Polymer dispersants

Abstract

The present invention relates to novel polymer dispersants and to a liquid compositions containing solid fine particles, such as organic or inorganic pigments and fillers, and the polymer dispersants. The polymer dispersants have at least one functional moiety of the formula I, which is bound to one of the termini or to the backbone of the polymer: (I) where # indicates the point of attachment to the terminus and/or to the polymer backbone; k is 0, 1, 2, 3 or 4; m is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; A is a chemical bond or a divalent moiety selected from the group consisting of C.sub.1-C.sub.6 alkylene, O(C.sub.2-C.sub.6 alkylene), C(O)O(C.sub.2-C.sub.6 alkylene), NR.sup.3(C.sub.2-C.sub.6 alkylene) and C(O)NR.sup.3(C.sub.2-C.sub.6 alkylene), where the C.sub.2-C.sub.6 alkylene part is attached to Q; Q is a divalent moiety selected from the group consisting of O, NH and S; R.sup.1 is independently selected from the group consisting of OH, COOH, COOCH.sub.3, NH.sub.2, NH(C.sub.1-C.sub.6 alkyl), N(C.sub.1-C.sub.6 alkyl).sub.2, NO.sub.2, S(O).sub.2R.sup.4, C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.4 alkoxy, halogen, aryloxy, aryl, heteroaryl, where aryl, hetaryl and aryloxy are unsubstituted or substituted by 1, 2, 3 or 4 radicals selected from the group consisting of OH, COOH, COOCH.sub.3, NH.sub.2, NH(C.sub.1-C.sub.6 alkyl), N(C.sub.1-C.sub.6 alkyl).sub.2, NO.sub.2, S(O).sub.2R.sup.4, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy and halogen; R.sup.2 is selected from the group consisting of hydrogen, S(O).sub.2R.sup.4, C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.10 cycloalkyl, aryl, heteroaryl, aryl-C.sub.1-C.sub.4-alkyl and heteroaryl-C.sub.1-C.sub.4-alkyl, where aryl and hetaryl in the four last mentioned radicals are unsubstituted or substituted by 1, 2, 3 or 4 radicals selected from the group consisting of OH, COOH, COOCH.sub.3, NH.sub.2, NH(C.sub.1-C.sub.6 alkyl), N(C.sub.1-C.sub.6 alkyl).sub.2, NO.sub.2, S(O).sub.2R.sup.4, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy and halogen; R.sup.3 is selected from the group consisting of hydrogen, S(O).sub.2R.sup.4, C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.10 cycloalkyl, aryl and heteroaryl, where aryl and hetaryl are unsubstituted or substituted by 1, 2, 3 or 4 radicals selected from the group consisting of OH, COOH, COOCH.sub.3, NH.sub.2, NH(C.sub.1-C.sub.6 alkyl), N(C.sub.1-C.sub.6 alkyl).sub.2, NO.sub.2, S(O).sub.2R.sup.4, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy and halogen; R.sup.4 is selected from the group consisting of OH, NH.sub.2, NH(C.sub.1-C.sub.6 alkyl), N(C.sub.1-C.sub.6 alkyl).sub.2, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy, aryl and heteroaryl, ##STR00001##

Claims

1. A polymer P which has a CC backbone comprising at least one functional moiety of the formula I: ##STR00012## bound to one of the termini and/or to the backbone of the polymer, where # indicates the point of attachment to the terminus and/or to the polymer backbone; k is 0, 1, 2, 3 or 4; m is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; A is a chemical bond or a divalent moiety selected from the group consisting of C.sub.1-C.sub.6 alkylene, O(C.sub.2-C.sub.6 alkylene), C(O)O(C.sub.2-C.sub.6 alkylene), NR.sup.3(C.sub.2-C.sub.6 alkylene) and C(O)NR.sup.3(C.sub.2-C.sub.6 alkylene), where the C.sub.2-C.sub.6 alkylene part is attached to Q; Q is a divalent moiety selected from the group consisting of O, NH and S; R.sup.1 is independently selected from the group consisting of OH, COOH, COOCH.sub.3, NH.sub.2, NH(C.sub.1-C.sub.6 alkyl), N(C.sub.1-C.sub.6 alkyl).sub.2, NO.sub.2, S(O).sub.2R.sup.4, C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.1 alkoxy, halogen, aryloxy, aryl and heteroaryl, where aryl, heteroaryl and aryloxy are unsubstituted or substituted by 1, 2, 3 or 4 radicals selected from the group consisting of OH, COOH, COOCH.sub.3, NH.sub.2, NH(C.sub.1-C.sub.6 alkyl), N(C.sub.1-C.sub.5 alkyl).sub.2, NO.sub.2, S(O).sub.2R.sup.4, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy and halogen; R.sup.2 is selected from the group consisting of hydrogen, S(O).sub.2R.sup.4, C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.10 cycloalkyl, aryl, heteroaryl, aryl-C.sub.1-C.sub.4-alkyl and heteroaryl-C.sub.1-C.sub.4-alkyl, where aryl, heteroaryl, aryl-C.sub.1-C.sub.4-alkyl and heteroaryl-C.sub.1-C.sub.4-alkyl are unsubstituted or substituted by 1, 2, 3 or 4 radicals selected from the group consisting of OH, COOH, COOCH.sub.3, NH.sub.2, NH(C.sub.1-C.sub.6 alkyl), N(C.sub.1-C.sub.6 alkyl).sub.2, NO.sub.2, S(O).sub.2R.sup.4, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy and halogen; R.sup.3 is selected from the group consisting of hydrogen, S(O).sub.2R.sup.4, C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.10 cycloalkyl, aryl and heteroaryl, where aryl and heteroaryl are unsubstituted or substituted by 1, 2, 3 or 4 radicals selected from the group consisting of OH, COOH, COOCH.sub.3, NH.sub.2, NH(C.sub.1-C.sub.6 alkyl), N(C.sub.1-C.sub.6 alkyl).sub.2, NO.sub.2, S(O).sub.2R.sup.4, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy and halogen; R.sup.4 is selected from the group consisting of OH, NH.sub.2, NH(C.sub.1-C.sub.6 alkyl), N(C.sub.1-C.sub.6 alkyl).sub.2, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy, aryl and heteroaryl, where aryl and hetaryl are unsubstituted or substituted by 1, 2, 3 or 4 radicals selected from the group consisting of C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy and halogen; where the radical A in formula I is attached to a carbon atom of said CC backbone or a terminal carbon atom of said polymer P.

2. The polymer P according to claim 1, wherein k is 0 or 1; m is 0 or 1; A is a chemical bond or a divalent moiety selected from the group consisting of C(O)O(C.sub.2-C.sub.4 alkylene) and C(O)NH(C.sub.2-C.sub.4 alkylene), where the alkylene part is attached to Q; Q is a divalent moiety selected from the group consisting of O and NH; R.sup.1 is independently selected from the group consisting of OH, COOH, COOCH.sub.3, NH.sub.2, NH(C.sub.1-C.sub.6 alkyl), N(C.sub.1-C.sub.6 alkyl).sub.2, NO.sub.2, S(O).sub.2R.sup.4, C.sub.1-C.sub.1 alkyl, C.sub.1-C.sub.4 alkoxy, halogen, phenyl and pyridyl; R.sup.2 is selected from the group consisting of hydrogen, C.sub.1-C.sub.4 alkyl and phenyl; R.sup.4 is selected from the group consisting of NH.sub.2, NH(C.sub.1-C.sub.6 alkyl), N(C.sub.1-C.sub.6 alkyl).sub.2 and C.sub.1-C.sub.4 alkyl.

3. The polymer P according to claim 1, where the polymer P has a CC backbone which comprises repeating units M1, selected from polymerized C.sub.1-C.sub.10-alkyl (meth)acrylates, polymerized C.sub.1-C.sub.10-alkyl-(poly-C.sub.2-C.sub.4-alkyleneglycol) (meth)acrylates and polymerized vinylaromatic hydrocarbon compounds.

4. The polymer P according to claim 1 wherein the polymer P has a number average weight of from 250 to 100,000 Dalton.

5. The polymer P according to claim 1 wherein polymer P is obtained by reacting a polymer P having at least one functional moiety of the formula A-Q-H attached to one of the termini and/or to the backbone of the polymer P with a compound of the formulae II, II or III ##STR00013## R.sup.L is hydrogen or a hydrocarbon radical having from 1 to 8 carbon atoms and polymer P does not have a functional group of the formula I.

6. The polymer P according to claim 1, wherein polymer P has an amine number from 3 to 500 mg KOH/g.

7. The polymer P according to claim 3 wherein the repeating units M1 comprise from 10 to 90% by weight of the polymer P.

8. The polymer P according to claim 1, wherein said polymer has a number average weight of from 250 to 100,000 Dalton.

9. The polymer P according to claim 3 wherein an amine number for said polymer is from 3 to 500 mg KOH/g.

10. A method of crosslinking a polymer comprising reacting a polymer with the polymer P of claim 1.

11. A method of modifying the rheology of a composition comprising adding the polymer P of claim 1 to a composition.

12. A method of modifying the impact strength of a composition comprising adding the polymer P of claim 1 to a composition.

13. A method of chain extending a polymer comprising reacting a polymer with the polymer P of claim 1.

14. A method of preparing a block- or graft-copolymer comprising reacting the polymer P of claim 1, which has a C.sub.1-C.sub.10-alkyl ester moieties, with a poly-(C.sub.2-C.sub.4-alkyleneglycol).

15. A method for dispersing fine particulate solid material comprising dispersing fine particulate solid material together with polymer P of claim 1.

16. The polymer P according to claim 1, comprising from 1 to 200 functional moieties of formula I.

Description

PREPARATION EXAMPLES

Abbreviations

(1) n-BA n-butyl acrylate

(2) DBTL dibutyltin dilaurate

(3) HEA 2-hydroxyl ethyl acrylate

(4) IA isatoic anhydride

(5) MPEG methoxy polyethylene glycol

(6) bis-MPA 2,2-dimethylolpropionic acid

(7) TABLE-US-00001 TABLE 1 Commercially available Polymers P used: Name of Polymer P Supplier Boltorn H20 (dentritic polymer based on bis-MPA, 16 Perstorp terminal hydroxyl groups, molecular mass approx. 2100 g/mol Boltorn H30 (dentritic polymer based on bis-MPA, 32 Perstorp terminal hydroxy groups, molecular mass approx. 3500 g/mol Boltorn H40 (dentritic polymer based on bis-MPA, 64 Perstorp terminal hydroxy groups, molecular mass approx. 5100 g/mol Oxymer M112, polyethylene carbonate diol, molecular Perstorp mass approx. 1000 g/mol Oxymer M56, polyethylene carbonate diol, molecular Perstorp mass approx. 2000 g/mol Jeffamine M2070 (polyether monoamine, molecular mass Huntmann approx. 2000 g/mol) Jeffamine ED2003 (polyether diamines, molecular mass Huntmann approx. 2000 g/mol) Jeffamine T5000 (polyether triamine, molecular mass Huntmann approx. 5000 g/mol) Pluriol A750E (Methyl polyethylene glycol, molecular BASF mass approx. 750 g/mol) Pluriol A1340PE (butyl poly(ethyleneglycol-co- BASF propyleneglycol), BASF molecular mass approx. 1340 g/mol) Pluriol A1350P (Alkyl polypropylene glycol, molecular BASF mass approx. 1350 g/mol) Lutensol ON 110 (C.sub.10-Oxo alcohol ethoxylate) Pluronic RPE 1740 (EO/PO block polymer, EO content BASF approx. 40) Acryflow P-120 (Acrylic polyol, OH number: Lyondell- 120 mg KOH/g) Basell

(8) The following polymers P1 to P9 were prepared as starting materials for polymers P

(9) Polymer P1: Polyester of Stearyl Alcohol and -Caprolactone

(10) A mixture of 27 g (0.1 mol) of stearyl alcohol and 250.0 g (2.2 mol) of epsilon-caprolactone was treated with 0.2 g of dibutyltin dilaurate (DBTL) under inert gas and heated to 160 C. until an SC (solids content) of 97% has been reached. The product was obtained as a white solid with an OH number of 21 mg KOH/g.

(11) Polymer P2: Polyester of Stearyl Alcohol, -Valerolactone and -Caprolactone

(12) A mixture of 27 g (0.1 mol) of stearyl alcohol, 137 g (1.2 mol) of epsilon-caprolactone and 120.0 g (1.2 mol) of delta-valerolactone was treated with 0.2 g of DBTL under inert gas and heated to 160 C. until an SC (solids content) of 97% has been reached. The product was obtained as a yellow solid with an OH number of 20 mg KOH/g.

(13) Polymer P3: Hyperbranched Polyester of Boltorn H20, -Valerolactone and -caprolactone

(14) A mixture of 10 g of Boltorn H20, 50.0 g (0.44 mol) of epsilon-caprolactone and 44.0 g (0.44 mol) of delta valerolactone was treated with 0.07 g of DBTL under inert gas and heated to 160 C. until a solid content of 97% was reached. The product was obtained as a yellow clear liquid with an OH number of 50 mg KOH/g.

(15) Polymer P4: PolynBA60-b-PolyHEA10

(16) ##STR00007##

(17) A mixture of 78 g (0.01 mol) of living linear polymer poly(BA) (prepared according to example 1 of US 2011/0224375) and 23.2 g (0.2 mol) of 2-hydroxyl ethyl acrylate was stirred under nitrogen at room temperature for 30 min. Then the mixture was heated at 120 C. until a SC of 88% was reached. Residual 2-hydroxyl ethyl acrylate monomer was removed under 5 mbar vacuum (at 130 C. for 2 hours). A viscous yellowish title compound PolynBA60-b-PolyHEA10 was obtained (SC of 98%) with an OH number of 65 mg KOH/g.

(18) Polymer P5: PolynBA60-b-PolyHEA20

(19) ##STR00008##

(20) A mixture of 78 g (0.01 mol) of living linear polymer poly(BA) (prepared according to example 1 of US 2011/0224375) and 46.4 g (0.4 mol) 2-hydroxyl ethyl acrylate was stirred under nitrogen at room temperature for 30 min. Then the mixture was heated at 120 C. until a SC of 81% was reached. Residual 2-hydroxyl ethyl acrylate monomer was removed under 5 mbar vacuum (at 130 C. for 2 hours). A viscous yellowish title compound PolynBA60-b-PolyHEA20 was obtained (SC of 98%) with an OH number of 110 mg KOH/g.

(21) Polymer P6: Mono-OH Functional Poly(nBA): HO-PnBA35-NOR

(22) ##STR00009##

(23) The title compound was prepared according to intermediate example 3 of WO 2011/120947

(24) Polymer P7: Poly(nBA30) End Functionalized with OH Group: PnBA30-OH

(25) ##STR00010##

(26) The title compound was prepared according to example 1 of WO 2011/120947

(27) Polymer P8: OH Telechelic Poly(nBA35): HO-PnBA35-OH

(28) ##STR00011##

(29) The title compound was prepared according to example 3 of WO2011/120947

(30) Polymer P9: OH-Terminated Polyetherester

(31) A mixture of 35 g (0.1 mol) of methyl polyethylene glycol (M.sub.w of 350 g/mol), 45.6 g (0.4 mol) of epsilon-caprolactone and 10.0 g (0.1 mol) of delta-valerolactone was treated with 0.1 g of dibutyltin dilaurate under inert gas and heated to 160 C. until a solids content of 97% had been reached. The polyetherester was obtained as a yellow/colorless liquid with an OH number of 65 mg KOH/g.

Example 1

(32) A mixture of 28.0 g (0.01 mol OH) of polymer P1, 1.63 g (0.01 mol) of isatoic anhydride and 0.1 g (0.3 wt.-%) of 4-dimethylaminopyridine were heated at 80140 C. until no more carbon dioxide was evolved. The obtained product was a yellowish solid with an amine number of 18 mg KOH/g.

Examples 2-27

(33) Examples 2-27 were prepared in a similar manner as Example 1, except that the type of OH or amine functionalized polymer and the ratio of OH (amine) group to isatoic anhydride were varied as detailed in Table 2 below.

(34) TABLE-US-00002 TABLE 2 OH/amine functionalized polymer Molar Amine OH/NH.sub.2 ratio .sup.2) No. .sup.3) No. .sup.1) OH/NH.sub.2 (mg Example (mg KOH/g) to II/III KOH/g) 2 Polymer P2 20 1:1 18 3 Polymer P3 50 1:1 44 4 Boltorn H30 500 1:1 420 6 Boltorn H40 490 1:1 420 7 Boltorn H40 490 1:0.5 230 8 Boltorn H40 490 1:2 500 9 Jeffamine M2070 30 1:1 32 10 Jeffamine M2070 30 1:3 35 11 Jeffamine ED2003 50 1:1 53 12 Jeffamine T5000 32 1:1 35 13 Pluriol A750E 75 1:1 70 14 Pluriol A1350P 40 1:1 38 15 LutensolON110 90 1:1 85 16 Pluriol A1340PE 45 1:1 40 17 Pluronic RPE1740 41 1:1 38 18 Acryflow P-120 120 1:1 112 19 Polymer P6 12 1:1 10 20 Polymer P7 15 1:1 14 21 Polymer P8 11 1:1 10 22 Polymer P4 65 1:1 60 23 Polymer P4 65 1:0.7 40 24 Polymer P5 110 1:1 104 25 Polymer P5 110 1:0.6 70 26 Oxymer M112 110 1:1 101 27 Oxymer M56 56 1:1 51 .sup.1) OH or amine number of the polymer P .sup.2) molar ratio of OH or amine groups to compounds II or III .sup.1) amine number of the resulting polymer P

Example 28

Transesterification of the Polymer P of Example 19 Using MPEG

(35) The mixture of 50.0 g of the polymer P of example 19 and 40 g of MPEG (Mn=500 g/mol) were heated under inert gas at 100160 C. for 4 h. Three portions of 0.1 g of tetra(isopropyl)orthotitanate were added. The formed n-butanol was distilled off under reduced pressure. The obtained product was a yellowish viscous liquid with an amine number of 6 mg KOH/g.

Example 29

Transesterification of the Polymer P of Example 21 Using MPEG

(36) The mixture of 50.0 g of the polymer P from example 21 and 100 g MPEG (Mn=500 g/mol) were heated under inert gas at 100160 C. for 4 h. Three portions of 0.1 g of tetra(isopropyl)orthotitanate were added. The formed n-butanol was distilled off under reduced. The obtained product was a yellowish viscous liquid with an amine number of 3 mg KOH/g.

Example 30

Transesterification of the Polymer P of Example 22 Using MPEG

(37) The mixture of 50.0 g of the compound from example 22 and 40 g MPEG (Mn=500 g/mol) were c were heated under inert gas at 100160 C. for 4 h. Three portions of 0.1 g of tetra(isopropyl)orthotitanate addition. The formed n-butanol is distilled off under vacuum system. The obtained product was a yellowish viscous liquid with an amine number of 35 mg KOH/g.

Example 31

Modification of Polymer P4 with 4-(4-pyridinyl)isatoic anhydride

(38) The mixture of 51.6 g (0.06 mol OH) of polymer P4, 14.4 g (0.06 mol) of 4-(4-pyridinyl)isatoic anhydride and 0.2 g (0.3 wt.-%) of 4-dimethylaminopyridine were heated at 80140 C. until no more carbon dioxide was evolved. The obtained product was a yellowish viscous liquid with an amine number of 95 mg KOH/g.

Example 32

Modification of Polymer P4 with Chloroisatoic Anhydride

(39) The mixture of 51.6 g (0.06 mol OH) of polymer P4, 11.9 g (0.06 mol) of chloroisatoic anhydride and 0.2 g (0.3 wt.-%) of 4-dimethylaminopyridine were heated at 80140 C. until no more carbon dioxide was evolved. The obtained product was a yellowish viscous liquid with an amine number of 58 mg KOH/g.

Example 33

(40) A mixture of 90.0 g (0.1 mol OH) of polymer P9, 16.3 g (0.1 mol) of isatoic anhydride and 0.3 g (0.3 wt.-%) of 4-dimethylaminopyridine was heated at 80 to 140 C. until no more carbon dioxide was evolved. The obtained product was a yellowish liquid with an amine number of 55 mg KOH/g.

Example 34

(41) A mixture of 50.0 g (0.1 mol OH) of methylpolyethylene glycol (M.sub.w of 500 g/mol), 13.7 g (0.1 mol) of anthranilic acid and 0.2 g (0.3 wt.-%) of 4-dimethylaminopyridine were heated at 160 C. until the acid number is less than 10 mg KOH/g. The obtained product was a yellowish/brownish liquid with an amine number of 90 mg KOH/g.

(42) Performance Testing

(43) First, competitive dispersants were synthesized according to WO 94/21368, U.S. Pat. No. 6,583,213, and U.S. Pat. No. 6,599,947. The performance of these dispersants was tested according to Formulations 1 and 2. Results showed that example 9 of U.S. Pat. No. 6,583,213 (2-hydroxyethylacrylate--caprolactone--valerolactone (1:8:8) PEI (13:1)), performs better than the others, which was then taken as a comparison dispersant.

(44) In order to test the dispersion effect of the obtained samples, Resin Free Pigment Concentrates (mill base) were prepared according to the following Formulations 1 and 2. The mill base was dispersed in Scandex Shaker for 4 h with the help of glass beads. Afterwards the mill base was filtered and stored at room temperature overnight.

(45) Preparation of Millbase (Formulations 1 and 2)

(46) TABLE-US-00003 Ingredients/Millbase No. 1 2 1) Polymer P (100% solid) 1.40 1.40 2) 1-methoxy-2-propyl acetate (MPA) 30.1 30.1 4) Pigment Blue 15:1 3.50 5) Pigment Blue 15:3 3.50 7) 2.0 mm glass beads 35.0 35.0 Total (g) 70.0 70.0 Pigment Blue 15:1 (Heliogen Blue L 6950) Pigment Blue 15:3 (Heliogen Blue L 7085)

(47) The performance of the polymers P of examples 1 to 32 was tested by determining the rheological behaviour of millbase formulations 1 and 2, including the specified amount of polymer P. The rheological behavior of the millbases was measured at 23 C. with a Thermo-Haake RheoStress 600 rheometer under CR-mode with rotation speed of 0.1 sec.sup.1, 1 sec.sup.1 or 100 sec.sup.1, respectively, using a cone-plate sensor. The millbases containing the polymers P flowed well and their viscosities were comparable or lower than the product of the comparative example. Results are summarized in table 3:

(48) TABLE-US-00004 TABLE 3 The dispersion effect in clear coat paint system Viscosity of Viscosity of Exam- millbase 1 (mPas).sup.2)3) millbase 2 (mPas).sup.2)3) ple 1 0.1 s.sup.1 1 s.sup.1 100 s.sup.1 0.1 s.sup.1 1 s.sup.1 100 s.sup.1 C.sup.1) 48.5k 5980 117 321k 95.2k 3380 3 65k 9540 154 351k 36k 3540 9 14k 3100 52 375k 66.9k 3040 10 4870 1420 29 316k 54.4k 3340 13 8380 2320 37 251k 27k 2970 19 33.5k 7390 115 405k 61.6k 3130 22 125k 15.8k 191 197k 24.4k 511 23 66.2k 8990 127 240k 51.8k 773 24 30.1k 6400 94 160k 43.2k 597 27 40.5k 8510 165 351k 23k 3640 30 680k 11k 258 150k 29k 2650 31 47k 6510 135 250k 86k 3060 .sup.1)Comparative Example: example 9 of U.S. Pat. No. 6,583,213 .sup.2)measured at constant rotation speed of 0.1 sec.sup.1, 1 sec.sup.1 or 100 sec.sup.1, respectively .sup.3)values characterized by k have to be multiplied by 1000

(49) The performance of Polymers P was also tested in clear coating systems with respect to gloss. For this, a let-down formulation (Formulation 2) based on a clear coating system was prepared. A paint preparation was prepared by mixing 4.50 g of the respective millbase and 10.5 g of formulation 2 for 5 minutes at 2000 rpm. The paint was applied on polyester film with a 75 m film thickness. After preparing draw-downs, the rest of paints were diluted 1:1 with 1-methoxy-2-propyl acetate for a pour-out test.

(50) The gloss of the obtained coatings at 20 angle was determined according to DIN 67530 using a commercial reflectometer (Micro-Tri-Gloss reflectometer from BYK Gardner). The performance was generally very good with satisfactory results, e.g. high gloss in let-down and pour out test. The results are summarized in table 4.

(51) Formulations 2. Let-Down Systems

(52) TABLE-US-00005 Ingredient active % b.w. % b.w. in Formulation Resin 1 60% 24.7% Resin 2 15% 23.1% Resin 3 55% 11.5% Plasticizer 95% 2.9% Butyl Acetate 100% 18.9% Xylene 18.9% Total 100% Resin 1: Saturated polyester resin in Solvent naphtha/Methoxy propanol/Xylene (Setal 173 VS-60) Resin 2: Mixture of 64.8 g of a first cellulose acetate butyrate (CAB 381.2) and 25.2 g of a second cellulose acetate butyrate (CAB 381.20) in 255 g butyl acetate and 255 g of xylene, commercially available from Eastman Chemical; Resin 3: Maprenal MF 650: highly reactive isobutylated melamine-formaldehyde resin, commercially available from Degussa Plasticizer: Resamine HF 480: Polyurea plasticizer, Carbamic resin based on butylurethane and formaldehyde, commercially available from Cytec

(53) TABLE-US-00006 TABLE 4 The dispersion effect in clear coat paint system Gloss 20 Gloss 20 Millbase 1 Millbase 2 Example Let down Pour out Let down Pour out C .sup.1) 55 103 39 23 3 50 91 47 35 9 47 42 40 21 10 44 27 35 18 13 46 36 41 26 19 46 84 42 23 22 48 96 57 28 23 46 91 56 41 24 36 69 42 12 27 45 87 53 31 30 52 93 60 28 31 54 97 51 31 .sup.1) Comparative Example: example 9 of U.S. Pat. No. 6,583,213