Vinyl functionalized urethane resins for powder coating compositions

Abstract

The invention relates to a vinyl functionalized urethane resin (VFUR) useful as a curing agent in thermosetting powder coating compositions, a process for making said vinyl functionalized urethane resin, a vinyl functionalized urethane resin composition (VFURC) useful as a curing agent in thermosetting powder coating compositions, a process for making vinyl functionalized urethane resin composition, a thermosetting powder coating composition (TPCC), a process for the preparation thereof, a cured thermosetting powder coating composition, processes for coating an article with said thermosetting powder coating composition and an article coated with said thermosetting powder coating composition as well as uses of the vinyl functionalized urethane resin or of the vinyl functionalized urethane resin composition or of the thermosetting powder coating composition or of the articles having coated and cured thereon said thermosetting powder coating composition. The invention relates also to thermosetting powder coating composition useful for powder-in-mold coating articles such as reinforced polymeric e.g. polyester resin articles and to powder-in-mold coating methods employing the thermosetting powder coating composition and use of the in-mold coated article.

Claims

1. A vinyl functionalized urethane resin (VFUR) wherein the VFUR is crystalline having a melting enthalpy measured via Differential Scanning calorimetry, of at least 35 J/g; and the VFUR has a ratio (R.sub.VFUR) of urethane bonds in the VFUR to vinyl groups in the VFUR as measured by .sup.1H-NMR spectroscopy of at least 1.04 and at most 1.80.

2. The VFUR according to claim 1, wherein the VFUR is prepared from: (A) at least a compound A comprising isocyanate groups; (B) at least a compound B comprising hydroxyl groups, wherein the compound B is selected from compounds in the group consisting of compounds comprising vinyl ether groups (VET), compounds comprising vinyl ester groups (VES), and compounds comprising vinyl ether and vinyl ester groups (VET-VES); and (C) at least one organic compound C comprising hydroxyl groups.

3. The VFUR according to claim 2, wherein the compound B is selected from the group consisting of compounds comprising vinyl ether groups (VET) and compounds comprising vinyl ester groups (VES).

4. The VFUR according to claim 2, wherein the compound B is a compound comprising vinyl ether groups (VET).

5. The VFUR according to claim 4, wherein the compound B is a vinyl ether alcohol.

6. The VFUR according to claim 1, wherein the VFUR has a R.sub.VFUR of at least 1.06 and of at most 1.80.

7. The VFUR according to claim 1, wherein the VFUR has a R.sub.VFUR of at least 1.10 and of at most 1.80.

8. The VFUR according to claim 1, wherein the VFUR has a R.sub.VFUR of at least 1.10 and of at most 1.71.

9. The VFUR according to claim 1, wherein the VFUR has a R.sub.VFUR of at least 1.18 and of at most 1.45.

10. The VFUR according to claim 5, wherein the VFUR has a R.sub.VFUR of at least 1.06 and of at most 1.80.

11. The VFUR according to claim 5, wherein the VFUR has a R.sub.VFUR of at least 1.10 and of at most 1.80.

12. The VFUR according to claim 5, wherein the VFUR has a R.sub.VFUR of at least 1.10 and of at most 1.71.

13. The VFUR according to claim 5, wherein the VFUR has a R.sub.VFUR of at least 1.18 and of at most 1.45.

14. The VFUR according to claim 1, wherein the VFUR is solid at 23 C. and at atmospheric pressure.

15. The VFUR according to claim 2, wherein the VFUR is solid at 23 C. and at atmospheric pressure.

16. The VFUR according to claim 3, wherein the VFUR is solid at 23 C. and at atmospheric pressure.

17. The VFUR according to claim 4, wherein the VFUR is solid at 23 C. and at atmospheric pressure.

18. The VFUR according to claim 5, wherein the VFUR is solid at 23 C. and at atmospheric pressure.

19. The VFUR according to claim 6, wherein the VFUR is solid at 23 C. and at atmospheric pressure.

20. The VFUR according to claim 7, wherein the VFUR is solid at 23 C. and at atmospheric pressure.

21. The VFUR according to claim 8, wherein the VFUR is solid at 23 C. and at atmospheric pressure.

22. The VFUR according to claim 9, wherein the VFUR is solid at 23 C. and at atmospheric pressure.

23. The VFUR according to claim 10, wherein the VFUR is solid at 23 C. and at atmospheric pressure.

24. The VFUR according to claim 11, wherein the VFUR is solid at 23 C. and at atmospheric pressure.

25. The VFUR according to claim 12, wherein the VFUR is solid at 23 C. and at atmospheric pressure.

26. The VFUR according to claim 13, wherein the VFUR is solid at 23 C. and at atmospheric pressure.

27. A process for making the VFUR as defined in claim 1, wherein the process comprises the step of reacting a compound A which comprises isocyanate groups with a compound B comprising hydroxyl groups and an organic compound C, wherein the compound B is selected from the group of compounds consisting of compounds comprising vinyl ether groups (VET), compounds comprising vinyl ester groups (VES), and compounds comprising vinyl ether and vinyl ester groups (VET-VES), and wherein the organic compound C comprises hydroxyl groups to form the VFUR, or alternatively the process comprises the steps of: (i) reacting the compound A with the organic compound C to form an isocyanate terminated adduct of the compound A with the organic compound C, and (ii) reacting the isocyanate terminated adduct of the compound A with the organic compound C obtained in step (i) with the compound B to form the VFUR.

28. The process according to claim 27, wherein the compound B is a vinyl ether alcohol.

29. The process according to claim 27, wherein the VFUR is solid at 23 C. and at atmospheric pressure.

30. The process according to claim 27, wherein the VFUR is solid at 23 C. and at atmospheric pressure, and the compound B is a vinyl ether alcohol.

31. A vinyl functionalized urethane resin composition (VFURC) comprising at least a first vinyl functionalized urethane resin (FVFUR) and a second vinyl functionalized urethane resin (SVFUR), wherein either the FVFUR or the SVFUR is a VFUR according to claim 1, and wherein the VFURC is crystalline having a melting enthalpy measured via Differential Scanning calorimetry, of at least 35 J/g; and the VFURC has a ratio (R.sub.VFURC) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by .sup.1H-NMR spectroscopy of at least 1.04 and at most 1.80.

32. A vinyl functionalized urethane resin composition (VFURC) comprising at least a first vinyl functionalized urethane resin (FVFUR) and a second vinyl functionalized urethane resin (SVFUR), wherein each of the FVUR and the SVFUR is a VFUR according to claim 1, and wherein the VFURC is crystalline having a melting enthalpy measured via Differential Scanning calorimetry, of at least 35 J/g; and the VFURC has a ratio (R.sub.VFURC) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by .sup.1H-NMR spectroscopy of at least 1.04 and at most 1.80.

33. A vinyl functionalized urethane resin composition (VFURC) comprising at least a first vinyl functionalized urethane resin (FVFUR) and a second vinyl functionalized urethane resin (SVFUR), wherein either the FVFUR or the SVFUR is a VFUR according to claim 6 wherein the compound B is a vinyl ether alcohol and the VFUR is solid at 23 C. and at atmospheric pressure, and wherein the VFURC is crystalline having a melting enthalpy measured via Differential Scanning calorimetry, of at least 35 J/g; and the VFURC has a ratio (R.sub.VFURC) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by .sup.1H-NMR spectroscopy of at least 1.04 and at most 1.80, and.

34. A vinyl functionalized urethane resin composition (VFURC) comprising at least a first vinyl functionalized urethane resin (FVFUR) and a second vinyl functionalized urethane resin (SVFUR), wherein either the FVFUR or the SVFUR is a VFUR according to claim 7 wherein the compound B is a vinyl ether alcohol and the VFUR is solid at 23 C. and at atmospheric pressure, and wherein the VFURC is crystalline having a melting enthalpy measured via Differential Scanning calorimetry, of at least 35 J/g; and the VFURC has a has a ratio (R.sub.VFURC) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by .sup.1H-NMR spectroscopy of at least 1.04 and at most 1.80, and.

35. A vinyl functionalized urethane resin composition (VFURC) comprising at least a first vinyl functionalized urethane resin (FVFUR) and a second vinyl functionalized urethane resin (SVFUR), wherein either the FVFUR or the SVFUR is a VFUR according to claim 8 wherein the compound B is a vinyl ether alcohol and the VFUR is solid at 23 C. and at atmospheric pressure, and wherein the VFURC is crystalline having a melting enthalpy measured via Differential Scanning calorimetry, of at least 35 J/g; and the VFURC has a ratio (R.sub.VFURC) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by .sup.1H-NMR spectroscopy of at least 1.04 and at most 1.80, and.

36. A vinyl functionalized urethane resin composition (VFURC) comprising at least a first vinyl functionalized urethane resin (FVFUR) and a second vinyl functionalized urethane resin (SVFUR), wherein either the FVFUR or the SVFUR is a VFUR according to claim 9 wherein the compound B is a vinyl ether alcohol and the VFUR is solid at 23 C. and at atmospheric pressure, and wherein the VFURC is crystalline having a melting enthalpy measured via Differential Scanning calorimetry, of at least 35 J/g; and the VFURC has a ratio (R.sub.VFURC) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by .sup.1H-NMR spectroscopy of at least 1.04 and at most 1.80.

37. A thermosetting powder coating composition comprising: (i) a VFUR as defined in claim 1 and/or a vinyl functionalized urethane resin composition (VFURC) comprising at least a first vinyl functionalized urethane resin (FVFUR) and a second vinyl functionalized urethane resin (SVFUR), and (ii) an unsaturated resin comprising ethylenic unsaturations, and wherein at least one of the FVFUR or the SVFUR is crystalline having a melting enthalpy measured via Differential Scanning calorimetry, of at least 35 J/g; the VFURC is crystalline having a melting enthalpy measured via Differential Scanning calorimetry, of at least 35 J/g; and the VFURC has a ratio (R.sub.VFURC) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by .sup.1H-NMR spectroscopy of at least 1.04 and at most 1.80.

38. The thermosetting powder coating composition according to claim 37, wherein the ethylenic unsaturations are di-acid ethylenic unsaturations.

39. The thermosetting powder coating composition according to claim 38, wherein the di-acid ethylenic unsaturations are 2-butenedioic acid ethylenic unsaturations.

40. The thermosetting powder coating composition according to claim 38, wherein the unsaturated resin comprising ethylenic unsaturations is selected from the group consisting of polyester resins, acrylic resins, polyurethanes, epoxy resins, polyamides, polyesteramides, polycarbonates, polyureas and combinations thereof.

41. The thermosetting powder coating composition according to claim 37, wherein the unsaturated resin comprising ethylenic unsaturations is an unsaturated polyester resin comprising 2-butenedioic acid ethylenic unsaturations.

42. The thermosetting powder coating composition according to claim 37, wherein the composition further comprises a radical initiator and optionally at least one of a) an accelerator, b) a co-accelerator and c) an inhibitor.

43. A thermosetting powder coating composition comprising: (i) a vinyl functionalized urethane resin (VFUR) as defined in claim 6 which is solid at 23 C. and at atmospheric pressure and/or a vinyl functionalized urethane resin composition (VFURC) comprising at least a first vinyl functionalized urethane resin (FVFUR) and a second vinyl functionalized urethane resin (SVFUR), (ii) an unsaturated resin comprising di-acid ethylenic unsaturations, (iii) a radical initiator, and (iv) an inhibitor, wherein at least one of the FVFUR or the SVFUR is crystalline having a melting enthalpy measured via Differential Scanning calorimetry, of at least 35 J/g; the VFURC is crystalline having a melting enthalpy measured via Differential Scanning calorimetry, of at least 35 J/g; and the VFURC has a ratio (R.sub.VFURC) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by .sup.1H-NMR spectroscopy of at least 1.04 and at most 1.80.

44. A thermosetting powder coating composition comprising: (i) a vinyl functionalized urethane resin (VFUR) as defined in claim 7 which is solid at 23 C. and at atmospheric pressure and/or a vinyl functionalized urethane resin composition (VFURC) comprising at least a first vinyl functionalized urethane resin (FVFUR) and a second vinyl functionalized urethane resin (SVFUR), (ii) an unsaturated resin comprising di-acid ethylenic unsaturations, (iii) a radical initiator, and (iv) an inhibitor, wherein at least one of the FVFUR or the SVFUR is crystalline having a melting enthalpy measured via Differential Scanning calorimetry, of at least 35 J/g; the VFURC is crystalline having a melting enthalpy measured via Differential Scanning calorimetry, of at least 35 J/g; and the VFURC has a ratio (R.sub.VFURC) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by .sup.1H-NMR spectroscopy of at least 1.04 and at most 1.80.

45. A thermosetting powder coating composition comprising: (i) a vinyl functionalized urethane resin (VFUR) as defined in claim 8 which is solid at 23 C. and at atmospheric pressure and/or a vinyl functionalized urethane resin composition (VFURC) comprising at least a first vinyl functionalized urethane resin (FVFUR) and a second vinyl functionalized urethane resin (SVFUR), (ii) an unsaturated resin comprising di-acid ethylenic unsaturations, (iii) a radical initiator, and (iv) an inhibitor, wherein at least one of the FVFUR or the SVFUR is crystalline having a melting enthalpy measured via Differential Scanning calorimetry, of at least 35 J/g; the VFURC is crystalline having a melting enthalpy measured via Differential Scanning calorimetry, of at least 35 J/g; and the VFURC has a ratio (R.sub.VFURC) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by .sup.1H-NMR spectroscopy of at least 1.04 and at most 1.80.

46. A thermosetting powder coating composition comprising: (i) a vinyl functionalized urethane resin (VFUR) as defined in claim 9 which is solid at 23 C. and at atmospheric pressure and/or a vinyl functionalized urethane resin composition (VFURC) comprising at least a first vinyl functionalized urethane resin (FVFUR) and a second vinyl functionalized urethane resin (SVFUR), (ii) an unsaturated resin comprising di-acid ethylenic unsaturations, (iii) a radical initiator, and (iv) an inhibitor, wherein at least one of the FVFUR or the SVFUR is crystalline having a melting enthalpy measured via Differential Scanning calorimetry, of at least 35 J/g; the VFURC is crystalline having a melting enthalpy measured via Differential Scanning calorimetry, of at least 35 J/g; and the VFURC has a ratio (R.sub.VFURC) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by .sup.1H-NMR spectroscopy of at least 1.04 and at most 1.80.

47. A process for making a thermosetting powder coating composition as defined in claim 37 comprising the steps of: (a) mixing the components (i)-(ii) of the thermosetting powder coating composition to obtain a premix; (b) heating the premix in an extruder, to obtain an extrudate; (c) cooling the extrudate to obtain a solidified extrudate; and (d) grinding the solidified extrudate into smaller particles to obtain the thermosetting powder coating composition.

48. The thermosetting powder coating composition of claim 37 which is cured.

49. The thermosetting powder coating composition of claim 38 which is cured.

50. The thermosetting powder coating composition of claim 39 which is cured.

51. The thermosetting powder coating composition of claim 40 which is cured.

52. The thermosetting powder coating composition of claim 41 which is cured.

53. The thermosetting powder coating composition of claim 42 which is cured.

54. The thermosetting powder coating composition of claim 43 which is cured.

55. The thermosetting powder coating composition of claim 44 which is cured.

56. The thermosetting powder coating composition of claim 45 which is cured.

57. The thermosetting powder coating composition of claim 46 which is cured.

58. An article having coated and cured thereon the thermosetting powder coating composition as defined in claim 37.

59. An article having coated and cured thereon the thermosetting powder coating composition as defined in claim 38.

60. An article having coated and cured thereon the thermosetting powder coating composition as defined in claim 42.

61. An article having coated and cured thereon the thermosetting powder coating composition as defined in claim 43.

62. An article having coated and cured thereon the thermosetting powder coating composition as defined in claim 44.

63. An article having coated and cured thereon the thermosetting powder coating composition as defined in claim 45.

64. An article having coated and cured thereon the thermosetting powder coating composition as defined in claim 46.

65. The article according to claim 58, wherein the article is selected from the group consisting of heat-sensitive articles and non-heat sensitive articles.

66. An article according to claim 65, wherein the article is selected from the group consisting of wood, low density fibre board, medium density fibreboard, high density fibreboard, plastic, thermoplastic composite, thermoset composite, fibre reinforced composites, sandwich materials, metal and combinations thereof.

67. A process for making a coated article comprising the steps of: (i) applying the thermosetting powder coating composition as defined in claim 37 to an article which is selected from the group consisting of articles comprising heat-sensitive components, articles comprising non-heat sensitive components and articles comprising a combination of heat-sensitive and non-heat sensitive components; and (ii) heating and/or irradiating the thermosetting powder coating composition applied to the article for enough time and at a suitable temperature to cure the thermosetting powder coating composition to obtain the coated article.

68. A process for making a coated article comprising the steps of: (i) applying the thermosetting powder coating composition as defined in claim 42 to an article which is selected from the group consisting of articles comprising heat-sensitive components, articles comprising non-heat sensitive components and articles comprising a combination of heat-sensitive and non-heat sensitive components; and (ii) heating and/or irradiating the thermosetting powder coating composition applied to the article for enough time and at a suitable temperature to cure the thermosetting powder coating composition to obtain the coated article.

69. A process for making a coated article comprising the steps of: (i) applying a thermosetting powder coating composition as defined in claim 37 to the interior wall of a mould; (ii) subsequently introducing a fill compound in the mould in order for the fill compound to form an article within the mould, wherein the article is selected from the group consisting of articles comprising heat-sensitive components, articles comprising non-heat sensitive components and articles comprising a combination of heat-sensitive and non-heat sensitive components; and (iii) heating and/or irradiating the thermosetting powder coating composition and optionally also the fill compound to obtain the coated article.

70. A vinyl functionalized urethane resin composition (VFURC) comprising at least a first vinyl functionalized urethane resin (FVFUR) and a second vinyl functionalized urethane resin (SVFUR), wherein at least one of the FVFUR and the SVFUR is crystalline having a melting enthalpy measured via Differential Scanning calorimetry, of at least 35 J/g; the VFURC is crystalline having a melting enthalpy measured via Differential Scanning calorimetry, of at least 35 J/g; and the VFURC has a ratio (R.sub.VFURC) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by .sup.1H-NMR spectroscopy of at least 1.04 and at most 1.80.

71. The VFURC according to claim 70, wherein at least one of the FVFUR and the SVFUR is prepared from: (A) at least a compound A comprising isocyanate groups; (B) at least a compound B comprising hydroxyl groups, wherein the compound B is selected from compounds in the group consisting of compounds comprising vinyl ether groups (VET), compounds comprising vinyl ester groups (VES), and compounds comprising vinyl ether and vinyl ester groups (VET-VES); and (C) at least one organic compound C comprising hydroxyl groups.

72. The VFURC according to claim 70, wherein the VFURC has a R.sub.VFURC of at least 1.06 and of at most 1.80.

73. The VFURC according to claim 70, wherein the VFURC has a R.sub.VFURC of at least 1.10 and of at most 1.80.

74. The VFURC according to claim 70, wherein the VFURC has a R.sub.VFURC of at least 1.10 and of at most 1.71.

75. The VFURC according to claim 70, wherein the VFURC has a R.sub.VFURC of at least 1.18 and of at most 1.45.

76. A process for making a VFURC as defined in claim 70, the process comprising the steps of: (i) providing the FVFUR; (ii) providing the SVFUR; (iii) mixing the FVFUR and SVFUR together to obtain the VFURC.

77. A process for making the VFURC as defined in claim 70, the process comprising making either the FVFUR or the SVFUR by reacting a compound A which comprises isocyanate groups, with a compound B comprising hydroxyl groups and an organic compound C, wherein the compound B is selected from the group of compounds consisting of compounds comprising vinyl ether groups (VET), compounds comprising vinyl ester groups (VES), and compounds comprising vinyl ether and vinyl ester groups (VET-VES), and wherein the organic compound C comprises hydroxyl groups to form the FVFUR or the SVFUR, or alternatively the process comprises the steps of: (i) reacting the compound A with the organic compound C to form an isocyanate terminated adduct of the compound A with the organic compound C, and (ii) reacting the isocyanate terminated adduct of the compound A with the organic compound C obtained in step (i) with the compound B to form the FVFUR or the SVFUR.

78. A vinyl functionalized urethane resin composition (VFURC) comprising at least a first vinyl functionalized urethane resin (FVFUR) and a second vinyl functionalized urethane resin (SVFUR), wherein either the FVFUR or the SVFUR is a VFUR according to claim 5 and the VFUR is solid at 23 C. and at atmospheric pressure, and wherein the VFURC is crystalline having a melting enthalpy measured via Differential Scanning calorimetry, of at least 35 J/g; and the VFURC has a ratio (R.sub.VFURC) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by .sup.1H-NMR spectroscopy of at least 1.04 and at most 1.80, and.

79. A thermosetting powder coating composition comprising: (i) a vinyl functionalized urethane resin (VFUR) as defined in claim 5 which is solid at 23 C. and at atmospheric pressure and/or a vinyl functionalized urethane resin composition (VFURC) comprising at least a first vinyl functionalized urethane resin (FVFUR) and a second vinyl functionalized urethane resin (SVFUR), (ii) an unsaturated resin comprising di-acid ethylenic unsaturations, (iii) a radical initiator, and (iv) an inhibitor, wherein at least one of the FVFUR or the SVFUR is crystalline having a melting enthalpy measured via Differential Scanning calorimetry, of at least 35 J/g; the VFURC is crystalline having a melting enthalpy measured via Differential Scanning calorimetry, of at least 35 J/g; and the VFURC has a ratio (R.sub.VFURC) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by .sup.1H-NMR spectroscopy of at least 1.04 and at most 1.80.

80. The thermosetting powder coating composition of claim 79 which is cured.

81. An article having coated and cured thereon the thermosetting powder coating composition as defined in claim 79.

82. A process for making a coated article comprising the steps of: (i) applying the thermosetting powder coating composition as defined in claim 79 to an article which is selected from the group consisting of articles comprising heat-sensitive components, articles comprising non-heat sensitive components and articles comprising a combination of heat-sensitive and non-heat sensitive components; and (ii) heating and/or irradiating the thermosetting powder coating composition applied to the article for enough time and at a suitable temperature to cure the thermosetting powder coating composition to obtain the coated article.

Description

EXAMPLES

(1) The invention is explained in more detail with reference to the following non-limiting examples.

(2) In the Examples section, the abbreviation UR represents unsaturated resin comprising ethylenic unsaturations, the abbreviation VFUR represents vinyl functionalized urethane resins used as curing agent, the abbreviation PCC represents thermosetting powder coating composition and the abbreviation PC represents powder coating.

(3) In all the examples the unsaturated resin comprising ethylenic unsaturations (UR) were unsaturated polyester resins comprising 2-butenedioic acid ethylenic unsaturations.

(4) In all the examples the vinyl functionalized urethane resins (VFUR) used as curing agent were vinyl ether functionalized urethane resins (VEFUR).

(5) All powder coating compositions presented in the Examples were thermosetting powder coating compositions.

(6) In the Examples section the abbreviation Comp denotes a Comparative Example of either the VFUR e.g. CompVFUR1, or a thermosetting powder coating composition e.g. CompPCC1, or a powder coating e.g. CompPC1.

(7) In the Examples section the abbreviation Inv denotes an Inventive Example of either the VFUR e.g. InvVFUR1, or a thermosetting powder coating composition e.g. InvPCC1, or a powder coating e.g. InvPC1.

(8) In the Examples the abbreviation n.m. denotes not measured.

(9) In the Examples the abbreviation n.p.e denotes not possible to extrude.

(10) In the Examples the abbreviation n.p.g denotes not possible to grind and/or to sieve and/or to flake.

(11) In the Examples the abbreviation n.a. denotes not applicable. For Tables 5-7, most often n.a. is used when material was n.p.e. or n.p.g. and therefore no coated panels could be prepared and tested.

(12) In the Examples, the abbreviation n.a.b. denotes no amorphous unsaturated resin comprising ethylenic unsaturations and therefore no value could be given.

(13) Analytical Methods and Techniques for the Measurement of the Properties of the Unsaturated Polyester Resins Comprising Ethylenic Unsaturations and the Vinyl Functionalized Urethane Resins Used as Curing Agents in the Thermosetting Powder Coating Compositions

(14) Unless otherwise stated the theoretical number average molecular weight (M.sub.n) is defined as follows:
M.sub.n=(.sub.iN.sub.iM.sub.i)/(.sub.iNi)
where N.sub.i is the number of molecules of molecular weight M.sub.i.

(15) In the case of the UR, the M.sub.n was calculated by multiplying the targeted (theoretical) functionality (f) with 56110 and dividing the outcome thereof by the sum of the targeted (theoretical) acid value (AV) (mg KOH/g of the polyester resin) and the targeted (theoretical) hydroxyl value (OHV) (mg KOH/g of the polyester resin) according to the following equation:
M.sub.n=(56110f)/(AV+OHV)

(16) In the case of the VFUR, the M.sub.n was calculated by the following equation:

(17) $M_n=\frac{\underset{i=1}{\overset{n}{.Math.}}\left(N_i*{\mathrm{MW}}_i\right)-M_{H2O}}{N_{\mathrm{VFUR}}}$
whereas
N.sub.i=mol of each monomer used for the preparation of the VFUR;
MW.sub.i=M.sub.n (Da) of each monomer used for the preparation of the VFUR;
M.sub.H2O=mass (g) of water formed during the preparation of the VFUR;
N.sub.VFUR=mol of VFUR prepared from said monomers.

(18) In case M.sub.n refers to a monomer then the M.sub.n corresponds to molecular weight values calculated on the basis of the molecular formula of said monomer, as such calculation is known to one skilled in the art.

(19) Melt viscosity (herein mentioned as viscosity, in Pa.Math.s) measurements were carried out at 160 C. on a Brookfield CAP 2000+H Viscometer. The applied shear-rate was 70 s.sup.1 and a 19.05 mm spindle [cone spindle CAP-S-05 (19.05 mm, 1.8)] was used.

(20) The acid and hydroxyl values of the unsaturated resins comprising ethylenic unsaturations (UR) that were unsaturated polyester resins comprising 2-butenedioic acid ethylenic unsaturations, were determined titrimetrically according to ISO 2114-2000 and ISO 4629-1978; in addition the targeted (theoretical) acid and hydroxyl values of said resins were also reported herein.

(21) .sup.1H-NMR Method for the Measurement of R.sub.VFUR or R.sub.VFURC(.sup.1H-NMR Method R)

(22) The R.sub.VFUR or R.sub.VFURC was measured via .sup.1H-NMR spectroscopy according to the method entitledfor simplicity.sup.1H-NMR method R which is presented herein. The estimated margin of error of this method for determining the WPU is +/1%; the margin of error was determined on the basis of measuring three samples of the same lot of a VFUR or VFURC.

(23) a. .sup.1H-NMR Method for the Measurement of R.sub.VFUR (.sup.1H-NMR Method R.sub.VFUR)

(24) The R.sub.VFUR was measured via .sup.1H-NMR spectroscopy according to the following Formula I:
R.sub.VFUR=[peak area of the chemical shift of the urethane proton ( . . . NH . . . ) of the urethane bonds ( . . . NHC(O)O . . . ) in VFUR]/[peak area of the chemical shift of the methine proton ( . . . CH . . . ) of the vinyl groups ( . . . CHCH.sub.2) in VFUR](Formula I).

(25) According to Formula I, R.sub.VFUR has no unit.

(26) The peak areas of the urethane protons of the urethane bonds and the methine protons ( . . . CH . . . ) of the vinyl groups ( . . . CHCH.sub.2) in the VFUR of Formula I were measured as follows: A sample of 75 mg of VFUR was diluted at 40 C. in a mixture of 0.200 ml methanol and 0.600 ml deuterated chloroform containing a known amount (mg) of pyrazine as internal standard for performing .sup.1H-NMR spectroscopy. Subsequently, the .sup.1H-NMR spectrum of the VFUR sample was recorded at 40 C. on a 400 MHz NMR-spectrometer such as those made by BRUKER. Afterwards, the chemical shifts (ppm) of the urethane protons of the urethane bonds and the methine protons ( . . . CH . . . ) of the vinyl groups ( . . . CHCH.sub.2) in the VFUR were identified; the chemical shifts (ppm) of the urethane protons of the urethane bonds and the methine protons ( . . . CH . . . ) of the vinyl groups ( . . . CHCH.sub.2) in the VFUR of Formula I measured on a 400 MHz BRUKER NMR-spectrometer in methanol and deuterated chloroform were at about 5.2-6.3 and at about 6.4-6.5 ppm, respectively. Subsequently, with the help of suitable commercially available software for analyzing .sup.1H-NMR spectra such as ACD/Spectrus Processor software provided by ACD/Labs, the peak areas of the urethane protons of the urethane bonds and the methine protons ( . . . CH . . . ) of the vinyl groups ( . . . CHCH.sub.2) in the VFUR of Formula I were measured and from these values the R.sub.VFUR was determined according to Formula I.

(27) In case in which 75 mg of a VFUR is not soluble at 40 C. in a mixture of 0.200 ml methanol and 0.600 ml deuterated chloroform, then any other suitable solvent or mixture of solvents known to the skilled person for performing the .sup.1H-NMR spectroscopy may be used; for example DMSO (dimethyl sulfoxide). The choice of a suitable solvent or a mixture of suitable solvents depends on the solubility of the sample of the VFUR in said solvents. In case in which 0.75 mg of VFUR is soluble in a mixture of 0.200 ml methanol and 0.600 ml deuterated chloroform at 40 C., then this mixture of methanol and deuterated chloroform is the solvent of choice for performing the .sup.1H-NMR spectroscopy for the VFUR. In case in which a different solvent or mixture of solvents is used for performing the .sup.1H-NMR Method R.sub.VFUR, then the chemical shifts of the protons of Formula I may shift from the ones reported herein for the selected solvents for the .sup.1H-NMR Method R.sub.VFUR since the actual chemical shifts may depend on the solvent or mixture of solvents used to record the .sup.1H-NMR spectrum; in such case one should identify and determine the chemical shifts of the corresponding protons and apply Formula I for the determination of the R.sub.VFUR.

(28) b. .sup.1H-NMR Method for the Measurement of R.sub.VFURC (.sup.1H-NMR Method R.sub.VFURC)

(29) The R.sub.VFURC was measured via .sup.1H-NMR spectroscopy according to the following Formula II:
R.sub.VFURC=[peak area of the chemical shift of the urethane proton ( . . . NH . . . ) of the urethane bonds ( . . . NHC(O)O . . . ) in VFURC]/[peak area of the chemical shift of the methine proton ( . . . CH . . . ) of the vinyl groups ( . . . CHCH.sub.2) in VFURC](Formula II).

(30) According to Formula II, R.sub.VFURC has no unit.

(31) The peak areas of the urethane protons of the urethane bonds and the methine protons ( . . . CH) of the vinyl groups ( . . . CHCH.sub.2) in the VFURC of Formula II were measured as follows: A sample of 75 mg of VFURC was diluted at 40 C. in a mixture of 0.200 ml methanol and 0.600 ml deuterated chloroform containing a known amount (mg) of pyrazine as internal standard for performing .sup.1H-NMR spectroscopy. Subsequently, the .sup.1H-NMR spectrum of the VFUR sample was recorded at 40 C. on a 400 MHz BRUKER NMR-spectrometer. Afterwards, the chemical shifts (ppm) of the urethane protons of the urethane bonds and the methine protons ( . . . CH . . . ) of the vinyl groups ( . . . CHCH.sub.2) in the VFURC were identified; the chemical shifts (ppm) of the urethane protons of the urethane bonds and the methine protons ( . . . CH . . . ) of the vinyl groups ( . . . CHCH.sub.2) in the VFURC of Formula II measured on a 400 MHz BRUKER NMR-spectrometer in methanol and deuterated chloroform were at about 5.2-6.3 and at about 6.4-6.5 ppm, respectively. Subsequently, with the help of suitable commercially available software for analyzing .sup.1H-NMR spectra such as ACD/Spectrus Processor software provided by ACD/Labs, the peak areas of the urethane protons of the urethane bonds and the methine protons ( . . . CH . . . ) of the vinyl groups ( . . . CHCH.sub.2) in the VFURC of Formula II were measured and from these values the R.sub.VFUR was determined according to Formula II.

(32) In case in which 75 mg of a VFURC is not soluble at 40 C. in a mixture of 0.200 ml methanol and 0.600 ml deuterated chloroform, then any other suitable solvent or mixture of solvents known to the skilled person for performing the .sup.1H-NMR spectroscopy may be used; for example DMSO (dimethyl sulfoxide). The choice of a suitable solvent or a mixture of suitable solvents depends on the solubility of the sample of the VFURC in said solvents. In case in which 0.75 mg of VFURC is soluble in a mixture of 0.200 ml methanol and 0.600 ml deuterated chloroform at 40 C., then the mixture of methanol and deuterated chloroform is the solvent of choice for performing the .sup.1H-NMR spectroscopy for the VFURC. In case in which a different solvent or mixture of solvents is used for performing the .sup.1H-NMR Method R.sub.VFURC, then the chemical shifts of the protons of Formula II may shift from the ones reported here for the selected solvents for the .sup.1H-NMR Method R.sub.VFURC since the actual chemical shifts may depend on the solvent or mixture of solvents used to record the .sup.1H-NMR spectrum; in such case one should identify and determine the chemical shifts of the corresponding protons and apply Formula II for the determination of the R.sub.VFURC.

(33) Estimation the R.sub.VFUR of the VFUR or the R.sub.VFURC of the VFURC of the Invention a. Estimation of the R.sub.VFUR of the VFUR of the Invention

(34) A way to estimate the R.sub.VFUR of the VFUR of the invention (referred herein as theoretical R.sub.VFUR) can be done by dividing the total equivalents of urethane groups of the VFUR (which corresponds in case of compound A is an isocyanate to the total equivalents of isocyanate groups) by the total equivalents of vinyl ether groups used for the preparation of the VFUR [for examples, see Table 2, CompCC1: 5.00 equivalents of isocyanate groups (2.50 moles of 1,6-hexamethylene diisocyanate*2 equivalents isocyanate per 1,6-hexamethylene diisocyanate monomer)/5.00 equivalents of vinyl ether (5.00 moles of 4-hydroxybutyl vinyl ether*1 equivalent of vinyl ether per 4-hydroxybutyl vinyl ether molecule)=1.00].

(35) Here, it needs to be stressed out that for the purpose of the invention, the aforementioned way of estimating the R.sub.VFUR is not by any means meant to replace or substitute the method used to measure the R.sub.VFUR that is disclosed herein (see Examples, .sup.1H-NMR method R.sub.VFUR). Any R.sub.VFUR value according to the invention must be measured according to the .sup.1H-NMR Method R.sub.VFUR as it is disclosed herein.

(36) b. Estimation of the R.sub.VFURC of the VFURC of the Invention

(37) A way to estimate the R.sub.VFURC of the VFURC of the invention (referred herein as theoretical R.sub.VFURC) can be done by a calculation based on the following formula A:

(38) $\begin{array}{cc}{R}_{\mathrm{VFURC}}=\frac{\underset{i=1}{\overset{n}{.Math.}}\frac{\mathrm{Wi}*R_{\mathrm{VFURi}}}{\mathrm{WPUi}}}{\underset{i=1}{\overset{n}{.Math.}}\frac{\mathrm{Wi}}{\mathrm{WPUi}}}& \left(\mathrm{Formula}A\right)\end{array}$
wherein,
Wi is the weight of VFURi;
R.sub.VFURi is the theoretical R.sub.VFURi of VFURi;
WPUi is the theoretical WPU of VFURi;
n denotes the amount of vinyl functionalized urethane resins contained in the VFURC;
n is an integer of at least 2.
Alternatively and in case measured values of Wi, R.sub.VFURi and WPU of the VFURi are available, Formula IV may also be used as follows:
Wi is the weight of VFURi;
R.sub.VFURi is the measured R.sub.VFURi of VFURi;
WPUi is the measured WPU of VFURi;
n denotes the amount of vinyl functionalized urethane resins contained in the VFURC;
n is an integer of at least 2.
For example, in case the VFURC consists of two VFURs, a FVFUR and a SVFUR, n=2, Formula A will afford:

(39) $R_{\mathrm{VFURC}}=\frac{\underset{i=1}{\overset{2}{.Math.}}\frac{\mathrm{Wi}*R_{\mathrm{VFURi}}}{\mathrm{WPUi}}}{\underset{i=1}{\overset{2}{.Math.}}\frac{\mathrm{Wi}}{\mathrm{WPUi}}}=\frac{\left[\frac{W1*R_{\mathrm{VFUR}1}}{\mathrm{WPU}1}+\frac{W2*R_{\mathrm{VFUR}2}}{\mathrm{WPU}2}\right]}{\left[\frac{W1}{\mathrm{WPU}1}+\frac{W2}{\mathrm{WPU}2}\right]}$

(40) Here, it needs to be stressed out that for the purpose of the invention, the aforementioned way of estimating the R.sub.VFURC is (theoretical R.sub.VFURC) is not meant to replace or substitute the method used to measure the R.sub.VFURC that is disclosed herein (see Examples, .sup.1H-NMR method R.sub.VFURC); any R.sub.VFURC value according to the invention must be measured according to the .sup.1H-NMR Method R.sub.VFURC as it is disclosed herein.

(41) .sup.1H-NMR Method for the Measurement of the WPU (.sup.1H-NMR Method WPU)

(42) The WPU was measured via .sup.1H-NMR spectroscopy according to the method entitledfor simplicity.sup.1H-NMR method WPU which is presented herein. The estimated margin of error of this method for determining the WPU is +/2%; the margin of error was determined on the basis of measuring three samples of the same lot of a VFUR or VFURC or UR.

(43) More specifically, said WPU was measured via .sup.1H-NMR spectroscopy as explained herein after and it was calculated according to the following Formula III:

(44) $\begin{array}{cc}\mathrm{WPU}={\left[\frac{W_{\mathrm{pyr}}}{W_{\mathrm{resin}}}\frac{1}{{\mathrm{MW}}_{\mathrm{pyr}}}\frac{A_{c=c}/N_{c=c}}{A_{\mathrm{pyr}}/N_{\mathrm{pyr}}}\right]}^{-1}& \left(\mathrm{Formula}\mathrm{III}\right)\end{array}$
wherein,
W.sub.pyr and W.sub.resin are the weights of pyrazine (internal standard) and resin, respectively, expressed in the same units.
MW.sub.pyr is the molecular weight of the pyrazine (=80 gr/mol).
A.sub.pyr is the peak area for methine protons attached to the aromatic ring of pyrazine and
N.sub.pyr is the number of the methine protons of pyrazine (=4).

(45) In case of a VFUR:

(46) A.sub.C=C is the peak area for the methine proton ( . . . CH . . . ) of the vinyl groups ( . . . CHCH.sub.2) in the VFUR; N.sub.CC is the number of methine protons ( . . . CH . . . ) of the vinyl groups ( . . . CHCH.sub.2) in the VFUR.

(47) In case of a VFURC:

(48) A.sub.C=C is the peak area for the methine proton ( . . . CH . . . ) of the vinyl groups ( . . . CHCH.sub.2) in VFURC; N.sub.CC is the number of methine protons ( . . . CH . . . ) of the vinyl groups ( . . . CHCH.sub.2) in the VFURC.

(49) In case of a UR:

(50) A.sub.C=C is the peak area for methine protons ( . . . CH . . . ) of the ethylenic unsaturations (>CC<) of the UR; N.sub.CC is the number of methine protons ( . . . CH . . . ) attached to the ethylenic unsaturations (>CC<) of the UR.

(51) The peak areas of the methine protons of pyrazine and methine protons ( . . . CH . . . ) of the vinyl groups ( . . . CHCH.sub.2) in the VFUR of Formula III were measured as follows: A sample of 75 mg of VFUR was diluted at 40 C. in a mixture of 0.200 ml methanol and 0.600 ml deuterated chloroform containing a known amount (mg) of pyrazine as internal standard for performing .sup.1H-NMR spectroscopy. Subsequently, the .sup.1H-NMR spectrum of the VFUR sample was recorded at 40 C. on a 400 MHz BRUKER NMR-spectrometer. Afterwards, the chemical shifts (ppm) of the methine protons of pyrazine and the methine protons ( . . . CH . . . ) of the vinyl groups ( . . . CHCH.sub.2) in the VFUR were identified; the chemical shifts (ppm) of the methine protons of pyrazine and methine protons ( . . . CH . . . ) of the vinyl groups ( . . . CHCH.sub.2) in the VFUR of Formula III measured on a 400 MHz BRUKER NMR-spectrometer in methanol and deuterated chloroform were at about 8.6 and at about 6.4-6.5 ppm, respectively. Subsequently, with the help of suitable commercially available software for analyzing .sup.1H-NMR spectra such as ACD/Spectrus Processor software provided by ACD/Labs, the peak areas of the methine protons of pyrazine and methine protons ( . . . CH . . . ) of the vinyl groups ( . . . CHCH.sub.2) in the VFUR of Formula III were measured and from these values the WPU was determined according to Formula III.

(52) The peak areas of the methine protons of pyrazine and methine protons ( . . . CH . . . ) of the vinyl groups ( . . . CHCH.sub.2) in the VFURC of Formula III were measured as follows: A sample of 75 mg of VFURC was diluted at 40 C. in a mixture of 0.200 ml methanol and 0.600 ml deuterated chloroform containing a known amount (mg) of pyrazine as internal standard for performing .sup.1H-NMR spectroscopy. Subsequently, the .sup.1H-NMR spectrum of the VFURC sample was recorded at 40 C. on a 400 MHz BRUKER NMR-spectrometer. Afterwards, the chemical shifts (ppm) of the methine protons of pyrazine and the methine protons ( . . . CH . . . ) of the vinyl groups ( . . . CHCH.sub.2) in the VFURC were identified; the chemical shifts (ppm) of the methine protons of pyrazine and methine protons ( . . . CH . . . ) of the vinyl groups ( . . . CHCH.sub.2) in the VFURC of Formula III measured on a 400 MHz BRUKER NMR-spectrometer in methanol and deuterated chloroform were at about 8.6 and at about 6.4-6.5 ppm, respectively. Subsequently, with the help of suitable commercially available software for analyzing .sup.1H-NMR spectra such as ACD/Spectrus Processor software provided by ACD/Labs, The peak areas of the methine protons of pyrazine and methine protons ( . . . CH . . . ) of the vinyl groups ( . . . CHCH.sub.2) in the VFURC of Formula III were measured and from these values the WPU was determined according to Formula III.

(53) The peak areas of the methine protons of pyrazine and methine protons ( . . . CH . . . ) of the ethylenic unsaturations (>CC<) of the UR in Formula III were measured as follows: A sample of 75 mg of UR was diluted at 25 C. in 1 ml deuterated chloroform containing a known amount (mg) of pyrazine as internal standard for performing .sup.1H-NMR spectroscopy. Subsequently, the .sup.1H-NMR spectrum of the UR sample was recorded at 25 C. on a 400 MHz BRUKER NMR-spectrometer. Afterwards, the chemical shifts (ppm) of the methine protons of pyrazine and the methine protons ( . . . CH . . . ) of the ethylenic unsaturations (>CC<) of the UR were identified; the chemical shifts (ppm) of the methine protons of pyrazine and the methine protons ( . . . CH . . . ) of the ethylenic unsaturations (>CC<) of the UR in Formula III measured on a 400 MHz BRUKER NMR-spectrometer in methanol and deuterated chloroform were at about 8.6 and at about 6.4-6.5 ppm, respectively. Subsequently, with the help of suitable commercially available software for analyzing .sup.1H-NMR spectra such as ACD/Spectrus Processor software provided by ACD/Labs, the peak areas of the methine protons of pyrazine and methine protons ( . . . CH . . . ) of the ethylenic unsaturations (>CC<) of the UR of Formula III were measured and from these values the WPU was determined according to Formula III.

(54) In case in which 75 mg of a VFUR or a VFURC is not soluble at 40 C. in a mixture of 0.200 ml methanol and 0.600 ml deuterated chloroform, then any other suitable solvent or mixture of solvents known to the skilled person for performing the .sup.1H-NMR spectroscopy may be used; for example DMSO (dimethyl sulfoxide). In case in which 75 mg of a UR is not soluble at 25 C. in 1 ml of deuterated chloroform, then any other suitable solvent or mixture of solvents known to the skilled person for performing the .sup.1H-NMR spectroscopy may be used; for example DMSO (dimethyl sulfoxide). The choice of a suitable solvent or a mixture of suitable solvents depends on the solubility of the sample of the VFUR or VFURC or UR in said solvents. In case in which 0.75 mg of VFUR or VFURC is soluble in a mixture of 0.200 ml methanol and 0.600 ml deuterated chloroform at 40 C., then a mixture of methanol and deuterated chloroform is the solvent of choice for performing the .sup.1H-NMR spectroscopy for the VFUR or VFURC. In case in which 0.75 mg of UR is soluble in 1 mL of deuterated chloroform at 25 C., then deuterated chloroform is the solvent of choice for performing the .sup.1H-NMR spectroscopy for the UR. In case in which a different solvent or mixture of solvents is used for performing the .sup.1H-NMR Method WPU, then the chemical shifts of the protons of Formula III may shift from the ones reported here for the selected solvents for the .sup.1H-NMR Method WPU since the actual chemical shifts may depend on the solvent or mixture of solvents used to record the .sup.1H-NMR spectrum; in such case one should identify and determine the chemical shifts of the corresponding protons and apply Formula III for the determination of WPU.

(55) DSC method for the measurement of T.sub.g, T.sub.m, T.sub.c, H.sub.m, H.sub.c

(56) The glass transition temperature (T.sub.g) (inflection point), the crystallization temperature (T.sub.c), the crystallization enthalpy (H.sub.c), the melting temperature (T.sub.m) and the melting enthalpy (H.sub.m) were measured via Differential Scanning calorimetry (DSC) on a Mettler Toledo, TA DSC821 apparatus, in N.sub.2 atmosphere as described herein after: A sample of 10 mg was placed in the DSC apparatus. The sample was brought to 25 C. In the first heating curve, the sample was heated to 150 C. with a heating rate of 5 C./min. The sample was kept at 150 C. for 1 min. The sample was subsequently cooled to 50 C. with a cooling rate of 5 C./min, resulting in a cooling curve. After reaching 50 C. the sample was immediately heated to 150 C. with a heating rate of 5 C./min, affording a second heating curve. The T.sub.c and the H.sub.c were determined from the cooling curve (150 C. to 50 C., cooling rate 5 C./min) whereas the T.sub.g, T.sub.m and H.sub.m were determined from the second heating curve (50 C. to 150 C., heating rate of 5 C./min).

(57) Measurements and Assessment of Properties of the Thermosetting Powder Coating Compositions

(58) After extrusion the sample was evaluated on processability aspects like ease to transport between the cooling rollers and stickiness on these rollers. Also was visually evaluated whether viscosity after extrusion was not too low and whether flaking was possible. Additionally the D value, as described in the method below was taken into account. All formulations with D values of 35 C. or lower displays good processing behaviour. Good overall processing results in a very good rating, poor overall processing results in a poor rating (see Tables 5-8).

(59) All thermosetting powder coating compositions described in the Examples and shown in the relevant Tables, had a particle size lower than 90 microns.

(60) The physical powder storage stability (PPS) of the thermosetting powder coating compositions of the present invention was tested according to ISO 8130/part 8, at 25 C. for a total of 28 days. Prior to assessing the storage stability the thermosetting powder coating composition was left to cool down to room temperature for at least 2 hours. The extent of the agglomeration was visually assessed and ranked according to the following rating on a 1-10 scale [1: very poor stability (extensive agglomeration, thermosetting powder coating composition was compacted into one solid block) and 10: excellent stability (no agglomeration, free flowing powder, powder flow same as a freshly prepared thermosetting powder coating composition)]. In the context of the present invention thermosetting powder coating compositions that are rated with at least 5, are regarded as storage stable.

(61) The T.sub.g of the thermosetting powder coating composition was measured after extrusion according to the DSC method mentioned herein.

(62) Method for the Measurement of D (Method D)

(63) The measurement of D was carried out according to the following method:

(64) An amount of 0.05 g of a compressed pill of a blend of UR with either i) VFUR or ii) VFURC or iii) VFUR and VFURC (depending on the presence of VFUR and/or VFURC in the thermosetting powder coating composition; see definition of D in the description); the composition of which the D values are to measured), was inserted in a 8 mm plate-plate system (plate-plate distance=0.6 mm) of the Physica MCR301 rheometer, at a temperature of 100 C. After 5 minutes at 100 C., the sample is cooled down to 0 C., at a cooling rate of 10 C./min. This standard cooling procedure is meant to mimic the cooling procedure of a thermosetting powder coating composition leaving the extruder at a temperature of 100 C. Immediately after the cooling step, the T.sub.g achieved during cooling is measured during an heating step from 0 up to 100 C., at a heating rate of 10 C./min. While heating, the sample is subjected to a small oscillatory shear deformation (strain amplitude=0.001) at a frequency of 1 Hz, in order to monitor the loss modulus (G) as a function of temperature. The T.sub.g is defined as the temperature at which G reaches its maximum value. The margin of error of this method+/1 C. In order to rule out the influence of the measuring method on the T.sub.g value, T.sub.g's have been considered relative to the T.sub.g values of the UR, measured according to the same procedure.

(65) Since all the thermosetting powder coating compositions of the Examples comprised only one UR and one VFUR, the reported D values of the thermosetting powder coating compositions of the Examples were calculated according to the following equation: D=(T.sub.g of UR)(T.sub.g of a blend of UR with VFUR).

(66) Methods for the Measurement of Properties of the Powder Coatings Derived Upon Heat-Curing of the Thermosetting Powder Coating Compositions Prepared Herein.

(67) The propertiesas mentioned hereinof the powder coatings CompPC1-16 and InvPC1-15 derived upon heat-curing of their corresponding thermosetting powder coating compositions presented in Tables 5-7 (CompPCC1-16 and InvPCC1-15) were measured on aluminum panels (type: AL36) cured for 10 minutes at 120 C. in a convection oven or on MDF panels (type: Medite MR) cured for 5 minutes at 120 C. in a gas-catalytic IR oven by Vulcan or on Class A type sheet molding compound (known also as Class A Type SMC) as described below, cured for 10 minutes at 150 C.

(68) Film Konig hardness measurements were carried out on aluminum panels (type: AL36) according to DIN 53157 (Byk 5840 apparatus).

(69) Gloss and haze measurements were carried out on aluminum panels (type: AL36) according to ASTM-D-523/70 at 20 and 60 with a haze-gloss meter (Byk-Gardner).

(70) Smoothness (or also known in the art as flow) of powder coatings derived upon full cure of the corresponding heat-curable thermosetting powder coating compositions was determined on aluminum panels (type: AL36) by comparing the smoothness of the coating with PCI Powder Coating Smoothness panels (ACT Test Panels Inc., APR22163 (A) Batch: 50708816) at a thickness of approximately 60 m. The rating of smoothness is from 1 to 10, with 1 representing the roughest coating and 10 representing the smoothest coating. For the heat-curable thermosetting powder coating compositions of the invention, their corresponding powder coatings had smoothness equal or higher to 1, more preferably equal or higher to 2, even more preferably equal or higher to 3, most preferably equal or higher to 4, are desirable. In addition, a score of 0 corresponds to a textured surface, in other words a poorer surface than available on the reference panels.

(71) Direct impact on MDF was measured on MDF panels (type: Medite MR) by dropping a steel ball with a diameter of inch (16 mm) and a weight of 1 pound (452 gram) from a defined height. The height at which the ball is dropped is measured in inch (1 inch is 25.4 mm). The experiment is repeated by increasing the height with steps of one inch till the coating is damaged. The height at which no damage to the coating is observed when dropping the ball of 1 pound represents the maximal value in inch pound. The direct impact resistance is viewed herein as a measure of the flexibility of a powder coating.

(72) Ethanol (48 vol % ethyl alcohol) resistance (16 hr), coffee resistance (16 hr), red wine resistance (5 hr) and acetone resistance (10 sec) were carried out according to DIN 68861 1B on aluminum panels (type: AL36).

(73) The minimum depth (mm) of indentation to cause failure [commonly known also as Erichsen Slow Penetration (ESP)] was determined on aluminum panels (type: AL36) according to ISO 1520:2006 (Cupping Test, especially 7.3), 7 days after curing the panels with the heat-curable thermosetting powder coating compositions as described herein (curing conditions 120 C. for 10 min). The minimum depth of indentation to cause failure was determined. ISO 1520:2006 specifies an empirical test procedure for assessing the resistance of a coating to cracking and/or detachment from a metal substrate when subjected to gradual deformation by indentation under standard conditions. The method was carried out by gradually increasing the depth of indentation to determine the minimum depth (mm) at which the coating cracks and/or becomes detached from the substrate. The maximum of two valid measurements of the minimum depth of indentation to cause failure was reported.

(74) The adhesion was determined on MDF panels (type: Medite MR) using a cross-cut test (Gitterschnitt) in accordance with ISO 2409 (edition 3, dated 15 May 2007). The degree of adhesion of the coating onto the substrate was classified with a scale from 0 to 5; 0 means cross-cut area was not affected (excellent adhesion); 1 means that the affected cross-cut area is significantly greater than 5%; 2 means that the affected cross-cut area is significantly greater than 5% but not significantly greater than 15%; 3 means that the affected cross-cut area is significantly greater than 15% but not significantly greater than 35%; 4 means that the affected cross-cut area is significantly greater than 35% but not significantly greater than 65%; 5 means any degree of flaking that cannot even be classified by classification 4 (very poor adhesion). A skilled person will appreciate that an adhesion value of 5 or less [as measured in accordance to ISO 2409 (edition 3, dated 15 May 2007)] on any common substrate such as alumimium (AL36), MDF (type: Medite MR), SMC (Class A Type SMC as described herein) of the powder coatings of the invention, is sufficient for the powder coatings of the invention to exhibit the desired advantages described herein; thus an adhesion value as described herein of 5 or less is sufficient to achieve the objects of the invention. The powder coatings of the invention have preferably a good adhesion on MDF; by good adhesion on MDF is meant herein that the adhesion (as this is defined and measured in the Examples) of powder coatings derived upon curing of thermosetting powder coating compositions is 5 or less, preferably is 4 or less, more preferably is 3 or less, even more preferably is 2 or less, most preferably is 1 or less.

(75) The scratch resistance (in Newtons) of the powder coatings InvPC14-15 derived upon heat-curing of their corresponding thermosetting powder coating compositions presented in Table 8 (InvPCC14-15) was measured on sheet molding compounds [Class A Type SMC, prepared from resin Palapreg P 0423-02 (supplied by DSM Composite Resins) suitable for the preparation of a sheet molding compound, impregnated with glass fibers; Palapreg P 0423-02 is an unsaturated polyester resin derived from maleic acid and standard glycols, dissolved in styrene) powder coated with the InvPCC14-15 and cured for 10 minutes at 150 C. in a heated mould as described herein after. The scratch resistance was measured with the Universal Scratch Tester model 413 from Erichsen, according to EN 438-2:2005 on powder coated class A Type SMC as the latter are exemplified herein. Increasing loads are applied in specified steps to a diamond scratching point of defined geometry. The resistance to scratching of the decorative laminate sheet under test is expressed as a numerical rating which defines the maximum applied load which does not produce a continuous surface scratch. The higher the reported applied load, the better the scratch resistance. The test result is verified by visually confirming that the next higher load-step produces a continuous scratch. The definition of a scratch mark is where the contrast medium is engrained in the scratch, and is clearly visible as a line of colour contrasting with the colour of the specimen. As contrast medium black stamp pad ink was used.

(76) Unsaturated Resins Comprising Ethylenic Unsaturations: Unsaturated Polyester Resins Comprising 2-Butenedioic Acid Ethylenic Unsaturations

(77) Table 1 presents the monomers used for the preparation of the unsaturated polyester resin comprising 2-butenedioic acid ethylenic unsaturations and the properties of said resins.

(78) Amorphous (UR1-UR3 and UR5) and crystalline (UR4) unsaturated polyesters comprising 2-butenedioic acid ethylenic unsaturations were prepared.

(79) All unsaturated polyester resin comprising 2-butenedioic acid ethylenic unsaturations (UR1-UR5) prepared herein were solid at room temperature and at atmospheric pressure.

(80) Synthesis of Amorphous Unsaturated Polyester Resins Comprising 2-Butenedioic Acid Ethylenic Unsaturations (UR1-UR3 and UR5)

(81) Amorphous Unsaturated Polyester Resin Comprising 2-Butenedioic Acid Ethylenic Unsaturations UR1

(82) A reaction vessel fitted with a thermometer, a stirrer and a distillation device for the removal of water formed during the synthesis, was filled with a tin catalyst (butyl stanoic acid, 1.0 g) and the monomers for the first step (terephthalic acid (477.5 g; 2.87 mol), neopentylglycol (383.0 g; 3.68 mol) and trimethylolpropane (38.3 g; 0.29 mol) as listed in Table 1. Stirring was then applied and a light nitrogen flow was passed over the reaction mixture while the temperature was raised to 220 C. The temperature was kept at 220 C. till an acid value of approximately 10 mg KOH/g resin was reached and till no water was being released. Subsequently, the temperature was lowered to 180 C. and for the second step fumaric acid (101,2 g; 0.87 mol) together with a small amount of radical inhibitor (2-t-butylhydroquinone, 0.1 g) was added at a temperature of 180 C. followed by esterification at 205 C. When an acid value of approximately 15 mg KOH/g resin was reached and nowater was being released, the third stage of the polyester resin preparation was initiated and carried out under reduced pressure at 205 C. till an acid value of approximately 5 mg KOH/g resin was reached. Subsequently, the vacuum was removed and the temperature was lowered to 185 C.; a small amount of catalyst (tetraethyl ammonium bromide, 1,8 g) and an amount of ethylene carbonate (7.8 g) were added to the resin; the reaction between ethylene carbonate and the acid groups of the resin continued for at least 30 minutes up until the resin reached an acid and a hydroxyl value as disclosed in Table 1. Subsequently, the polyester resin was discharged onto an aluminum foil kept at room temperature.

(83) Amorphous Unsaturated Polyester Resin Comprising 2-Butenedioic Acid Ethylenic Unsaturations UR2

(84) A reaction vessel fitted with a thermometer, a stirrer and a distillation device for the removal of water formed during the synthesis, was filled with a tin catalyst (butylchlorotin dihydroxide, 0.5 g) and the monomers for the first step (terephthalic acid (468.2 g; 2.82 mol), neopentylglycol (394.3 g; 3.79 mol) and trimethylolpropane (38.3 g; 0.29 mol)) as listed in Table 1. Stirring was then applied and a light nitrogen flow was passed over the reaction mixture while the temperature was raised to 220 C. The temperature was kept at 220 C. till an acid value of less than 100 mg KOH/g resin was reached. Subsequently, the temperature was lowered to 140 C. and for the second step fumaric acid (99.2 g; 0.85 mol) together with a small amount of tin catalyst (butylchlorotindihydroxide, 0.5 g) and a radical inhibitor (2-t-butylhydroquinone, 0.1 g) were added at 140 C. followed by esterification at 215 C. When an acid value of approximately 12 mg KOH/g resin was reached and no water was being released, the temperature was lowered to 180 C. The third stage of the polyester resin preparation was carried out under reduced pressure at 180 C. till an acid and a hydroxyl value as disclosed in Table 1 were reached. Subsequently, the polyester resin was discharged onto an aluminum foil kept at room temperature.

(85) Amorphous Unsaturated Polyester Resin Comprising 2-Butenedioic Acid Ethylenic Unsaturations UR3

(86) A reaction vessel fitted with a thermometer, a stirrer and a distillation device for the removal of water formed during the synthesis, was filled with a tin catalyst (butyl stannoic acid, 1,0 g) and the monomers for the first step (isophthalic acid (281,7 g; 1.70 mol), neopentylglycol (276.8 g; 2.66 mol) and hydrogenated bisphenol A (237.7 g; 0.99 mol)) as listed in Table 1. Stirring was then applied and a light nitrogen flow was passed over the reaction mixture while the temperature was raised to 220 C. The temperature was kept at 220 C. till an acid value of approximately 5 mg KOH/g resin was reached and till no water being was released. Subsequently, the temperature was lowered to 180 C. and for the second step fumaric acid (203.8 g; 1.76 mol) together with a small amount of radical inhibitor (2-t-butylhydroquinone, 0.2 g) was added followed by esterification at 205 C. When an acid value of approximately 15 mg KOH/g resin was reached and no water was being released, the third stage of the polyester resin preparation was carried out under reduced pressure at 205 C. till an acid and a hydroxyl value as disclosed in Table 1 were reached. Subsequently, the polyester resin was discharged onto an aluminum foil kept at room temperature.

(87) Amorphous Unsaturated Polyester Resin Comprising 2-Butenedioic Acid Ethylenic Unsaturations UR5

(88) A reaction vessel fitted with a thermometer, a stirrer and a distillation device for the removal of water formed during the synthesis, was filled with a tin catalyst (butyl stannoic acid, 1,0 g) and the monomers for the first step (terephthalic acid (547.9 g; 3.30 mol), 1,2-propylene glycol (314.2 g; 4.13 mol) and trimethylolpropane (39.1 g; 0.29 mol) as listed in Table 1. Stirring was then applied and a light nitrogen flow was passed over the reaction mixture while the temperature was raised to 220 C. The temperature was kept at 220 C. till an acid value of approximately 12 mg KOH/g resin was reached and till no water was being released. Subsequently, the temperature was lowered to 180 C. and for the second step fumaric acid (98.9 g; 0.85 mol) together with a small amount of radical inhibitor (2-t-butylhydroquinone, 0.1 g) was added at a temperature of 180 C. followed by esterification at 205 C. When an acid value of approximately 15 mg KOH/g resin was reached and no water was being released, the third stage of the polyester resin preparation was carried out under reduced pressure at 205 C. till an acid value of approximately 5 mg KOH/g resin was reached. Subsequently, the vacuum was removed and the temperature was then lowered to 185 C.; at this temperature an amount of 2,3-epoxy propyl neodecanoate (20.3 g) was added to the resin; the reaction between 2,3-epoxy propyl neodecanoate and the acid groups of the resin continued for at least 30 minutes up until the resin reached an acid and a hydroxyl value as disclosed in Table 1. Subsequently, the polyester resin was discharged onto an aluminum foil kept at room temperature.

(89) Synthesis of Crystalline Unsaturated Polyester Resin Comprising 2-Butenedioic Acid Ethylenic Unsaturations (UR4)

(90) Crystalline Unsaturated Polyester Resin Comprising 2-Butenedioic Acid Ethylenic Unsaturations (UR4)

(91) A reaction vessel fitted with a thermometer, a stirrer and a distillation device for the removal of water formed during the synthesis, was filled with a tin catalyst (butyl stannoic acid, 0.4 g) and radical inhibitor (2-t-butylhydroquinone, 0.2 g) and the monomers for the first and second step (terephthalic acid (303.5 g; 1.83 mol), hexane diol (475.8 g; 4.03 mol and fumaric acid (220.7 g; 1.90 mol) as listed in Table 1. Stirring was then applied and a light nitrogen flow was passed over the reaction mixture while the temperature was raised to 225 C. and kept at 225 C. up until an acid value of approximately 12 mg KOH/g resin was reached and no water was being released; subsequently, the temperature was lowered to 180 C. The second stage of the polyester resin preparation was carried out under reduced pressure at 180 C. till an acid and a hydroxyl value as disclosed in Table 1 were reached. Subsequently, the polyester resin was discharged onto an aluminum foil kept at room temperature.

(92) Vinyl Functionalized Urethane Resins (VFUR)

(93) Amorphous and crystalline vinyl functionalized urethane resins (VFUR) were prepared and they were used as curing agents in the thermosetting powder coating compositions prepared herein.

(94) Table 2 presents the monomers used for the preparation of the comparative VFUR and the properties of said resins.

(95) Table 3 presents the monomers used for the preparation of the inventive VFUR and the properties of said resins.

(96) CompVFUR1

(97) URACROSS P3307 (supplied by DSM) was used as CompVFUR1. URACROSS P3307 is a crystalline vinyl ether functionalized urethane resin (VEFUR), solid at room temperature and at atmospheric pressure.

(98) The properties of the URACROSS P3307 were: T.sub.m=100 C.; T.sub.c=76 C.; H.sub.m=163 J/g; Theoretical WPU=200 g/mol; Theoretical M.sub.n=400 Da [this was calculated by adding up 1 mol of hexanediisocyanate (168.20 Da) with 2 mol of 4-hydroxybutyl vinyl ether (116.16 Da)];

(99) CompVFUR2-4, 8-11 and InvVFUR1-11

(100) A reaction vessel fitted with a thermometer and a stirrer, was filled with a tin catalyst (dibutyltin dilaurate, 0.1 g) and the monomers for the first step as listed in Tables 2-3. Stirring was then applied and a light nitrogen flow was passed over the reaction mixture while the temperature was raised to approximately 60 C. Subsequently, for the second step an isocyanate as listed in Tables 2-3 was dosed such that the reaction mixture was kept below 120 C. during addition. After all the isocyanate was dosed, the temperature was kept or set at 120 C. and maintained at this temperature for approximately half an hour. The temperature was kept at 120 C. and vacuum was applied to remove all volatiles. After vacuum the content of the vessel was discharged.

(101) CompVFUR5

(102) A reaction vessel fitted with a thermometer and a stirrer, was filled with a tin catalyst (dibutyltin dilaurate, 0.1 g) and hexamethylene diisocyanate as listed in Table 2. Stirring was then applied and a light nitrogen flow was passed over the reaction mixture while the temperature was raised to approximately 60 C. Subsequently, trimethylol propane, the triol, as listed in Table 2 was dosed such that the reaction mixture was kept below 65 C. during addition. After all triol was dosed, 4-hydroxybutyl vinyl ether as listed in Table 2 was dosed such that the reaction mixture was kept below 100 C. during addition.

(103) After the addition of the 4-hydroxybutyl vinyl ether was completed, the temperature was set at 120 C. and maintained at this temperature for approximately half an hour. The temperature was kept at 120 C. and vacuum was applied to remove all volatiles. After vacuum the content of the vessel was discharged.

(104) CompVFUR6-7, 12-13 and InvVFUR12

(105) A reaction vessel fitted with a thermometer, a stirrer and a distillation device for the removal of water formed during the synthesis, was filled with a tin catalyst (butyl stannoic acid, 0.5 g) and the monomers for the first step (except 4-hydroxybutyl vinyl ether) as listed in Tables 2-3. Stirring was then applied and a light nitrogen flow was passed over the reaction mixture while the temperature was raised to 220 C. The temperature was kept at 220 C. till an acid value of approximately 10 mg KOH/g resin was reached and till no water was being released. Subsequently, the temperature was lowered to 120 C. and as last monomer of the first step the 4-hydroxybutyl vinyl ether and a tin catalyst (dibutyltin dilaurate, 0.5 g) were added at a temperature of 120 C. Subsequently, for the second step the isocyanate as listed in Tables 2-3 was dosed such that the reaction mixture was kept below 120 C. during addition. After all the isocyanate was dosed, the temperature was kept or set at 120 C. and maintained at this temperature for approximately half an hour. The temperature was kept at 120 C. and vacuum was applied to remove all volatiles. After vacuum the content of the vessel was discharged.

(106) Preparation of Thermosetting Powder Coating Compositions: General Procedure

(107) The compositions of the thermosetting powder coating compositions are presented in Tables 5-7.

(108) The thermal radical initiators for example peroxides, the inhibitors and the pigments used for the preparation of the heat-curable thermosetting powder coating compositions are presented in Table 4. Luparox A75 is a dibenzoyl peroxide from Arkema, Kronos 2310 is titanium dioxide from Kronos Titan GmbH, Resiflow PV-5 is a flow control agent from Worle-Chemie GmbH and Byk 361 is a flow control agent from BYK.

(109) The thermosetting powder coating compositions were prepared by first mixing in a blender the unsaturated resin comprising ethylenic unsaturations (UR) (see PE1-PE5) and the vinyl functionalized urethane resin (VFUR) used as curing agents (see CompVFUR1-13 and InvVFUR1-12) as presented in Tables 5-8; said mixture was subsequently extruded in a PRISM TSE16 PC twin screw extruder at 120 C. with a screw speed of 200 rpm and a torque higher than 90%. The extrudate of UR and VFUR was allowed to cool to room temperature and broken into chips. Subsequently, the extrudate of UR and VFUR was mixed with the rest of the ingredients of the thermosetting powder composition presented in Tables 5-8 in a blender; subsequently, the mixture obtained was extruded in a PRISM TSE16 PC twin screw extruder at 65 C. with a screw speed of 200 rpm and a torque higher than 90%. The extrudate was allowed to cool at room temperature and broken into chips. These chips were then ground in an ultra-centrifugal mill at 14,000 rpm and sieved in a Retsch ZM100 sieve. The sieve fraction with particle size below 90 m was collected (by means of a Fritsch Analysette Spartan sieving apparatus equipped with a 90 micron sieve, sieving performed for 15 minutes at 2.5 mm amplitude) and used for further experiments.

(110) Preparation of the Powder Coatings CompPC1-16 and InvPC1-15

(111) a. Preparation of CompPC1-16 and InvPC1-15

(112) The thermosetting powder coating compositions CompPCC1-16, and InvPCC1-15 prepared herein were electrostatically sprayed (corona spray gun, 60 kV) onto on aluminum (type: AL36) and MDF (type: Medite MR) test panels to a coating thickness upon curing of approximately 60 m and cured at a temperature of 120 C. for 10 minutes in an air-circulation oven (Heraeus Instruments UT6120) (for the AL36 panels) or at a temperature of 120 C. for 5 minutes in a gas-catalytic IR (for the MDF panels) oven affording white powder coatings CompPC1-16 and InvPC1-15, respectively

(113) b. Preparation of InvPC14-15 Via Powder-in-Mould-Coating Process

(114) The thermosetting powder coating compositions InvPCC14-15 were also applied through electrostatic spraying (corona spray gun, 60 kV), as a powder to the interior wall of a (pre-heated) mould. Subsequently, a fill compound, a Class A Type SMC as described herein, is then put in the mould. The powder in mould coating was heat cured (10 minutes at 150 C.) on the hot mould and together with the Class A Type SMC as described herein (fill compound). After curing the mould was opened, and the moulded article coated with the powder coatings InvPC14 and InvPC15, respectively were obtained and removed from the mould.

(115) TABLE-US-00001 TABLE 1 Composition and characterization of unsaturated polyester resins comprising 2-butenedioic acid ethylenic unsaturations UR UR1 UR2 UR3 UR4 UR5 Monomers first step Isophthalic acid (mol) 1.70 Terephthalic acid (mol) 2.87 2.82 1.83 3.30 Neopentylglycol (mol) 3.68 3.79 2.66 Trimethylol propane (mol) 0.29 0.29 0.29 1,2-propylene glycol (mol) 4.13 Hydrogenated bisphenol A (mol) 0.99 Hexane diol (mol) 4.03 Monomers second step Fumaric acid (mol) 0.87 0.85 1.76 1.90 0.85 Total (mol) 7.71 7.74 7.10 7.75 8.57 Monomers first step Isophthalic acid (g) 281.7 Terephthalic acid (g) 477.5 468.2 303.5 547.9 Neopentylglycol (g) 383.0 394.3 276.8 Trimethylol propane (g) 38.3 38.3 39.1 1,2-propylene glycol (g) 314.2 Hydrogenated bisphenol A (g) 237.7 Hexane diol (g) 475.8 Monomers second step Fumaric acid (g) 101.2 99.2 203.8 220.7 98.9 Total weight (g) 1000.0 1000.0 1000.0 1000.0 1000.0 Water formed during synthesis (g) 133.6 132.2 123.4 134.1 148.2 Weight (g) of resin produced 866.4 867.8 876.6 865.9 851.8 Characterisation of UR Theoretical values AV (mg KOH/g UR) 1 0 4 1 1 OHV (mg KOH/g UR) 57 70 29 39 60 Functionality (f) 2.9 2.7 2.0 2.0 2.9 M.sub.n (Da) 2806 2164 3401 2792 2668 WPU (g/mol) 993 1016 499 455 1000 Measured values WPU (g/mol) 1031 1053 524 471 1028 T.sub.g ( C.) 48 48 53 n.a. 52 T.sub.c ( C.) n.a. n.a. n.a. 45 n.a. H.sub.c (J/g) n.a. n.a. n.a. 55 n.a. T.sub.m ( C.) n.a. n.a. n.a. 67 n.a. H.sub.m (J/g) n.a. n.a. n.a. 39 n.a. Viscosity (Pa .Math. s) @ 160 C. 20.4 9.1 41.1 2.2 2.7 AV (mg KOH/g UR) 0.7 5.3 4.7 1.7 1.5 OHV (mg KOH/g UR) 49.8 69.8 35.7 35.6 56.7

(116) TABLE-US-00002 TABLE 2 Composition and characterization of: i) comparative (amorphous) vinyl ether functionalized urethane resins and ii) comparative crystalline vinyl ether functionalized urethane resins having R.sub.VFUR outside the relevant claimed range. VFUR CompVFUR1 CompVFUR2 CompVFUR3 CompVFUR4 CompVFUR5 CompVFUR6 CompVFUR7 Monomers first step Isophthalic acid (mol) Terephthalic acid (mol) 2.08 Dodecane diolic acid (mol) 1.98 Ethylene glycol (mol) 3.14 Neopentylglycol (mol) Diethylene glycol (mol) 1.48 Trimethylol propane (mol) 1.01 Hydrogenated bisphenol A (mol) Hexane diol (mol) 1.45 2.71 Butane diol (mol) 1.51 4-hydroxybutyl vinyl ether (mol) 5.00 2.90 3.02 2.95 3.03 1.16 1.20 Monomers second step Toluene diisocyanate (mol) Isophorone diisocyanate (mol) Hexamethylene diisocyanate 2.50 2.90 3.02 2.95 3.03 1.19 1.20 (mol) Total (mol) 7.50 7.25 7.55 7.38 7.06 7.13 7.52 Total weight (g) 1000 1000 1000 1000 1000 1000 1000 Water formed during synthesis 0 0 0 0 0 75 71 (g) Weight (g) of resin produced 1000 1000 1000 1000 1000 925.1 928.7 RVFUR Theoretical 1.00 2.00 2.00 2.00 2.00 2.06 2.07 Measured 1.02 2.22 2.42 2.02 1.82 2.62 2.45 Characterisation of VFUR Amorphous or crystalline Cryst Cryst Cryst Cryst Cryst Cryst Cryst Theoretical values Mn (Da) 400 688 660 670 987 1600 1540 WPU (g/mol) 200 345 331 339 330 801 772 Measured values WPU (g/mol) 202 417 408 337 335 907 906 Tg ( C.) n.a. n.a. n.a. n.a. n.a. n.a. n.a. Tc ( C.) 77 100 128 65 n.a. 84 53 Hc (J/g) 157 92 141 106 n.a. 52 87 Tm ( C.) 100 120 150 108 82 119 70 Hm (J/g) 162 102 142 128 39 77 85 VFUR CompVFUR8 CompVFUR9 CompVFUR10 CompVFUR11 CompVFUR12 CompVFUR13 Monomers first step Isophthalic acid (mol) 0.39 0.84 Terephthalic acid (mol) Dodecane diolic acid (mol) Ethylene glycol (mol) Neopentylglycol (mol) 0.39 0.84 Diethylene glycol (mol) Trimethylol propane (mol) Hydrogenated bisphenol A (mol) 0.39 0.84 Hexane diol (mol) 0.46 1.25 Butane diol (mol) 4-hydroxybutyl vinyl ether (mol) 4.92 4.40 3.70 2.50 3.12 1.68 Monomers second step Toluene diisocyanate (mol) 2.46 Isophorone diisocyanate (mol) 2.20 2.31 2.50 1.95 1.68 Hexamethylene diisocyanate (mol) Total (mol) 7.38 6.60 6.47 6.25 6.25 5.89 Total weight (g) 1000 1000 1000 1000 1000 1000 Water formed during synthesis 0 0 0 0 14 30 (g) Weight (g) of resin produced 1000 1000 1000 1000 986 969.8 RVFUR Theoretical 1.00 1.00 1.25 2.00 1.25 2.00 Measured 0.99 1.01 1.29 3.56 1.63 3.29 Characterisation of VFUR Amorphous or crystalline Cryst Amorp Amorp Amorp Amorp Amorp Theoretical values M.sub.n (Da) 406 454 538 788 625 1152 WPU (g/mol) 203 227 270 400 316 576 Measured values WPU (g/mol) 197 228 288 640 294 680 Tg ( C.) n.a. 28 22 7 20 42 Tc ( C.) n.a. n.a. n.a. n.a. n.a. n.a. Hc (J/g) n.a. n.a. n.a. n.a. n.a. n.a. Tm ( C.) 57 n.a. n.a. n.a. n.a. n.a. Hm (J/g) 93 n.a. n.a. n.a. n.a. n.a.

(117) TABLE-US-00003 TABLE 3 Composition and characterization of inventive crystalline vinyl ether functionalized urethane resins VFUR InvVFUR1 InvVFUR2 InvVFUR3 InvVFUR4 InvVFUR5 InvVFUR6 Monomers first step Dodecane dioic acid (mol) Ethylene glycol (mol) Diethylene glycol (mol) Trimethylol propane (mol) Hexane diol (mol) 0.13 0.26 0.32 0.39 0.53 0.82 Butane diol (mol) 4-hydroxybutyl vinyl ether (mol) 4.83 4.60 4.53 4.42 4.22 3.81 Monomers second step Hexamethylene diisocyanate (mol) 2.52 2.56 2.58 2.60 2.64 2.72 Total (mol) 7.48 7.42 7.43 7.41 7.38 7.35 Total weight (g) 1000 1000 1000 1000 1000 1000 Water formed during synthesis (g) 0 0 0 0 0 0 Weight (g) of resin produced 1000 1000 1000 1000 1000 1000 R.sub.VFUR Theoretical 1.05 1.11 1.14 1.18 1.25 1.43 Measured 1.05 1.14 1.17 1.19 1.29 1.44 Characterisation of VFUR Amorphous or crystalline VFUR Cryst Cryst Cryst Cryst Cryst Cryst Theoretical values M.sub.n (Da) 414 430 440 450 470 520 WPU (g/mol) 207 217 221 226 237 262 Measured values WPU (g/mol) 207 218 229 237 242 270 T.sub.c ( C.) 85 84 83 83 82 78 H.sub.c (J/g) 195 182 165 172 185 176 T.sub.m ( C.) 100 98 99 98 97 97 H.sub.m (J/g) 204 184 172 179 184 177 VFUR InvVFUR7 InvVFUR8 InvVFUR9 InvVFUR10 InvVFUR11 InvVFUR12 Monomers first step Dodecane dioic acid (mol) 1.13 Ethylene glycol (mol) 1.79 Diethylene glycol (mol) 0.53 0.82 1.14 Trimethylol propane (mol) 0.56 Hexane diol (mol) Butane diol (mol) 0.54 4-hydroxybutyl vinyl ether (mol) 4.30 4.25 3.85 3.40 3.90 2.83 Monomers second step Hexamethylene diisocyanate (mol) 2.68 2.65 2.75 2.84 2.78 1.77 Total (mol) 7.51 7.44 7.42 7.38 7.24 7.52 Total weight (g) 1000 1000 1000 1000 1000 1000 Water formed during synthesis (g) 0 0 0 0 0 41 Weight (g) of resin produced 1000 1000 1000 1000 1000 959 R.sub.VFUR Theoretical 1.25 1.25 1.43 1.67 1.43 1.25 Measured 1.29 1.27 1.42 1.69 1.35 1.36 Characterisation of VFUR Amorphous or crystalline VFUR Cryst Cryst Cryst Cryst Cryst Cryst Theoretical values M.sub.n (Da) 464 468 516 580 762 675 WPU (g/mol) 233 235 260 294 256 339 Measured values WPU (g/mol) 233 233 260 290 279 366 T.sub.c ( C.) 81 74 68 66 66 61 H.sub.c (J/g) 177 161 147 124 86 99 T.sub.m ( C.) 97 91 91 89 94 74 H.sub.m (J/g) 185 165 139 124 91 102

(118) TABLE-US-00004 TABLE 4 Radical initiator, flow agents, inhibitors and pigment used for the preparation of the thermosetting powder coating compositions Chemical name Structure Commercial name Description or use Benzoyl peroxide (BPO) Luperox A75 from Arkema Radical initiator/ organic peroxide/ peranhydride Byk 361 from Byk Flowagent Resiflow PV5 from Flowagent Worle-Chemie Hydroquinone Inhibitor 2-t-butyl hydroquinone Inhibitor Titanium dioxide Kronos 2310 from White pigment Kronos Titan GmbH

(119) TABLE-US-00005 TABLE 5 Comparative thermosetting powder coating compositions and powder coatings comprising a crystalline vinyl functionalized urethane resin (VFUR) as curing agent said VFUR having R.sub.VFUR outside the relevant claimed range. CompPCC1 CompPCC2 CompPCC3 CompPCC4 CompPCC5 CompPCC6 Thermosetting powder coating composition Unsaturated resin UR1 UR5 UR1 UR1 UR1 UR1 (g) 146.7 150.0 131.5 132.8 150.0 127.8 Vinyl functionalized urethane resin CompVFUR1 CompVFUR1 CompVFUR2 CompVFUR3 CompVFUR4 CompVFUR5 (g) 29.9 30.6 45.2 43.8 50.3 48.9 Peroxide Luparox A75 (g) 11.4 11.7 11.4 11.4 12.9 11.4 Inhibitor 0.071 0.072 0.071 0.071 0.080 0.071 2-t-butylhydroquinone (g) Byk 361 (g) Flowagent Resiflow PV 5 (g) 3.53 3.61 3.53 3.53 4.01 3.53 Pigment Kronos 2310 (g) 58.3 59.6 58.3 58.3 66.1 58.3 Amorphous or crystalline VFUR Crystalline Crystalline Crystalline Crystalline Crystalline Crystalline R.sub.VFUR theoretical 1.00 1.00 2.00 2.00 2.00 2.00 R.sub.VFUR measured 1.02 1.02 2.22 2.42 2.02 1.82 Assesment of processability before, during and after extrusion Processability Poor Poor Very good Very good Very good Very good D ( C.) 39.4 41.2 18.3 18.8 22.0 28.1 TPCC properties PPS 1 month (0-10, 10 = best) 2 3 5 3 3 3 T.sub.g ( C.) 30 39 40 42 44 35 Powder coating properties CompPC1 CompPC2 CompPC3 CompPC4 CompPC5 CompPC6 Curing as mentioned in the Examples Knig hardness (sec) 186 216 n.a. n.a. 130 144 Adhesion (0-5, 0 = best) 0 n.m. 0 3 1 0 Direct impact on MDF (inch pounds) 3 2 5 4 4 4 ESP (mm) 0.9 0.6 0.6 0.8 6.3 6.4 Gloss 20 78 71 n.a. n.a. 31 59 Gloss 60 93 93 n.a. n.a. 78 92 Gloss haze 112 219 n.a. n.a. 494 341 Smoothness (1-10, 10 = best) 2 2 0 0 2 1 Ethanol resistance (1-5, 5 = best) 3 5 5 5 4 3 Coffee resistance (1-5, 5 = best) 4 4 2 2 3 2 Red Wine resistance (1-5, 5 = best) 4 4 3 3 3 3 Aceton resistance (1-5, 5 = best) 2 3 3 3 3 3 CompPCC7 CompPCC8 CompPCC9 CompPCC10 CompPCC11 Thermosetting powder coating composition Unsaturated resin UR4 UR2 UR2 UR2 UR1 (g) 173.3 135.0 120.0 138.3 146.7 Vinyl functionalized urethane resin CompVFUR1 CompVFUR6 CompVFUR7 CompVFUR1 CompVFUR8 (g) 76.7 115.0 130.0 111.7 29.9 Peroxide Luparox A75 (g) 16.1 16.1 16.1 16.1 11.4 Inhibitor 2-t-butylhydroquinone (g) 0.100 0.100 0.100 0.100 0.071 Byk 361 (g) 1.70 Flowagent Resiflow PV 5 (g) 2.50 2.50 1.70 3.53 Pigment Kronos 2310 (g) 82.5 82.5 82.5 82.5 58.3 Amorphous or crystalline VFUR Crystalline Crystalline Crystalline Crystalline Crystalline R.sub.VFUR theoretical 1.00 2.06 2.07 1.00 1.00 R.sub.VFUR measured 1.02 2.62 2.45 1.02 0.99 Assesment of processability before, during and after extrusion Processability Poor Poor Poor Poor Poor D ( C.) n.a.b. n.m. n.m. n.m. 39.8 TPCC properties PPS 1 month (0-10, 10 = best) 2 6 7 1 n.p.g. T.sub.g ( C.) 28 41 41 41 n.p.g. Powder coating properties CompPC7 CompPC8 CompPC9 CompPC10 CompPC11 Curing as mentioned in the Examples Knig hardness (sec) 175 88 25 17 n.a. Adhesion (0-5, 0 = best) 1 1 1 1 n.a. Direct impact on MDF (inch pounds) 5 14 10 12 n.a. ESP (mm) 6.6 7.4 6.5 7.0 n.a. Gloss 20 54 70 43 20 n.a. Gloss 60 88 93 78 51 n.a. Gloss haze 307 222 220 43 n.a. Smoothness (1-10, 10 = best) 3 3 6 7 n.a. Ethanol resistance (1-5, 5 = best) 3 4 3 2 n.a. Coffee resistance (1-5, 5 = best) 3 2 2 2 n.a. Red Wine resistance (1-5, 5 = best) 3 3 3 3 n.a. Aceton resistance (1-5, 5 = best) 3 2 2 2 n.a.

(120) TABLE-US-00006 TABLE 6 Comparative thermosetting powder coating compositions and their powder coatings comprising an amorphous vinyl functionalized urethane resin as curing agent. CompPCC12 CompPCC13 CompPCC14 CompPCC15 CompPCC16 Thermosetting powder coating composition Unsaturated resin UR1 UR1 UR1 UR1 UR1 (g) 141.3 141.3 150.0 150.0 112.1 Vinyl functionalized urethane resin CompVFUR9 CompVFUR10 CompVFUR11 CompVFUR12 CompVFUR13 (g) 32.1 38.0 59.1 47.0 64.6 Peroxide Luparox A75 (g) 11.2 11.6 13.5 12.7 11.4 Inhibitor 2-t-butylhydroquinone (g) 0.069 0.072 0.084 0.079 0.071 Flowagent Resiflow PV 5 (g) 3.47 3.59 4.18 3.94 3.53 Pigment Kronos 2310 (g) 57.2 59.2 69.0 65.0 58.3 Amorphous or crystalline VFUR Amorphous Amorphous Amorphous Amorphous Amorphous R.sub.VFUR theoretical 1.00 1.25 2.00 1.25 2.00 R.sub.VFUR measured 1.01 1.29 3.56 1.63 3.29 Assesment of processability before, during and after extrusion Processability n.p.e. n.p.e. n.p.e. n.p.e. Very good D ( C.) n.a. n.a. n.a. n.a. 1.9 TPCC properties PPS 1 month (0-10, 10 = best) n.a. n.a. n.a. n.a. 6 T.sub.g ( C.) n.a. n.a. n.a. n.a. 42 Powder coating properties CompPC12 CompPC13 CompPC14 CompPC15 CompPC16 Curing as mentioned in the Examples Knig hardness (sec) n.a. n.a. n.a. n.a. 204 Adhesion (0-5, 0 = best) n.a. n.a. n.a. n.a. 4 Direct impact on MDF (inch pounds) n.a. n.a. n.a. n.a. 0 ESP (mm) n.a. n.a. n.a. n.a. 0.4 Gloss 20 n.a. n.a. n.a. n.a. 21 Gloss 60 n.a. n.a. n.a. n.a. 69 Gloss haze n.a. n.a. n.a. n.a. 527 Smoothness (1-10, 10 = best) n.a. n.a. n.a. n.a. 1 Ethanol resistance (1-5, 5 = best) n.a. n.a. n.a. n.a. 3 Coffee resistance (1-5, 5 = best) n.a. n.a. n.a. n.a. 4 Red Wine resistance (1-5, 5 = best) n.a. n.a. n.a. n.a. 3 Aceton resistance (1-5, 5 = best) n.a. n.a. n.a. n.a. 3

(121) TABLE-US-00007 TABLE 7 Inventive thermosetting powder coating compositions and powder coatings comprising a crystalline vinyl functionalized urethane resin (VFUR) as curing agent, said VFUR having R.sub.VFUR within the relevant claimed range. InvPCC1 InvPCC2 InvPCC3 InvPCC4 InvPCC5 InvPCC6 InvPCC7 Thermosetting powder coating composition Unsaturated resin UR1 UR1 UR1 UR1 UR1 UR5 UR1 (g) 146.4 150.0 150.0 150.0 150.0 150.0 150.0 Vinyl functionalized urethane resin InvVFUR1 InvVFUR2 InvVFUR3 InvVFUR4 InvVFUR5 InvVFUR5 InvVFUR6 (g) 30.3 32.3 33.0 33.8 35.3 35.3 39.0 Luparox A75 (g) 11.4 11.8 11.8 11.9 12.0 12.0 12.2 2-t-butylhydroquinone (g) 0.071 0.073 0.073 0.074 0.074 0.074 0.076 Hydroquinone (g) Resiflow PV 5 (g) 3.53 3.65 3.66 3.68 3.71 3.71 3.78 Kronos 2310 (g) 58.3 60.1 60.4 60.6 61.1 61.1 62.4 Amorphous or crystalline VFUR Crystalline Crystalline Crystalline Crystalline Crystalline Crystalline Crystalline R.sub.VFUR theoretical 1.05 1.11 1.14 1.18 1.25 1.25 1.43 R.sub.VFUR measured 1.05 1.14 1.17 1.19 1.29 1.29 1.44 Assesment of processability before, during and after extrusion Processability Very good Very good Very good Very good Very good Very good Very good D ( C.) 22.4 18.8 21.3 22.3 21.8 22.8 19.8 TPCC properties PPS 1 month (0-10, 10 = best) 5 6 6 5 6 5 7 T.sub.g ( C.) 34 35 33 32 41 41 41 Powder coating properties InvPC1 InvPC2 InvPC3 InvPC4 InvPC5 InvPC6 InvPC7 Curing as mentioned in the Examples Knig hardness (sec) 185 176 181 176 174 197 64 Adhesion (0-5, 0 = best) 1 0 0 0 1 0 1 Direct impact on MDF (inch pounds) 2 6 4 3 4 2 3 ESP (mm) 7 1.9 6.2 6.5 3.5 0.4 0.4 Gloss 20 73 51 65 61 47 53 1 Gloss 60 92 89 90 91 88 91 5 Gloss haze 131 408 220 270 415 421 9 Smoothness (1-10, 10 = best) 2 3 2 2 2 2 1 Ethanol resistance (1-5, 5 = best) 3 4 4 4 4 5 5 Coffee resistance (1-5, 5 = best) 3 3 4 4 3 4 3 Red Wine resistance (1-5, 5 = best) 4 4 4 4 4 4 3 Aceton resistance (1-5, 5 = best) 2 3 3 3 3 3 3 InvPCC8 InvPCC9 InvPCC10 InvPCC11 InvPCC12 InvPCC13 InvPCC14 InvPCC15 Thermosetting powder coating composition Unsaturated resin UR1 UR1 UR1 UR1 UR1 UR2 UR3 UR3 (g) 150.0 150.0 150.0 150.0 150.0 78.5 300.0 300.0 Vinyl functionalized urethane resin InvVFUR7 InvVFUR8 InvVFUR9 InvVFUR10 InvVFUR11 InvVFUR12 InvVFUR5 InvVFUR8 (g) 34.8 35.1 38.7 43.5 38.1 26.5 129.1 128.6 Luparox A75 (g) 11.9 11.9 12.2 12.5 12.1 6.8 13.8 13.8 2-t-butylhydroquinone (g) 0.074 0.074 0.075 0.077 0.075 0.042 Hydroquinone (g) 0.300 0.300 Resiflow PV 5 (g) 3.70 3.70 3.77 3.87 3.76 2.10 8.58 8.57 Kronos 2310 (g) 61.0 61.1 62.3 63.9 62.1 34.6 128.7 128.6 Amorphous or crystalline VFUR Crystalline Crystalline Crystalline Crystalline Crystalline Crystalline Crystalline Crystalline R.sub.VFUR theoretical 1.25 1.25 1.43 1.67 1.43 1.25 1.25 1.25 R.sub.VFUR measured 1.29 1.27 1.42 1.69 1.35 1.36 1.29 1.27 Assesment of processability before, during and after extrusion Processability Very good Very good Very good Very good Very good Very good Very good Very good D ( C.) 18.9 35.0 24.3 23.3 31.9 n.m. 30.3 33.6 TPCC properties PPS 1 month (0-10, 10 = best) 7 6 6 6 5 5 8 8 T.sub.g ( C.) 40 47 41 41 32 29 42 40 Powder coating properties InvPC8 InvPC9 InvPC10 InvPC11 InvPC12 InvPC13 InvPC14 InvPC15 Curing as mentioned in the Examples Knig hardness (sec) 125 172 150 130 168 140 168 162 Adhesion (0-5, 0 = best) 1 1 1 1 1 0 1 1 Direct impact on MDF 5 6 6 6 3 2 2 2 (inch pounds) ESP (mm) 2.8 4.5 6 5.8 0.8 2 n.m. n.m. Gloss 20 6 58 63 33 71 78 57 49 Gloss 60 32 88 87 81 92 91 90 89 Gloss haze 237 228 142 469 166 82 92 200 Smoothness (1-10, 10 = best) 1 3 4 2 3 5 3 4 Ethanol resistance (1-5, 5 = best) 5 3 3 3 4 4 5 5 Coffee resistance (1-5, 5 = best) 4 4 3 3 3 3 4 4 Red Wine resistance (1-5, 5 = best) 4 3 3 3 3 3 3 3 Aceton resistance (1-5, 5 = best) 3 3 3 3 3 3 3 3

(122) TABLE-US-00008 TABLE 8 Inventive thermosetting powder coating compositions InvPCC14 and InvPCC15 and their powder coatings comprising a crystalline vinyl functionalized urethane resin (VFUR) as curing agent, said VFUR having R.sub.VFUR within the relevant claimed range; The powder coatings of these thermosetting powder coating compositions were produced as described in Examples/b. Preparation of InvPC14-15 via powder-in-mould-coating process. InvPCC14 InvPCC15 Thermosetting powder coating compositior Unsaturated resin UR3 UR3 (g) 300.0 300.0 Vinyl functionalized urethane resin InvVFUR5 InvVFUR8 (g) 129.1 128.6 Peroxide Luparox A75 (g) 13.8 13.8 Inhibitor Hydroquinone (g) 0.300 0.300 Flowagent Resiflow PV 5 (g) 8.58 8.57 Pigment Kronos 2310 (g) 128.7 128.6 Amorphous or crystalline VFUR Crystalline Crystalline RVFUR theoretical 1.25 1.25 RVFUR measured 1.29 1.27 Assesment of processability before, during and after extrusion Processability Very good Very good D ( C.) 30.3 33.6 Powder coating properties InvPC14 InvPC15 Curing a mentioned in the Examples Scratch resistance (N) 7 7

(123) Examples of crystalline vinyl functionalized urethane resins having a R.sub.VFUR outside the relevant claimed range (comparative examples) used as a curing agent in thermosetting powder coating compositions, are given Table 5. As it can be seen from the comparative Examples in Table 5 most of said comparative compositions demonstrated poor processability (CompPCC1, CompPCC2, CompPCC7-12) whilst the ones who demonstrated good processability (CompPCC3-6), had either at least poor storage stability (<5) (CompPCC4-6), or at least unacceptable smoothness (<1) (CompPCC3-4), or poor coffee resistance (<3) (CompPCC3-4 and CompPCC6). Thus, it is clear that none of the comparative Examples of Table 5 combined enhanced processability with good storage stability, good smoothness, good coffee resistance.

(124) Uracross P3307 was used as a curing agent in the comparative thermosetting powder coating compositions CompPCC1, CompPCC2, CompPCC7, CompPCC10. Uracross P3307 is an example of a crystalline solid vinyl functionalized urethane resin which is a vinyl ether terminated urethane resin that does not read on the vinyl functionalized urethane resin of the invention since it has a R.sub.VRUF equal to 1.02 that is outside the claimed range of R.sub.VRUF for the VFUR of the invention. The processability of all these comparative thermosetting powder coating compositions comprising Uracross P3307 as a curing agent was poor since upon extrusion the composition was sticky (on the cooling rollers), was difficult to flake (poor flaking) and it was hard to grind and sieve (poor grinding and sieving). In addition the storage stability of all these comparative thermosetting powder coating compositions comprising Uracross P3307 as a curing agent was poor (<5) and furthermore all these comparative compositions had a D value of higher than 35 C. Moreover, CompPCC1 and CompPCC10 failed also on acetone resistance whilst CompPCC10 failed further on coffee resistance (<3).

(125) Examples of amorphous vinyl functionalized urethane resins (comparative examples) used as a curing agent in thermosetting powder coating compositions, are given Table 6. As it can be seen from the comparative Examples in Table 6 almost all powder coatings comprising an amorphous VFUR (see CompPCC13-16) failed in processability since these compositions failed during pre-mixing, thus it was not even possible to extrude/prepare these compositions as a consequence of stickiness, flaking, grinding and sieving as well the D values were not assessed/measured; the CompPCC16 which had good processability had no flexibility (i.e., direct impact resistance equal to 0 inch pounds). Thus, it is clear that none of the comparative Examples of Table 6 combined enhanced processability with good flexibility.

(126) In addition, upon comparing the properties of the comparative thermosetting powder coating compositions and those of their corresponding powder coatings of Table 5 (comparative crystalline VFUR as explained herein) with the properties of the comparative thermosetting powder coating compositions and those of their corresponding powder coatings of Table 6 (amorphous VFUR as explained herein), it is was found that when amorphous vinyl ether functionalized urethane resins were used in thermosetting powder coating compositions said powder coating compositions and their powder coatings presented inferior coating film properties such as smoothness and/or flexibility in comparison to the coating film properties of powder coating compositions and their powder coatings obtained compositions comprising (comparative) crystalline vinyl ether functionalized urethane resins.

(127) Examples of crystalline vinyl functionalized urethane resins having a R.sub.VFUR within the relevant claimed range (inventive examples) used as a curing agent in thermosetting powder coating compositions, are given Table 7. As it can be seen from the inventive examples in Table 7, all said inventive compositions had enhanced processability, good storage stability, acceptable smoothness, good flexibility, good coffee resistance.

(128) Examples of inventive thermosetting powder coating compositions InvPCC14 and InvPCC15 and their powder coatings comprising a crystalline vinyl functionalized urethane resin (VFUR) as curing agent, said VFUR having R.sub.VFUR within the relevant claimed range are presented in Table 8. The powder coatings of these thermosetting powder coating compositions were produced as described in Examples/b. Preparation of InvPC14-15 via the powder-in-mould-coating process. As can be seen from Table 8, the inventive thermosetting powder coating compositions had good scratch resistance (>1 N).

(129) Therefore, as can be seen from the Examples in Tables 5, 6, 7 and 8, thermosetting powder coating compositions having enhanced processability, good storage stability and once cured provided powder coatings having acceptable smoothness, good flexibility, good coffee resistance, good scratch resistance, can only be prepared from a thermosetting powder coating composition comprising a VFUR and/or a VFURC according to claim 1.