Aqueous composition with improved elongation at break

Abstract

An aqueous polymer composition which when in the form of a film shows excellent elongation at break comprising (i) 5 to 30 wt. % of polyurethane where the acid value of the polyurethane is between 3 to 40 mg KOH/g; (ii) 70 to 95 wt. % of vinyl polymer comprising 20 to 90 wt. % of vinyl polymer with Tg<20 C.; 10 to 80 wt. % of vinyl polymer with Tg20 C.; where at least one of the vinyl polymers contains acid functional groups with acid value in the range of from 15 and 240 mg KOH/g.

Claims

1. An aqueous polymer composition comprising (i) 5 to 30 wt. % of polyurethane obtained by the reaction of: (a) (1) 9 to 31 wt. % of at least one polyisocyanate; (2) 0 to 8 wt. % of at least one isocyanate-reactive compound with a weight average molecular weight in the range of from 50 to 500 g/mol, containing ionic or potentially ionic water-dispersing groups; (3) 0 to 91 wt. % of at least one isocyanate-reactive compound with a weight average molecular weight in the range of from 501 to 5000 g/mol containing ionic or potentially ionic water-dispersing groups; (4) 0 to 91 wt. % of at least one isocyanate-reactive compound with a weight average molecular weight in the range of from 501 to 5000 g/mol not comprised by (3); where (3) and (4) add up to 57 to 91 wt. %; (5) 0 to 10 wt. % of at least one isocyanate-reactive compound with a weight average molecular weight in the range of from 50 to 500 g/mol not comprised by (2); where (1), (2), (3), (4) and (5) add up to 100%; and (b) at least one chain-extending compound; where the acid value of the resulting polyurethane (i) is between 3 to 40 mg KOH/g; (ii) 70 to 95 wt. % of vinyl polymer comprising (c) 20 to 90 wt. % of vinyl polymer with Tg<20 C.; (d) 10 to 80 wt. % of vinyl polymer with Tg20 C.; wherein (c) and (d) add up to 100%; where at least one of (c) and (d) contains acid functional groups with an acid value in the range of from 15 to 240 mg KOH/g; and wherein (i) and (ii) add up to 100%.

2. An aqueous polymer composition according to claim 1 wherein the weight percentage of (i) and (ii) together is more than 60 wt. % of the total composition.

3. An aqueous polymer composition according to claim 1 wherein at least one of (c) and (d) contains acid functional groups so that the acid value of the resulting vinyl polymer is in the range of from 15 to 100 mg KOH/g.

4. An aqueous polymer composition according to claim 1 wherein at least one of (c) and (d) contains acid functional groups so that the acid value of the resulting vinyl polymer is in the range of from 101 to 240 mg KOH/g.

5. An aqueous polymer composition according to claim 1 wherein the Tg of vinyl polymer (d) is at least 30 C. higher than the Tg of vinyl polymer (c).

6. An aqueous polymer composition according to claim 1 wherein the weight ratio of vinyl polymer (c) to vinyl polymer (d) is within the range of from 35/65 to 90/10.

7. An aqueous polymer composition according to claim 1 wherein at least 50 wt. % of the total amount of polyisocyanate (1) used comprises aliphatic polyisocyanate.

8. An aqueous polymer composition according to claim 1 wherein at least 30 wt. % of the total amount of polyisocyanate (1) used is selected from HDI, pentamethylene diisocyanate and or mixtures thereof.

9. An aqueous polymer composition according to claim 1 wherein the acid value of the polyurethane is in the range of from 6 to 35 mg KOH/g.

10. An aqueous polymer composition according to claim 1 containing less than 10 wt. % solvent.

11. A clear lacquer comprising the aqueous polymer composition according to claim 1 wherein said lacquer comprises: I) 2 to 15 wt. % of the polyurethane (i); II) 25 to 50 wt. % of the vinyl polymer (ii); III) 35 to 74 wt. % of water; IV) 0 to 4 wt. % of transparent inorganic additives where I), II), III) and IV) all add up to 100%.

12. A clear lacquer as defined in claim 11 which when in the form of a film has an elongation at break of at least 140% at 10 wt. % of polyurethane at room temperature.

13. A clear lacquer as defined in claim 11 which when in the form of a film has an elongation at break of at least 160% at 10 wt. % of polyurethane at room temperature.

14. A pigmented lacquer comprising the aqueous ploymer composition according to claim 1 as wherein said lacquer comprises: I) 1 to 10 wt. % of the polyurethane (i); II) 10 to 40 wt. % of the vinyl polymer (ii); III) 30 to 79 wt. % of water; IV) 10 to 30 wt. % of pigment; where I), II), III) and IV) all add up to 100%.

15. A pigmented lacquer as defined in claim 14 with a pigment volume concentration range of 10 to 30 vol. % which when in the form of a film has an elongation at break of at least 60% at 10 wt. % of polyurethane at room temperature.

16. A method of coating a substrate comprising applying to the substrate the lacquer according to claim 11.

17. A substrate having a coating comprising a lacquer according to claim 11.

Description

EXAMPLES

(1) Components and Abbreviations Used: IPDI=Isophorone diisocyanate available from Bayer DMPA=Dimethylolpropionic acid available from Perstorp polyols HDI=1,6-hexamethylene diisocyanate NCO=iscocyanate group TEA=triethylamine CHDM=1,4-Cyclohexanedimethanol available from Eastman Chemical bv Desmodur W=dicyclohexyl methane diisocyanate available from Bayer EDA=Ethylene diamine available from Delamine bv MMA=Methyl methacrylate available from ECEM European Chemical Marketing by (Tg 377K) MAA=Methacrylic acid (Tg 501K) BMA=n-Butyl methacrylate available from Arkema Nederland by (Tg 293K) n-BA=n-Butyl acrylate available from BASF UK ltd (Tg 219K) 2-EHA=2-Ethylhexyl acrylate available from Dow Benelux nv (Tg 223K) DAAM=diacetone acrylamide (Tg 338K) 3-MPA=3-mercaptopropionic acid IAA=Isoascorbic acid available from Brenntag Volkers Benelux bv tBHPO=tert-butyl Hydroperoxide available from Azko Nobel Chemicals bv Fe(III)EDTA=Iron-ethylenediaminetetracetic acid complex, 1% in water Proxel Ultra 10=Preservative (1,2-benzi9sothiazolin-3-one in water) available from Lonza Parmetol K-40=Preservative (Water based combination of chloromethyl-/methylisothiazolone) available from Schuelke & Mayr GmbH SR-10PG=glycol free styrene acrylic solid resin available from Indulor Chemie with an acid value of 221 mg KOH/g, Mw of 10K Dalton and a theoretical Tg of 115 C. PolyTHF=Poly(tetramethylene ether) glycol with various average molecular weights e.g. 2000, 1000 and 2900 g/mol available from BASF NeoRez R980=Water based soft anionic aliphatic urethane dispersion available from DSM with an acid value of 21 mgKOH/g an HDI content of 0 wt. % and DesmodurW content above 35 wt %. BYK 346=Silicone surfactant for aqueous coatings available from Altana Coatex BR100P=Polyurethane thickener available from Coatex (Arkema) NeoCryl A1131=An acrylic copolymer dispersion available from DSM with one phase with a Tg of 105 C., an acid value of 17.2 mg KOH/g and a second phase with a Tg of 64 C. and an acid value of 0 mgKOH/g. NeoCryl XK-99=An acrylic emulsion available from DSM with one phase with a Tg of 16.4 C. and acid value of 28.8 mgKOH/g and second phase with a Tg of 80 C. and acid value of 28.8 mgKOH/g and a minimum film forming temperature <0 C. Borchigel L75=urethane thickener available from Bayer Dehydran 1293=Defoamer additive available from Cognis; 10% in butyl glycol Disperbyk 2015=VOC- and solvent-free wetting and dispersing additive available From Altana Tego Foamex 810=Defoamer concentrate polyether siloxane copolymer, contains fumed silica, available from Evonik Tioxide TR-92=titanium dioxide pigment available from Huntsman
Vinyl Polymers

(2) Vinyl polymers VP1, VP2, VP4, VP7 as described herein have a molecular weight higher than 100,000 g/mol. Vinyl polymer VP5 and VP6 as described herein have a molecular weight less than 60,000 g/mol. VP3 is a combination of a vinyl polymer having a molecular weight higher than 100,000 g/mol and a vinyl polymer having a molecular weight less than 60,000 g/mol.

(3) Vinyl Polymer (d) [VP1]

(4) A 2000 cm.sup.3 flask equipped with a thermometer and overhead stirrer was charged with water (627 g), sodium lauryl sulphate (8.6 g) and ammonium persulphate (0.44 g) and heated to 85 C. At 85 C. a mixture of water (415 g), sodium lauryl sulphate (36.8 g), ammonium persulphate (3.96 g), MAA (26.4 g), MMA (826.7 g), and 2-EHA (26.3 g) was added over a period of 120 minutes. At the end of the feed, the reaction was stirred at 85 C. for 30 minutes. Then tBPHO (2.93 g of a 30 wt. % solution in water) was added followed by isoascorbic acid (17.6 g of a 5 wt. % solution in water). After 15 minutes at 85 C., the reaction mixture was cooled to room temperature and the pH was adjusted to 7.5 to 8.0 with ammonia (25% in water). Proxel Ultra 10 (8.79 g) was added and the batch was filtered through a filter cloth to remove any coagulum formed during the reaction. Solids: 45%; pH 8.0; viscosity 64 mPas; particle size: 74 nm; acid value 48.4 mgKOH/g; Tg 100 C.

(5) Vinyl Polymer (c): [VP2]

(6) Same procedure as described above for VP1 with a monomer feed: MAA (26.38 g), MMA (233.41 g), and 2-EHA (619.55 g). Solids: 45%; pH 8.0; viscosity 51 mPas; particle size: 98 nm; acid value 48.4 mgKOH/g; Tg 18 C.

(7) Vinyl Polymer [VP3] (Sequential Oligomer Polymer Composition)

(8) A 2000 cm.sup.3 flask equipped with a thermometer and overhead stirrer was charged with water (533.2 g) and sodium lauryl sulphate (1.6 g) and heated to 85 C. under a nitrogen atmosphere. At 70 C. 10% of a mixture of water (97.0 g), sodium lauryl sulphate (4.6 g), MAA (28.8 g), DAAM (14.4 g), BMA (28.8 g), MMA (168.4 g) and 3-MPA (5.8 g) was added. At 75 C. a mixture of water (11.0 g) and ammonium persulphate (0.2 g) was added. At 85 C. the remaining 90% mixture was added over a period of 60 minutes. Together with this mixture a mixture of water (33.2 g) and ammonium persulphate (0.6 g) was added over a period of 70 minutes. At the end of the feed, the reaction was stirred at 85 C. for 20 minutes. Then the batch was cooled to 80 C. and a mixture of water (21.0 g) and ammonia (23.0 g, 25% in water) was added in 15 minutes. The batch was stirred for 20 minutes and cooled to 60 C. At 60 C. 33% of the mixture of water (7.2 g) and tBHPO (1.0 g of a 70 wt. % solution in water) was added. Followed by the addition of 33% of the mixture of DAAM (12.4 g), n-BA (406.6 g) and MMA (197.0 g). After mixing for 15 minutes 40% of a solution of water (23.2 g) and isoascorbic acid (1.4 g) which is adjust at pH =8.5 with ammonia (25% in water) is added. After a peak temperature of 86 C. is reached, the batch was stirred for 10 minutes. Water (100.6 g) was added and the batch was cooled to 60 C. 33% of the monomer mixture was added. Fe(III)EDTA 1% in water (0.02 g) is added and the batch was stirred for 15 minutes. 33% of the tBHPO/water mixture was added followed by 33.3% of the remaining isoascorbic acid/water mixture. After a peak temperature of 86 C. is reached, the batch was stirred for 10 minutes. Water (138.2 g) was added and the batch was cooled to 60 C. 33% of the monomer mixture was added and the batch was stirred for 15 minutes. 33% of the tBHPO/water mixture was added followed by the remaining isoascorbic acid/water mixture. After the peak temperature of 86 C. was reached the batch was cooled to room temperature. Water was added (115.0 g) followed by Parmetol K-40 (2.2 g) and Proxel Ultra 10 (10.0 g). The batch was filtered through a filter cloth to remove any coagulum formed during the reaction. Solids: 43.5%; pH: 7.5; viscosity: 185 mPas; particle size: 89 nm. Vinyl polymer (d): Tg 99 C.; acid value 107 mgKOH/g. Vinyl polymer (c): Tg 18 C.; acid value 0 mgKOH/g.

(9) Vinyl Polymer (c) [VP4]

(10) A 2000 cm.sup.3 flask equipped with a thermometer and overhead stirrer was charged with water (627.6 g), sodium lauryl sulphate (8.6 g) and ammonium persulphate (0.4 g) and heated to 85 C. under a nitrogen atmosphere. At 85 C. a mixture of water (340.0 g), sodium lauryl sulphate (32.8 g), MAA (26.4 g), 2-EHA (620.2 g) and MMA (233.6 g) was added over a period of 120 minutes. Together with this mixture a mixture of water (75.4 g), sodium lauryl sulphate (4.0 g) and ammonium persulphate (4.0 g) was added (also over 120 minutes). At the end of the feed, the reaction was stirred at 85 C. for 15 minutes. Then tBHPO (2.8 g of a 30 wt. % solution in water) was added followed by isoascorbic acid (17.6 g of a 4.5 wt. % solution in water). After 15 minutes at 85 C., the reaction mixture was cooled to room temperature and the pH was adjusted to 8,0 with ammonia (12.5% in water). Proxel Ultra 10 (6.6 g) was added and the batch was filtered through a filter cloth to remove any coagulum formed during the reaction. Solids: 45%; pH 8.0; viscosity 67 mPas; particle size 92 nm; Tg 18 C.; acid value 48.4 mgKOH/g.

(11) Vinyl Oligomer (d) [VP5]

(12) A 2000 cm.sup.3 flask equipped with a thermometer and overhead stirrer was charged with water (1071.4 g) and sodium lauryl sulphate (3.0 g) and heated to 85 C. under a nitrogen atmosphere. At 70 C. 10% of a mixture of water (194.8 g), sodium lauryl sulphate (9.0 g), MAA (58.0 g), DAAM (29.0 g), BMA (58.0 g), MMA (338.2 g) and 3-MPA (11.6 g) was added. At 75 C. a mixture of water (22.0 g) and ammonium persulphate (0.4 g) was added. At 85 C. the remaining 90% mixture was added over a period of 60 minutes. Together with this mixture a mixture of water (66.6 g) and ammonium persulphate (1.0 g) was added over a period of 70 minutes. At the end of the feed, the reaction was stirred at 85 C. for 20 minutes. Then the batch was cooled to 80 C. and a mixture of water (42.0 g) and ammonia (46.2 g, 25% in water) was added in 15 minutes. The batch was stirred for 20 minutes and cooled to room temperature. Parmetol K-40 (4.2 g) and Proxel Ultra 10 (19.98 g) are added and the batch was filtered through a filter cloth to remove any coagulum formed during the reaction. Solids: 23.8%; pH: 7.5; viscosity: 10 mPas; Mwt: 16.6 kDa; Tg 100 C.; acid value 107 mgKOH/g.

(13) High Acid Styrene-Acrylic Co-Polymer (d) [VP6]

(14) A 2000 cm3 flask equipped with a thermometer and overhead stirrer was charged with water (777.3 g) and SR-10PG (259.1 g) and heated to 85 C. under a nitrogen atmosphere. During heating ammonia (68.36 g, 25% in water) was added and the batch was stirred for 70 minutes. The batch was cooled down to room temperature and filtered through a filter cloth to remove any coagulum. Solids: 22.3%; pH: 8.5; viscosity: 22 mPas.

(15) Vinyl Polymer (d) [VP7]

(16) Same procedure as described above for VP1 with in the monomer feed: MAA (26.38 g), MMA (580.92 g), and 2-EHA (272.04 g). Solids: 45%; pH=8.1; viscosity 30 mPas; particle size: 84 nm; acid value 48.4 mgKOH/g; Tg 40 C.

(17) Polyurethanes:

(18) All of the polyurethanes as described herein have 0 mmoles per g of olefinically unsaturated bonds (i.e. no olefinically unsaturated bonds at all).

(19) The weight average molecular weight (Mw) of the polyurethanes (after chain-extension) in the examples below is within the range from 30,000 g/mol to 1,200,000 g/mol.

(20) The acid value of the polyurethanes in the examples below is in the range of from 10 to 30 mg KOH/g.

(21) Polyurethane [PU1]:

(22) A polyurethane prepolymer was prepared by mixing PolyTHF2000 (382 g), DMPA (26 g), HDI (78 g) and dibutyltin dilaurate catalyst in acetone (262 g). The mixture was heated to 60 C. and maintained at this temperature until the NCO-content reached <1.5% NCO/g resin. The mixture was cooled and TEA was added (12 g) before adding water as chain-extender and disperse the prepolymer. The solvent was removed by vacuum distillation until the solids content reached a plateau value. The reactor content was cooled further and the vacuum released. The solids content was 38 wt. %. Viscosity 200 mPas; pH 71, particle size: 90 nm, sediment below 0.1%; acid value 22.4 mg KOH/g.

(23) Polyurethane [PU2]

(24) A polyurethane prepolymer was prepared by mixing PolyTHF1000 (308 g), DMPA (18 g), CHDM (4 g), HDI (110 g) and dibutyltin dilaurate in acetone (237 g). The mixture was heated to 60 C. and maintained at this temperature until the NCO-content reached <2.33% NCO/g resin. The mixture was cooled and TEA was added (8 g) before adding water as chain-extender and disperse the prepolymer. The solvent was removed by vacuum distillation until the solids content reached a plateau value. The reactor content was cooled further and the vacuum released. The solids content was 40 wt. %. Viscosity 6030 mPas; pH 7.7, particle size: 145 nm, sediment below 0.3%; acid value 16.7 mg KOH/g; M.sub.w 121,136 g/mol.

(25) Polyurethane [PU3]

(26) A polyurethane prepolymer was prepared by mixing PolyTHF2900 (372 g), DMPA (18 g), HDI (53 g) and dibutyltin dilaurate in acetone (239 g). The mixture was heated to 60 C. and maintained at this temperature until the NCO-content reached <0.65% NCO/g resin. The mixture was cooled and TEA was added (9 g) before adding water as chain-extender and disperse the prepolymer. The solvent was removed by vacuum distillation until the solids content reached a plateau value. The reactor content was cooled further and the vacuum released. The solids content was 40 wt. %. Viscosity 450 mPas; pH 7.1, particle size: 104 nm, sediment below 0.3%, acid value 16.7 mg KOH/g; M.sub.w 59,734 g/mol.

(27) Polyurethane [PU4]

(28) A polyurethane prepolymer was prepared by mixing PolyTHF1000 (282 g), DMPA (18 g), CHDM (4 g), HDI (53g), DesmodurW (83 g) and dibutyltin dilaurate in acetone (237 g). The mixture was heated to 60 C. and maintained at this temperature until the NCO-content reached <2.24% NCO/g resin. The mixture was cooled and TEA was added (8 g) before adding water as chain-extender and disperse the prepolymer. The solvent was removed by vacuum distillation until the solids content reached a plateau value. The reactor content was cooled further and the vacuum released. The solids content was 40 wt. %. Viscosity 25 mPas; pH 7,2, particle size: 127 nm, sediment below 0.3%; acid value 16.7 mg KOH/g; M.sub.w 50,998 g/mol.

(29) Polyurethane [PU-5]

(30) A polyurethane prepolymer was prepared by mixing PolyTHF2000 (528 g), DMPA (40 g), HDI (69 g), IPDI (162 g) and dibutyltin dilaurate. The mixture was heated to 90 C. and maintained at this temperature until the NCO-content reached <5.9% NCO/g resin. The mixture was cooled to 60 C. and TEA was added (24 g). The prepolymer was dispersed into water and extended with EDA (29 g). The solids content was 34 wt. %. Viscosity 30 mPas; pH 7.7, particle size: 80 nm; sediment below 0.1%; acid value 20.9 mg KOH/g.

EXAMPLES

(31) All polymer blends were prepared by mixing the polymers described above. First the blends between the acrylic polymers were made by starting with the acrylic polymer with the largest amount and then blending the second acrylic polymer to the first acrylic polymer under stirring and subsequently the polyurethane dispersions were added under stirring. All of these blends comprised less than 0.5 wt. % solvent based on the total composition.

(32) The blends are shown below in Table 1

(33) TABLE-US-00001 TABLE 1 Polymers in grams of Example Polymers dispersion in the blend Ratio % s/s 1# PU1/VP1/VP2 10/45/45 8.6/45.7/45.7 2 PU-2/VP3 3.88/31.12 10/90 3 PU-3/VP4/VP5 7.71/55.7/44.3 8/64.4/27.6 4 PU-3/VP4/VP5 3.14/17.7/14.1 10/63/27 5 PU-3/VP4/VP5 4.73/16.85/13.4 15/59.5/25.5 6 PU-3/VP4/VP5 6.35/15.9/12.7 20/56/24 7 PU-4/VP4/VP6 4.27/27.6/13.1 10/72/18 8* PU-4/VP4/VP6 31.42/67.7/32.3 25/60/15 9 PU-5/VP4/VP6 4.73/24.6/15.6 10/67.5/22.5 10 PU-5/VP4/VP6 14.4/61.2/38.8 12/66/22

Comparative Examples

Comparative Example C1

(34) Consisted of a blend of a 90 wt. % of the vinyl polymer [VP7] with a Tg of 40 C. with 10 wt. % of polyurethane [PU1].

Comparative Example C2

(35) GB 2362387, Example 5: Synthesis and subsequent blending of the soft/hard sequential acrylic polymer composition AP5 as described on pg 18 line 36 to pg 19 line 2 and Table 2 with 10% and 30% R-980.

(36) (10% R-980/90% AP5) 16.67 gs of NeoRez R-980 was added under stirring to 150 g of AP5. To 45 g of the binder, 1.1 g butylglycol 50 wt. % in water with a droplet ammonia, 0.3 g BYK 346, and 0.35 g Coatex BR100P 50 wt. % were added under stirring.

(37) (30% R-980/70% AP5) 42.86 g of R-980 was added under stirring to 100 gs of AP5. To 45 g of the binder, 1.1 g butylglycol 50 wt. % in water with a droplet ammonia, 0.3 g BYK 346, and 0.35 g Coatex BR100P 50 wt. % were added under stirring.

Comparative Example C3

(38) WO99/16805, example 7: Synthesis of the 25/75 urethane/acrylic polymer as described on page 26, line 30 to page 28 line 19. The isocyanate content was 76%. To 45 g of this urethane/acrylic polymer dispersion 1.1 g butylglycol 50 wt. % in water with a droplet ammonia, 0.3 g BYK 346, and 0.35 g Coatex BR100P 50 wt. % were added under stirring.

Comparative Example C4

(39) WO2005/023947, example 3 was prepared at lower urethane-acrylic ratios because the disclosed urethane-acrylic ratio of example 3 is 45 wt. % of polyurethane A1 and 55 wt % acrylic, this corresponds to 39.4% solid on solid of the polyurethane A1 (35% Polymer B1: NeoCryl A1131 and 20% of vinyl polymer C2: NeoCryl XK-99). A urethane-acrylic ratio (10% and 30% on solids maintaining the same ratio between polymer B1 and vinyl polymer C2) was prepared.

Comparative Example C5

(40) WO2012/084668, example 1 with a 30/70 urethane-acrylic ratio was reproduced as described on page 29 lines 9 to 30 (polyurethane PU-1 with an polyisocyanate content of 42 wt. %) and urethane-acrylic was described on page 31 line 37 to page32 line 38 (example 1.) PU-1 had a polyisocyanate content of 42 wt. %. The acrylic had an acid value of 0 mgKOH/g.

(41) Formulations:

(42) Subsequently the blends were formulated into coating compositions. The clear formulations contained less than 1.5 wt % of solvent based on the total formulation. The pigmented formulations contained less than 2 wt % of solvent based on the total formulation.

(43) Clear Formulation 1:

(44) To 30 g of the binder mixture as described in examples 2 to 7, 9 & 10, 12.09 g of water, 0.38 g of butyldiglycol (BDG), 0.32 g Dehydran 1293, and 1.53 g 25 wt. % Borchigel L75 were added under stirring.

(45) Clear Formulation 2:

(46) To 45 g of the binder mixture as described in example 8, 1.1 g butylglycol (BG) 50 wt. % in water with a droplet ammonia, 0.3 g BYK 346, and 0.35 g Coatex BR100P 50 wt. % were added under stirring.

(47) Clear Formulation 3:

(48) To 75 g of binders as described in example 1 and comparative Example 1, 32.14 g of water, 0.94 g of butyldiglycol (BDG), 0.81 g Dehydran 1293, and 1.91 g 50 wt. % Borchigel L75 were added under stirring.

(49) Pigmented Formulation:

(50) Pigment paste preparation is shown in Table 2 below.

(51) To 35 g of the binder mixture as described in examples 4 and 6, 0.88 g butylglycol (BG) 50% wt. % in water with a droplet ammonia, 1.7 g 25 wt. % Borchigel L75 and 16.5 gs of pigment paste was added under stirring.

(52) TABLE-US-00002 TABLE 2 Pigment paste Parts by weight 100 Demi water 6 19.8 Disperbyk 2015 1 3.3 Tego Foamex 810 0.2 0.66 Coatex BR100P/demi 1:1 0.1 0.33 Tioxide TR-92 22.8 75.91 Total 30.1 100 The PVC of all pigmented examples is 21% (v/v)
Testing Methods of the Blends
Determination of Elongation at Break

(53) Free films of the formulated films were made by applying 400 micron wet films onto glass plates containing release paper. These films were allowed to dry during 4 hours under ambient conditions followed by ageing for 16 hours at 52 C. The film was subsequently removed from the glass plate and at least 4 dumb bell shaped samples were cut from the free films using a DIN 52-910-53 cutter. The thickness of the film was measured. A stress-strain experiment was performed using an Instron 5565 instrument at a draw-bench speed of 30 mm/min.

(54) For Example 1 and comparative example 1 ageing was carried out for 16 hours at 50 C. and the draw-bench speed was 100 mm/min.

(55) Determination of Blocking Resistance

(56) Films were made by applying 100 micron wet films on Leneta chart 2A. These films were allowed to dry during 1 hour under ambient conditions followed by ageing for 16 hours at 52 C. Blocking resistance was tested by putting the films face to face and placing a 1 kG/cm2 weight for 4 hours under ambient conditions. After this test period the films are separated by hand and a rating (0-5) of the block resistance was given. [0]=poor separation and [5]=excellent separation.

(57) Test results of the Examples are shown below in Table 3:

(58) TABLE-US-00003 TABLE 3 Elongation Elongation at break- at break- clear pigmented Ratio [blocking [blocking Example Polymers % s/s resistance] resistance] 1# PU1/VP1/VP2 10/45/45 450% 2 PU-2/VP3 10/90 305% [5] 3 PU-3/VP4/VP5 8/64.4/27.6 368% [2] 4 PU-3/VP4/VP5 10/63/27 438% [4] 83% [4-5] 5 PU-3/VP4/VP5 15/59.5/25.5 456% [4] 6 PU-3/VP4/VP5 20/56/24 654% 132% [5] 7 PU-4/VP4/VP6 10/72/18 486% 8* PU-4/VP4/VP6 25/60/15 688% 9 PU-5/VP4/VP6 10/67.5/22.5 195% [2] 10 PU-5/VP4/VP6 12/66/22 176% [4]

(59) Test results of the comparative examples are shown below in Table 4

(60) TABLE-US-00004 TABLE 4 Comparative Example Elongation at break % Remark Comparative example C1: 130% 90 wt. % [VP3] with 10 wt. % [PU1]. Comparative Example C2 <10% Film too brittle to Blend ratio R-980/AP5 10/90 remove from the (solid/solid) release paper Comparative Example C2 <10% Film too brittle to Blend ratio R-980/AP5 30/70 remove from the (solid/solid) release paper Comparative example C3 <10% Film too brittle to WO99/16805 ex 7 25/75 remove from the urethane/acrylic release paper Comparative example C4 <10% Film too brittle to Blend ratio polyurethane remove from the A1/polymer B1/vinyl polymer C2 release paper (solid/solid) 10/57.3/32.7 Comparative example C4 <10% Film too brittle to Blend ratio polyurethane remove from the A1/polymer B1/vinyl polymer C2 release paper (solid/solid) 30/44.5/25.5 Comparative example C5 111% (unformulated) WO2012/084668 10% pigmented

(61) The examples show that the elongation at break is substantially improved with regard to the comparative examples.

(62) Comparative example C1 shows elongation at break by blending 10 wt. % of a polyurethane with an vinyl composition consisting of single phase with Tg of 40 C., which is the average composition of the two vinyl polymers from Example 1.

(63) Comparative example C2 shows that simply lowering the wt. % of polyurethane of the disclosed example is not sufficient to get good elongation at break.

(64) Comparative example C3 and C5 show that a high wt. % of polyisocyanate is detrimental to the elongation at break.

(65) Comparative example C4 shows that simply lowering the wt. % of polyurethane of the disclosed example is not sufficient to get good elongation at break.