Amphiphilic block copolymer

Abstract

The invention relates to block copolymer comprising i) A first block wherein at least 65 mol-% of the repeating units of the first block are repeating units of the formula (I)[CH.sub.2CH.sub.2O], ii) A second block wherein at least 90 mol-% of the repeating units of the second block are repeating units of at least one of formulae (II) or (III), wherein the groups R.sup.1, R.sup.2, and R.sup.3 independent of each occurrence are selected from hydrocarbyl groups having 1 to 40 carbon atoms, which are optionally substituted by ether or hydroxyl groups, and wherein the groups R.sup.1 and R.sup.2 are optionally linked to each other such that a nitrogen heterocyclic structure is present, iii) A third block which is different from the first block and the second block and which is more hydrophobic than the first block. ##STR00001##

Claims

1. A block copolymer comprising i) A first block wherein at least 65 mol-% of the repeating units of the first block are repeating units of formula (I)
[CH.sub.2CH.sub.2O](I), ii) A second block wherein at least 90 mol-% of the repeating units of the second block are repeating units of at least one of formulae (II) or (III), ##STR00006## wherein the groups R.sup.1, R.sup.2, and R.sup.3 independent of each occurrence are selected from hydrocarbyl groups having 1 to 40 carbon atoms, which are optionally substituted by ether or hydroxyl groups, and wherein the groups R.sup.1 and R.sup.2 are optionally linked to each other such that a nitrogen heterocyclic structure is present, iii) A third block which is different from the first block and the second block and which is more hydrophobic than the first block.

2. The block copolymer of claim 1, wherein the second block is located between the first block and the third block.

3. The block copolymer of claim 1, wherein the first block consists essentially of repeating units of formula (I).

4. The block copolymer of claim 1, wherein the first block is terminated by an alkyl group having 1 to 12 carbon atoms.

5. The block copolymer of claim 1, wherein the first block comprises 10 to 100 repeating units of formula (I).

6. The block copolymer of claim 1, wherein the sum of repeating units for formulae (II) and (III) in the second block is in the range of 2 to 10.

7. The block copolymer of claim 1, wherein counter ions of the repeating units of formula (III) comprise at least one of chloride, bromide, iodide, tosylate, methylsulfate, and carboxylate.

8. The block copolymer of claim 1, wherein the groups R.sup.1, R.sup.2, and R.sup.3 independent of each occurrence are selected from hydrocarbyl groups having 1 to 18 carbon atoms, which are optionally substituted by ether or hydroxyl groups.

9. The block copolymer of claim 1, wherein the third block comprises repeating units of the formula (IV)
[CH.sub.2CHR.sup.4O](IV), wherein the groups R.sup.4 independent of each occurrence are selected from hydrocarbyl groups having 1 to 18 carbon atoms, which are optionally substituted by ether groups.

10. The block copolymer according to claim 9, wherein the third block comprises 15 to 100 repeating units of formula (IV).

11. The block copolymer of claim 1, wherein the third block comprises repeating units having ester-functional groups.

12. The block copolymer of claim 1, wherein the third block is linked to the second block via a linking group having two urethane groups.

13. The block copolymer of claim 1, wherein the third block is linked to the second block via an ester or ether group.

14. A composition comprising solid particles and the block copolymer of claim 1.

15. A process of dispersing solid particles, the process comprising: a) Mixing at least one type of solid particles, and the block copolymer of claim 1 in a dispersion medium, and b) Exerting shear force to the mixture prepared in a).

16. A pigment dispersion comprising the block copolymer of claim 1 and a pigment.

17. A process of preparing a block copolymer, the process comprising: a) Providing a first polymer block having at least 65 mol-% of repeating units of formula (I) [CH2-CH2-O](I), and having one end group selected from hydroxyl and secondary amine, b) Providing a glycidyl amine of general formula (V) ##STR00007## wherein R.sup.1 and R.sup.2 independent of each occurrence are selected from hydrocarbyl groups having 1 to 40 carbon atoms, which are optionally substituted by ether or hydroxyl groups, and wherein the groups R1 and R2 are optionally linked to each other such that a nitrogen heterocyclic structure is present, and subjecting the glycidyl amine of formula (V) to ring opening polymerization in the presence of the first polymer block provided i a) to prepare a diblock copolymer, c) Providing a monomer mixture comprising at least one of epoxide and lactone, and subjecting the monomer mixture to ring opening polymerization in the presence of the diblock copolymer prepared in b).

Description

EXAMPLES

Synthesis of Glycidylamine Monomer

(1) In a 500 mL round bottom flask 85.7 mL (60.0 g, 820 mmol, 1.00 eq.) Diethylamine were solved in a 40 wt % sodium hydroxide solution (49.5 g, 1230 mmol, 1.50 eq. NaOH in 73.8 ml H.sub.2O). Under stirring and ice cooling epichlorohydrin (96.5 mL, 114 g, 1230 mmol, 1.50 eq.) was added slowly. After complete addition, the reaction mixture was stirred for additional 24 h while warming up slowly to room temperature. During the reaction, sodium chloride precipitated as a white solid. Water was added to the reaction mixture until the white solid was completely dissolved. The aqueous reaction mixture was extracted three times with diethyl ether and the organic phase was dried with MgSO.sub.4. The diethyl ether was removed in vacuum to gain the crude product.

(2) The crude product was purified via fractional distillation in vacuum. In the first fraction, excess epichlorohydrin was collected. In the second fraction diethyl glycidylamine was received with a yield of about 60% (T.sub.b=35-40 C., 12-20 mbar).

(3) The synthesis procedure is identically for other glycidyl amine monomers like pyrrolidine glycidyl amine (PyGA) and dibenzyl glycidyl amine (DBGA).

(4) PyGA: Yield=60% (T.sub.b=45 C., 2 mbar).

Synthesis of Amphiphilic Triblock Copolymers Via Ring-Opening Polymerization Reaction

Synthesis of Diblock Copolymer mPEG-Block-PDEGA-OH

(5) Variant A with Catalyst 18-Crown-6:

(6) In a 500 mL flask equipped with a stirrer and a cooler 37.0 g (18.5 mmol, 1.00 eq.) mPEG were mixed with 0.623 g (5.60 mmol, 0.30 eq.) potassium-tert-butoxide and 1.71 g (6.50 mmol, 0.35 eq.) 18-crown-6. In the next step, 25 mL benzene and 3 mL methanol were added. The mixture was stirred 30 min at 60 C. followed by removal of the solvents and the resulting tert-butanol in vacuum gaining the deprotonated mPEG macro-initiator. The glycidyl amine monomer DEGA was added (8.1 mL, 7.2 g, 56 mmol, 3.0 eq.) into the flask under inert gas atmosphere and the reaction mixture was stirred at 75 C. for 8 hours. The full conversion of the glycidylamine epoxide monomer was verified via .sup.1H-NMR spectroscopy and size exclusion chromatography (SEC) measurements. The hydroxyl-functional diblock copolymer was used in the next reaction step without further clean-up procedure.

(7) The synthesis procedure is analogous for other glycidyl amine monomers like PyGA and DBGA.

(8) If so desired, the preparation can be carried out without 18-crown-8 (Variant B).

Synthesis of the Amphiphilic Triblock Copolymer mPEG-Block-PDEGA-Block-PPO

(9) The reaction mixture of the previously described step was cooled down to 40 C. and propylene oxide was added (59.7 mL, 851 mmol, 60 eq.). The reaction mixture was stirred at 40 C. for 24 h to gain the amphiphilic triblock copolymer. The conversion of the propylene oxide was monitored via .sup.1H NMR spectroscopy and the final polymer was analyzed via SEC. Residual PO was removed in vacuum.

Quaternization of Tertiary Amine Groups of the Amphiphilic Triblock Copolymer mPEG-Block-P(DEGA)-block-PPO

(10) The triblock copolymer of the previous procedure was dissolved in 250 mL methanol and 5.17 mL (11.9 g, 83.9 mmol, 4.5 eq.) methyl iodide were added. Then the reaction mixture was heated to 70 C. under reflux. After 24 hours the methanol and the residual methyl iodide were removed in vacuum. The successful quaternization of the tertiary amine groups was verified via the proton shift in the .sup.1H NMR of the methylene protons of the ethyl moieties. The molecular weights and polydispersities PDI (M.sub.w/M.sub.n) reported in Table 1 were determined by size exclusion chromatography using dimethyl formamide as eluent and polystyrene as calibration standard.

(11) Table 1 provides an overview of amphiphilic triblock copolymers prepared.

(12) TABLE-US-00001 TABLE 1 Overview of the synthesized amphiphilic triblock copolymers: Hydrophilic Macroinitiator Diblock Copolymer EO PO Glycidyl Triblock copolymer content content M.sub.n amine M.sub.n Hydrophobic M.sub.n Route Nr. (mol %) (mol %) (g/mol) PDI monomer (g/mol) PDI monomer (g/mol) PDI (catalyst) P1 100 0 1890 1.04 DEGA 2120 1.05 PO 3600 1.05 A P2 100 0 2120 1.05 DEGA 2430 1.05 PO 4700 1.05 A P3 100 0 1890 1.04 DEGA 2090 1.05 PO 4390 1.05 A P6 100 0 940 1.05 DEGA 1160 1.05 PO 2310 1.05 A P11 100 0 1970 1.04 DEGA 2020 1.06 PO 3190 1.06 A P12 100 0 1970 1.04 DBGA 2070 1.08 PO 2130 1.12 A P13 100 0 1890 1.07 DBGA 2280 1.08 PO 3250 1.13 A P14 100 0 1890 1.07 DBGA 2230 1.11 PO 3480 1.14 A P15 100 0 1890 1.07 PyGA 2330 1.06 PO 3460 1.10 A P16 100 0 1890 1.07 PyGA 2330 1.07 PO 3470 1.10 A P17 100 0 1890 1.07 DEGA 3080 1.06 EHGE 3800 1.19 A P20 100 0 1890 1.07 DEGA 2100 1.05 PO 3370 1.12 B P22 100 0 1890 1.07 PyPA 1970 1.07 PO 3340 1.12 B P23* 100 0 1890 1.07 DEGA 3010 1.19 PO 3050 1.15 B P24* 100 0 1890 1.07 PyGA 4030 1.18 PO 4130 1.13 B P25 100 0 1960 1.04 DEGA 2130 1.06 BO 3310 1.05 B P26 100 0 1960 1.04 DEGA 2100 1.05 BO 3610 1.06 A P27 100 0 1960 1.04 PyGA 2000 1.07 BO 3430 1.08 A P28 100 0 1960 1.04 PyGA 1970 1.05 BO 3100 1.11 B P31 90 10 2140 1.07 DEGA 2620 1.08 PO 3840 1.09 A

(13) In the block copolymers the second block is located between the first block and the third block. Samples P23 and P24 have a different block sequence. In these samples the third block is located between the first block and the second block (mPEG-block-PPO-block-PDEGA and mPEG-block-PPO-block-PPyGA).

(14) Table 2 provides an overview of quaternized amphiphilic triblock copolymers prepared.

(15) TABLE-US-00002 TABLE 2 Overview of the quaternized amphiphilic block copolymers: Sample of amphiphilic Quaternization Nr. tri block copolymer reagent Q1 P1 Mel Q2 P2 Mel Q3 P3 Mel Q6 P6 Mel Q11 P14 Mel Q12 P15 Mel Q13 P16 Mel Q14 P17 Mel Q15 P20 Mel Q16 P22 Mel Q17 P23* Mel Q18 P24* Mel Q19 P25 Mel

Synthesis of Amphiphilic Triblock Copolymer Having Ester Units in the Non-Polar Block

Polyester Synthesis with the Diblock Copolymer Macroinitiator

(16) In a 250 mL Schlenk flask, 37.0 g (15.9 mmol, 1.00 eq.) of the diblock copolymer mPEG-PDEGA as described above were dissolved in 30 mL benzene and the mixture was dried via azeotrope distillation of the benzene for 12 h at 60 C. under reduced pressure. Then 31.8 mL (32.7 g, 287 mmol, 18.0 eq.) freshly distilled and dried c-caprolactone were added under inert gas atmosphere and 0.46 mL (0.58 g, 1.43 mmol, 0.005 eq.) tin(II)-octanoate were added. The mixture was heated at 120 C. until full conversion of lactone monomer was reached. The full conversion was verified via .sup.1H NMR spectroscopy and SEC measurements.

(17) Table 3 provides an overview of amphiphilic triblock copolymers having ester units:

(18) TABLE-US-00003 Diblock Copolymer Hydrophilic Macroinitiator Glycidyl Triblock copolymer EO M.sub.n amine M.sub.n Hydrophobic M.sub.n (mol %) (g/mol) PDI monomer (g/mol) PDI monomer (g/mol) PDI PE1 100 1960 1.04 DEGA 2030 1.06 CL 4010 1.48 PE2 100 1960 1.04 DEGA 2140 1.06 CL/VL (3:1) 3790 1.40 PE3 100 1960 1.04 DEGA 2140 1.06 CL/VL (1:1) 3690 1.36 PE4 100 1960 1.04 DEGA 2150 1.06 L-Lactide 2480 1.42
CL in Table 3 represents c-caprolactone, VL represents -valerolactone. The ratios of CL and VL are molar ratios.

Synthesis of Isocyanate-functional Non-polar Block

(19) 0.25 mol (500 g) of polypropylenegycol monobutylether (Mn 2000 g/mol) was added over 2 hours at room temperature to 0.62 mol (108.75 g) of 2,4-toluene diisocyanate (TDI). The temperature was held below 45 C. After the end of the addition, stirring was continued for 2.5 h. The excess isocyanate was removed by vacuum (0.1 mbar) distillation from 150 to 170 C. The NCO content was 2.36%, the free TDI content <0.5%.

Synthesis of the Amphiphilic Triblock Copolymer Via Isocyanate Coupling

(20) In a 250 mL Schlenk-flask, 30.0 g (12.5 mmol, 1.00 eq.) of the diblock copolymer mPEG-PDEGA of polymer P1 described above and 22.4 g Bu-PPONCO of step 4.1 (NCO-value=2.36%, 12.5 mmol, 1.00 eq.) were mixed and stirred under inert gas atmosphere at 95 C. for 24 h. The successful coupling was verified via SEC measurements.

(21) The results are summarized in Table 4 below:

(22) TABLE-US-00004 Diblock Copolymer Glycidyl Terblock copolymer amine M.sub.n Hydrophobic M.sub.n Nr. monomer (g/mol) PDI building block (g/mol) PDI PX2 DEGA 2160 1.05 PPO.sub.43-NCO 3280 1.23 PX3 PyGA 1980 1.06 PPO.sub.43-NCO 2740 1.25

(23) Use of the polymers of the invention as additive for production of pigment concentrates and use thereof in varnish systems

(24) TABLE-US-00005 TABLE 5 Starting Materials Setal 1715 VX-74 Saturated polyester, manufacturer: ALLNEX Setamine US-138 BB-70 Partly butylated melamine, manufacturer: ALLNEX Paraloid B-66* Thermoplastic acrylate resin, 50% in Xylol manufacturer: DOW Chemicals Laropal A 81 60% Aldehyde resin, manufacturer: BASF Macrynal SM 515 (70%) Hydroxyl functional acrylic resin, manufacturer: ALLNEX Desmodur N 75 Aliphatic polyisocyanate (HDI biuret), manufacturer: COVESTRO Setalux 1756 VV-65 Thermosetting hydroxylated acrylic copolymer, manufacturer: ALLNEX Walsroder NC-Chips Nitrocellulose mixture with plasticizer, E510 ESO manufacturer: DOW Chemicals Synthalat E405 Short-oil non-drying alkyd resin, 60% Xylol manufacturer: SYNTHOPOL Dowanol PMA Propylene glycol methyl ether acetate, manufacturer: Dow Chemicals Shellsol A Solvent naphtha, light aromatic, C9 and C10 DIDP Diisodecylphthalat Hostaperm Violet ER02 Quinacridone pigment (P.V. 19), manufacturer: CLARIANT Spezial schwarz 4 Carbon black pigment (P. Bk. 7), manufacturer: ORION Engineered Carbons GmbH Paliogen Maroon transparent organic pigment PR 179 (perylene), L 3920 manufacturer: BASF Carbon Black FW 200 Carbon black pigment (P. Bk. 7), manufacturer: Orion Engineered Carbons GmbH Raven 5000 Ultra Carbon black pigment for high jetness, III beads manufacturer: Birla Carbon Hostaperm Pink E Quinacridone red (P.R. 122), manufacturer: Clariant Bayferrox Red 130M Iron oxide red (P.R. 101), manufacturer Lanxess BYK-052 Silicone-free defoamer, manufacturer: BYK-Chemie GmbH BYK-300 Polyether modified polydimethylsiloxane, manufacturer: BYK-Chemie GmbH BYK-306 Substrate wetting agent, manufacturer: BYK-Chemie GmbH BYK-310 Substrate wetting agent, manufacturer: BYK-Chemie GmbH Garamite 7305 Benzalkonium Sepiolite (and) Benzalkonium Montmorillonite, manufacturer BYK-Chemie GmbH
System 1: Saturated Polyester-Melamine Baking System
Production of the Millbases Based on Saturated Polyester Resin

(25) The Setal 1715 resin, solvent, dispersing additive and pigment were weighed into 100 mL glass bottles to obtain 50 g millbase. Subsequently, 50 g of glass beads (1 mm) were weighed in.

(26) TABLE-US-00006 TABLE 6 Composition of the Saturated Polyester millbases: SP 1 SP 2 (black) (violet) Setal 1715 VX-74 12.1 14.6 Spezial schwarz 4 6.0 Hostaperm Violet ER02 6.0 PMA 28.9 28.2 Dispersing Additive 3.0 1.2 Total Pigment content (%) 12 12 Dispersant (% s.o.p.) 50 20
Grinding Conditions

(27) Equipment: Lau Disperser DAS 200

(28) Dispersing Time: 180 min, air cooling power at level 3

(29) Ratio of millbase to glass beads (diameter 1 mm): 1:1 (parts by weight)

(30) Evaluation of the viscosity of compositions was assessed using grades: 1 (low viscous), 2 (viscous), 3 (sheer thinning), 4 (high viscous), 5 (not flowable).

(31) Production of the Saturated Polyester Letdown System

(32) Setal 1715 VX-74, Setamine US 138 BB-70, solvent and surface additive were weighed into a 2.5 L PE bucket and homogenized with a Dispermat CV (65 mm toothed disk) at 2000 rpm for 5 min.

(33) TABLE-US-00007 TABLE 7 Composition of the Saturated Polyester Letdown System: Setal 1715 VX-74 400 Setamine US 138 BB-70 210 Shellsol A 108 Butyl glycol acetate 30 BYK-310 2
Production of the Pigmented Saturated Polyester Top Coats

(34) The Saturated Polyester Letdown System and the Saturated Polyester millbase were weighed into a PE cup and mixed with a spatula. Subsequently, the completed Setal 1715 Top Coat systems were homogenized in an ANDALOK shaker for 10 min.

(35) TABLE-US-00008 TABLE 8 Composition of the Pigmented Saturated Polyester Top Coat Systems Setal Setal 1715-T1 1715-T2 Saturated Polyester 15.0 15.0 Letdown System SP 1 (black) 2.0 SP 2 (violet) 5.0 Pigment content (%) 1.4 3.0
Application and Evaluation of the Pigmented Saturated Polyester Top Coat Systems

(36) The pigmented saturated polyester top coat systems were bar-coated onto a Polyethylene terephthalate (PET) film (50 m). After a flash-off time of 15 min, the films were cured in the oven at 140 C. for 15 min. Subsequently, gloss was measured with a BYK micro haze plus instrument at an angle of 20. In each case, high values for gloss are considered to be positive results, as they are generally a sign for an even and homogenous distribution of well dispersed pigment in the coating. In addition, the optical color intensity and transparency through the drawdowns onto the PE film was assessed using grades: 1 (excellent), 2 (good), 3 (satisfactory), 4 (sufficient), 5 (unacceptable).

(37) TABLE-US-00009 TABLE 9 Setal 1715-T1 Setal 1715-T2 (black) (violet) Viscos- Gloss Trans- Viscos- Gloss Trans- Sample ity 20 parency ity 20 parency control 3 85 5 3 81 5 P2 1 88 1 Q2 1 88 3 1 89 2 P3 1 88 1 Q3 1 88 2 1 89 2 Q6 1 85 2 Q12 1 87 3 1 89 2 P16 1 87 2 Q13 1 87 4 1 89 2 P22 1 88 2 Q16 1 88 3 2 88 2 P23 1 88 2-3 2-3 82 4 Q17 1 88 5 2-3 82 4-5 P24 1 87 3 2-3 83 4-5 Q18 1 88 5 2-3 84 4 P25 1 85 1 Q19 1 88 3 2 86 2 P26 1 86 1 P27 1 87 1 P28 1 87 1 PX2 1 87 1 PX3 1 87 3

(38) Viscosity ratings in Table 8 relate to the viscosity of the mill bases. The control sample was prepared without wetting and dispersing additive.

(39) System 2: Thermoplastic Acrylate Resin

(40) Production of Millbases Based on a Thermoplastic Acrylate Resin

(41) The Paraloid B-66 resin, solvent, dispersing additive and pigment were weighed into 100 mL glass bottles to obtain 50 g millbase. Subsequently, 50 g of glass beads (1 mm) were weighed in.

(42) TABLE-US-00010 TABLE 10 Composition of the TPA millbases: TPA 1 TPA 2 (black) (red) Paraloid B-66 (50% in 20.5 15.5 xylene) Carbon Black FW 200 3.0 Perylen Red Paliogen 6.0 Maroon L 3920 Dispersing Additive 2.1 1.5 n-Butanol 5.0 5.0 Butyl acetate:Xylene (1:1) 19.4 22.0 Total Pigment content (%) 6 12 Dispersant (% s.o.p.) 70 25
Grinding Conditions

(43) Equipment: Lau Disperser DAS 200

(44) Dispersing Time: 180 min, air cooling power at level 3

(45) Ratio of millbase to glass beads (diameter 1 mm): 1:1 (parts by weight)

(46) Evaluation of the millbase viscosity was assessed using grades: 1 (thin viscous), 2 (viscous), 3 (sheer thinning), 4 (high viscous), 5 (not flowable).

(47) Production of the TPA-Based Letdown System:

(48) Paraloid B-66, solvent, surface additive and plasticizer were weighed into a 2.5 L PE bucket and homogenized with a Dispermat CV (65 mm toothed disk) at 2000 rpm for 5 min.

(49) TABLE-US-00011 TABLE 11 Composition of the TPA Letdown System: Paraloid B-66 (50% in xylene) 705 n-Butanol 140 Shellsol A 47 Xylene 47 DIDP 60 BYK-306 1
Production of the Pigmented TPA Letdown System

(50) The TPA letdown system and the TPA-based millbases were weighed into a PE cup and mixed with a spatula. Subsequently, the completed letdown systems were homogenized in an ANDALOK shaker for 10 min.

(51) TABLE-US-00012 TABLE 12 Composition of the Pigmented TPA Letdown Systems TPA-B1 TPA-B2 TPA letdown system 15.0 15.0 TPA 1 (black) 5.0 TPA 2 (red) 5.0 Pigment content (%) 1.5 3.0
Application and Evaluation of the Pigmented TPA Letdown System

(52) The pigmented TPA letdown system were bar-coated onto a PET film (50 m) and dried at 22 C. for 24 h. Subsequently, gloss was measured with a BYK micro haze plus instrument at an angle of 20. In each case, high values for gloss are considered to be positive results. In addition, the optical color intensity and transparency through the drawdowns onto the PE film was assessed using grades: 1 (excellent), 2 (good), 3 (satisfactory), 4 (sufficient), 5 (unacceptable).

(53) TABLE-US-00013 TABLE 13 TPA-B1 TPA-B2 (black) (red) Viscos- Gloss Trans- Viscos- Gloss Trans- Sample ity 20 parency ity 20 parency control 5 43 4 3 70 5 P1 2 80 3 3 71 3 P2 1 80 1 4 72 3 Q2 2 78 3 4 62 2 P3 1 80 1 3 73 3 Q3 2 79 3 3 77 3 P6 2-3 79 3 3 76 3 P11 2 80 1 3 72 2 P23 2-3 79 4 4 67 3 Q17 2-3 74 5 2 60 5 P24 2-3 75 4-5 4 66 3 Q18 2-3 74 5 2 54 5 P25 2 80 1 Q19 2-3 79 3 P26 2 79 1 P27 2 80 1 P28 2 80 1 PX2 2 80 3

(54) Viscosity ratings in Table 12 relate to the viscosity of the mill bases. The control sample was prepared without wetting and dispersing additive.

(55) System 3: Two-Component Acrylic-Isocyanate Coating

(56) Production of Millbases Based on an Aldehyde Resin

(57) The Laropal A81 resin, solvent, dispersing additive, pigment and optionally Garamite 7305 were weighed into 100 mL glass bottles to obtain 50 g millbase. Subsequently, 50 g of glass beads (1 mm) were weighed in.

(58) TABLE-US-00014 TABLE 14 Composition of the aldehyde resin (AR) millbases: AR 1 AR 2 AR 3 (black) (pink) (red) Laropal A81 (60%) 16.7 11.5 10.1 PMA 27.3 30.5 10.1 Dispersing Additive 2.0 2.0 2.1 Raven 5000 Ultra III 4.0 beads Hostaperm Rosa E 6.0 Bayferrox 130M 27.5 Garamite 7305 0.2 Total Pigment 8 12 55 content (%) Dispersant (% s.o.p.) 50 33 7.5
Grinding Conditions

(59) Equipment: Lau Disperser DAS 200

(60) Dispersing Time: 180 min for Laropal 3, 240 min for Laropal 1 and Laropal 2, air cooling power at level 3

(61) Ratio of millbase to glass beads (diameter 1 mm): 1:1 (parts by weight)

(62) Evaluation of the millbase viscosity was assessed using grades: 1 (thin viscous), 2 (viscous), 3 (sheer thinning), 4 (high viscous), 5 (not flowable).

(63) Production of the Letdown for Two-Component Acrylic-Isocyanate Coating

(64) Marcynal SM 515, solvent and surface additive were weighed into a 2.5 L PE bucket and homogenized with a Dispermat CV (65 mm toothed disk) at 2000 rpm for 5 min.

(65) TABLE-US-00015 TABLE 15 Composition of the letdown for the Two- Component Acrylic-Isocyanate Coating: Marcynal SM 515 (70%) 750 Shellsol A 128 Butylacetate 120 BYK-300 2
Production of the Pigmented Two-Component Acrylic-Isocyanate Top Coats

(66) The letdown and the aldehyde resin based millbases were weighed into a PE cup and mixed with a spatula. Subsequently, all the mixtures were homogenized in an ANDALOK shaker for 10 min. Afterwards, the Desmodur N-75 was added and the pigmented 2 component Acrylic-Isocyanate top coats were homogenized in an ANDALOK shaker for 2 min.

(67) TABLE-US-00016 TABLE 16 Composition of the Pigmented 2 Component Acrylic-Isocyanate Top Coats TC AI 1 TC AI 2 TC AI 3 Clear Coat 15.0 15.0 12.5 AR 1 (black) 4.5 AR 2 (pink) 6.6 AR 3 (red) 3.0 Desmodur N 75 5.0 5.0 4.5 Pigment content (%) 1.45 3 8
Application and Evaluation of the Pigmented Two-Component Acrylic-Isocyanate Top Coats
TC Al 1 (Black) and TC Al 2 (Pink):

(68) The pigmented two-component Acrylic-Isocyanate top coats were bar-coated onto a PET film (50 m). After a flash-off time of 30 min, the films were cured in the oven at 60 C. for 30 min. Subsequently. Subsequently, haze was measured with a BYK micro haze plus instrument at an angle of 20. Transparency through the drawdowns onto the PE film was assessed using grades: 1 (excellent), 2 (good), 3 (satisfactory), 4 (sufficient), 5 (unacceptable).

(69) TC Al 3 (Red):

(70) The pigmented two-component Acrylic-Isocyanate top coats were bar-coated onto a contrast chart (100 m). After a while, when film become tacky, a Rub-Out Test was performed. The films were cured in the oven at 60 C. for 30 min. Subsequently, haze was measured with a BYK micro haze plus instrument at an angle of 20. Low values for haze are considered to be positive results. In addition, the E-valuescomparing the color values of rubbed vs. non-rubbed surfacewere measured by using a BYK Spectro Guide Sphere d8. Low values for E are considered to be positive results.

(71) TABLE-US-00017 TABLE 17 TC AI TC AI 2 TC AI 3 (black) (Pink) (red) Sample Haze Transp Haze Transp Haze E Control 13 4 12 5 13 1.00 P1 10 1 10 0.60 Q1 12 2 11 0.36 P2 10 1 13 3 10 0.78 Q2 10 2 12 1 11 0.41 P3 10 1 11 3 10 0.73 Q3 10 1 12 1 13 0.53
System 4: Acrylic-Melamine Baking Finish
Production of Millbases Based on an Aldehyde Resin

(72) Usage of the aldehyde resin millbases previously produced: AR 1, AR 2 and AR 3

(73) Production of the Letdown for the Acrylic-Melamine Baking Finish

(74) Setalux 1756 VV-65, Setamine US 138 BB-70, solvent and surface additive were weighed into a 2.5 L PE bucket and homogenized with a Dispermat CV (65 mm toothed disk) at 2000 rpm for 5 min.

(75) TABLE-US-00018 TABLE 18 Composition of the letdown for the Acrylic-Melamine Baking Finish: Setalux 1756 VV-65 600 Setamine US 138 BB-70 240 Shellsol A 80 Xylene 78 BYK-310 2
Production of the Pigmented Acrylic-Melamine Baking Finish Top Coats

(76) The letdown for the Acrylic-Melamine Baking Finish and the aldehyde resin based millbases were weighed into a PE cup and mixed with a spatula. Subsequently, the completed Acrylic-Melamine baking finish top coat systems were homogenized in an ANDALOK shaker for 10 min.

(77) TABLE-US-00019 TABLE 19 Composition of the Pigmented Acrylic- Melamine Baking Finish Top Coats AM BF 1 AM BF 2 AM BF 3 Clear Coat 15.0 15.0 17.0 AR 1 (black) 3.3 AR 2 (pink) 5 AR 3 (red) 3.0 Pigment content (%) 1.45 3 8
Application and Evaluation of the Acrylic-Melamine Baking Finish Top Coats
AM BF 1 (Black) and AM BF 2 (Pink):

(78) The pigmented Acrylic-Melamine Baking Finish Top Coats were bar-coated onto a PET film (50 m). After a flash-off time of 15 min, the films were cured in the oven at 140 C. for 25 min. Subsequently, haze was measured with a BYK micro haze plus instrument at an angle of 20. Transparency through the drawdowns onto the PE film was assessed using grades: 1 (excellent), 2 (good), 3 (satisfactory), 4 (sufficient), 5 (unacceptable). Transparency through the drawdowns onto the PE film was assessed using grades: 1 (excellent), 2 (good), 3 (satisfactory), 4 (sufficient), 5 (unacceptable).

(79) BF 3 (Red):

(80) The pigmented Acrylic-Melamine Baking Finish Top Coats were bar-coated onto a contrast chart (100 m). After a while, when film become tacky, Rub-Out Tests were performed. The films were cured in the oven at 140 C. for 25 min. Subsequently, haze was measured with a BYK micro haze plus instrument at an angle of 20. Low values for haze are considered to be positive results. In addition, the E-valuescomparing the color values of rubbed vs. non-rubbed surface were measured by using a BYK Spectro Guide Sphere d8. Low values for E are considered to be positive results.

(81) TABLE-US-00020 TABLE 20 AM BF 1 (black) AM BF 2 (pink) AM BF 3 (red) Sample Haze Transp. Haze Transp. Haze E Control 13 5 21 5 47 1.04 P1 10 1 P2 10 1 Q2 10 3 16 2 19 0.56 P3 10 1 Q3 12 1 16 2 18 0.50