POLYMER COMPOSITION AND COATINGS PREPARED FROM THE SAME

Abstract

The present disclosure relates to a composition comprising: at least one dendritic polymer prepared from hyper-branched polymer with hydroxyl groups, having a plurality of peripheral functional groups, wherein the peripheral functional groups comprising at least one cyclic ether group that is covalently bound to said hyperbranched polymer by urethane linkages; and a melamine-based crosslinker. Such compositions have improved flexibility. The present disclosure further relates to the use of such compositions to form coatings after cure, or as an additive component to binder resins.

Claims

1-21. (canceled)

22. A composition comprising: at least one dendritic polymer having a plurality of peripheral functional groups, said peripheral functional groups comprising at least one cyclic ether group; and at least one melamine-based crosslinker, said crosslinker is tris(alkoxycarbonylamino)triazine (TACT).

23. The composition of claim 22, wherein said dendritic polymer is a hyperbranched polymer.

24. The composition of claim 22, wherein the dendritic polymer is a second generation, third generation or fourth generation dendritic polymer.

25. The composition of claim 22, wherein the peripheral functional groups comprises hydroxyl groups, said hydroxyl groups being optionally esterified with a C6-18 fatty acid.

26. The composition of claim 23, wherein said dendritic polymer has been chain extended to express at least one peripheral functional group reactive with said crosslinker group.

27. The composition of claim 22, wherein from at least one to all the peripheral functional groups are cyclic ether groups.

28. The composition of claim 22, wherein from about 25% to about 50% of the peripheral functional groups are cyclic ether groups.

29. The composition of claim 22, wherein the cyclic ether groups are covalently bound to said dendritic polymer by urethane linkages.

30. The composition of claim 22, wherein the melamine-based crosslinker comprises at least one, at least two or at least three carbamate moieties.

31. The composition of claim 30, wherein the melamine-based crosslinker is present in an amount of about 20% to about 40% by weight of the composition.

32. The composition of claim 22, further comprising, as a binder resin, an additional polymer selected from the group consisting of polyacrylates, polyesters, polyols, polyester polyols, polyurethanes, polycarbonates, polyamides, co-polymers and blends thereof; and wherein said binder resin, if present, is provided in an amount of at least from about 60% to 80% by weight of the composition.

33. The composition of claim 32, wherein the binder resin comprises about 5 to 10 wt. % of said dendritic polymer comprising at least one cyclic ether functional group.

34. A method of preparing a coating composition, the method comprising a step of: mixing a binder composition with a melamine resin comprising at least one carbamate moiety, said melamine resin is tris(alkoxycarbonylamino)triazine (TACT); wherein the binder composition comprises a dendritic polymer having at least one peripheral cyclic ether group.

35. The method of claim 34, wherein the binder comprises at least one additional hydroxyl functional polymer and said dendritic polymer.

36. The method of claim 35, wherein the dendritic polymer is provided in an amount of about from about 5% to about 20% by weight, or from 5% to about 10% by weight, based on the weight of the coating composition.

37. The method of claim 34, wherein the binder composition consists essentially of said dendritic polymer.

38. A method of providing a coating on a surface, the method comprising: providing a composition comprising: at least one dendritic polymer having a plurality of peripheral functional groups, said peripheral functional groups comprising at least one cyclic ether group; and at least one melamine-based crosslinker, said crosslinker is tris(alkoxycarbonylamino)triazine (TACT). or obtained from the method of mixing a binder composition with a melamine resin comprising at least one carbamate moiety, said melamine resin is tris(alkoxycarbonylamino)triazine (TACT); wherein the binder composition comprises a dendritic polymer having at least one peripheral cyclic ether group; applying said composition to a surface; and curing said composition.

39. The method of claim 38, wherein said curing comprises thermal curing.

40. A method of improving the flexibility of a coating, the method comprising: i) blending a dendritic polymer having at least one epoxy functional group with a binder resin, said binder resin comprising at least one melamine resin as crosslinker, said crosslinker is tris(alkoxycarbonylamino)triazine (TACT); ii) curing the blended resin to form the coating.

41. The method of claim 40, wherein the blending step is characterized by blending said epoxy-functional dendritic polymer with at least one hydroxyl functional polymer in a ratio of from about 1:9 to about 1:4.

Description

EXAMPLES

[0080] Non-limiting examples of the invention and comparative examples will be further described in greater detail by reference to specific Examples, which should not be construed as in any way limiting the scope of the invention.

Materials Used

[0081] Below is a list of the raw materials used in the following Examples. The commercial names or their abbreviations of the following raw chemicals will be used in the Examples for convenience. [0082] (1) Boltorn H20 (H20): Hyperbranched polyester-polyol with theoretically 16 peripheral hydroxyl groups, having a molecular weight of about 2100 g/mol, and a hydroxyl number of 490 to 530 mgKOH/g, procured from Perstorp Singapore Pte Ltd. [0083] (2) Boltorn H40 (H40): Hyperbranched polyester-polyol with theoretically 64 peripheral hydroxyl groups, having a molecular weight of about 5100 g/mol solid, OH value 470-500 mgKOH/g, procured from Perstorp Singapore Pte Ltd. [0084] (3) Boltorn H4001 (H4001): light yellow liquid, the solid content being 50%-55%, provided by Perstorp Company, the derivative of the fourth generation hyperbranched polyester, and about 20%-40% hydroxyls are esterified by C.sub.8-C.sub.12 saturated fatty acid. The hydroxyl value is 300-340 mgKOH/g by solid content, and the acid value is 2-8 mgKOH/g. Mn=3600, Mw=8200. [0085] (4) CYMEL NF2000 (NF2000): Tris(alkoxycarbonylamino) triazine (TACT), A trifunctional melamine-based crosslinker containing reactive carbamate functionality. Its solid content is 48-52%, provided by Cytec Industries Inc. [0086] (5) Desmophen A 870 BA (A870): A polyisocyanate cross-linking acrylic resin, 70% in BA, with approximate 4.2% OH content on solid, provided by Nuplex. [0087] (6) Surfynol DF110C: A non-ionic defoamer provided by Air Products. [0088] (7) DMAP: 4-(dimethylamino)pyridine purchased from Sigma Aldrich [0089] (8) ECOSURF BD405: a non-ionic alcohol ethoxylate surfactant provided by Dow Chemicals. [0090] (9) Proglyde DMM: dipropylene glycol dimethyl ether provided by Dow Chemicals.

Testing Methods

[0091] In the following Examples, the following industrially recognized testing methods are used to characterize the water-dispersible coatings:

[0092] Adhesion (1 mm1 mm): ASTM D3359;

[0093] Pencil Hardness (Break/Scratch): ASTM D3363;

[0094] Flexibility (): ASTM D522;

[0095] Tensile Strength (Elongation): ASTM D412

[0096] In addition, the following protocol will be adopted for the methyl ethyl ketone (MEK) rub test: (1) prepare a film on a glass panel with 100 m wet film thickness (WFT); (2) dry the panel at a predetermined temperature for a predetermined duration (temperature and curing time depend on specific coatings) prior to testing; (3) saturate a cotton bud with MEK and hold it at 45 angle to the test surface, rub the test surface with moderate pressure. A complete rub consisting of one forwards rub and one backwards rub motion is considered one double rub. The surface is rubbed continuously until the substrate glass panel is exposed. Record the total number of double rubs.

Example 1

Preparation of an Epoxy-Modified Dendritic Polymer H4001-25% IPDI-Glycidol [4.SUP.th .Generation Dendritic Polymer, 25% Epoxy Substitution]

(1A) Preparation of IPDI-Glycidol Adduct in Butyl Acetate

[0097] Under a nitrogen atmosphere, at room temperature (RT), with stirring, glycidol (8.15 g) was added over 30 min into a mixture of IPDI (24.45 g), butyl acetate (BA) (32.3 g) and dibutyltin dilaurate (DBTDL) (0.326 g). The stirring was continued for 2 h until the NCO % of the reaction mixture reached theoretical value of 7.1%. An IPDI-glycidol adduct was formed as intermediate compound.

(1B) Preparation of H4001-25% IPDI-Glycidol

[0098] In a nitrogen atmosphere, the IPDI-glycidol adduct solution (50.0 g) was added into H4001 (118.0 g) at 80 C. over 30 min. The stirring was continued at the same temperature for about 3 h until the NCO % was less than 0.1%.

Example 2

Preparation of an Epoxy-Modified Dendritic Polymer H4001-50% IPDI-Glycidol [4.SUP.th .Generation, 50% Epoxy Substitution]

[0099] In a nitrogen atmosphere, IPDI-glycidol adduct solution (57.7 g, as described in Example 1) was added into H4001 (68.1 g) at 80 C. over 30 min. The stirring was continued at the same temperature for about 5 h until the NCO % was less than 0.1%.

Example 3

Preparation of an Epoxy-Modified Dendritic Polymer: H20-40% Capa-25% IPDI-Glycidol [2.SUP.nd .Generation Dendritic Polymer, Chain Extended, 25% Epoxy Substitution]

[0100] (3A) Chain Extension of Boltorn H.sub.2O with 40 wt. % of Caprolactone (H20-40% Capa)

[0101] Under nitrogen atmosphere, Boltorn H.sub.2O (95.0 g) and DMM (95.0 g) were mixed and heated to 135-140 C. with stirring until Boltorn H.sub.2O was complete melted and a suspension was formed. Caprolactone (38.0 g) was then added and the resulting mixture was stirred at the same temperature for 1 h until all caprolactone was consumed as monitored by GC.

(3B) Preparation of IPDI-Glycidol Adduct in DMM

[0102] In a nitrogen atmosphere, glycidol (32.0 g) was added into a mixture of IPDI (80.0 g), DMM (32.0 g) and DBTDL (0.15 g) with stirring over 20 min at RT. The resulting mixture was stirred at RT for about 2 h until NCO % reached the theoretical value of 8.4%. The IPDI-Glycidol adduct was used with one day of preparation.

(3C) Preparation of H20-40% Capa-25% IPDI-Glycidol

[0103] In a nitrogen atmosphere, IPDI-Glycidol adduct in DMM (45.1 g) was added into H20-40% capa (121.3 g) at 80 C. over 30 min. The resulting mixture was stirred at 80 degree for about 3 h until NCO % was less than 0.1%.

Example 4

Preparation of an Epoxy-Modified Dendritic Polymer: H20-40% Cap-50% IPDI-Glycidol [2nd Generation, Chain Extended, 50% Epoxy Substitution]

[0104] In a nitrogen atmosphere, IPDI-Glycidol adduct in DMM (77.4 g, as described in 3B) was added into H20-40% capa (104.1 g, as described in Example 3A) at 80 C. over 30 min. The resulting mixture was stirred at 80 C. for about 4 h until NCO % was less than 0.1%.

Example 5

Preparation of an Epoxy Dendritic Polymer: (H40-25% IPDI-Glycidol)

(5A) Preparation of IPDI-Glycidol Adduct in Cyclohexanone

[0105] In a nitrogen atmosphere, at RT, glycidol (12.96 g) was added into a mixture of IPDI (38.90 g), cyclohexanone (51.45 g) and DBTDL solution (0.52 g, 10% solution in BA). The resulting mixture was stirred at RT for about 3 hours until NCO % reached theoretical value of 7.1%.

(5B) Preparation of H40-25% IPDI-Glycidol

[0106] In a nitrogen atmosphere, Boltorn H40 (36.0 g) was dissolved in cyclohexanone (36.0 g) were mixed and heated to 110 C. to afford a clear solution. The solution was then cooled down to 80 C., followed by addition of IPDI-Glycidol adduct in cyclohexanone (47.5 g) over 30 min. The reaction was stirred for about 4 h at the same temperature until NCO % was less than 0.1%.

Example 6

[0107] Preparation of an epoxy-dendritic polymer: H40-50% IPDI-Glycidol [4.sup.th generation, 50% epoxy substitution]

[0108] In a nitrogen atmosphere, IPDI-Glycidol adduct in cyclohexanone (95.0 g, as described in Example 5) was added into a 50 wt. % solution of Boltorn H40 in cyclohexanone (72 g, as described in Example 5) at 80 C. over 30 min. The mixture was stirred at the same temperature for about 5 h until NCO % was less than 0.1%.

Exemplary Formulations 1-15

[0109] Coating formulations 1 to 15 have been prepared according to the components and materials listed in Tables 1-10 below.

[0110] Formulations 1, 8 and 12 are comparative formulations prepared without the epoxy-modified dendritic polymer of the present disclosure. The performance of the coatings prepared from the various formulations are tabulated and compared under Tables 8, 9 and 10.

Preparation of a Typical Formulation and Film Application:

[0111] As shown in Table 1, A870 (51.6 wt %), Cymel NF 2000 (26.9 wt %), miscellaneous additives (total 0.8 wt %), catalyst (DMAP, 0.1 wt %) and solvent butanol (to adjust the final NV % to 50%) were mixed thoroughly. The mixture was then applied to glass and tin panels using a wire-bar with 100 m wet film thickness (WFT). Panels were dried at RT for 15 min then in an oven at 150 C. for 30 min. The films obtained appeared clear and glossy. Pencil hardness, flexibility and MEK double rub tests were then carried out with these panels.

TABLE-US-00001 TABLE 1 Formulation 1 Entry Materials Weight percentage (%) Weight (g) 1 A870 51.6 15.00 2 Butanol 20.6 6.00 3 Surfynol DF110C 0.2 0.058 4 BYK345 0.2 0.058 5 ECOSURF BD405 0.4 0.115 6 DMAP 0.1 0.029 7 Cymel NF2000 26.9 7.826 Total 100 29.086

TABLE-US-00002 TABLE 2 Formulation 2 Entry Materials Weight percentage (%) Weight (g) 1 Example 3 47.6 15.00 2 Butanol 12.9 4.050 3 Surfynol DF110C 0.2 0.062 4 BYK345 0.2 0.062 5 ECOSURF BD405 0.4 0.125 6 DMAP 0.1 0.031 7 Cymel NF2000 38.6 12.162 Total 100 31.492

TABLE-US-00003 TABLE 3 Formulation 3 Entry Materials Weight percentage (%) Weight (g) 1 Example 4 50.3 15.00 2 Butanol 16.7 4.980 3 Surfynol DF110C 0.2 0.059 4 BYK345 0.2 0.059 5 ECOSURF BD405 0.4 0.118 6 DMAP 0.1 0.030 7 Cymel NF2000 32.1 9.574 Total 100 29.82

TABLE-US-00004 TABLE 4 Formulation 4 Entry Materials Weight percentage (%) Weight (g) 1a A870 46.2 13.5 1b Example 3 5.7 1.654 2 Butanol 20.5 6.000 3 Surfynol 0.2 0.058 DF110C 4 BYK345 0.2 0.058 5 ECOSURF 0.4 0.115 BD405 6 DMAP 0.1 0.029 7 Cymel NF2000 26.8 7.826 Total 100 29.24

TABLE-US-00005 TABLE 5 Formulation 5 Entry Material Weight percentage (%) Weight (g) 1a A870 40.8 12.000 1b Example 3 11.3 3.307 2 Butanol 20.4 6.000 3 Surfynol DF110C 0.2 0.058 4 BYK345 0.2 0.058 5 ECOSURF BD405 0.4 0.115 6 DMAP 0.1 0.029 7 Cymel NF2000 26.6 7.826 Total 100 29.393

TABLE-US-00006 TABLE 6 Formulation 6 Entry Material Weight percentage (%) Weight (g) 1a A870 46.3 13.5 1b Example 4 5.4 1.577 2 Butanol 20.6 6.000 3 Surfynol DF110C 0.2 0.058 4 BYK345 0.2 0.058 5 ECOSURF BD405 0.4 0.115 6 DMAP 0.1 0.029 7 Cymel NF2000 26.8 7.826 Total 100 29.163

TABLE-US-00007 TABLE 7 Formulation 7 Entry Material Weight percentage (%) Weight (g) 1a A870 41.0 12.00 1b Example 4 10.8 3.153 2 Butanol 20.5 6.000 3 Surfynol DF110C 0.2 0.058 4 BYK345 0.2 0.058 5 ECOSURF BD405 0.4 0.115 6 DMAP 0.1 0.029 7 Cymel NF2000 26.8 7.826 TOTAL 100 29.239

TABLE-US-00008 TABLE 8 Film properties of Formulations 1-7 Pencil Flexibility MEK hardness (Mandrel double rub Adhesion Formulation (mark/break) test) (cycles) (% peel-off) 1 [Comparative] .sup.F/3H fail 440 0 2 3H/4H pass >1500 0 3 4H/5H pass >1500 0 4 H/3H pass >1500 0 5 2H/4H pass >1500 0 6 2H/4H pass >1500 0 7 2H/4H pass 1098 0

[0112] The above data indicates that the TACT crosslinker (CYMEL NF2000) reacts with both hydroxyl and epoxy functional resins at about 125 C. In Formulations 1 to 3, CYMEL NF 2000 is used to react with A870, the epoxy-modified dendritic polymers of Examples 3 and 4 respectively.

[0113] The coating film of comparative Formulation 1 (prepared with A870) showed fair pencil hardness of F/3H (scratch/break), and reasonably good MEK resistance with 440 cycles. However, the flexibility is markedly poor and the comparative film does not even pass a/2 inch Mandrel test. In contrast, coating films prepared from Formulations 2 and 3 comprising the disclosed epoxy-functionalized dendritic polymer demonstrated improved pencil hardness (scratch/break) to 3H/4H and 4H/5H, respectively. Additionally, the MEK resistance of the inventive coating films are also clearly superior with >1500 cycles as compared to the comparative film (440 cycles). Even more notably, the film flexibilities of the inventive coating films also experienced drastic improvements from a fail to pass in the Mandrel test.

Use of Epoxy-Modified Dendritic Polymer as Additive Blend

[0114] As shown in Formulations 4 to 7, even when a small amount of A870 (about 10 wt % to about 20% based on solid content) was replaced with the epoxy-modified dendritic polymer [obtained from Example 3 or 4], the resultant coating films benefitted from much improved physical and chemical properties compared to the comparative Formulation 1.

[0115] In Formulation 4, about 5.6 wt. % of the epoxy-modified dendritic polymer from Example 3 was added to the formulation containing about 46.2 wt. % of the main binder A870. The weight ratio of A870 to Example 3 was about 9:1 (based on solid content). The resulting coating film shows pencil hardness of H/3H, and passed the inch Mandrel test. Importantly, the coating film did not show any visible damage with 1500 cycles of MEK rub.

[0116] In Formulation 5, about 11.2 wt. % of the epoxy-modified dendritic polymer from Example 3 was added to the formulation containing about 40.8 wt. % of the main binder A870. The weight ratio of A870 to Example 3 was about 4:1 (based on solid content). The pencil hardness of the resultant coating film is further improved to 2H/4H (scratch/break) and the flexibility is maintained with passing inch Mandrel test.

[0117] In Formulations 6 and 7, similarly advantageous results can be observed by the addition of a small portion (5.4 wt. % and 10.8 wt. % respectively) of the epoxy-modified dendritic polymer from Example 4 to the formulation containing A870 as the main binder. The resultant films displayed greatly improved pencil hardness, flexibility and MEK resistance.

Additional Formulations 8 to 11

[0118] Additional films were prepared based on the protocol described above using Formulations 8-11 (shown below in Table 9). Final NV %=55%, adjusted by BA. WFT=100 m, RT flash 15 min, 150 degree, 30 min or 1 h. DMAP used as catalyst.

TABLE-US-00009 TABLE 9 Formulation 8(Comparative) 9 10 11 Dendritic polymer of 0 g 1.327 g 2.760 g 15.00 g Example 1 CYMEL NF 2000 7.819 g 7.934 g 8.208 g 9.042 g A870 15.00 g 13.68 g 12.33 g 0 g Film properties MEK (30 min) 61 70 100 195 MEK (1 h) 230 366 408 >1500 Hardness (30 min) H/2H 2H/2H 2H/2H 2H/3H Hardness (1 h) 2H/3H 2H/3H 3H/3H 3H/3H Flexibility(30 min) Flexibility (1 h)

[0119] The data in Table 9 investigates the addition of the epoxy-modified, carboxylic acid esterified, dendritic polymer of Example 1 into an A870/Cymel NF2000 (TACT) system. The results confirm that the addition of the dendritic polymer according to the present disclosure improves the hardness and flexibility of the film. It is postulated that the dendritic polymer of Example 1 crosslinks with Cymel NF2000 to give a film with excellent MEK resistance (>1500) good hardness (3H/3H) and flexibility ( pass).

Additional Formulations 12 to 15

[0120] Additional films were prepared using the protocol as described above based on Formulations 12 to 15. Final NV=55%, adjusted by BA. WFT 100 m, RT flash 15 min, 150 C. thermal cure, 30 min or 1h. DMAP used as catalyst. The contents of each formulation are provided in Table 10.

TABLE-US-00010 TABLE 10 Formulations 12 (com- parative) 13 14 15 Example 2 0 g 14.993 g 1.495 g 3.010 g Cymel NF2000 7.839 g 6.698 g 7.832 g 7.815 g A870 14.964 g 0 13.519 g 12.018 g Film properties MEK (30 min) 318 >1500 658 1300 MEK (1 h) 390 >1500 830 1033 Hard- 2H/3H 2H/2H 2H/2H 2H/3H ness(30 min) Hardness (1 h) 2H/3H 2H/3H 3H/3H 3H/3H Flexi- bility(30 min) Flexi- bility(1 h)

[0121] The data found in Table 10 shows that the addition of the epoxy-modified, carboxylic acid esterified, dendritic polymer H4001-50% IPDI-Glycidol of Example 2 into A870/Cymel NF2000 system substantially improves the hardness and flexibility of the resultant coating films. The magnitude of improvement is observed to be greater than that obtained by using the epoxy-modified, chain-extended, dendritic polymer from Example 3.

[0122] The following Examples are epoxy-dendritic polymers prepared based on glycerol diglycidyl ether (which is a di-epoxy compound with one active hydroxyl group)

Additional Materials Used in Examples 7-8:

[0123] Glycerol diglycidyl ether (GDGE): purchased from Nagase ChemteX;
Iron(III) acetylacetonate: provide by TIB Chemicals;
YD-128: a liquid type standard epoxy resin derived from Bisphenol-A, provided by Kukdo Chemical.

Example 7

Preparation of an Epoxy-Dendritic Polymer: H4001-25% IPDI-Glycerol Diglycidyl Ether [4th Generation Dendritic Polymer, 25% Di-Epoxy Substitution]

(7A) Preparation of IPDI-GDGE Adduct

[0124] In a nitrogen atmosphere, at RT, glycerol diglycidyl ether (GDGE) (51.73 g) was added into a mixture of IPDI (50.00 g), butyl acetate (40.00 g) and Iron(III) acetylacetonate (5.0 mg). The resulting mixture was stirred at RT for about 5 hours until NCO % reached theoretical value of 6.7%.

(7B) Preparation of H4001-25% IPDI-GDGE

[0125] Under nitrogen atmosphere, at RT, freshly prepared IPDI-GDGE adduct (50.56 g) according to (7A), H4001 (120.00 g) and DBTDL (0.085 g) were mixed. The mixture was stirred at 80 C. for 2.5 hours until NCO % was less than 0.1%.

Example 8

Preparation of an Epoxy-Dendritic Polymer: H20-25% IPDI-Glycerol Diglycidyl Ether [2th Generation, 25% Di-Epoxy Substitution]

(8A) Preparation of IPDI-GDGE Adduct

[0126] In a nitrogen atmosphere, at RT, glycerol diglycidyl ether (37.25 g) was added into a mixture of IPDI (30.00 g), butyl acetate (24.00 g) and Iron(III) acetylacetonate (5.0 mg). The resulting mixture was stirred at RT for about 3 hours until NCO % reached theoretical value of 5.0%.

(8B) Preparation of H20-25% IPDI-Glycidol

[0127] Under nitrogen atmosphere, a mixture of Boltorn H.sub.2O (50.00 g) and DMM (25.00 g) was heated to 140 C. Caprolactone (20.00 g) was then added. The resulting mixture was stirred at the same temperature for 1 hour and was then cooled down to 80 C. Freshly prepared IPDI-GDGE adduct (75.32 g) according to (8A) and DBTDL (0.098 g) were then charged in turn. The resulting mixture was stirred at 80 C. for 3 hours until NCO % was less than 0.1%.

Exemplary Formulations

(Example 7, 8 and a Commercial Epoxy Resin YD-128)

[0128] Additional films were prepared using the protocol as described above based on Formulations 12 to 15. Final NV=50%, adjusted by butanol. WFT 100 m, RT flash 15 min, 150 C. thermal cure, 30 min or 1h. DMAP used as catalyst. The contents of each formulation are provided in Tables 11-17 below.

TABLE-US-00011 TABLE 11 Formulation 16 (Example 7) Entry Material Wt (%) Weight (g) 1 Example 7 60.2% 20.000 2 Butanol 13.5% 4.480 3 Surfynol DF110C 0.2% 0.066 4 BYK345 0.2% 0.066 5 ECOSURF BD405 0.4% 0.132 6 DMAP 0.1% 0.033 7 Cymel NF2000 25.5% 8.463 Total 100% 33.240

TABLE-US-00012 TABLE 12 Formulation 17 (Example 8) Entry Material Wt (%) Weight (g) 1 Example 8 55.2% 20.348 2 Butanol 15.7% 5.779 3 Surfynol DF110C 0.2% 0.073 4 BYK345 0.2% 0.073 5 ECOSURF BD405 0.4% 0.146 6 DMAP 0.1% 0.037 7 Cymel NF2000 28.3% 10.435 Total 100% 36.891

TABLE-US-00013 TABLE 13 Formulation 18 (YD-128) Entry Material Wt (%) Weight (g) 1 YD-128 27.7% 10.000 2 Butanol 27.7% 10.000 3 Surfynol DF110C 0.2% 0.072 4 BYK345 0.2% 0.072 5 ECOSURF BD405 0.4% 0.143 6 DMAP 0.1% 0.036 7 Cymel NF2000 43.7% 15.789 Total 100% 36.112

TABLE-US-00014 TABLE 14 Formulation 19 (A870/Example 7 9:1 wt/wt) Entry Material Wt (%) Weight (g) 1a A870 (90%) 46.4% 18.000 1b Example 7 5.9% 2.288 2 Butanol 19.9% 7.712 3 Surfynol DF110C 0.2% 0.077 4 BYK345 0.2% 0.077 5 ECOSURF BD405 0.4% 0.154 6 DMAP 0.1% 0.038 7 Cymel NF2000 26.9% 10.435 Total 100% 38.781

TABLE-US-00015 TABLE 15 Formulation 20 (A870/Example 7 8:2 wt/wt) Entry Material Wt (%) Weight (g) 1a A870 41.3% 16.000 1b Example 7 11.8% 4.575 2 Butanol 19.1% 7.425 3 Surfynol DF110C 0.2% 0.077 4 BYK345 0.2% 0.077 5 ECOSURF BD405 0.4% 0.154 6 DMAP 0.1% 0.038 7 Cymel NF2000 26.9% 10.435 Total 100% 38.781

TABLE-US-00016 TABLE 16 Formulation 21 (A870/Example 8 9:1 wt/wt) Entry Material Wt (%) Weight (g) 1a A870 46.4% 18.000 1b Example 8 5.6% 2.181 2 Butanol 20.2% 7.819 3 Surfynol DF110C 0.2% 0.077 4 BYK345 0.2% 0.077 5 ECOSURF BD405 0.4% 0.154 6 DMAP 0.1% 0.038 7 Cymel NF2000 26.9% 10.435 Total 100% 38.781

TABLE-US-00017 TABLE 17 Formulation 22 (A870/Example 8 8:2 wt/wt) Entry Material Wt (%) Weight (g) 1a A870 41.3% 16.000 1b Example 8 11.2% 4.361 2 Butanol 19.7% 7.639 3 Surfynol DF110C 0.2% 0.077 4 BYK345 0.2% 0.077 5 ECOSURF BD405 0.4% 0.154 6 DMAP 0.1% 0.038 7 Cymel NF2000 26.9% 10.435 Total 100% 38.781

TABLE-US-00018 TABLE 18 Film properties of Formulations 16-18 Formulations 18 16 17 Epoxy resin YD-128 Example 7 Example 8 MEK double rub >1500 >1500 >1500 Pencil hardness 3H/4H 2H/4H 3H/5H (scratch/break) Impact (kg cm) 45 170 115 Flexibility (Mandrel pass pass pass test) Flexibility (mandrel pass pass pass test, 20 C.)

[0129] The results in Table 18 show that the coatings prepared from Examples 16 and 17 provided superior impact resistances than that of YD-128; and their flexibilities at the temperature of 20 C. were also better.

TABLE-US-00019 TABLE 19 Film properties of Formulations 19-22 Pencil Flexibility MEK hardness (Mandrel double rub Adhesion Formulation (scratch/break) test) (cycles) (% peel-off) 1 [Comparative] F/3H fail 440 0 19 2H/4H pass >1500 0 20 2H/4H pass >1500 0 21 2H/3H pass >1500 0 22 2H/4H pass >1500 0

[0130] Similar to Examples 1-6, replacement of 10 wt %-20 wt % of A870 by Examples 7 and 8 improved the hardness, chemical resistances and flexibility of the coating.

Applications

[0131] As is substantiated by the disclosure provided herein, the disclosed epoxy-modified dendritic polymer and coatings prepared from the same are capable of addressing and overcoming at least one or more technical issues associated with conventional coatings melamine resins, e.g., a lack of flexibility, pencil hardness, chemical resistance.

[0132] Accordingly, the disclosed modified dendritic polymer may be advantageously applied in industry, e.g., the provision of surface protective coatings for automotive industries, and/or surface coatings that are intended for application to deformable or bendable surfaces.

[0133] Furthermore, the disclosed polymer compositions may also be used for preparing pigments and masterbatches.

[0134] It will be apparent that various other modifications and adaptations of the invention will be apparent to the person skilled in the art after reading the foregoing disclosure without departing from the spirit and scope of the invention and it is intended that all such modifications and adaptations come within the scope of the appended claims.