Low temperature heat-curable powder coating composition comprising a crystalline polyester resin, an amorphous resin and a peroxide
View Patent ↗Heat-curable powder coating compositions are provided which include i) at least one crystalline polyester resin present in an amount of at least 7.5 wt %; ii) at least one amorphous polyester resin present in an amount of at most 92.5 wt %; and iii) at least one peroxide present in an amount of at least 0.65 parts of peroxide in hundred parts of i)+ii) (pph), wherein the at least one crystalline polyester resin has 2-butenedioic acid ethylenic unsaturations and/or the at least one amorphous polyester resin has 2-butenedioic acid ethylenic unsaturations. The compositions may be cured to an acceptable degree at low temperature, e.g., 130° C. /20 minutes offering powder coatings that may exhibit enhanced flexibility and good adhesion. In addition, the compositions can suitably be used on heat- and/or non heat-sensitive substrates, even if the composition is highly pigmented.
1. A heat-curable powder coating composition comprising:
i) at least one crystalline polyester resin present in an amount of at least 7.5 wt %;
ii) at least one amorphous polyester resin present in an amount of at most 92.5 wt % ; and
iii) at least one peroxide present in an amount of at least 0.65 parts of peroxide in hundred parts of i)+ii) (pph), wherein,
the composition contains no crosslinking agent; and wherein
the at least one crystalline polyester resin and/or the at least one amorphous polyester resin has 2-butenedioic acid ethylenic unsaturations, and wherein
the at least one crystalline polyester resin has a melting temperature (T m ) of at least 30° C. and at most 160° C., a theoretical weight per ethylenic unsaturation (WPU) of at least 250 and at most 2000 g/mol and a crystallization temperature (T c ) which is at most 55° C. lower than its Tm; and wherein
if the at least one amorphous polyester resin has 2-butenedioic acid ethylenic unsaturations, then the theoretical weight per ethylenic unsaturation (WPU) of the at least one amorphous polyester resin is at most 850 g/mol;
each of T m and T c is measured via differential scanning calorimetry (DSC); and
the wt % is based on the total amount of i)+ii); and wherein
the peroxide is at least one selected from the group consisting of:
(a) peresters and monopercarbonates according to formula (I)
wherein
R 1 represents an optionally substituted C 1-20 alkyl, a C 6-20 aryl or OR 5 , where R 5 represents an optionally substituted C 1-20 alkyl or an optionally substituted C 6-20 aryl; and
R 2 represents an optionally substituted C 1-20 alkyl or an optionally substituted C 6-20 aryl;
(b) peranhydrides of formula (II)
wherein R 3 and R 4 each independently stand for an optionally substituted C 1-20 alkyl, a C 6-20 aryl or OR 6 , wherein R 6 represents an optionally substituted C 1-10 alkyl or a C 6-20 aryl; and
(c) any combination of peroxides according to formula (I) and formula (II) thereof.
2. The composition according to claim 1 , wherein the at least one crystalline polyester resin is present in an amount of at most 85 wt % and wherein the at least one amorphous polyester resin is present in an amount of at least 15 wt %.
3. The composition according to claim 1 , wherein the at least one crystalline polyester resin is present in an amount of at least 10 and at most 40 wt % and wherein the at least one amorphous polyester resin is present in an amount of at least 60 and at most 90 wt %.
4. The composition according to claim 1 , wherein the at least one crystalline polyester resin is present in an amount of at least 17.5 and at most 50 wt % and wherein the at least one amorphous polyester resin is present in an amount of at least 50 and at most 82.5 wt %.
5. The composition according to claim 1 , wherein the at least one crystalline polyester resin is present in an amount of at least 20 and at most 50 wt % and wherein the at least one amorphous polyester resin is present in an amount of at least 50 and at most 80 wt %.
6. The composition according to claim 1 , wherein the at least one crystalline polyester resin is present in an amount of at least 20 and at most 40 wt % and wherein the at least one amorphous polyester resin is present in an amount of at least 60 and at most 80 wt %.
7. The composition according to claim 1 , wherein each of the at least one crystalline polyester resin and the at least amorphous polyester resin, have a theoretical Mn of at least 2,200 Da and at most 8,000 Da.
8. The composition according to claim 6 , wherein each of the at least one crystalline polyester resin and the at least amorphous polyester resin, have a theoretical Mn of at least 2,200 Da and at most 8,000 Da.
9. The composition according to claim 1 , wherein the at least one crystalline polyester resin and/or the at least one amorphous polyester resin has other ethylenic unsaturations based on di-acid or anhydride monomers other than 2-butenedioic acid ethylenic unsaturations.
10. The composition according to claim 7 , wherein the at least one crystalline polyester resin and/or the at least one amorphous polyester resin has other ethylenic unsaturations based on di-acid or anhydride monomers other than 2-butenedioic acid ethylenic unsaturations.
11. The composition according to claim 8 , wherein the at least one crystalline polyester resin and/or the at least one amorphous polyester resin has other ethylenic unsaturations based on di-acid or anhydride monomers other than 2-butenedioic acid ethylenic unsaturations.
12. The composition according to claim 1 , wherein each of the at least one crystalline polyester resin and the at least one amorphous polyester resin, has 2-butenedioic acid ethylenic unsaturations.
13. The composition according to claim 6 , wherein each of the at least one crystalline polyester resin and the at least one amorphous polyester resin, has 2-butenedioic acid ethylenic unsaturations.
14. The composition according to claim 7 , wherein each of the at least one crystalline polyester resin and the at least one amorphous polyester resin, has 2-butenedioic acid ethylenic unsaturations.
15. The composition according to claim 8 , wherein each of the at least one crystalline polyester resin and the at least one amorphous polyester resin, has 2-butenedioic acid ethylenic unsaturations.
16. The composition according to claim 9 , wherein each of the at least one crystalline polyester resin and the at least one amorphous polyester resin, has 2-butenedioic acid ethylenic unsaturations.
17. The composition according to claim 10 , wherein each of the at least one crystalline polyester resin and the at least one amorphous polyester resin, has 2-butenedioic acid ethylenic unsaturations.
18. The composition according to claim 11 , wherein each of the at least one crystalline polyester resin and the at least one amorphous polyester resin, has 2-butenedioic acid ethylenic unsaturations.
19. The composition according to claim 1 , wherein the peroxide is present in an amount of at least 0.8 pph.
20. The composition according to claim 6 , wherein the peroxide is present in an amount of at least 0.8 pph.
21. The composition according to claim 7 , wherein the peroxide is present in an amount of at least 0.8 pph.
22. The composition according to claim 8 , wherein the peroxide is present in an amount of at least 0.8 pph.
23. The composition according to claim 9 , wherein the peroxide is present in an amount of at least 0.8 pph.
24. The composition according to claim 10 , wherein the peroxide is present in an amount of at least 0.8 pph.
25. The composition according to claim 11 , wherein the peroxide is present in an amount of at least 0.8 pph.
26. The composition according to claim 12 , wherein the peroxide is present in an amount of at least 0.8 pph.
27. The composition according to claim 13 , wherein the peroxide is present in an amount of at least 0.8 pph.
28. The composition according to claim 14 , wherein the peroxide is present in an amount of at least 0.8 pph.
29. The composition according to claim 15 , wherein the peroxide is present in an amount of at least 0.8 pph.
30. The composition according to claim 16 , wherein the peroxide is present in an amount of at least 0.8 pph.
31. The composition according to claim 17 , wherein the peroxide is present in an amount of at least 0.8 pph.
32. The composition according to claim 18 , wherein the peroxide is present in an amount of at least 0.8 pph.
33. The composition according to claim 19 , wherein the peroxide is present in an amount of at most 10 pph.
34. The composition according to claim 20 , wherein the peroxide is present in an amount of at most 10 pph.
35. The composition according to claim 21 , wherein the peroxide is present in an amount of at most 10 pph.
36. The composition according to claim 22 , wherein the peroxide is present in an amount of at most 10 pph.
37. The composition according to claim 23 , wherein the peroxide is present in an amount of at most 10 pph.
38. The composition according to claim 24 , wherein the peroxide is present in an amount of at most 10 pph.
39. The composition according to claim 25 , wherein the peroxide is present in an amount of at most 10 pph.
40. The composition according to claim 26 , wherein the peroxide is present in an amount of at most 10 pph.
41. The composition according to claim 27 , wherein the peroxide is present in an amount of at most 10 pph.
42. The composition according to claim 28 , wherein the peroxide is present in an amount of at most 10 pph.
43. The composition according to claim 29 , wherein the peroxide is present in an amount of at most 10 pph.
44. The composition according to claim 30 , wherein the peroxide is present in an amount of at most 10 pph.
45. The composition according to claim 31 , wherein the peroxide is present in an amount of at most 10 pph.
46. The composition according to claim 32 , wherein the peroxide is present in an amount of at most 10 pph.
47. The composition according to claim 1 , wherein the composition further comprises a transition metal compound comprising a transition metal salt, a transition metal complex, or mixtures thereof, of a transition metal selected from the group consisting of Mn, Fe, Co and Cu.
48. The composition according to claim 8 , wherein the composition further comprises a transition metal compound comprising a transition metal salt, a transition metal complex, or mixtures thereof, of a transition metal selected from the group consisting of Mn, Fe, Co and Cu.
49. The composition according to claim 11 , wherein the composition further comprises a transition metal compound comprising a transition metal salt, a transition metal complex, or mixtures thereof, of a transition metal selected from the group consisting of Mn, Fe, Co and Cu.
50. The composition according to claim 18 , wherein the composition further comprises a transition metal compound comprising a transition metal salt, a transition metal complex, or mixtures thereof, of a transition metal selected from the group consisting of Mn, Fe, Co and Cu.
51. The composition according to claim 32 , wherein the composition further comprises a transition metal compound comprising a transition metal salt, a transition metal complex, or mixtures thereof, of a transition metal selected from the group consisting of Mn, Fe, Co and Cu.
52. The composition according to claim 46 , wherein the composition further comprises a transition metal compound comprising a transition metal salt, a transition metal complex, or mixtures thereof, of a transition metal selected from the group consisting of Mn, Fe, Co and Cu.
53. The composition according to claim 1 , wherein the composition further comprises an inhibitor selected from the group consisting of phenolic compounds, stable radicals, catechols, phenothiazines, hydroquinones, benzoquinones and mixtures thereof.
54. The composition according to claim 8 , wherein the composition further comprises an inhibitor selected from the group consisting of phenolic compounds, stable radicals, catechols, phenothiazines, hydroquinones, benzoquinones and mixtures thereof.
55. The composition according to claim 11 , wherein the composition further comprises an inhibitor selected from the group consisting of phenolic compounds, stable radicals, catechols, phenothiazines, hydroquinones, benzoquinones and mixtures thereof.
56. The composition according to claim 18 , wherein the composition further comprises an inhibitor selected from the group consisting of phenolic compounds, stable radicals, catechols, phenothiazines, hydroquinones, benzoquinones and mixtures thereof.
57. The composition according to claim 32 , wherein the composition further comprises an inhibitor selected from the group consisting of phenolic compounds, stable radicals, catechols, phenothiazines, hydroquinones, benzoquinones and mixtures thereof.
58. The composition according to claim 46 , wherein the composition further comprises an inhibitor selected from the group consisting of phenolic compounds, stable radicals, catechols, phenothiazines, hydroquinones, benzoquinones and mixtures thereof.
59. The composition according to claim 52 , wherein the composition further comprises an inhibitor selected from the group consisting of phenolic compounds, stable radicals, catechols, phenothiazines, hydroquinones, benzoquinones and mixtures thereof.
60. A process for the preparation of a heat-curable powder coating composition as defined in claim 1 , the process comprising the steps of:
(a) mixing the components of the heat-curable powder coating composition to obtain a premix;
(b) heating the premix in an extruder, to obtain an extrudate;
(c) cooling down the extrudate to obtain a solidified extrudate; and
(d) grinding the solidified extrudate into smaller particles to obtain the heat-curable powder coating composition.
61. A process for the preparation of a heat-curable powder coating composition as defined in claim 59 , the process comprising the steps of:
(a) mixing the components of the heat-curable powder coating composition to obtain a premix;
(b) heating the premix in an extruder, to obtain an extrudate;
(c) cooling down the extrudate to obtain a solidified extrudate; and
(d) grinding the solidified extrudate into smaller particles to obtain the heat-curable powder coating composition.
62. A process for coating a substrate comprising the steps of:
(a) applying a heat-curable powder coating composition as defined in claim 1 , to a substrate; and
(b) heating the substrate.
63. A process for coating a substrate comprising the steps of:
(a) applying a heat-curable powder coating composition as defined in claim 59 , to a substrate; and
(b) heating the substrate.
64. An at least partially cured form of a powder coating composition as defined in claim 1 .
65. An at least partially cured form of a powder coating composition as defined in claim 32 .
66. An at least partially cured form of a powder coating composition as defined in claim 46 .
67. An at least partially cured form of a powder coating composition as defined in claim 52 .
68. An at least partially cured form of a powder coating composition as defined in claim 59 .
69. A substrate that is at least partially coated with a heat-curable powder coating composition as defined in claim 1 .
70. A substrate that is at least partially coated with a heat-curable powder coating composition as defined in claim 59 .
71. A substrate that is fully or partially coated with a coating prepared from the heat-curable powder coating composition as defined in claim 1 .
72. A substrate that is fully or partially coated with a coating prepared from the heat-curable powder coating composition as defined in claim 59 .