Polyolefin dispersion and epoxy dispersion blends for improved damage tolerance

Abstract

The present invention provides aqueous compositions for making damage tolerant coatings comprising a blend of (i) from 2 to 30 wt. %, based on the total weight of solids in the composition, of an acid or anhydride functionalized polyolefin dispersion having an average particle size of from 0.2 to 5 microns, and (ii) a film forming dispersion of one or more epoxy resins chosen from epoxy resins having an epoxy equivalent weight (EEW) of from 150 to 4,000 having an average particle size of from 0.2 to 1.0 microns, wherein the polyolefin dispersion is stabilized with from 2 to 8 wt. %, based on the total weight of solids in the composition, one or more anionic surfactants, such as a sulfate containing surfactant, and, further wherein, the compositions have a pH of from 3 to 8.

Claims

1. An aqueous composition for forming polyolefin particles dispersed in an epoxy matrix comprising a blend of (i) from 2 to 30 wt. %, based on the total weight of solids in the composition, of a functionalized polyolefin having an average particle size of from 0.2 to 5 microns wherein the functionalized polyolefin consists of an acid functionalized or anhydride functionalized polyolefin elastomer, an acid functionalized or anhydride functionalized high density polyethylene, an acid functionalized or anhydride functionalized ethylene-propylene copolymer, an acid functionalized or anhydride functionalized polypropylene, an acid functionalized or anhydride functionalized polyolefin plastomer, an acid functionalized or anhydride functionalized linear low density polyethylene, an acid functionalized or anhydride functionalized ethylene-C4 to C12 olefin copolymer, or a combination thereof, wherein the acid or anhydride functionalized polyolefin has an acid number of 5 to 60 and (ii) a dispersion of one or more epoxy resins having an epoxy equivalent weight of from 150 to 4,000 and having an average particle size of from 0.2 to 1.0 microns, wherein the functionalized polyolefin is stabilized in the composition with from 2 to 8 wt. %, based on the total weight of solids in the composition, of one or more anionic surfactants, and, further wherein, the composition has a pH of from 3 to 8, wherein the particle size ratio of the functionalized polyolefin to the epoxy resin ranges from 10:1 to 1:1.

2. The aqueous composition as claimed in claim 1, wherein the particle size ratio of the (i) functionalized polyolefin to the (ii) epoxy ranges from 7:1 to 1.7:1.

3. The aqueous composition as claimed in claim 1, wherein the (i) acid or anhydride functionalized polyolefin contains from 0.1 to 2.0 wt. % of acid or anhydride groups, based on the total solids weight of the functionalized polyolefin.

4. The aqueous composition as claimed in claim 3, wherein the acid or anhydride functionalized polyolefin contains, in polymerized form, maleic anhydride groups.

5. The aqueous composition as claimed in claim 4 wherein the aqueous composition is substantially solvent free.

6. The aqueous composition as claimed in claim 3 wherein the aqueous composition is substantially solvent free.

7. The aqueous composition as claimed in claim 1, wherein the (ii) epoxy resin dispersion comprises at least one epoxy resin which is a linear or difunctional glycidyl ether of a polyol.

8. The aqueous composition as claimed in claim 7 wherein the aqueous composition is substantially solvent free.

9. The aqueous composition as claimed in claim 1, further comprising a hardener for the epoxy resin.

10. The aqueous composition as claimed in claim 9 wherein the aqueous composition is substantially solvent free.

11. The aqueous composition as claimed in claim 1, wherein the (the anionic surfactant comprises a lauryl sulfate alkali metal salt or an ethoxylated lauryl sulfate alkali metal salt.

12. The aqueous composition as claimed in claim 11 wherein the aqueous composition is substantially solvent free.

13. The aqueous composition as claimed in claim 1 wherein the aqueous composition is substantially solvent free.

14. A method comprising applying the aqueous composition of claim 1 to a construction substrate and drying to form a coating layer wherein the particles of the acid or anhydride functionalized polyolefin or epoxy adduct thereof is dispersed in the epoxy resin matrix.

15. The method of claim 14 wherein the construction substrate is selected from steel, aluminum, wood, wood composites, gypsum board, stone, cement, cement board, and glass mat facers and/or the coating layer has a thickness of 1 to 250 microns.

16. The aqueous composition of claim 1 wherein the functionalized polyolefin consists of an anhydride functional copolymer of ethylene and C4-C20 olefin.

17. A method of making an aqueous composition comprising providing an epoxy resin in the form of melt, pellets, powder or flakes and water, extruding or melt kneading the epoxy resin in the water with one or more surfactant, to form (ii) an aqueous epoxy resin dispersion, and, separately, providing an acid or anhydride functionalized polyolefin or an epoxy adduct thereof, in the form of melt, pellets, powder or flakes and extruding or kneading the acid or anhydride functionalized polyolefin or the epoxy adduct thereof in water with an anionic surfactant to form a (i) functionalized polyolefin dispersion and blending the (i) functionalized polyolefin dispersion in an amount of 2 to 30 wt. %, based on the total weight of solids in the composition with (ii) the epoxy dispersion.

Description

EXAMPLES

(1) The Examples that follow illustrate the present invention. Unless otherwise stated, in all of the Examples that follow, temperature is room temperature and pressure is atmospheric pressure.

Synthesis Examples: Dispersion Preparation: Dispersions A to J

(2) Aqueous dispersions A to J having compositions as disclosed in Table 2, below, were prepared from raw materials disclosed in Table 1, below, using the conditions as described in Table 2, below, using the following general procedure:

(3) Components 1 to 3 listed in Table 2, below, were fed into a 25 mm diameter twin screw extruder using a controlled rate feeder; using the feed rate in grams/minute (g/min) as indicated in Table 2, below. Components 1 to 3 were forwarded through the extruder and melted to form a liquid melt material.

(4) The extruder temperature profile was ramped up to the temperature listed in the “Polymer Melt Zone” column of Table 2, below. Water and volatile base and/or neutralizing agent were mixed together and fed to the extruder at a rate indicated in Table I for neutralization at an initial water introduction site. Then dilution water was fed into the extruder in one or two locations (1.sup.st and 2.sup.nd locations) via two separate pumps at the rates indicated in Table 2. The extruder temperature profile was cooled back down to a temperature below 100° C. near the end of the extruder. The extruder speed was around 470 rpm in most cases as recorded in Table 2. At the extruder outlet, a backpressure regulator was used to adjust the pressure inside the extruder barrel to a pressure adapted to reduce steam formation (generally, the pressure was from 2 MPa to 4 MPa).

(5) Each aqueous dispersion exited from the extruder and was filtered through a 200 micrometer (μm) filter. The resultant filtered aqueous dispersions had a solids content measured in weight percent (wt %); and the solids particles of the dispersion had a volume mean particle size measured in microns and recorded in Table 2, below. In some cases the particle size mode is also recorded. The solids content of the aqueous dispersion was measured using an infrared solids analyzer; and the particle size of the solids particles of the aqueous dispersion was measured using a COULTER™ LS-230 particle size analyzer (Beckman Coulter Corporation, Fullerton, Calif.). The solids content and the average particle size (PS) of the solids particles of the indicated dispersions are indicated in Table 2.

(6) TABLE-US-00001 TABLE 1 Raw Materials for Polyolefin Dispersions Melting Point Melt Density TE* Material Composition (° C.) Index (g/cm.sup.3) (%) Polyolefin 1 Ethylene/ethylacrylate 95  .sup. 21.sup.1 0.93 750 copolymer (20% EA) Polyolefin 3 Ethylene/octene olefin 68 1000  0.87 110 plastomer Polyolefin 2 Ethylene/octene olefin 68 660 0.878 170 plastomer, maleic anhydride grafted (MAH-g) at 1 wt. % Base 1 Dimethyl ethanolamine (DMEA) Base 2 Potassium hydroxide (KOH) Surfactant 1 Sodium laureth (2EO) sulfate anionic surfactant (70% w/w in water) Polyolefin 4 Ethylene/octene olefin 59  .sup. 5.sup.1 0.87 >600 plastomer Polyolefin 5 Ethylene/octene olefin 60  30 0.87 1000 elastomer Acid dispersing (80/20) Long chain (26C) 92 120 — agent linear primary carboxylic acid/polyethylene Epoxy Resin 1 Bisphenol A diglycidyl — — — — ether type IV Epoxy resin (EEW 875-955) Epoxy Resin 2 Bisphenol A diglycidyl ether type I Epoxy resin, EEW 475-500 Hardener Modified aliphatic amine — — — — (AHEW = 280) Betaine surfactant Lauramidopropyl betaine — — — — Epoxy Dispersion 1 Aqueous dispersion of Epoxy Resin 2 including, as solids, ~11 phr of a surfactant combination of an anionic surfactant di-epoxy functional non-ionic surfactant. Surfactant 2 Ammonium nonylphenol ether sulfate surfactant (Rhodapex ™.sup., 2 Co 436 surfactant) *Tensile elongation at break; .sup.15 g/10 min at 190° C.; .sup.2 Rhodia Solvay Group, Cranbury, NJ.;

(7) TABLE-US-00002 TABLE 2 Composition and Extrusion Conditions for Aqueous Dispersions Extruder Initial Base/ Dilution Temp. in Component Component Component Water Surfactant Water Polymer Extruder V.sub.mean Viscosity Exam- 1 feed rate 2 feed rate 3 feed rate feed rate feed rate feed rate Melt Zone Speed Solids P.S. (cP, Rv3, ple (g/min) (g/min) (g/min) (g/min) (g/min) (g/min) (° C.) (rpm) (wt. %) (μm) pH 50 rpm) A* Polyolefin 1 n/a Acid (2.4) 30 wt. % 100 160 800 54.3 1.2 11.3 202 (108.9) dispersing KOH agent (1.6) (4.5) B* Polyolefin 1 n/a Acid (3.05) DMEA 132.3 150 450 46.2 1.4 10.1 328 (107.5) dispersing (2.33) agent (9.28) C Polyolefin 2 n/a n/a (1.75) Surfactant 1 58 90 470 46.2 0.7 3.9 n/m (56.3) (3.3) D* Polyolefin 2 Polyolefin 2 Acid (3.18) 30 wt. % 122.2 150 450 ~50 0.547 10.9  93 (90.4) (17.2) dispersing KOH agent (1.7) (4.54) E* Polyolefin 2 Polyolefin 2 Acid (7.62) DMEA 110.8 150 450 48.1 0.446 9.9 276 (90.1) (17.8) dispersing (2.78) agent (9.38) F Polyolefin 2 n/a n/a (2.96) Surfactant 1 101.7 80 450 46.9 0.5 3.5 100 (90.4) (5.56) G* Polyolefin 3 n/a n/a (1.75) Surfactant 1 58 90 470 49.5 0.9 10.4 276 (56.3) (3.3) H* Polyolefin 5 Polyolefin 2 n/a (4.55) Surfactant 1 109 140 450 52.36 0.699 4.55 458 (90.4) (17.5) (6.66) I Polyolefin 2 Epoxy n/a (2.3) Surfactant 1 75 110 470 48.7 1.2 3.8 126 (57.0) Resin 1 (4.4) (14.2) J* Polyolefin 2 Epoxy n/a (2.3) Surfactant 1 75 110 470 49.0 0.8 3.9 191 (49.8) Resin 1 (4.4) (21.3) *denotes Comparative Example.

(8) TABLE-US-00003 TABLE 3 Composition of Rotor/Stator Epoxy Resin And Functionalized Polyolefin Dispersions Initial Dilution Component Water Surfactant Water Mixer Temp. in Mixer V.sub.mean 1 feed rate feed rate 2 feed rate feed rate Emulsification Speed Solids P.S. Example (g/min) (g/min) (g/min) (g/min) Zone (° C.) (rpm) (wt. %) (nm) pH Viscosity K (91%/5% 4.5 g/min 2.4 g/min 58.0 g/min 80 400 rpm 50% 400 Not Not Polyolefin 2/ Determined Determined Epoxy dispersion 1 25%), Toluene 75% 60 g/min L (81%/15%) 4.5 g/min 2.4 g/min 58.0 g/min 80 400 rpm 50% 400 Not Not Polyolefin 2/ Determined Determined Epoxy dispersion 1) Toluene 75% 60 g/min

(9) Epoxy Dispersion 1:

(10) Separately from the polyolefin dispersions in Table 2, above, Epoxy Dispersion 1 in Table 1, above, was formed by pre-blending a Type I epoxy resin (Epoxy Resin 2) with a di-functional epoxy group containing nonionic surfactant at a ratio of 89.52:9.17 in a jacketed reactor at 95° C. Once uniform, the material was cooled to 80° C. The cooled pre-blend material was then pumped to a 125 mm (4 inch) rotor/stator mixer at a flow rate of 60 g/min through a heated feed line (80° C.) using a Witte gear pump (Witte Pumps and Technology GmbH, Lawrenceville, Ga.). A stream of an anionic sulphosuccinate surfactant was pumped to the rotor/stator mixer at 1.31 g/min. Water was also added to the mixer at 10 g/min. The rotor/stator mixer was operated at 750 rpm, resulting in stable waterborne epoxy dispersion. The resulting high internal phase emulsion was then diluted in a second rotor stator with additional water to achieve a 47 wt. % solids dispersion and an average particle size of ˜0.5 microns.

(11) Aqueous Epoxy Dispersion Compositions K and L:

(12) In Table 3, above, aqueous dispersion compositions of Example K and L, which contained 5 wt. % and 15 wt. %, respectively, of epoxy resin 1, were prepared using a rotor/stator device. In the preparation, separately, the indicated epoxy resin and polyolefin resin were placed in a 20 liter fluted Rotavapor™ flask (Model Buchi R-220, Buchi Corporation, New Castle, Del.) with the indicated amount of solvent (75 wt. % toluene in Example K), based on the total weight of the compositions and heated at 90° C. until the tumbled material became a uniform polymer blend. The blend was then transferred to the resin feed tank of a dispersion apparatus having a first a 125 mm (4 inch) stainless steel rotor/stator mixer and a second a 125 mm (4 inch) stainless steel rotor/stator mixer, wherein the first rotor stator mixer was fitted with a rotor that has every other tooth removed on both sides and the second rotor/stator was fitted with an every row/every tooth rotor design. The resin feed tank and a polymer line leading into the first rotor/stator mixer were each set at a temperature of 70° C. A 200 mPA (30 psig) nitrogen head pressure was placed on the feed tank to assist the blend reaching the feed pump. The polymer blend was then pumped into the dispersion apparatus using a standard Zenith gear pump (BPB Series, capacity=1.752 cc/rev, Colfax Corp., Monroe, N.C.). The gear pump was set at 45 Hz to get a feed rate of 60 g/min. The gear pump was heated to 70° C., with heat tracing, to heat the polymer blend. The heated polymer blend was introduced to the first rotor-stator mixer. Surfactant 2 (Table 1, above) was fed into the polymer line just upstream of the initial aqueous (IA) addition and entrance to the first rotor stator using an Isco syringe pump (Teledyne Isco, Lincoln, Nebr.). The IA, deionized water, was added coaxially with the polymer and was pumped using an Altech™ 301 HPLC pump (Alltech Supply, Inc., Woodridge, Ill.). The frequency of the rotor/stator was set at 700 rpm. The head jacket was cooled with a Neslab™ RTE 20 bath (Thermo Fisher Scientific, Waltham, Mass.) set to 20° C. The IA was started at a feed ratio of ˜1:1 of the ratio of total polymer or resin solids plus surfactants, considered as solids, or “Oil to IA”. The amount of IA was then slowly lowered to increase high internal phase emulsion (HIPE) solids level. As the solids level increased, the average particle size became smaller and the Oil to IA ratio approached the inversion point where the system went from an oil in water emulsion to a water in oil emulsion. This gradual decrease in IA allowed a systematic lowering of the particle size to the desired size. In this case, the smallest, most narrow particle size distribution was achieved at 93 wt. % HIPE solids. The HIPE was then pumped to the second rotor/stator and diluted with DI water to the desired, 50 wt. % solids (including toluene as solids). The dispersion was poured into a rotary evaporator flask (Buchi R220) and stripped. Water was back added 3 times and stripped off to assure that the level of toluene in the dispersion was minimal. After the final strip the solids was adjusted to 50 wt. %. Particle size was re-measured to assess any changes during solvent removal.

(13) Several aqueous dispersions were formulated from the functionalized polyolefin dispersion as indicated in Tables 2 and 3, above, and Epoxy Dispersion 1, together in the proportions indicated in Tables 4 and 5, below, by simple mixing. In Tables 4 and 6A, below, the ratio of total amine hydrogen equivalents in the hardener to the total epoxy equivalents of the epoxy resin is 2:1; and in Tables 5 and 6B, below, the ratio of total amine hydrogen equivalents in the hardener to the total epoxy equivalents of the epoxy resin is 1:1. The test results are reported in Tables 6A, 6B, 7, and 9, below, with Examples numbered using a convention wherein the first letter of the Example is the polyolefin dispersion from one of Table 2 or Table 3, above, and the second character of the Example is the proportion indicated in one of Tables 4 and 5, below. For example, Example “F-1” has polyolefin dispersion F from Table 2, above, in the proportions of 70 wt. % epoxy solids, as indicated in Example proportion 1 in Table 5, below.

(14) TABLE-US-00004 TABLE 4 Blend Ratios of Polyolefin Dispersions A to E (Table 2) and Epoxy Dispersion 1 Wt % Wt. % Example Epoxy Polyolefin g g Proportion solids solids Epoxy solids Hardener 1 70 30 14 16.07 2 80 20 16 18.46 3 90 10 18 20.88 4 95 5 19 22.10

(15) TABLE-US-00005 TABLE 5 Blend Ratios of Polyolefin Dispersions F to K (Tables 2 and 3) and Epoxy Dispersion 1 Wt % Wt. % Epoxy Polyolefin g g Example solids solids Epoxy solids Hardener 1 70 30 14.00 7.82 2 80 20 16.00 8.93 3 90 10 18.00 10.05 4 95 5 18.98 10.60

(16) Coating Preparation:

(17) Films of each Example were made using a 152.4 micron (6 mil) drawdown bar on phosphate treated steel panels and cured at room temperature for 7 days.

(18) Test Methods:

(19) The following test methods were used in the Examples:

(20) Particle Size Measurement:

(21) Particle size was measured using a COULTER™ LS-230 or COULTER LS-13-320 particle size analyzer (Beckman Coulter Corporation). The volume average particle size of the polyolefin dispersions were determined.

(22) Percent Solids:

(23) Percent solids was measured using a microwave solids analyzer or an infrared solids analyzer. One analyzer used was the OHAUS™ MB45 infrared moisture analyzer (Ohaus Corporation, Parsippany, N.J.).

(24) Adhesion:

(25) The “cross-hatch adhesion” of the indicated coating layer on a coated panel was measured according to ASTM-D 3359-08 (2008). This method includes making a square lattice pattern with 10 cuts in each direction with 1 millimeter (mm) distance between neighboring cuts on the coating layer. A pressure sensitive tape over the cut area is applied and then the tape is pulled parallel to the substrate surface. Adhesion is evaluated by visual observation and designating the results using a scale from “OB” to “5B” as described in Table 5-1, below, with “5B” indicating perfect adhesion to the substrate and “OB” indicating complete removal of the coating from the substrate.

(26) TABLE-US-00006 TABLE 5-1 Cross-Hatch Adhesion Rating Description 5B The edges of the cuts are completely smooth; none of the squares of the lattice is detached. 4B Small flakes of the coating are detached at intersections; less than 5% of the area is affected. 3B Small flakes of the coating are detached along the edges and at intersections of cuts. The area affected is 5-15% of the lattice. 2B The coating has flaked along the edges and on parts of the squares. The area affected is 15-35% of the lattice. 1B The coating has flaked along the edges of cuts in large ribbons and whole squares have detached. The area affected is 35-65% of the lattice. 0B Flaking and detachment is worse than 1B.

(27) Solvent Resistance (MEK Double Rub):

(28) The solvent resistance of the indicated coating layer on a coated panel was tested according to ASTM D4752 (2015) using methyl ethyl ketone (MEK). In this method, samples are tested using a piece of cotton cheesecloth attached with copper wire to a 0.68 kg hammer. The cheesecloth was saturated with MEK and then placed on the coating. The hammer was pushed forward and then back at a rate of approximately 1 second per cycle. The coating layer was visually inspected after every 20 double rub cycle for any signs of damage or delaminating. This procedure was repeated until a bare panel is showing (at this observation point, record the number of double rubs as the MEK double rub (DR) result for the sample) or until a total of 200 double rubs is reached. Alternatively, an automated tester, available from DJH Designs may be used to measure the number of double rubs. The automated tester works in a semi-automatic fashion by moving a cotton pad, attached to a weighted block, that applies about 0.15 kg/cm.sup.2 pressure, in a back and forth motion across the coated panel. Each back and forth is referred to as one double rub.

(29) Impact Resistance:

(30) The impact resistance of the coating layer was measured using a GARDNER™ falling weight impact tester (Byk Gardner Inc., Columbia, Md.) according to ASTM D-2794 (2010). In this method, indentation in both direct and indirect modes was measured; and the units of measure are kg-cm (inch-lbs).

(31) Pendulum Hardness:

(32) Performed following ASTM D4366-95 (1995) using a BYK Pendulum Hardness tester.

(33) Corrosion Resistance:

(34) Corrosion resistance was measured by comparing field rusting and corrosion along the scribe after a certain number of exposure hours, and comparing the samples to a control consisting of just the epoxy dispersion. The salt fog cabinet settings were consistent with ASTM B117-11: Standard Practice for Operating Salt Spray (Fog) Apparatus (2011). The test results are presented in Table 6A, 6B and 7 below.

(35) TABLE-US-00007 TABLE 6A Performance of Polyolefin and Epoxy Dispersions at Various Ratios MEK Pendulum 20° 60° Double Forward Reversed Example Hardness Gloss Gloss Rubs Impact Impact A-1* 124 27 68 90 80 140 A-2* 132 64 89 102 140 140 A-3* 150 86 98 121 120 140 A-4* 139 99 105 150 120 160 B-1* 87 27 68 80 60 <20 B-2* 110 67 93 130 60 <20 B-3* 141 97 101 200 60 160 B-4* 150 100 104 150 40 160 C-1 124 78 94 200 60 160 C-2 127 91 98 >200 160 160 C-3 111 97 100 150 160 160 C-4 141 101 103 >200 80 160 D-1* 63 24 69 83 120 40 D-2* 113 92 99 150 80 30 D-3* 124 96 101 200 120 50 D-4* 140 100 107 200 80 40 E-1* 48 98 100 200 30 40 E-2* 103 99 101 200 50 30 E-3* 118 103 104 200 60 30 E-4* 127 108 108 200 80 40 Epoxy 133 111 120 200 100 70 Disper- sion 1*.sup., ** *Indicates comparative; ** Epoxy Dispersion 1 from Table 1, above.

(36) As shown in Table 6A, above, Inventive Examples C-1 through C-4 have improved impact resistance over the epoxy control without significant loss in gloss, hardness, and MEK double rubs, whereas the comparative Examples A, B, D, and E have poorer impact resistance, especially reverse impact resistance, relative to the control and the inventive Examples C-1 to C-4. Further, the overall MEK double rubs and forward and reverse impact was improved through use of an excess of amine hydrogen equivalents of hardener.

(37) TABLE-US-00008 TABLE 6B Performance of Polyolefin and Epoxy Dispersions at Various Ratios Wt % MEK poly- Pendulum 20° 60° Double Forward Reverse Example olefin Hardness Gloss Gloss Rubs Impact Impact F-3 10 66 94.2 101 18 30 <2 F-4* 5 75 106 108 19 22 <2 Epoxy 0 85 ± 125 ± 144 ± 24 ± 16 ± <2 disper- 21 7 24 4 8 sion 1*.sup., 1 G-1* 30 65 4.9 30.8 11 24 <2 G-2* 20 74 2.6 17.1 17 13 <2 G-3* 10 93 11.5 47.4 21 13 <2 G-4* 5 96 42.9 89.9 25 15 <2 H-1* 5 126 ND ND 400 10 <10 H-2* 10 70 ND ND 300 10 <10 H-3* 15 141 ND ND 200 10 <10 *Denotes Comparative. .sup.1 Epoxy dispersion 1 was run in duplicate.

(38) As shown in Table 6B, above, the impact resistance of the inventive Examples F-3 and F-4 have better forward impact resistance than proper Comparative Examples G-3, G-4 and H-3. However, the F-3 and F-4 MEK resistance is not improved, thereby suggesting that where the average particle size of the polyolefin particles and the epoxy resin particles in F-3 and F-4 are the same, the two dispersions do not readily mix together sufficiently well. In the H-1, H-2 and H-3 compositions, it appears that the polyolefin does not disperse into the epoxy continuous phase of the compositions and instead have polyolefin on the surface and so exhibit lower gloss but give dramatically improved MEK resistance.

(39) TABLE-US-00009 TABLE 7 Performance of Polyolefin Epoxy Dispersions Wt. % Pendulum Forward Reverse Example POD Hardness MEK Adhesion Impact Impact I-1 * 5 122 90 5 15 <10 I-2 * 10 115 60 5 22 <10 I-3 15 126 500 5 27 <10 K-1 * 5 134 80 5 10 <10 K-2 * 10 133 80 5 10 <10 K-3 15 132 150 5 20 <10

(40) Comparative Examples I-1 and I-2 and K1 and K2 provide no improvement in impact resistance, or MEK resistance, whereas inventive Example 1-3 (at 15 wt. % POD solids) provide improved MEK and impact resistance relative to the epoxy dispersion 1 control in Table 6B, above. The data suggest that the average particle size of the functionalized polyolefin dispersion K in Comparatives K-1 to K-3 is too large. The data also suggest that functionalized polyolefin dispersions that are epoxy adducts as in dispersion 1 should be used in preferred larger amounts of 10 to 18 wt. % of polymer and resin solids.

(41) TABLE-US-00010 TABLE 8 Formulation For Coating Part A Weight (g) Wt. % Epoxy Dispersion 1 99.245 23.71 water 12.19 2.91 Flash Rust Inhibitor.sup.1 4.47 1.07 Dispersant.sup.2 190 14.59 3.49 Defoamer.sup.3 0.995 0.24 TiO.sub.2 Pigment 118.625 28.34 grind to 7+ Let Down Epoxy Dispersion 1 166.235 39.72 Defoamer 2.185 0.52 let down Total 418.535 .sup.1Flash X ™ material, ICL Advanced Additives; .sup.2Disperbyk ™ material, BYK Additives & Instruments; .sup.3Byk ™ 019 material, BYK Additives & Instruments; 4. RCL ™ 9 pigment, Cristal Corporation; 5. TegoFoamex ™ 823 defoamer, Evonik Industries.

(42) After making the above formulation, a known amount of POD was added to obtain the wt. % polyolefin solids listed in parentheses in Table 9, below.

(43) TABLE-US-00011 TABLE 9 Performance of Fully Formulated Coatings Pendulum Reverse Example Hardness Adhesion MEK Impact Impact H-1 (5%) 100 5 180 80 <10 H-2 (10%) 86 5 90 40 <10 H-3 (15%) 103 5 120 120 <10 C-1 (5%) 106 5 60 100 <10 C-2 (10%) 95 5 35 105 <10 C-3 (15%) 84 5 30 100 <10 F-1(5%) 96 5 240 60 <10 F-2 (10%) 100 5 300 50 <10 F-3 (15%) 93 5 150 50 <10 Epoxy Dispersion 1 * 86 4 100 60 <10 * Denotes Comparative Example

(44) As shown in Table 9, above, formulations of the inventive Examples C-1 to C-3 deliver improved impact resistance, hardness, and adhesion versus the Epoxy Dispersion 1, and formulations of the inventive Examples F-1 to F-3 have improved MEK resistance with similar impact resistance to the Epoxy Dispersion 1. This shows that formulated compositions having pigments, fillers and extenders perform distinctively from compositions that are not formulated. A formulation of the inventive Example H-3 exhibits improved MEK, impact resistance, hardness, and adhesion versus the control epoxy, while a formulation of inventive Example H-1 delivers improved impact resistance and much improved MEK resistance; and a formulation of inventive Example H-2 delivers better adhesion and decent MEK resistance.