Vinyl functionalized urethane resins for powder coating compositions
View Patent ↗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.
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 VFUR ) of urethane bonds in the VFUR to vinyl groups in the VFUR as measured by 1 H-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 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 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 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 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 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 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 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 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 VFURC ) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by 1 H-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 VFURC ) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by 1 H-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 VFURC ) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by 1 H-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 VFURC ) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by 1 H-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 VFURC ) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by 1 H-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 VFURC ) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by 1 H-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 VFURC ) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by 1 H-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 VFURC ) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by 1 H-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 VFURC ) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by 1 H-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 VFURC ) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by 1 H-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 VFURC ) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by 1 H-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 VFURC ) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by 1 H-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 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 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 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 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 VFURC ) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by 1 H-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 VFURC ) of urethane bonds in the VFURC to vinyl groups in the VFURC as measured by 1 H-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.