Hyperbranched phosphoric acid esters

Abstract

The present invention is directed to a process for preparing hyperbranched phosphoric acid esters as well as a hyper-branched phosphoric acid ester, its use for dispersing solid substances and in the production of water- and/or solvent-based coatings and paints, printing inks and/or plastics such as unsaturated polyesters, PVC or plastisols and a pigment dispersion comprising the at least one hyperbranched phosphoric acid ester or salt thereof and its use as a component in paints or lacquers.

Claims

1. A process for preparing a hyperbranched phosphoric acid ester, the process comprising: providing at least one hyperbranched polymer comprising terminal primary hydroxyl groups, secondary hydroxyl groups, or both, wherein the at least one hyperbranched polymer is a polyether, a polyetheramine or a polycarbonate; and reacting the at least one hyperbranched polymer directly with at least one phosphoric acid ester-forming compound to obtain a hyperbranched phosphoric acid ester, in which there is no (chain extender) linking chain present or added prior to reacting, between the terminal primary or secondary hydroxyl groups of the at least one hyperbranched polymer and the at least one phosphoric acid ester-forming compound.

2. The process according to claim 1, wherein the at least one hyperbranched polymer is a polycarbonate.

3. The process according to claim 1, wherein the at least one hyperbranched polymer is a polyether.

4. The process according to claim 1, therein the at least one phosphoric acid ester-forming compound is at least one of polyphosphoric acid and P.sub.2O.sub.5.

5. The process according to claim 1, wherein an amount of the at least one phosphoric acid ester forming compound is such that a degree of functionalization in the hyperbranched phosphoric acid ester is in the range of from 0.5 to 100%, based on a total amount of the terminal primary hydroxyl groups, the secondary hydroxyl groups, or both, in the at least one hyperbranched polymer.

6. The process according to claim 1, wherein an amount of the at least one phosphoric acid ester forming compound is such that a degree of functionalization in the hyperbranched phosphoric acid ester is in the range of from 0.5 to 50%, based on a total amount of the terminal primary hydroxyl groups, the secondary hydroxyl groups in the polymer, or both, in the at least one hyperbranched polymer.

7. The process according to claim 1, wherein an amount of the at least one phosphoric acid ester forming compound is such that a degree of functionalization of the hyperbranched phosphoric acid ester is in the range of from 0.5 to 25%, based on a total amount of the terminal primary hydroxyl groups, the secondary hydroxyl groups, or both, in the at least one hyperbranched polymer.

8. The process according to claim 1, wherein the reacting occurs at a temperature of from 20 C. to 200 C.

9. The process according to claim 1, wherein the reacting occurs in an inert atmosphere.

10. The process according to claim 1, further comprising forming a phosphate salt by neutralizing the hyperbranched phosphoric acid ester with an amine or inorganic base.

11. The process according to claim 1, wherein the at least one hyperbranched polymer is a homo-polymer or copolymer of tris-2-hydroxyethylisocyanurate.

12. The process of claim 10, wherein the phosphate salt is formed by neutralizing the hyperbranched phosphoric acid ester with an alkali hydroxide.

13. The process according to claim 1, wherein the at least one hyperbranched polymer is a polyetheramine.

Description

EXAMPLES

Example 1

(1) This example illustrates the prior art and concerns the preparation of a hyperbranched polycarbonate as hyperbranched polymer.

(2) The multifunctional alcohol (B3), the diethyl carbonate (A2) and the catalyst (250 ppm based on the total weight of the alcohol) are mixed at room temperature in a 4 L three-necked flask.

(3) Then, the temperature is slowly raised to 140 C. under reflux for two hours. During conversion, ethanol is formed and thus the boiling temperature decreases continuously. When the boiling temperature remains constant, the reflux condenser is then replaced by an inclined condenser, ethanol is distilled off and the temperature is slowly raised to 160 C.

(4) The degree of conversion is estimated by quantifying the amount of separated ethanol. After controlling the molecular weight via GPC (PMMA as reference, DMAc as solvent) the reaction mixture is cooled down, depending on the amount of catalyst, phosphoric acid is added to the reaction mixture, which is then stripped with nitrogen. The analytics of the hyperbranched polycarbonates are set out in Table 1.

(5) The hydroxyl number of the polymers was measured according to DIN 53240. The acid numbers of the polymers were measured according to DIN 53402.

(6) A. Detailed Description of the Synthesis of Polycarbonate PC1

(7) This exemplified description illustrates a detailed preparation procedure of a hyperbranched polycarbonate as hyperbranched polymer.

(8) 2400 g Trimethylolpropane x 1,2 Propylenoxid, 1417.5 g Diethylcarbonat and 0.6 g K.sub.2CO.sub.3 as catalyst (250 ppm based on the total weight of the alcohol) are mixed at room temperature in a 4 L three-necked flask equipped with stirrer, reflux condenser and internal termomether.

(9) Then, the temperature is slowly raised to 140 C. under reflux for two hours. During conversion, ethanol is formed and thus the boiling temperature decreases continuously. When the boiling temperature remains constant, the reflux condenser is then replaced by an inclined condenser, ethanol is distilled off and the temperature is slowly raised to 160 C.

(10) 795 g of Ethanol were collected here.

(11) TABLE-US-00001 TABLE 1 GK Mn Mw OH Number (g/mol) (g/mol) Number A2 B3 Catalyst PC1 820 1250 416 mgKOH/g DEC Trimethylolpropane 1.2 PO (Propylenoxide) PC2 3200 9300 238 mgKOH/g DEC Glycerin 5 EO (Ethylenoxide) PC3 2350 4716 291 mgKOH/g DEC Trimethylolpropane 3 EO K.sub.2CO.sub.3 (Ethylenoxide) PC4 3400 6400 134 mgKOH/g DEC Trimethylolpropane 12 EO KOH (Ethylenoxide) PC5 1800 3300 206 mgKOH/g DEC Trimethylolpropane 5.4 PO KOH (Propylenoxide)

Example 2

(12) This example illustrates the invention and concerns the preparation of a hyperbranched polycarbonate phosphoric acid ester as hyperbranched phosphoric acid ester.

(13) 1369.2 g of polycarbonate PC 3 were placed in a 4 L flat flange reactor, equipped with inner thermometer and anchor mixture. The polymer mass was heated at 85 C. under nitrogen atmosphere.

(14) 200 g of polyphosphoric acid (polyphosphoric acid 115% H.sub.3PO.sub.4 equiv) were heated at 80 C. and then were dropped within one hour into the polymer melt by using a drop funnel. The reaction mixture was then kept for 2 hours at 85 C. Then, the polymer was cooled down up to room temperature.

(15) The analytical details of the obtained hyperbranched phosphoric acid ester were as follows: Functionalization degree: 25% (25% of the OH groups of the polycarbonates were reacted to phosphoric acid ester groups). Mn: 1100 g/mol Mw: 12900 g/mol Acid number: 157 mgKOH/g

Example 3

(16) This example illustrates the invention and concerns the preparation of a hyperbranched polycarbonate phosphoric acid ester as hyperbranched phosphoric acid ester.

(17) 1369.2 g of polycarbonate PC 3 were placed in a 4 L flat flange reactor, equipped with inner thermometer and anchor mixture. The polymer mass was heated at 85 C. under nitrogen atmosphere.

(18) 400 g of polyphosphoric acid (polyphosphoric acid 115% H.sub.3PO.sub.4 equiv) were heated at 80 C. and then were dropped within one hour into the polymer melt by using a drop funnel. The reaction mixture was then kept for 2 hours at 85 C. Then the polymer was cooled down up to room temperature.

(19) The analytical details of the obtained hyperbranched phosphoric acid ester were as follows: Functionalization degree: 50%. Mn: 620 g/mol Mw: 830 g/mol Acid number: 231 mgKOH/g

Example 4

(20) This example illustrates the invention and concerns the preparation of a hyperbranched polycarbonate phosphoric acid ester as hyperbranched phosphoric acid ester.

(21) 1374.2 g of polycarbonate PC 1 were placed in 2 L flat flange reactor, equipped with inner thermometer and anchor mixture. The polymer mass was heated at 85 C. under nitrogen atmosphere.

(22) 200 g of polyphosphoric acid (polyphosphoric acid 115% H.sub.3PO.sub.4 equiv) were heated at 80 C. and then were dropped within one hour into the polymer melt by using a drop funnel. The reaction mixture was then kept for 2 hours at 85 C. Then, the polymer was cooled down up to room temperature.

(23) The analytical details of the obtained hyperbranched phosphoric acid ester were as follows: Functionalization degree: 25%. Mn: 2100 g/mol Mw: 24400 g/mol Acid number: 141.56 mgKOH/g

Example 5

(24) This example illustrates the invention and concerns the preparation of a hyperbranched polycarbonate phosphoric acid ester as hyperbranched phosphoric acid ester.

(25) 500 g of polycarbonate PC 5 were placed in 4 L flat flange reactor, equipped with inner thermometer and anchor mixture. The polymer mass was heated at 85 C. under nitrogen atmosphere.

(26) 103.4 g of polyphosphoric acid (polyphosphoric acid 115% H.sub.3PO.sub.4 equiv) were heated at 80 C. and then were dropped within one hour into the polymer melt by using a drop funnel. The reaction mixture was then kept for 2 hours at 85 C. Then, the polymer was cooled down up to room temperature.

(27) The analytical details of the obtained hyperbranched phosphoric acid ester were as follows: Functionalization degree: 50%. Mn: 1210 g/mol Mw: 2980 g/mol Acid number: 165.30 mgKOH/g

Example 6

(28) This example illustrates the prior art and concerns the preparation of a hyperbranched polyether as hyperbranched polymer.

(29) 1351 g triethylenglycol (TEG), 1225 g pentaerythritol (PE) and 4 g p-toluene sulfonic acid were placed at room temperature in a 2 L four necked flask, equipped with inner thermometer, stirrer, gas inlet, vacuum connection and distillation bridge. The pressure was reduced to 200 mbar and the reaction mixture was heated to 200 C. 424 g water were distilled out within 10 hours.

(30) The reaction mixture was then neutralized via adding 8 g of a 50% NaOH solution in water. The polymer was then dried under vacuum (300 mbar) for four hours.

(31) Subsequently, the resulting polymer was analyzed via GPC (hexafluoroisopropanol as solvent, PMMA as standard).

(32) The analytical data of the obtained product are reported in Table 2.

(33) TABLE-US-00002 TABLE 2 GK Mn Mw Number (g/mol) (g/mol) OH Number A2 B4 Catalyst PE1 (GK 749 8670 510 mgKOH/g TEG PE p- 3095/13) toluene sulfonic acid

Example 7

(34) This example illustrates the invention and concerns the preparation of a hyperbranched polyether phosphoric acid ester as hyperbranched phosphoric acid ester.

(35) 400 g of polyether PE 1 were placed in 2 L flat flange reactor, equipped with inner thermometer and anchor mixture. The polymer mass was heated at 85 C. under nitrogen atmosphere.

(36) 103 g of polyphosphoric acid (polyphosphoric acid 115% H.sub.3PO.sub.4 equiv) were heated at 80 C. and then were dropped within one hour into the polymer melt by using a drop funnel. The reaction mixture was then kept for 2 hours at 85 C. Then, the polymer was cooled down up to room temperature.

(37) The analytical details of the obtained hyperbranched phosphoric acid ester were as follows: Functionalization degree: 25%. Acid number: 227.00 mgKOH/g Mn: 1310 g/mol Mw: 9790 g/mol

Example 8

(38) This example illustrates the prior art and concerns the preparation of a hyperbranched polyether as hyperbranched polymer.

(39) In a 2 L four necked flask, equipped with inner thermometer, stirrer, gas inlet, vacuum connection and distillation bridge, tris-2-hydroxyethylisocyanurate (THEIC) (B3), distilled water, sulphuric acid (93-95% ig) and a di- or multifunctional alcohol (Cn) or a monofunctional alcohol (Dn) were mixed. The reaction mixture was heated at 80 C. under nitrogen stream and stirred for one hour.

(40) The reaction temperature was increased up to 120-130 C. and water was distilled out. After 1 hour the temperature was increased up to 150 C. and the pressure was reduced to 100 mbar. After 40 minutes the reaction was stopped by neutralization of the catalyst by addition of a 50% aqueous solution of NaOH (pH=7). The reaction mixture was then cooled down and analyzed. Gel permeation chromatography was used for determining the molecular weight of the product. As solvent dimethylacetamide (DMAc) was used and as standard for the calibration of the GPC polymethylmethacrylate (PMMA) was chosen.

(41) The OH numbers were measured according to DIN 53240, part 2.

(42) The acid numbers were measured according to DIN 53402.

(43) The analytical data of the obtained product are reported in table 3.

(44) TABLE-US-00003 TABLE 3 GK Mn Mw OH B3 Dn Number (g/mol) (g/mol) Number Cn (n = 2 or 3) (n = 1 ) PE2 1150 2914 213 mgKOH/g THEIC Trimethylol- / propane 12 EO (Ethyleneoxide) PE3 1038 3252 268 mgKOH/g THEIC Polyethylene- / glycol (Pluriol E 200, BASF SE) PE4 1024 3400 325 mgKOH/g THEIC Trimethylol- / propane 3 EO (Ethyleneoxide) PE5 1474 8209 298 mgKOH/g THEIC Trimethylol- Methylpoly- propane 12 EO ethyleneglykol (Ethyleneoxide) 500 (Pluriol A 500 E, BASF SE)

(45) For the synthesis of polyether PE4, 533.0 g THEIC and 1366.8 g trimethylolpropane12 EO were mixed with 3.0 g sulphuric acid (93-95% ig) as a catalyst and 200.0 g water. The reaction temperature was increased up to 120-130 C. and water was distilled out. After 1 hour the temperature was increased up to 150 C. and the pressure was reduced to 100 mbar. After 40 minutes 716.0 g methylpolyethylene-glykol 500 were added to the reaction mixture.

(46) The temperature was increased up to 150 C. and kept for 4 hours. After 40 minutes the reaction was stopped by neutralization of the catalyst by adding a 50% aqueous solution of NaOH (pH=7). The reaction mixture was then cooled down and analyzed.

Example 9

(47) This example illustrates the invention and concerns the preparation of a hyperbranched polyether phosphoric acid ester as hyperbranched phosphoric acid ester.

(48) 1500 g of polyether PE 2 were placed in 4 L flat flange reactor, equipped with inner thermometer and anchor stirrer. The polymer mass was heated at 85 C. under nitrogen atmosphere.

(49) 160.4 g of polyphosphoric acid (polyphosphoric acid 115% H.sub.3PO.sub.4 equiv) were heated at 80 C. and then were dropped within one hour into the polymer melt by using a drop funnel. The reaction mixture was then kept for 2 hours at 85 C. Then, the polymer was cooled down up to room temperature.

(50) The analytical details of the obtained hyperbranched phosphoric acid ester were as follows: Functionalization degree: 25%. Mn: 1540 g/mol Mw: 6240 g/mol Acid number: 117 mgKOH/g

Example 10

(51) This example illustrates the invention and concerns the preparation of a hyperbranched polyether phosphoric acid ester as hyperbranched phosphoric acid ester.

(52) 500 g of polyether PE 2 were placed in 2 L flat flange reactor, equipped with inner thermometer and anchor stirrer. The polymer mass was heated at 85 C. under nitrogen atmosphere.

(53) 20.1 g of polyphosphoric acid (polyphosphoric acid 115% H.sub.3PO.sub.4 equiv) were heated at 80 C. and then were dropped within one hour into the polymer melt by using a drop funnel. The reaction mixture was then kept for 2 hours at 85 C. Then the polymer was cooled down up to room temperature.

(54) The analytical details of the obtained hyperbranched phosphoric acid ester were as follows: Functionalization degree: 10%. Mn: 1870 g/mol Mw: 5480 g/mol Acid number: 52 mgKOH/g

Example 11

(55) This example illustrates the invention and concerns the preparation of a hyperbranched polyether phosphoric acid ester as hyperbranched phosphoric acid ester.

(56) 1500 g of polyether PE 3 were placed in 4 L flat flange reactor, equipped with inner thermometer and anchor stirrer. The polymer mass was heated at 85 C. under nitrogen atmosphere.

(57) 201 g of polyphosphoric acid (polyphosphoric acid 115% H.sub.3PO.sub.4 equiv) were heated at 80 C. and then were dropped within one hour into the polymer melt by using a drop funnel. The reaction mixture was then kept for 2 hours at 85 C. Then, the polymer was cooled down up to room temperature.

(58) The analytical details of the obtained hyperbranched phosphoric acid ester were as follows: Functionalization degree: 25%. Mn: 1330 g/mol Mw: 8030 g/mol Acid number: 163.17 mgKOH/g

Example 12

(59) This example illustrates the invention and concerns the preparation of a hyperbranched polyether phosphoric acid ester as hyperbranched phosphoric acid ester.

(60) 1400 g of polyether PE 4 were placed in 4 L flat flange reactor, equipped with inner thermometer and anchor stirrer. The polymer mass was heated at 85 C. under nitrogen atmosphere.

(61) 228 g of polyphosphoric acid (polyphosphoric acid 115% H.sub.3PO.sub.4 equiv) were heated at 80 C. and then were dropped within one hour into the polymer melt by using a drop funnel. The reaction mixture was then kept for 2 hours at 85 C. Then, the polymer was cooled down up to room temperature.

(62) The analytical details of the obtained hyperbranched phosphoric acid ester were as follows: Functionalization degree: 25%. Mn: 1360 g/mol Mw: 11100 g/mol Acid number: 141.56 mgKOH/g

Example 13

(63) This example illustrates the invention and concerns the preparation of a hyperbranched polyether phosphoric acid ester as hyperbranched phosphoric acid ester.

(64) 500 g of polyether PE 5 were placed in 2 L flat flange reactor, equipped with inner thermometer and anchor stirrer. The polymer mass was heated at 85 C. under nitrogen atmosphere.

(65) 30.9 g of polyphosphoric acid (polyphosphoric acid 115% H.sub.3PO.sub.4 equiv) were heated at 80 C. and then were dropped within one hour into the polymer melt by using a drop funnel. The reaction mixture was then kept for 2 hours at 85 C. Then, the polymer was cooled down up to room temperature.

(66) The analytical details of the obtained hyperbranched phosphoric acid ester were as follows: Functionalization degree: 10%. Mn: 1430 g/mol Mw: 8100 g/mol Acid number: 82 mgKOH/g

Example 14

(67) This example illustrates the invention and concerns the preparation of a hyperbranched polyether phosphoric acid ester as hyperbranched phosphoric acid ester.

(68) 500 g of polyether PE 5 were placed in 2 L flat flange reactor, equipped with inner thermometer and anchor stirrer. The polymer mass was heated at 85 C. under nitrogen atmosphere.

(69) 14.9 g of polyphosphoric acid (polyphosphoric acid 115% H.sub.3PO.sub.4 equiv) were heated at 80 C. and then were dropped within one hour into the polymer melt by using a drop funnel. The reaction mixture was then kept for 2 hours at 85 C. Then, the polymer was cooled down up to room temperature.

(70) The analytical details of the obtained hyperbranched phosphoric acid ester were as follows: Functionalization degree: 5%. Mn: 1450 g/mol Mw: 5330 g/mol Acid number: 40 mgKOH/g

Example 15

(71) This example illustrates the prior art and concerns the preparation of linear dispersing agents.

(72) MPEG350-phosphoric ester (comparative 1) used as reference to compare the dispersing efficiency of the transparent iron oxide pigments Sicotrans Yellow L 1916 and Sicotrans Red L 2817. It is prepared according to the following procedure:

(73) 232 g of methoxy polyethylene glycol with an average molecular weight of 350 g/mol (Pluriol A 350 E, BASF) is placed in a three necked flask and heated to 30 C. 68.1 g of polyphosphoric acid (polyphosphoric acid 115% H.sub.3PO.sub.4 equiv) were heated to 60 C. and then were dropped within one hour into the polyglycol by using a drop funnel. After addition, the reaction mixture was kept at 70 C. for 2 hours until the acid number dropped to 300 mg KOH/g. The slightly yellowish liquid was finally cooled to room temperature and used without further purification.

Example 16

(74) This example illustrates the invention and concerns the testing of a hyperbranched phosphoric acid ester according to the present invention as dispersing agent with regard to its dispersing efficiency for the transparent iron oxide pigments Sicotrans Yellow L 1916 and Sicotrans Red L 2817. In particular, the inventive hyperbranched phosphoric acid ester is tested in comparison to a dispersing agent of the prior art.

(75) The inventive hyperbranched phosphoric acid esters were provided as 100% solid material. For incorporating the inventive hyperbranched phosphoric acid esters into the respective pigment dispersion the samples were first dissolved in water by using a minimum concentration of 20 wt.-%, based on the total weight of the dispersion. The pH of this dispersing agent solution was adjusted with aqueous NaOH to a value of 8-8.5. Depending on the degree of phosphatation of the hyperbranched phosphoric acid ester samples large amounts of NaOH were added to get slightly basic solutions. Dispersions were prepared by mixing the components in the respective addition. The characterization of the pigments and the corresponding dispersant level are outlined in Table 4a below. Furthermore, dispersions were prepared by mixing the components in the respective addition level as outlined in Table 4b below,

(76) TABLE-US-00004 TABLE 4a Dispersing agent BET Pigment concentration Pigment name CI (m2/g) Load DOP Sicotrans Yellow L PY 42 80 35% 15% 1916 Sicotrans Yellow L PY 42 80 35% 30% 1916 Sicotrans Red L 2817 PR 101 93 35% 25% Sicotrans Red L 2817 PR 101 93 35% 50%

(77) TABLE-US-00005 TABLE 4b millbase formulations Component Sicotrans Yellow L 1916 Sicotrans Red L 2817 remark Water 58.45% 53.2% 54.95% 46.2% Dispersing 5.25% 10.5% 8.75% 17.5% DOP = active agent (solid) (15% DOP) (30% DOP) (25% DOP) (50% DOP) dispersant on solid pigment NaOH 10% max 1% max 1% max 1% max 1% pH adjustment solution to 8-8.5 Pigment 35% 35% 35% 35% Transparent iron oxides EFKA- 0.3% 0.3% 0.3% 0.3% defoamer 2580 Total 100% 100% 100% 100% Millbase A Millbase B Millbase C Millbase D

(78) The obtained dispersions were Skandex shaken for 4 hours at room temperature and the rheology of the obtained millbase was measured after 24 hrs by using a Paar Physika UDS 200 rheometer with a cone/plate geometry. Viscosities were measured in the shear rate ranges from 0.01 to 1024 l/s. For evaluation the viscosities at a shear rate of 1.0 l/s were compared. The viscosity (Brookfield viscosity) is measured in accordance with DIN 53214. Subsequently, 0.3% defoamer (EFKA-2550), were added to the obtained millbase.

(79) A paint was prepared by mixing part of the obtained millbase (pigment paste) with a modified acrylic water based system, The details regarding the modified acrylic water based system are outlined in Table 5 below.

(80) TABLE-US-00006 TABLE 5 Pos. Trade name Function w/w % 1. Neocryl XK-98 (45%) Binder (1) 91.20 2. Water, deionized Solvent 4.70 3. Diethylene glycolmonoethylether Solvent 3.40 4. Dehydran 1293 Defoamer (2) 0.40 5. BorchiGel L75 N/water (1/1) Thickener (3) 0.30 100.00

(81) The positions 1 to 5 as outlined in Table 5 were added and stirred with efficient agitation. Subsequently, 8.6 wt.-% of millbase as outlined in Table 4b was mixed with 91.4 wt.-% of the clear coat, based on the total weight of the obtained pigmented coating. The final pigmented coating (wet) that is applied on the substrate thus contains 3 wt.-% of pigment, based on the total weight of the obtained pigmented coating.

(82) The final pigmented coating was applied to a polyester sheet with a 75 wire bar coater, and the film was dried overnight at room temperature.

(83) For evaluation coloristic values, the gloss values at a 20-angle and 60-angle, the lightness (L*), chroma (C) and hue (h) were measured. For the measurements a Spectrophotometer CM-2600d from Minolta was used and the calculations on the measured values were done with the BASF internal software BSC-Win.

(84) Negative impacts on appearance were seeding, surface roughness and haze. Rating for appearance is: 1=very poor; 2=poor; 3=mediocre; 4=good; 5=excellent.

(85) The Screening results for the pigment pastes and the corresponding dispersing agent added in the composition set out in Table 4 are outlined in the following Tables 6 (for pigment Sicotrans Yellow L 1916) and 7 (for pigment Sicotrans Red L 2817).

(86) TABLE-US-00007 TABLE 6 Gloss @ Viscosity @ 1 Trans- sample DOP Millbase 20 s1 millbase parency Example 15 15% A 59 50400 3 (comparative) 30% B 52 61500 1 Example 5 15% A 54 22200 2 30% B 38 138000 1 Example 2 15% A 67 47200 4 30% B 38 317000 1 Example 3 15% A 44 279000 3 30% B 47 328000 1 Example 4 15% A 73 73900 1 30% B 59 81900 3 Example 12 15% A 60 102000 3 30% B 50 196000 1 Example 9 15% A 73 53800 3 30% B 49 96200 2 Example 11 15% A 66 43800 2 30% B 44 107000 1 DOP: active dispersant on solid pigment.

(87) It can be gathered from Table 6 that the hyperbranched phosphoric acid ester obtained in accordance with the present invention show clearly improved mechanical and optical properties. In particular, it can be gathered that the hyperbranched phosphoric acid ester obtained in Examples 2 and 11 show clearly improved properties compared to comparative 1 (as prepared in Example 15) at 15% addition level of dispersant on pigment Sicotrans Yellow L 1916 with regard to the film gloss, viscosity and transparency.

(88) TABLE-US-00008 TABLE 7 Gloss @ Viscosity @ 1 Trans- sample DOP Millbase 20 s1 millbase parency Example 15 25% C 66 59100 3 (comparative) 50% D 57 36900 3 Example 7 25% C 53 32500 2 50% D 52 21000 1 Example 9 25% C 63 2200 3 50% D 56 41100 2 Example 11 25% C 48 2410 1 50% D 65 33000 3

(89) It can be gathered from Table 7 that also hyperbranched phosphoric acid ester obtained in Examples 7, 9 and 11 show significant better viscosities at a comparable gloss and transparency compared to comparative 1 (as prepared in Example 15) at 25% addition level of dispersant on pigment Sicotrans Red L 2817.

Example 17

(90) This example illustrates the invention and concerns the testing of a hyperbranched phosphoric acid ester according to the present invention as dispersing agent in a white opaque coating further comprising a wetting agent.

(91) The wetting agent has been prepared as follows:

(92) A reaction flask with a nitrogen inlet, overhead stirrer and thermometer, was charged with 160 g of sec. butanol, flushed with N.sub.2 and heated to 100 C. A premix consisting of 6.5 g of fluorinated monomer (intermediate B from U.S. Pat. No. 7,173,084, maleic ester of HOCH.sub.2CH.sub.2(CF.sub.2CF.sub.2).sub.m.1CF.sub.2CF.sub.3, m.1 being selected that the average molecular weight is 443 g/mol), 30.6 g of acrylic acid, 181.4 g of n-butyl acrylate, and 21.8 g of t-butylperoxy-2-ethylhexanoate was added during a period of 4 h to the reaction flask at 100 C. After the addition of the premix, the resulting polymer solution was stirred for 4 h at 100 C. Then, the sec. butanol was distilled off under reduced pressure at 100 C. until a solid content of >98% was reached. The resulting mass was cooled to 60 C. Then 36 g of N,N-dimethyl ethanolamine were added. After homogenization for at 60 C., 124 g of water were added over a period of 30 minutes until a clear solution was obtained. The resulting solution contained (D.3), with a M.sub.n of 1170 g/mol and a polydispersity of 1.6, a solid content of 59.7%, and an acid number of 55 mg KOH/g as a clear light yellow viscous liquid. The solution of (D.3) was used as such, without further purification.

(93) Afterwards, the positions 1 to 3 as outlined in Table 8 below were added to a glass jar in the listed order. Then, an equal weight of the total mass of glass beads with a diameter of 2 mm were added, the mixture was well stirred with a spatula and then ground in a skandex shaker for 2 hours. Afterwards, the glass beads were removed by filtration from the TiO.sub.2 paste.

(94) TABLE-US-00009 TABLE 8 Pos. Trade name Function w/w % 1. Water, deionized Solvent 23.5 2. Dispersant (100% delivery form) Additive 1.5 3. Kronos 2310 (Kronos) TiO.sub.2 pigment 75.0 100.00

(95) The viscosity of the obtained millbase (TiO.sub.2 paste) was measured after 24 h with a Paar Physika UDS 200 rheometer having a cone/plate geometry. For evaluation the viscosities at a shear rate of 1.0 l/s were compared. The viscosity (Brookfield viscosity) is measured in accordance with DIN 53214.

(96) A paint was prepared by mixing part of the obtained millbase (TiO.sub.2 paste) with a modified acrylic water based system as outlined in Table 9 below.

(97) TABLE-US-00010 TABLE 9 Pos. Trade name Function w/w % 1. Neocryl XK 90 (DSM Binder 82.6 Neoresins) 2 TiO.sub.2 paste (75%) Pigment concentrate 16.5 3. Wetting agent Substrate wetting 0.9 100.00

(98) The positions 1 to 3 as outlined in Table 9 were added and stirred with a spatula for 2 minutes. The final paint was applied to a polyester sheet with a 75 wire bar coater, and the film was dried overnight at room temperature.

(99) For evaluation the gloss values at an 20-angle were compared. The gloss values were determined by a Byk-Gardner mirco-TRI-gloss apparatus (Nr. 4430).

(100) Negative impacts on appearance were seeding, surface roughness and haze. Rating for appearance is: 1=very poor; 2=poor; 3=mediocre; 4=good; 5=excellent.

(101) The Screening results for the TiO.sub.2 pigment paste and the corresponding dispersing agent added in the composition set out in Table 8 are outlined in the following Table 10.

(102) TABLE-US-00011 TABLE 10 Dispersant Acid number Viscosity Gloss Sample used mgKOH/g millbase 1/s 20 appearance Example 13 82 10700 56 4 Example 14 40 2650 52 3 Comparative 1 300 7220 51 3 (Example 15)

(103) From Table 10 it can be gathered that the paint comprising the inventive hyperbranched phosphoric acid ester as dispersing agent (Example 14) shows a significantly improved millbase viscosity compared to the prior art dispersing agent of Example 15 while featuring a comparable gloss and surface quality. It can be further gathered that Example 13 shows a significantly improved gloss and features good film properties.