.sub.n of 32 to 15000 g/mol and do not fall within the definition of component (c1) or component (c2), and n is 1, 2 or 3, where n is 1 for at least 50 mol. % of the one or more compounds (b) of the formula (I), with the proviso that 20% to 90% of the isocyanate groups of the one or more polyisocyanates (a) are reacted with the one or more compounds of the formula (I), and one or more compounds (c1) of the general formula (IIa)
Z-Q  (IIa) in which Q is —NH.sub.2, —NHR or OH, in which R is a linear or branched organic group having 1 to 18 carbon atoms, and Z is an organic group comprising at least one tertiary amino group and containing no isocyanate-reactive groups, and optionally one or more compounds (c2) different from the one or more compounds (c1), the one or more compounds (c2) being of the general formula (IIb)
M-Q  (IIb) in which Q is —NH.sub.2, —NHR or OH, in which R is a linear or branched organic group having 1 to 18 carbon atoms, and M is an organic group having a number-average molar mass of not more than 1000 g/mol and comprising at least one tertiary amino group and at least one hydroxyl group, with the proviso that at least 10% of the isocyanate groups of the one or more polyisocyanates (a) are reacted with component (c1).

10. The composition according to claim 9, wherein for at least 70 wt. % of the component (B), Z comprises one or more of j) an aliphatic and/or cycloaliphatic group comprising at least one tertiary amino group, or k) a heterocyclic group comprising at least one basic ring nitrogen atom that does not contain a hydrogen atom, the heterocyclic group optionally being attached to the group Q via an organic coupling group.

11. The composition according to claim 9, wherein for at least 70 wt. % of the component (B), mono-functional species of the formula (I) are selected from monohydroxy-functional polyethers, polyesters, polyether-polyesters, aliphatic and/or cycloaliphatic monoalcohols having 2 to 30 carbon atoms, and mixtures thereof.

12. The composition according to claim 9, wherein for at least 70 wt. % of the component (B), the one or more polyisocyanates (a) are products containing one or more isocyanurate groups, of diisocyanates based on hexamethylene diisocyanate, diisophorone diisocyanate and/or tolylene diisocyanate.

13. The composition according to claim 1, wherein the composition is a liquid at a temperature of 23° C.

14. The composition according to claim 1, wherein the composition has an amine value in the range of 2-50 mg KOH/g.

15. The composition according to claim 1 containing no primary and no secondary amines.

16. The composition according to claim 1 containing no free radical initiator.

17. A coating composition comprising solid particles and the composition according to claim 1.

18. The composition according to claim 1, wherein: component (A) consists of compounds having 1-8 ethylenically unsaturated bonds and a molar mass of 100-1400 g/mol, and component (A) contains no amino groups; component (B) contains no primary and no secondary amino groups, component (B) consists of compound having 2-10 functional groups selected from urethane and urea groups, having 1-40 groups selected from tertiary amino groups and salts thereof, quaternary ammonium groups, and mixtures thereof, component (B) contains not more tertiary amino groups than the sum of urethane and urea groups, and component (B) has a nitrogen content in the range of 1.0 to 12.0 wt. %; and component (C) consists of organic compounds having a molar mass of less than 1000 g/mol.

19. The composition according to claim 1, wherein at least 70 wt. % of component (A) comprises species including 2-3 ethylenically unsaturated bonds.

20. An ink comprising solid particles and the composition according to claim 1.

21. A polymer system comprising solid particles and the composition according to claim 1.

Description

(1) The invention will be explained below in more detail, using examples. Unless otherwise remarked, parts are parts by weight and percentages are percentages by weight.

(2) Measurement Methods:

(3) In the case of substances without molecular uniformity the stated molecular weights (molar mass)—below as already in the foregoing description—represent average values of the numerical mean. The molar mass or number-average molecular weights M.sub.n, are determined, when titratable hydroxyl or amino groups are present, by end-group determination via the determination of the OH number or amine number, respectively. In the case of compounds to which an end-group determination cannot be applied, the molar mass or number-average molecular weights (Mr) is determined by means of gel permeation chromatography against a polystyrene standard.

(4) Applied Gel Permeation Chromatography (GPC)

(5) The gel permeation chromatography was carried out at 40° C. with a high-pressure liquid chromatography pump (Bischoff HPLC 2200) and a refractive index detector (Waters 419). The eluent used was tetrahydrofuran, with an elution rate of 1 ml/min. The calibration was performed using polystyrene standards.

(6) Measurement of Non-Volatile Content (Solids Content)

(7) The sample (2.0±0.2 g of the tested substance) was weighed accurately into a previously dried aluminum dish and dried for 20 minutes at 150° C. in the varnish drying cabinet, cooled in a desiccator and then reweighed. The residue corresponds to the solids content in the sample (ISO 3251).

(8) Measurement of Hydroxyl Numbers

(9) Determination of the hydroxyl numbers was done according to DIN ISO 4629. The alcoholic hydroxyl groups were reacted by acetylation with an excess of acetic anhydride. The excess acetic anhydride was hydrolyzed to acetic acid by adding water and titrated back using ethanolic KOH solution. The hydroxyl number is understood to be the KOH quantity in mg, which is equivalent to the acetic acid quantity bound when acetylating 1 g of substance.

(10) Measurement of Amine Numbers

(11) The amine number is the amount KOH in mg which corresponds to the amine content of 1 g of substance. The amine number is determined according to DIN 16945 by potentiometric titration with 0.1 N perchloric acid in acetic acid.
R—NH.sub.2+HClO.sub.4.fwdarw.R—NH.sub.3.sup.++ClO.sub.4.sup.−

(12) NCO Content

(13) The free NCO content of the polyisocyanates employed and also the course of the NCO addition reactions, are determined in accordance with EN ISO 9369 by reaction with dibutylamine and subsequent titration of the amine excess. These methods are also described in Saul Patai's “The Chemistry of Cyanates and their Thio Derivatives”, Part 1, Chapter 5, 1977.

(14) Iodine Value

(15) The amount of unsaturation is determined by the iodine value according to DIN 53241-1:1995-05 using the method of Wijs. The sample is dissolved in carbon tetrachloride and reacted 30 minutes at 25° C. with an excess of iodine monochloride solution (Wijs reagent). Unreacted halogens are determined by back titrating with 0.1 N sodium thiosulfate solution. The iodine number is defined as the grams of halogen, expressed as iodine, reacting with 100 g of substance

(16) Nitrogen Content

(17) The Nitrogen content is determined by the Dumas method according to ISO 16634-1.

(18) Abbreviations:

(19) SR 9020=3-mole propoxylated glyceryl triacrylate, purchased from Sartomer

(20) Genorad 16=polymerization inhibitor in acrylic acid ester, purchased from Rahn A G

(21) MEHQ=4-Methoxyphenol

(22) MPEG 350=polyethylene glycol monomethyl ether, average molecular weight Mn=350

(23) MPEG 500=polyethylene glycol monomethyl ether, average molecular weight Mn=500

(24) PEG 400=polyethylene glycol (dihydroxy-functional), average molecular weight Mn=400

(25) Preparation of Monoadduct 1

(26) Into a four-necked flask equipped with stirrer, thermometer, dropping funnel, reflux condenser and nitrogen inlet tube 44.7 g of Desmodur T100 (TDI) (approx. 100% 2,4-toluene diisocyanate, NCO content=48.2) and 0.2 g of benzoyl chloride are introduced and thoroughly mixed, 22.5 g of MPEG 350 and 32.8 g of MPEG 500, which are anhydrous and alkaline free, are slowly metered in so that the temperature does not exceed 55° C. After the addition, the mixture is stirred at 55° C. for 3 hours. The excess TDI is removed from the reaction mixture by means of a thin film evaporator at 150° C. The residual TDI content is <1%.

(27) Preparation of SR9020 Mono—Unsaturated Component (A)

(28) Under an inert atmosphere, 200 g of SR9020 and 53.83 g of Monoadduct 1 are homogenized, 0.005 g of dibutyltin dilaurate and a mixture of stabilizers (Genorad 16 and MEHQ, 0.15% and 0.07% on total weight of the reaction mixture) are added and the mixture is heated to 80° C. The reaction mixture is stirred at this temperature for about 10 hours until a NCO content of 0% and an OH number of 0 mg KOH/g is reached.

(29) Preparation of compounds having the general formula Y—(XH).sub.n
Y—XH

(30) Intermediate A1

(31) Polyester of n-decanol and epsilon-caprolactone (molar ratio 1:8.3)

(32) Under an inert atmosphere, 144 g of n-decanol and 857 g of epsilon-caprolactone are homogenized, 0.02 parts of dibutyltin dilaurate is added and the mixture heated to 170° C. The reaction mixture is stirred at this temperature for about 6 hours until a solids content of 99% is reached. The product with a number-average molar mass M.sub.n of about 1100 g/mol is solid at room temperature and has an OH number of 51 mg KOH/g.

(33) Intermediate A2

(34) Polyester of isodecanol and epsilon-caprolactone (molar ratio 1:8.3)

(35) Under an inert atmosphere, 144 g of isodecanol and 857 g of epsilon-caprolactone are homogenized, 0.04 parts of dibutyltin dilaurate is added and the mixture heated to 180° C. The reaction mixture is stirred at this temperature for about 4 hours until a solids content of 98% is reached. The product with a number-average molar mass M.sub.n of about 1100 g/mol is solid at room temperature and has an OH number of 51 mg KOH/g

(36) Intermediate A3

(37) Polyester of MPEG 500 and epsilon-caprolactone (molar ratio 1:3.5)

(38) Under an inert atmosphere, 58 g of MPEG 500 and 42 g of epsilon-caprolactone are homogenized, 0.3 parts of dodecylbenzenesulphonic acid is added and the mixture heated to 80° C. The reaction mixture is stirred at this temperature for about 2 hours until a solids content of 98% is reached. The product with a number-average molar mass M.sub.n of about 900 g/mol is liquid at room temperature and has an OH number of 62 mg KOH/g.

(39) Intermediate A4

(40) Polyester of monophenyl glycol and epsilon-caprolactone (molar ratio 1:5.8)

(41) Under an inert atmosphere, 178 g of monophenyl glycol and 822 g of epsilon-caprolactone are homogenized, 0.04 parts of dibutyltin dilaurate is added and the mixture heated to 160° C. The reaction mixture is stirred at this temperature for about 7 hours until a solids content of 98% is reached. The product with a number-average molar mass M.sub.n of about 800 g/mol is solid at room temperature and has an OH number of 70 mg KOH/g.

(42) Intermediate A5

(43) Polyester of butoxypolypropylene glycol (having an average molar mass of about 700), epsilon-caprolactone and delta-valerolactone (molar ratio 1:10.5:10.5)

(44) Under an inert atmosphere, 250 g of butoxypolypropylene glycol, 428 g of epsilon-caprolactone and 375 g of delta-valerolactone are homogenized, 0.04 parts of dibutyltin dilaurate is added and the mixture heated to 160° C. The reaction mixture is stirred at this temperature for about 11 hours until a solids content of 98% is reached. The product with a number-average molar mass M.sub.n of about 2950 g/mol has an OH number of 19 mg KOH/g.

(45) Intermediate A6

(46) Polyester of isodecanol and epsilon-caprolactone (molar ratio 1:5.2)

(47) Under an inert atmosphere, 210 g of isodecanol and 790 g of epsilon-caprolactone are homogenized, 0.04 part of dibutyltin dilaurate is added and the mixture heated to 180° C. The reaction mixture is stirred at this temperature for about 4 hours until a solids content of 98% is reached. The product with a number-average molar mass M.sub.n of about 750 g/mol is solid at room temperature and has an OH number of 75 mg KOH/g.
Y—(XH).sub.2

(48) Intermediate A7

(49) Polyester of PEG 400 and epsilon-caprolactone (molar ratio 1:6.1)

(50) Under an inert atmosphere, 9.0 g of PEG 400 and 15.6 g of epsilon-caprolactone are homogenized, 0.003 part of dibutyltin dilaurate is added and the mixture heated to 170° C. The reaction mixture is stirred at this temperature for about 7 hours until a solids content of 98% is reached. The product with a number-average molar mass M.sub.n of about 1100 g/mol is solid at room temperature and has an OH number of 102 mg KOH/g.

(51) Intermediate A8

(52) Polyester of 1,4-butanediol and epsilon-caprolactone (molar ratio 1:8.0)

(53) Under an inert atmosphere, 9.0 g of 1,4-butanediol and 91 g of epsilon-caprolactone are homogenized, 0.003 part of dibutyltin dilaurate is added and the mixture heated to 160° C. The reaction mixture is stirred at this temperature for about 7 hours until a solids content of 98% is reached. The product with a number-average molar mass M.sub.n of about 1000 g/mol is solid at room temperature and has an OH number of 112 mg KOH/g.
Y—(XH).sub.3

(54) Intermediate A9

(55) Polyester of trimethylolpropane and epsilon-caprolactone (molar ratio 1:11.1)

(56) Under an inert atmosphere, 9.6 g of trimethylolpropane and 90.5 g of epsilon-caprolactone are homogenized, 0.003 part of dibutyltin dilaurate is added and the mixture heated to 170° C. The reaction mixture is stirred at this temperature for about 7 hours until a solids content of 98% is reached. The product with a number-average molar mass M.sub.n of about 1400 g/mol is solid at room temperature and has an OH number of 120 mg KOH/g.

(57) Synthesis of Final Products

(58) General Manufacturing Procedure 1* (Not Inventive Examples)

(59) xx g of Polyisocyanate P are homogenized with xx g of Y—XH and xx g of solvent. The mixture is heated to 70° C. under inert gas, and xx g of dibutyltin dilaurate is added. The mixture is stirred at this temperature until xx % of the NCO groups used have undergone reaction. Then xx g Z-Q and xx g of M-Q are added and stirring is continued at 80° C. until all of the NCO groups have been consumed by reaction.

(60) General Manufacturing Procedure 2* (Not Inventive Examples)

(61) xx g of Polyisocyanate P are homogenized with xx g of Y—XH and xx g of solvent. The mixture is heated to 70° C. under inert gas, and xx g of dibutyltin dilaurate is added. The mixture is stirred at this temperature until xx % of the NCO groups used have undergone reaction. Then xx g of Y—(XH).sub.2-3 are added. Stirring is continued at 70° C. until further xx % of the NCO groups used have undergone reaction. Then xx g Z-Q and xx g of M-Q are added and stirring is continued at 80° C. until all of the NCO groups have been consumed by reaction.

(62) General Manufacturing Procedure 3A

(63) xx g of Polyisocyanate P are homogenized with xx g of Y—XH and xx g of solvent. The mixture is heated to 60° C. under inert gas, and xx g of dibutyltin dilaurate is added. The mixture is stirred at this temperature until xx % of the NCO groups used have undergone reaction. Then xx g Z-Q and xx g of M-Q is added and stirring is continued at 60° C. until all of the NCO groups have been consumed by reaction. The reaction mixture is cooled down to room temperature and xx g of the unsaturated component (A) is added to the reaction mixture together with a mixture of stabilizers (Genorad 16 and MEHQ, 0.15% and 0.07% on total weight of the final composition). The mixture is homogenized and heated to 60° C. then the pressure is reduced stepwise down to 28 mbar until the solvent is removed completely.

(64) General Manufacturing Procedure 3B

(65) To xx g of Polyisocyanate P xx g of the unsaturated component (A) is added together with a mixture of stabilizers (Genorad 16 and MEHQ, 0.15% and 0.07% on total weight of the final composition). The mixture is homogenized and heated to 60° C., then the pressure is reduced stepwise to 28 mbar and the solvent is distilled off. After complete removal of the solvent, the solution is cooled down to room temperature and homogenized with xx g of Y—XH. Then the mixture is heated to 70° C. under inert gas and xx g of dibutyltin dilaurate is added. The mixture is stirred at this temperature until xx % of the NCO groups used have undergone reaction. Then xx g of Z-Q and xx g of M-Q are added and stirring is continued at 80° C. until all of the NCO groups have been consumed by reaction.

(66) General Manufacturing Procedure 3C

(67) xx g of Polyisocyanate P are homogenized with xx g of the unsaturated component (A), a mixture of stabilizers (Genorad 16 and MEHQ, 0.15% and 0.07% on total weight of the final composition) and with xx g of Y-XH. Then the mixture is heated to 70° C. under inert gas, and xx g of dibutyltin dilaurate is added. The mixture is stirred at this temperature until xx % of the NCO groups used have undergone reaction. Then xx g of Z-Q and xx g of M-Q are added and stirring is continued at 80° C. until all of the NCO groups have been consumed by reaction.

(68) General Manufacturing Procedure 4A

(69) xx g of Polyisocyanate P are homogenized with xx g of Y—XH and xx g of solvent. The mixture is heated to 60° C. under inert gas, and xx g of dibutyltin dilaurate is added. The mixture is stirred at this temperature until xx % of the NCO groups used have undergone reaction. Then xx g of Y—(XH).sub.2-3 is added. Stirring is continued at 60° C. until further xx % of the NCO groups used have undergone reaction.

(70) Then xx g Z-Q and xx g of M-Q are added and stirring is continued at 60° C. until all of the NCO groups have been consumed by reaction. The reaction mixture is cooled down to room temperature and xx g of the unsaturated component (A) is added to the reaction mixture together with a mixture of stabilizers (Genorad 16 and MEHQ, 0.15% and 0.07% on total weight of the final composition). The mixture is homogenized and heated to 60° C. then the pressure is reduced stepwise down to 28 mbar until the solvent is removed completely.

(71) General Manufacturing Procedure 4B

(72) To xx g of Polyisocyanate P xx g of the unsaturated component (A) is added together with a mixture of stabilizers (Genorad 16 and MEHQ, 0.15% and 0.07% on total weight of the final composition). The mixture is homogenized and heated to 60° C. then the pressure is reduced stepwise to 28 mbar and the solvent is distilled off. After complete removal of the solvent, the solution is cooled down to room temperature and homogenized with xx g of Y—XH. Then the mixture is heated to 70° C. under inert gas, and xx g of dibutyltin dilaurate is added. The mixture is stirred at this temperature until xx % of the NCO groups used have undergone reaction. Then xx g of Y—(XH).sub.2-3 are added and stirring is continued until further xx % of the NCO groups used have undergone reaction.

(73) Then xx g of Z-Q and xx g of M-Q are added and stirring is continued at 80° C. until all of the NCO groups have been consumed by reaction.

(74) General Manufacturing Procedure 4C

(75) xx g of Polyisocyanate P are homogenized with xx g of the unsaturated component (A), a mixture of stabilizers (Genorad 16 and MEHQ, 0.15% and 0.07% on total weight of the final composition) and with xx g of Y—XH. Then the mixture is heated to 70° C. under inert gas, and xx g of dibutyltin dilaurate is added. The mixture is stirred at this temperature until xx % of the NCO groups used have undergone reaction. Then xx g of Y—(XH).sub.2-3 are added and stirring is continued until further xx % of the NCO groups used have undergone reaction. Then xx g of Z-Q and xx g of M-Q are added and stirring is continued at 80° C. until all of the NCO groups have been consumed by reaction.

(76) TABLE-US-00001 Nitrogen unsaturated Ratio P solvent catalyst Y-XH % NCO Y-(XH).sub.2-3 % NCO Z-Q M-Q content component (A) (weight) Example GMP (grams) (grams) (grams) (grams) reacted (grams) reacted (grams) (grams) (%) (grams) A:B Example 1 P1 BA DBTL A6 65.0 — — API — 6.6% — — 1* (28.1) (86.7) (0.003) (26.2) (2.5) Example 1 P1 PMA DBTL A6 65.0 — — API — 6.6% — — 2* (28.1) (86.7) (0.003) (26.2) (2.5) Example 3A P3 EA DBTL A6 65.0 — — API — 6.6% Butyl 70:30 3 (28.1) (86.7) (0.003) (26.2) (2.5) acrylate (100.45) Example 3A P3 EA DBTL A6 65.0 — — API — 6.6% HDDA 70:30 4 (28.1) (86.7) (0.003) (26.2) (2.5) (100.45) Example 3A P3 EA DBTL A6 65.0 — — API — 6.6% TPGDA 70:30 5 (28.1) (86.7) (0.003) (26.2) (2.5) (100.45) Example 3A P3 EA DBTL A6 65.0 — — API — 6.6% SR9020 70:30 6 (28.1) (86.7) (0.003) (26.2) (2.5) (100.45) Example 3A P3 EA DBTL A6 65.0 — — API — 6.6% TMPTA 70:30 7 (28.1) (86.7) (0.003) (26.2) (2.5) (100.45) Example 3A P3 EA DBTL A6 65.0 — — API — 6.6% Ebecryl160 70:30 8 (28.1) (86.7) (0.003) (26.2) (2.5) (100.45) Example 3A P3 EA DBTL A6 65.0 — — API — 6.6% PETA 70:30 9 (28.1) (86.7) (0.003) (26.2) (2.5) (100.45) Example 3A P3 EA DBTL A1 55.0 — — DMAPA — 5.7% PETA 60:40 10 (28.1) (35.4) (0.002) (32.4) (2.5) (73.8) Example 3A P3 EA DBTL A2 50.0 — — DEEA — 5.4% PETA 50:50 11 (28.1) (33.2) (0.002) (29.4) (3.2) (47.00) Example 3A P3 EA DBTL A3 60.0 — — API — 6.4% PETA 60:40 12 (28.1) (32.2) (0.003) (28.9) (2.7) (68.9) Example 3A P3 EA DBTL A4 60.0 — — API TEA 6.5% PETA 70:30 13 (28.1) (86.2) (0.003) (25.7) (2.05) (0.80) (100.0) Example 3A P3 EA DBTL A5 65.0 — — DMAPA — 2.3% PETA 70:30 14 (28.1) (167.2) (0.004) (104.4) (1.95) (281.5) Example 3A P2 EA DBTL A6 50.0 — — API — 7.4% Butyl 50:50 15 (50.0) (163.8) (0.002) (97.3) (16.5) acrylate (163.8) Example 3A P3 EA DBTL A6 65.0 — — API — 6.6% Sartomer 70:30 16 (28.1) (86.7) (0.003) (26.2) (2.5) SR DFM (100.45) Example 3A P3 EA DBTL A6 65.0 — — API — 6.6% DAP 70:30 17 (28.1) (86.7) (0.003) (26.2) (2.5) (100.45) Example 3A P3 EA DBTL A6 65.0 — — API — 6.6% TEGDVE 70:30 18 (28.1) (86.7) (0.003) (26.2) (2.5) (100.45) Example 3A P3 EA DBTL A6 65.0 — — API — 6.6% DEGDVE 70:30 19 (28.1) (86.7) (0.003) (26.2) (2.5) (100.45) Example 2 P1 BA DBTL A6 40.0 PEG600PR 62.0 API — 9.6% — — 20* (15.7) (39.9) (0.001) (9.0) (1.9) (1.5) Example 2 P1 PMA DBTL A6 40.0 PEG600PR 62.0 API — 9.6% — — 21* (15.7) (39.9) (0.001) (9.0) (1.9) (1.5) Example 4A P3 EA DBTL A6 40.0 PEG600PR 62.0 API — 9.6% HDDA 70:30 22 (15.7) (39.9) (0.001) (9.0) (1.9) (1.5) (47.6) Example 4A P3 EA DBTL A6 40.0 PEG600PR 62.0 API — 9.6% TPGDA 70:30 23 (15.7) (39.9) (0.001) (9.0) (1.9) (1.5) (47.6) Example 4A P3 EA DBTL A6 40.0 PEG600PR 62.0 API — 9.6% DPGDA 70:30 24 (15.7) (39.9) (0.001) (9.0) (1.9) (1.5) (47.6) Example 4A P3 EA DBTL A6 40.0 PEG600PR 62.0 API — 9.6% SR9020 70:30 25 (15.7) (39.9) (0.001) (9.0) (1.9) (1.5) (47.6) Example 4A P3 EA DBTL A6 40.0 PEG600PR 62.0 API — 9.6% TMPTA 70:30 26 (15.7) (39.9) (0.001) (9.0) (1.9) (1.5) (47.6) Example 4A P3 EA DBTL A6 40.0 PEG600PR 62.0 API — 9.6% Ebecryl160 70:30 27 (15.7) (39.9) (0.001) (9.0) (1.9) (1.5) (47.6) Example 4A P3 EA DBTL A6 40.0 PEG600PR 62.0 API — 9.6% PETA 70:30 28 (15.7) (39.9) (0.001) (9.0) (1.9) (1.5) (47.6) Example 4A P2 EA DBTL A6 50.0 A7 75.0 DMAPA TEA 8.8% Butyl 50:50 29 (50.0) (190.3) (0.002) (97.3) (35.7) (5.4) (1.9) acrylate (190.3) Example 4A P2 EA DBTL A6 60.0 PEG600PR 80.0 API — 5.1% HDDA 60:40 30 (25.0) (94.5) (0.002) (58.4) (7.8) (3.3) (141.75) Example 4A P3 EA DBTL A6 45.0 A7 65.0 DMAP — 8.1% PETA 70:30 31 (20.0) (33.2) (0.001) (12.85) (4.2) (1.4) (66.85) Example 4A P3 EA DBTL A6 45.0 A8 60.0 DMAE — 6.3% PETA 70:30 32 (20.0) (31.15) (0.001) (12.85) (2-9) (1.35) (63.7) Example 4A P3 EA DBTL A6 55.0 A9 65.0 DMAPA — 6.5% PETA 70:30 33 (20.0) (33.85) (0.001) (15.7) (1-8) (1.4) (67.9) Example 4A P3 EA DBTL A6 40.0 PEG600PR 62.0 API — 7.9% Sartomer 70:30 34 (15.7) (39.9) (0.001) (9.0) (1.9) (1.5) SR DFM (47.6) Example 4A P3 EA DBTL A6 40.0 PEG600PR 62.0 API — 7.9% DAP 70:30 35 (15.7) (39.9) (0.001) (9.0) (1.9) (1.5) (47.6) Example 4A P3 EA DBTL A6 40.0 PEG600PR 62.0 API — 7.9% TEGDVE 70:30 36 (15.7) (39.9) (0.001) (9.0) (1.9) (1.5) (47.6) Example 4A P3 EA DBTL A6 40.0 PEG600PR 62.0 API — 7.9% DEGDVE 70:30 37 (15.7) (39.9) (0.001) (9.0) (1.9) (1.5) (47.6) Example 1 P1 BA DBTL A6 65.0 — — DMAP — 5.7% — — 38* (28.1) (85.5) (0.003) (26.2) (2.0) Example 3B P3 — DBTL A6 65.0 — — DMAP — 5.7% Butyl 70:30 39 (28.1) (0.003) (26.2) (2.0) acrylate (100.5) Example 3B P3 — DBTL A6 65.0 — — DMAP — 5.7% TMPTA 70:30 40 (28.1) (0.003) (26.2) (2.0) (100.5) Example 3B P3 — DBTL A6 65.0 — — DMAP — 5.7% SR9020 80:20 41 (28.1) (0.003) (26.2) (2.0) Mono (169.65) Example 3C P2 — DBTL A6 60.0 — — DEEA — 5.0% Butyl 70:30 42 (25.0) (0.003) (58.4) (6.2) acrylate (209.0) Example 3C P2 — DBTL A3 55.0 — — DMAP — 4.8% HDDA 70:30 43 (20.0) (0.003) (51.4) (4.8) (177.8) Example 1 P1 BA DBTL A6 40.0 PEG600PR 62.0 DMAP — 6.7% — — 44* (15.7) (39.3) (0.001) (9.0) (1.9) (1.22) Example 4B P3 — DBTL A6 40.0 PEG600PR 62.0 DMAP — 6.7% Butyl 70:30 45 (15.7) (0.003) (9.0) (1.9) (1.22) acrylate (47.6) Example 4B P3 — DBTL A6 40.0 PEG600PR 62.0 DMAP — 6.7% Isooctyl 70:30 46 (15.7) (0.003) (9.0) (1.9) (1.22) acrylate (47.6) Example 4B P3 — DBTL A6 40.0 PEG600PR 62.0 DMAP — 6.7% HDDA 70:30 47 (15.7) (0.003) (9.0) (1.9) (1.22) (47.6) Example 4B P3 — DBTL A6 40.0 PEG600PR 62.0 DMAP — 6.7% TMPTA 70:30 48 (15.7) (0.003) (9.0) (1.9) (1.22) (47.6) Example 4C P2 — DBTL A1 40.0 PEG 1000 65.0 DEEA — 4.3% Butyl 70:30 49 (25.0) (0.002) (57.1) (16.2) (5.4) acrylate (242.0) Example 4C P2 — DBTL A3 30.0 A8 60.0 DMAP — 5.3% HDDA 70:30 50 (20.0) (0.002) (28.0) (15.6) (4.3) (158.4) Example 3A P3 EA DBTL BP1100 55.0 — — DMAPA — 5.7% PETA 60:40 51 (28.1) (35.4) (0.002) (32.4) (2.5) (73.8) Example 3A P3 EA DBTL A6 65.0 — — API — 6.6% BDDMA 70:30 52 (28.1) (86.7) (0.003) (26.2) (2.5) (100.45) Example 3A P3 EA DBTL A6 65.0 — — API — 6.6% TMPTMA 70:30 53 (28.1) (86.7) (0.003) (26.2) (2.5) (100.45) Example 4A P3 EA DBTL A6 40.0 PEG600PR 62.0 API — 7.9% BDDMA 70:30 54 (15.7) (39.9) (0.001) (9.0) (1.9) (1.5) (47.6) Example 4A P3 EA DBTL A6 40.0 PEG600PR 62.0 API — 7.9% TMPTMA 70:30 55 (15.7) (39.9) (0.001) (9.0) (1.9) (1.5) (47.6) Key: P = polyisocyanate *= not inventive examples GMP = General Manufacturing Procedure P1 = aromatic TDI polyisocyanurate having a free NCO content of 8.0% as a 51% strength solution in butyl acetate, e.g. Desmodur ® IL, Bayer AG P2 = aliphatic polyisocyanate (HDI trimer) having a free NCO content of 21.8%, e.g. Desmodur ® N3300, Bayer AG P3 = aromatic TDI polyisocyanurate having a free NCO content of 8.0%; as a 51% strength solution in ethyl acetate, e.g. Desmodur ® IL EA, Bayer AG BA = butyl acetate EA = ethyl acetate PMA = 1-methoxy-2-propylacetate DBTL = dibutyltin dilaurate PEG600PR = Polyglykol PR 600 (dihydroxy-functional), purchased from Clariant AG, average molecular weight Mn = 600 PEG1000 = polyethylene glycol (dihydroxy-functional), average molecular weight Mn = 1000 API = 3-aminopropyl imidazole DMAPA = N,N-dimethyl-3-aminopropylamine DEEA = N,N-diethylaminoethanol DMAP = N,N-dimethylaminopropanol DMAE = N,N-dimethylaminoethanol TEA = triethanol amine HDDA = 1,6-hexanediol diacrylate TPGDA = tripropylene glycol diacrylate SR9020 = 3-mole propoxylated glyceryl triacrylate TMPTA = trimethylolpropane triacrylate Ebecryl160 = propylidynetrimethanol, ethoxylated, esters with acrylic acid (<6.5 EO), purchased from Arkema PETA = pentaerythritol triacrylate Sartomer SR DFM = trimethylpropane diallyl ether monomethacrylate DPGDA = dipropylene glycol diacrylate SR9020 Mono = monoadduct 1 modified 3-mole propoxylated glyceryl triacrylate BP1100 = monohydroxy-functional PO polyether, prepared starting from butanol, average molecular weight Mn = 1100 BDDMA = 1,4-butanediol dimethacrylate TMPTMA = trimethylolpropane trimethacrylate TEGDVE = triethyleneglycol divinyl ether DEGDVE = diethyleneglycol divinyl ether DAP = diallyl phthalate

(77) Application Testing

(78) Used Raw Materials:

(79) TABLE-US-00002 Ebecryl 81 Allnex, UV/EB Curable Resins, amine modified polyester acrylate. Ebecryl 450 Allnex, UV/EB Curable Resins, fatty acid modified polyester hexaacrylate. BYK-085 BYK Chemie GmbH, Solvent-free, silicone-containing leveling additive with good defoaming properties for solvent-borne and solvent-free coatings and adhesives. BYK-377 BYK Chemie GmbH, Silicone surface additive for solvent- free, radiation curable, and solvent-borne coatings, adhesives, and printing inks with a strong reduction of surface tension. Irgacure 907 BASF, photoinitiator which is used to initiate the photo- polymerisation of chemically unsaturated prepolymers

(80) Pigments: P.R.57:1—Irgalite Rubine D4230 (L4 BH) P.B.15:4—Fastogen Blue 249-5452

(81) Preparation of the Pigment Dispersions (Millbases):

(82) According to the formulation below, millbases with 15% of component (B) solid on pigment are prepared.

(83) Formulation Millbase:

(84) TABLE-US-00003 W&D additive W&D additive 30% content 20% content of component (B) of component (B) Ebecryl 81 60.54 56.21 Ebecryl 450 9.36 8.69 W&D additive 10.0 15.0 BYK-085 0.1 0.1 Pigment 20.0 20.0 100.0 100.0

(85) All the components from the table above are added in the same order as in the table into a temperature controlled grinding vessel. After addition of each component the mixture is homogenized with a spatula. The dispersion is done with a vertical beadmill using a teflon disk, 4.5 cm Ø (Dispermat CV, Getzmann GmbH) with the following parameters:

(86) Grinding Conditions:

(87) TABLE-US-00004 Grinding time: 30 min Speed: 10000 rpm Grinding media: Glass beads (1.0-1.3 mm ∅), removed after dispersion by filter (Glass beads: pigment concentrate 1.5:1 by weight), Temperature: 40° C.

(88) Let down Solution:

(89) TABLE-US-00005 Ebecryl 81 89.8 g BYK-377 0.2 g lrgacure 907 10.0 g

(90) All components are weighed into a glass vessel and homogenized with a spatula. Afterwards the vessel is covered with an aluminum foil to protect the mixture from light. The vessel is placed in an oven for 3 hours at 50° C. until all components are dissolved, after cooling down to room temperature the let down solution is ready to be used.

(91) Let Down: 6 g Millbase: 4 g Let Down Solution

(92) First the Let down solution is put into the Speedmixer cup and then the Millbase is added on the top. Then the samples are mixed for 30 seconds at 2000 rpm with the Speedmixer (DAC 150.1 FVZ, Hauschild Engineering). Afterwards a draw down with a 6 μm wired bar onto morest chart and PET-Film is done to check the colour strength/transparency. UV curing (80 W/cm/3 passes) is done with AKTIPRINT Dryer (Omnilab). After curing the colour strength/transparency is judged visually and the gloss (20/60°) is measured with a MICRO TRI GLOSS (BYK Gardner).

(93) Results:

(94) Example 20* and Example 21* are comparative not inventive examples to the inventive Examples 22-28,

(95) Example 44* is the comparative not inventive example to the inventive Examples 45-48,

(96) Example 1* and Example 2* are comparative not inventive examples to the inventive Examples 3-9 and Example 38* is the comparative not inventive example to the inventive Examples 39-41.

(97) TABLE-US-00006 Irgalite Rubine D4230 Fastogen Blue 249-5452 (L4 BH) (P.R.57:1) (P.B.15:4) colour colour Gloss strength/ Gloss strength/ Product 20°/60° transparency Product 20°/60° transparency Example 20* 71/86 3 Example 20* 67/82 3 Example 21* 71/87 3 Example 21* 67/83 3 Example 22 77/91 2 Example 22 70/83 2 Example 23 76/92 2 Example 23 69/83 2-3 Example 24 78/92 1-2 Example 24 69/83 3 Example 25 74/91 2 Example 25 70/83 3 Example 26 71/90 2-3 Example 26 70/83 2 Example 27 73/91 2-3 Example 27 71/83 2 Example 28 76/91 1-2 Example 28 71/84 2 Example 44* 72/88 2-3 Example 44* 68/82 3-4 Example 45 73/88 2 Example 45 69/83 3 Example 46 73/90 2 Example 46 70/83 3 Example 47 73/90 2-3 Example 47 69/83 3 Example 48 75/89 2 Example 48 70/84 2 Example 1* 68/88 3 Example 1* 69/84 3-4 Example 2* 70/88 3 Example 2* 69/83 3-4 Example 3 73/88 3 Example 3 70/84 3 Example 4 75/91 2-3 Example 4 70/84 3 Example 5 74/92 3 Example 5 70/84 3 Example 6 74/90 2 Example 6 70/84 3 Example 7 74/91 2 Example 7 71/84 3 Example 8 73/90 3 Example 8 70/84 3 Example 9 71/92 2 Example 9 71/84 2 Example 38* 74/88 2-3 Example 38* 69/82 3 Example 39 76/91 2 Example 39 70/82 2-3 Example 40 76/91 2 Example 40 72/84 3 Example 41 73/90 2-3 Example 41 71/84 2 *not inventive example 1 = good; 5 = bad

(98) Flexo printing, like letterpress printing, is one of the relief printing processes and is used for printing newspapers, books and packaging, particularly for high-quality food packaging. Color strength/transparency is for the application in Flexographic printing inks of great importance. In general different pigmented inks are applied in several layers and inks of low transparency would hide the color of the layers applied before and would have a negative impact on the coloristic quality of the printed image.

(99) The application results show that component (B) shows in combination with component (A) a synergistic effect. Color strength/transparency as well as gloss can be improved in comparison to the samples prepared with component (B) in solvent as wetting & dispersing additive. Especially samples prepared with component (A) having 2-3 unsaturated groups showed the best results of the tested samples.

(100) The measurement of Gloss values is an established method to evaluate the quality of a pigment dispersion, higher Gloss values indicate a better dispersion and stabilization of the pigments.