2K thermosetting powder coating compositions

Abstract

A thermosetting powder coating composition C (PCC C) includes a physical mixture of a thermosetting powder coating composition A (PCC A) with a separate, distinct thermosetting powder coating composition B (PCC B). Also provided are processes for making the thermosetting powder coating composition C and for coating an article with the thermosetting powder coating composition C. A cured thermosetting powder coating composition C (c-PCC C) is also provided so as to obtain articles having coated and cured thereon the thermosetting powder coating composition C. Heat-curing can occur at low temperatures. The cured c-PCC C is a powder coating having at least one desirable property such as excellent resistance to swelling, good smoothness, good chemical resistance, low gloss, and/or low yellowness.

Claims

1. A two component (2K) thermosetting powder coating composition C (PCC C) comprising a physical mixture of two different, separate and distinct thermosetting powder coating compositions A (PCC A) and B (PCC B), wherein the weight ratio R=weight PCC A/weight PCC B, is at least 0.01 and at most 99 and the total weight of the mixture of PCC A and PCC B in PCC C, is at least 10% w/w based on the total weight of PCC C, and wherein, i) PCC A comprises: A1: an unsaturated polyester resin comprising ethylenic unsaturations having a measured weight per ethylenic unsaturation (WPU) of at least 250 and at most 2200 g/mol; A2: a copolymerizable agent comprising reactive unsaturations that are different from and are capable of reacting with the ethylenic unsaturations of the unsaturated resin A1, wherein the copolymerizable agent A2 is selected from the group consisting of: a) a crystalline copolymerizable resin (CCR) having a WPU of at least 190 and at most 1500 g/mol and a M.sub.n equal to or higher than 350 Da, and b) a mixture of a crystalline copolymerizable resin (CCR) with an amorphous copolymerizable resin (ACR) wherein each of the CCR and ACR has a WPU of at least 190 and at most 1500 g/mol and a M.sub.n equal to or higher than 350 Da and wherein the mixture has a weight ratio M of weight ACR/weight CCR of at most 1; wherein the total weight of A1 and A2 in PCC A, is at least 10% w/w based on the total weight of PCC A; A3: an unsaturated monomer, in an amount of 0-0.9% w/w based on the total weight of PCC A; A4: a thermal radical initiator in an amount of at least 1 and at most 500 mmol thermally labile groups/Kg of total weight of A1 and A2, said thermal radical initiator comprising: A4-1: a peroxide selected from the group consisting of peresters, monopercarbonates and mixtures thereof, said peroxide is present in an amount of at least 1 and at most 245 mmol peroxy groups/Kg of total weight of A1 and A2; A5: a transition metal substance in an amount of 0-4.5 mmol metal/Kg of total weight of A1 and A2, said transition metal substance is selected from the group consisting of Co, Mn, Cu, Fe, V, Ti, transition metal compounds of Co, transition metal compounds of Mn, transition metal compounds of Cu, transition metal compounds of Fe, transition metal compounds of V, transition metal compounds of Ti and mixtures thereof; A6: an inhibitor in an amount of at least 13 and at most 5000 mg inhibitor/Kg of total weight of A1 and A2; and wherein ii) PCC B comprises: B1: an unsaturated polyester resin comprising ethylenic unsaturations having a WPU of at least 250 and at most 2200 g/mol; B2: copolymerizable agent comprising reactive unsaturations that are different from and are capable of reacting with the ethylenic unsaturations of the unsaturated resin B1, wherein the copolymerizable agent B2 is selected from the group consisting of: a) a crystalline copolymerizable resin (CCR) having a WPU of at least 190 and at most 1500 g/mol and a M.sub.n equal to or higher than 350 Da, and b) a mixture of a crystalline copolymerizable resin (CCR) with an amorphous copolymerizable resin (ACR) wherein each of the CCR and ACR has a WPU of at least 190 and at most 1500 g/mol and a M.sub.n equal to or higher than 350 Da and wherein the mixture has a weight ratio M of weight ACR/weight CCR of at most 1; wherein the total weight of B1 and B2 in PCC B, is at least 10% w/w based on the total weight of PCC B; B3: an unsaturated monomer, in an amount of 0-0.9% w/w based on the total weight of PCC B; B4: a thermal radical initiator in an amount of at least 1 and at most 500 mmol thermally labile groups/Kg of total weight of B1 and B2, said thermal radical initiator comprising: B4-1: a peranhydride in an amount of at least 0.5 and at most 300 mmol peroxy groups/Kg of total weight of B1 and B2; B5: a transition metal substance in an amount of at least 0.5 and at most 50 mmol metal/Kg of total weight of B1 and B2, said transition metal substance is selected from the group consisting of Co, Mn, Cu, Fe, V, Ti, transition metal compounds of Co, transition metal compounds of Mn, transition metal compounds of Cu, transition metal compounds of Fe, transition metal compounds of V, transition metal compounds of Ti and mixtures thereof; B6: an inhibitor in an amount of at least 16 and at most 5000 mg inhibitor/Kg of total weight of B1 and B2; and wherein iii) the total amount of unsaturated monomer in PCC C ranges from 0 up to 0.9% w/w based on the total weight of PCC C; and wherein iv) the total amount of thermal radical initiator in PCC C is at least 22 and at most 500 mmol thermally labile groups/kg of total weight of unsaturated resins and copolymerizable agent in PCC C; and wherein the thermally labile groups are selected from peroxy and azo groups, and wherein (v) a cured powder coating derived from PCC C on medium density fiberboard has a gloss at 60° equal to or lower than 45 as measured according to ASTM-D-523/70.

2. The PCC C according to claim 1, wherein PCC A further comprises: A7: a thiol in an amount of 0-5 mmol thiol groups/Kg of total weight of A1 and A2; and/or A8: an acetoacetamide compound in an amount of 0-200 mmol acetoacetamide compound/Kg of total weight of A1 and A2; and/or A9: a 1,2,3 trihydroxy aryl compound in an amount of 0-10 mmol 1,2,3 trihydroxy aryl compound/Kg of total weight of A1 and A2, if the A5 comprises one or both of Cu and a transition metal compound of Cu.

3. The PCC C according to claim 1 wherein PCC A further comprises: A10: a free amine in an amount such that a ratio L of mmol thermally labile groups/mmol free amine is at least 1.1, wherein the mmol thermally labile groups and the mmol free amine each refers to 1 Kg of total weight of A1 and A2.

4. The PCC C according to claim 1, wherein PCC B further comprises: B7: a thiol in an amount of 0-5 mmol thiol groups/Kg of total weight of B1 and B2; and/or B8: an acetoacetamide compound in an amount of 0-5 mmol acetoacetamide compound/Kg of total weight of B1 and B2; and/or B9: a 1,2,3 trihydroxy aryl compound in an amount of 0-5 mmol 1,2,3 trihydroxy aryl compound/Kg of total weight of B1 and B2, if B5 comprises one or both of Cu and a transition metal compound of Cu.

5. The PCC C according to claim 1, wherein PCC B further comprises: B10: a free amine in an amount such that a ratio L of mmol thermally labile groups/mmol free amine is at least 1.1, wherein the mmol thermally labile groups and the mmol free amine each refers to 1 Kg of total weight of B1 and B2.

6. The PCC C according to claim 1, wherein B4 further comprises: B4-2 a: a hydroperoxide in an amount of 0-5 mmol h-peroxy groups/Kg of total weight of B1 and B2; and/or B4-2 b: a perester in an amount 0-25 mmol p-peroxy groups/Kg of total weight of B1 and B2; and/or B4-2 c: an alkylperoxy carbonate in an amount of 0-25 mmol ac-peroxy groups/Kg of total weight of B1 and B2.

7. The PCC C according to claim 1, wherein vi) the total amount of transition metal substance in PCC C is at least 0.25 and at most 50 mmol metal/Kg of total weight of unsaturated resins and copolymerizable agent in PCC C; vii) the total amount of inhibitor in PCC C is at least 13 and at most 5000 mg inhibitor/Kg of total weight of unsaturated resins and copolymerizable agent in PCC C.

8. The PCC C according to claim 1, wherein R is at least 0.1 and at most 9.

9. The PCC C according to claim 1, wherein R is at least 0.2 and at most 4.

10. The PCC C according to claim 1, wherein a molar ratio K.sub.A of mol of the reactive unsaturations in A2/mol of the ethylenic unsaturations in A1 is at least 0.90 and at most 1.10.

11. The PCC C according to claim 1, wherein a molar ratio K.sub.B of mol of the reactive unsaturations in B2/mol of the ethylenic unsaturations in B1 is at least 0.90 and at most 1.10.

12. The PCC C according to claim 1, wherein the unsaturated resin comprising ethylenic unsaturations in A1 is an unsaturated polyester resin comprising 2-butenedioic acid ethylenic unsaturations.

13. The PCC C according to claim 1, wherein the unsaturated resin comprising ethylenic unsaturations in B1 is an unsaturated polyester resin comprising 2-butenedioic acid ethylenic unsaturations.

14. The PCC C according to claim 1 wherein the crystalline copolymerizable resin in A2 is selected from the group consisting of vinyl ether resin, vinyl ester resin, vinyl(ether-ester) resin, vinyl functionalized urethane resin and mixtures thereof.

15. The PCC C according to claim 1 wherein the crystalline copolymerizable resin in B2 is selected from the group consisting of vinyl ether resin, vinyl ester resin, vinyl(ether-ester) resin, vinyl functionalized urethane resin and mixtures thereof.

16. The PCC C according to claim 1, wherein the ratio M of each of A2 and B2 is at most 0.3.

17. The PCC C according to claim 1, wherein the total amount of transition metal substance in PCC C is at least 0.25 and at most 50 mmol metal/Kg of total weight of unsaturated resins and copolymerizable agent in PCC C; the total amount of inhibitor in PCC C is at least 13 and at most 5000 mg inhibitor/Kg of total weight of unsaturated resins and copolymerizable agent in PCC C; R is at least 0.2 and at most 4; a molar ratio K.sub.A of mol of the reactive unsaturations in A2/mol of the ethylenic unsaturations in A1 is at least 0.90 and at most 1.10; a molar ratio K.sub.B of mol of the reactive unsaturations in B2/mol of the ethylenic unsaturations in B1 is at least 0.90 and at most 1.10; the crystalline copolymerizable resin in A2 is selected from the group consisting of vinyl ether resin, vinyl ester resin, vinyl(ether-ester) resin, vinyl functionalized urethane resin and mixtures thereof; and the crystalline copolymerizable resin in B2 is selected from the group consisting of vinyl ether resin, vinyl ester resin, vinyl(ether-ester) resin, vinyl functionalized urethane resin and mixtures thereof.

18. The PCC C according to claim 1, wherein the total amount of transition metal substance in PCC C is at least 0.25 and at most 50 mmol metal/Kg of total weight of unsaturated resins and copolymerizable agent in PCC C; the total amount of inhibitor in PCC C is at least 13 and at most 5000 mg inhibitor/Kg of total weight of unsaturated resins and copolymerizable agent in PCC C; R is at least 0.2 and at most 4; a molar ratio K.sub.A of mol of the reactive unsaturations in A2/mol of the ethylenic unsaturations in A1 is at least 0.90 and at most 1.10; a molar ratio K.sub.B of mol of the reactive unsaturations in B2/mol of the ethylenic unsaturations in B1 is at least 0.90 and at most 1.10; the crystalline copolymerizable resin in A2 is selected from the group consisting of vinyl ether resin, vinyl ester resin, vinyl(ether-ester) resin, vinyl functionalized urethane resin and mixtures thereof; the crystalline copolymerizable resin in B2 is selected from the group consisting of vinyl ether resin, vinyl ester resin, vinyl(ether-ester) resin, vinyl functionalized urethane resin and mixtures thereof; and the ratio M of each of A2 and B2 is at most 0.3.

19. A process for making the thermosetting powder coating composition C (PCC C) as defined in claim 1 comprising the steps of: (a) providing the thermosetting powder coating composition A (PCC-A) and the different, separate, distinct thermosetting powder coating composition B (PCC-B); and (b) physically mixing the PCC A with the PCC B in a weight ratio R of weight PCC A/weight PCC B, that is at least 0.01 and at most 99, to obtain the PCC C.

20. A cured thermosetting powder coating composition (c-PCC C), wherein the c-PCC C is derived from the thermosetting powder coating composition C (PCC C) as defined in claim 1 which is cured to form the c-PCC C.

21. The cured thermosetting powder coating composition c-PCC C according to claim 20, wherein the cured thermosetting powder coating composition c-PCC C is a powder coating.

22. An article having a coating thereon of the thermosetting powder coating composition C (PCC-C) as defined in claim 1.

23. The article according to claim 22, 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.

24. An article having a cured coating thereon, wherein the cured coating is comprised of the c-PCC C as defined in claim 20.

25. The article according to claim 24, wherein the total amount of transition metal substance in PCC C is at least 0.25 and at most 50 mmol metal/Kg of total weight of unsaturated resins and copolymerizable agent in PCC C; the total amount of inhibitor in PCC C is at least 13 and at most 5000 mg inhibitor/Kg of total weight of unsaturated resins and copolymerizable agent in PCC C; R is at least 0.2 and at most 4; a molar ratio K.sub.A of mol of the reactive unsaturations in A2/mol of the ethylenic unsaturations in A1 is at least 0.90 and at most 1.10; a molar ratio K.sub.B of mol of the reactive unsaturations in B2/mol of the ethylenic unsaturations in B1 is at least 0.90 and at most 1.10; the crystalline copolymerizable resin in A2 is selected from the group consisting of vinyl ether resin, vinyl ester resin, vinyl(ether-ester) resin, vinyl functionalized urethane resin and mixtures thereof; and the crystalline copolymerizable resin in B2 is selected from the group consisting of vinyl ether resin, vinyl ester resin, vinyl(ether-ester) resin, vinyl functionalized urethane resin and mixtures thereof.

26. The article according to claim 24, wherein the total amount of transition metal substance in PCC C is at least 0.25 and at most 50 mmol metal/Kg of total weight of unsaturated resins and copolymerizable agent in PCC C; the total amount of inhibitor in PCC C is at least 13 and at most 5000 mg inhibitor/Kg of total weight of unsaturated resins and copolymerizable agent in PCC C; R is at least 0.2 and at most 4; a molar ratio K.sub.A of mol of the reactive unsaturations in A2/mol of the ethylenic unsaturations in A1 is at least 0.90 and at most 1.10; a molar ratio K.sub.B of mol of the reactive unsaturations in B2/mol of the ethylenic unsaturations in B1 is at least 0.90 and at most 1.10; the crystalline copolymerizable resin in A2 is selected from the group consisting of vinyl ether resin, vinyl ester resin, vinyl(ether-ester) resin, vinyl functionalized urethane resin and mixtures thereof; the crystalline copolymerizable resin in B2 is selected from the group consisting of vinyl ether resin, vinyl ester resin, vinyl(ether-ester) resin, vinyl functionalized urethane resin and mixtures thereof; and the ratio M of each of A2 and B2 is at most 0.3.

27. A process for making an article having a cured coating thereon of the thermosetting powder coating composition C (PCC C) as defined in claim 1, comprising the steps of: (a) applying the thermosetting powder coating composition C (PCC C) to an article; and (b) heating and/or radiating the PCC C for enough time and at a suitable temperature to cure the PCC C and obtain the article having the cured coating thereon.

Description

17. 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) The abbreviation PA denotes a thermosetting powder coating composition A and the abbreviation PB denotes a thermosetting powder coating composition B.

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

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

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

(7) In the Examples section the abbreviation “Comp” denotes a Comparative Example associated to either a comparative thermosetting powder coating composition e.g. CompPCC1, or to a comparative powder coating e.g. CompPC1.

(8) In the Examples section the abbreviation “Inv” denotes an Inventive Example associated to a thermosetting powder coating composition according to the invention e.g. InvPCC1, or to a powder coating e.g. InvPC1, according to the invention.

(9) In the Examples the abbreviation “n.m.” denotes “not measured”.

(10) In the Examples the abbreviation “n.a.” denotes “not applicable”.

(11) In the Examples the abbreviation “n.r.” denotes not recorded with the method applied.

(12) In the Examples the abbreviation “n.p.m.” denotes “not possible to measure”.

(13) In the numbers shown in the Tables 1-10, the decimal sign is denoted by a comma “,”. for any other number shown in the application, the decimal sign is denoted by a point “.”.

(14) Tables 3-4 present the composition and properties of comparative thermosetting powder coating compositions CompPCC1-22 and of their corresponding powder coatings.

(15) Tables 5-7 present the composition and properties of inventive thermosetting powder coating compositions InvPCC1-29 and of their corresponding powder coatings.

(16) Table 8 presents the composition and properties of inventive thermosetting powder coating compositions InvPCC30-36 and of their corresponding powder coatings.

(17) Table 9 presents the composition and properties of: i) inventive thermosetting powder coating compositions InvPCC37-38 and of their corresponding powder coatings, as well as of ii) comparative thermosetting powder coating compositions CompPCC23-24 and of their corresponding powder coatings.

(18) Table 10 presents the composition and properties of: i) inventive thermosetting powder coating compositions InvPCC39-41 and of their corresponding powder coatings as well as of ii) comparative thermosetting powder coating composition CompPCC25 and of its corresponding powder coating.

(19) 17.1 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

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

(21) In the case of the UR, the M.sub.n was calculated by multiplying the theoretical (targeted) functionality (f) with 56110 and dividing the outcome thereof by the sum of the theoretical (targeted) acid value (AV) (mg KOH/g of UR) and the theoretical (targeted) hydroxyl value (OHV) (mg KOH/g UP) according to the following equation EX1a:
M.sub.n=(56110×f)/(AV+OHV)   (EX1a)

(22) EX1a applies analogously for the calculation of the M.sub.n of any UR as described herein when the theoretical f, theoretical AV and theoretical OHV are available. If the theoretical values of AV, OHV are not available, then the M.sub.n can be calculated according to EX1a by factoring in EX1a the measured values of AV and OHV and wherein in this case f is calculated from analytical data on the chemical composition of the UR, said analytical data being obtained from analytical techniques e.g. NMR spectroscopy, well-known to one skilled in the art.

(23) In the case of the VFUR, the M.sub.n was calculated by the following equation EX1:

(24) $\begin{array}{cc}{M}_n=\frac{{.Math.}_{i=1}^n\left(N_i*{\mathrm{MW}}_i\right)-M_{H2O}}{N_{\mathrm{VFUR}}}& \left(\mathrm{EX1}\right)\end{array}$
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.

(25) EX1 applies analogously for determining the M.sub.n of any curing agent as described herein, wherein N.sub.i, MW.sub.i, M.sub.H2O, N.sub.VFUR in EX1, would stand for:

(26) N.sub.i=mol of each monomer used for the preparation of the curing agent;

(27) MW.sub.i=M.sub.n (Da) of each monomer used for the preparation of the curing agent;

(28) M.sub.H2O=mass (g) of a by-product produced during the preparation of said curing agent, for example water or alcohol e.g. methanol, ethanol, depending on the chemical composition of said curing agent;

(29) N.sub.VFUR=mol of curing agent prepared from said monomers.

(30) 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.

(31) 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.

(32) 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.

(33) 17.2 .sup.1H-NMR Method for the Measurement of the WPU (“.sup.1H-NMR Method WPU”)

(34) The WPU was measured via .sup.1H-NMR spectroscopy according to the method entitled—for 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 UR.

(35) More specifically, said WPU was measured via .sup.1H-NMR spectroscopy as explained herein after and it was calculated according to the following equation EX2:

(36) $\begin{array}{cc}\mathrm{WPU}={\left[\frac{W_{\mathrm{pyr}}}{W_{\mathrm{resin}}}\frac{1}{{\mathrm{MW}}_{\mathrm{pyr}}}\frac{A_{c=c}\text{/}{N}_{c=c}}{A_{\mathrm{pyr}}\text{/}{N}_{\mathrm{pyr}}}\right]}^{-1}& \left(\mathrm{EX2}\right)\end{array}$
wherein,
W.sub.pyr is the weight of pyrazine (internal standard),
W.sub.resin is the weight of UR such as an unsaturated polyester resin comprising 2-butenedioic acid ethylenic unsaturations, or the weight of a curing agent such as a VFUR; W.sub.pyr and W.sub.resin are expressed in the same units.
MW.sub.pyr is the molecular weight of the pyrazine (=80 Da) (internal standard).
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).

(37) In case of a VFUR:

(38) A.sub.C═C is the peak area for the methine proton ( . . . —CH═ . . . ) of the vinyl groups ( . . . —CH═CH.sub.2) in the VFUR; N.sub.C═C is the number of methine protons ( . . . —CH═ . . . ) of the vinyl groups ( . . . —CH═CH.sub.2) in the VFUR.

(39) In case of a UR:

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

(41) The peak areas of the methine protons of pyrazine and methine protons ( . . . —CH═ . . . ) of the vinyl groups ( . . . —CH═CH.sub.2) in the VFUR of Formula EX2 were measured as follows: A sample of 30 mg of VFUR was diluted at 105° C. in 0.800 ml deuterated dimethylsulfoxide 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 ( . . . —CH═CH.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 ( . . . —CH═CH.sub.2) in the VFUR of Formula EX2 measured on a 400 MHz BRUKER NMR-spectrometer deuterated dimethylsulfoxide were at about 8.6 and at about 6.4-6.9 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 ( . . . —CH═CH.sub.2) in the VFUR of Formula EX2 were measured and from these values the WPU was determined according to Formula EX2.

(42) In case in which 30 mg of a VFUR is not soluble at 105° C. in 0.800 ml deuterated dimethylsulfoxide, 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 a mixture of methanol and deuterated chloroform The choice of a suitable solvent or a mixture of suitable solvents depends on the solubility of the sample of the VFUR in said deuterated solvents. In case in which 30 mg of VFUR is soluble in a mixture of 0.800 ml deuterated dimethylsulfoxide at 105° C., then dimethylsulfoxide 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 WPU, then the chemical shifts of the protons of Formula EX2 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 EX2 for the determination of WPU.

(43) The peak areas of the methine protons of pyrazine and methine protons ( . . . —CH═ . . . ) of the ethylenic unsaturations (>C═C<) of the UR in EX2 were measured as follow: 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 (>C═C<) of the UR were identified; the chemical shifts (ppm) of the methine protons of pyrazine and the methine protons ( . . . —CH═ . . . ) of the ethylenic unsaturations (>C═C<) of the UR in EX2 measured on a 400 MHz BRUKER NMR-spectrometer in methanol and deuterated chloroform were at about 8.6 and at about 6.8-6.9 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 (>C═C<) of the UR of EX2 were measured and from these values the WPU was determined according to EX2.

(44) 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 deuterated dimethylsulfoxide, pyridine, tetra-chloro ethane, and mixtures thereof. The choice of a suitable solvent or a mixture of suitable solvents depends on the solubility of the sample of the UR in said solvents. In case in which 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 EX2 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 EX2 for the determination of WPU. 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 EX2 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 addition, one may perform the measurement at different temperature than the one disclosed herein, for example the measurement can be performed at higher temperature than the one disclosed herein in order to solubilize the sample intended to be analyzed for measuring its WPU according to this method and/or may use a lower amount of sample e.g. 25 mg, depending on the resolution of the NMR instrument; in such case one should identify and determine the chemical shifts of the corresponding protons and apply EX2 for the determination of WPU.

(45) The method—as described herein—for the measurement of the WPU of the samples mentioned in the Examples, applies analogously for any UR and any curing agent in connection with this application, taking of course into account common general knowledge in performing and analyzing results of NMR spectroscopy, the particular chemical nature of the UR or the curing agent and the skills of one skilled in the art of NMR spectroscopy; for example, the chemical shifts may be somewhat shifted from the ones disclosed herein, and/or the temperatures used to perform the measurement different e.g. higher than the ones disclosed herein, or the amount of the sample used can be lower e.g. 25 mg, depending on the resolution of the NMR instrument; in such case one should identify and determine the chemical shifts of the corresponding protons and apply EX2 for the determination of WPU.

(46) 17.3 DSC Method for the Measurement of T.sub.g, T.sub.m, T.sub.c, ΔH.sub.m, ΔH.sub.c, (Mentioned as “DSC Method”)

(47) The glass transition temperature of the inventive and comparative thermosetting powder coating compositions (T.sub.g PCC in ° C.), glass transition temperature of the UR (T.sub.g UR in ° C.), glass transition temperature of the crystalline copolymerizable resin (that is a crystalline VFUR) (T.sub.g VFUR in ° C.), the crystallization temperature (T.sub.c in ° C.), the crystallization enthalpy (ΔH.sub.c in J/g), the melting temperature (T.sub.m in ° C.), and the melting enthalpy (ΔH.sub.m in J/g) of the crystalline copolymerizable resin (that is a crystalline VFUR) were measured via Differential Scanning calorimetry (DSC) on a TA instruments DSC Q2000 apparatus, in N.sub.2 atmosphere calibrated with indium, within 24 hours from the time of preparation of the entity (freshly prepared entities) e.g. UR, VFUR, PCC C, etc., intended to be subject to this method for the measurement of any one (those applicable) of the aforementioned parameters. The processing of the signal (DSC thermogram, Heat Flow vs. Temperature) was carried out using Universal Analysis 2000 software version 4.5a provided by TA instruments, as described herein after:

(48) For the determination of the T.sub.g PCC of the inventive and comparative thermosetting powder coating compositions (InvPCC and CompPCC) a sample of 10±0.5 mg was weight and placed in the DSC cell. The sample was cooled down to −20° C. and the temperature was kept at −20° C. for 1 minute; Subsequently the sample was heated up to 200° C. at a heating rate of 5° C./minute (thermograph A). Thermograph A was used for measuring the T.sub.g PCC.

(49) For the determination of the T.sub.g UR of the UR a sample of 10±0.5 mg was weight and placed in the DSC cell. The sample was heated up to 150° C. at a heating rate of 40° C./minute. Once the sample has reached 150° C., the temperature was maintained at 150° C. for 10 minutes. Subsequently, the sample was cooled down to 0° C. at a cooling rate of 40° C./minute (thermograph B); once the sample has reached 0° C., the temperature was maintained at 0° C. for 10 minute. Subsequently, the sample was heated up to 100° C. at a heating rate of 5° C./minute (thermograph C). Thermographs A, B and C were processed as the Y axis of the thermographs representing the heat flow having exotherm up and endotherm down. Thermograph C was used to measure the T.sub.g UR.

(50) For the determination of T.sub.g VFUR, ΔH.sub.m, T.sub.m, ΔH.sub.c and T.sub.c of the crystalline copolymerizable resin, that is a VFUR, a sample of 10±0.5 mg was weighed and placed in the DSC cell. The sample was equilibrated at 25° C. for 1 minute; Subsequently the sample was heated up to 150° C. at a heating rate of 5° C./minute. Once the sample has reached 150° C., the temperature was maintained at 150° C. for 1 minute. Subsequently, the sample was cooled down to −50° C. at a cooling rate of 5° C./minute (thermograph B); once the sample has reached −50° C., the temperature was maintained at −50° C. for 1 minute. Subsequently, the sample was heated up to 150° C. at a heating rate of 5° C./minute (thermograph C) Thermographs A, B and C were processed as the Y axis of the thermographs representing the heat flow has exotherm up and endotherm down. Thermograph B was used for measuring the T.sub.g VFUR, ΔH.sub.m and T.sub.m; thermograph C was used to measure the ΔH.sub.c and T.sub.c.

(51) Each one of the T.sub.g UR, T.sub.g VFUR, T.sub.g PCC was the midpoint temperature of the temperature range over which the glass transition took place, said midpoint temperature was the point at which the curve was intersected by a line that was equidistant between the two extrapolated baselines, as defined in § 3.2 and § 3.3 in ISO 11357-2 edition 1999 Mar. 15 [for midpoint temperature see § 3.3.3 in ISO 11357-2; edition 1999 Mar. 15].

(52) The T.sub.m was measured as the temperature recorded at the minimum heat flow of the endothermic signal attributed to the melting of the sample.

(53) The ΔH.sub.m was measured as the integrated heat flow over the temperature range of the melting.

(54) The T.sub.c was measured as the temperature recorded at the maximum heat flow of the exothermic signal attributed to the crystallization of the sample.

(55) The ΔH.sub.c was measured as the integrated heat flow over the temperature range of the crystallization.

(56) The DSC Method—as described herein—for the measurement of any property measured in this section that is or may be related to the UR, applies analogously for any UR disclosed in this application.

(57) The DSC Method—as described herein—for the measurement of any property measured in this section that is or may be related to the VFUR, applies analogously for any curing agent disclosed in this application.

(58) The DSC Method—as described herein—for the measurement of any property measured in this section that is or may be related to the PCC C, applies analogously for any PCC C disclosed in this application.

(59) The DSC Method—as described herein—for the measurement of any property measured in this section that is or may be related to the PCC A or PCC B, applies analogously for any PCC A or PCC B disclosed in this application.

(60) The DSC Method described herein applies analogously for the measurement of the glass transition temperature (T.sub.g), the melting temperature (T.sub.m), the crystallization temperature (T.sub.c), the melting enthalpy (ΔH.sub.m), the crystallization enthalpy (ΔH.sub.c), in connection with any resin, any resin composition, any compound, any composition, disclosed in this application.

(61) 17.4 Method to Determine Presence of Unreacted N═C═O Groups (Free Isocyanate Groups) (Method NCO)

(62) If necessary, in order to determine any unreacted —N═C═O groups an FT-IR spectrum can be recorded on a infrared spectrometer such as the Digilab Excalibur infrared spectrometer, using a Golden gate ATR accessory from Specac. FT-IR spectra can be taken using a resolution of 4 cm.sup.−1, over a range of 700 cm.sup.−1 to 4000 cm.sup.−1 over 64 scans and processed with proper software such as the Varian Resolutions pro software version 5.1. A characteristic peak for unreacted —N═C═O groups can be found around 2250 cm.sup.−1; the presence of this peak is indicative of unreacted N═C═O groups (free isocyanate groups).

(63) 17.5 Synthesis of Unsaturated Resins Comprising Ethylenic Unsaturations Said Resins being Amorphous Unsaturated Polyester Resin Comprising 2-Butenedioic Acid Ethylenic Unsaturations

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

(65) Amorphous (UR1-UR3) unsaturated polyesters comprising 2-butenedioic acid ethylenic unsaturations were prepared.

(66) All unsaturated polyester resins comprising 2-butenedioic acid ethylenic unsaturations (UR1-UR3) prepared herein were solid at room temperature and at atmospheric pressure.

(67) Each of UR1, UR2 and UR3 contains t-butyl hydroquinone (inhibitor). This amount of inhibitor was factored in the amount of inhibitor in the thermosetting powder coating compositions that contained any one of UR1-UR3.

(68) UR1

(69) A reactor 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 g) and the monomers for the first step (isophthalic acid (320.1 g; 1.93 mol), neopentylglycol (314.5 g; 3.02 mol) and hydrogenated bisphenol A (270.1 g; 1.12 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 no water was released. Subsequently, the reaction mixture was cooled down to 180° C.; once the temperature reached 180° C. fumaric acid (231.6 g; 2.0 mol) together with a small amount of t-butyl hydroquinone (0.2 g; 0.0012 mol) was added at a temperature of 180° C. followed by esterification at 205° C. (second step). When an acid value of less than 15 mg KOH/g resin was reached and water stopped being released, the third step of the polyester preparation was carried out under reduced pressure at 205° C. till an acid value of 6.5 mg KOH/g was reached. In order to lower the acid value of the resin below 5 mgKOH/g resin, 2,3-epoxy propyl neodecanoate (7.7 g; 0.03 mol) was added to the resin in order to react with the acid groups of the resin; upon the addition of 2,3-epoxy propyl neodecanoate the reaction continued for at least 30 minutes. Subsequently, the polyester resin was discharged onto an aluminum foil kept at room temperature. The polyester resin obtained had an acid value of 4.7 mgKOH/g resin and a hydroxyl value of 35.7 mgKOH/g resin.

(70) UR2

(71) A reactor 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 g) and the monomers for the first step (terephthalic acid (631.6 g; 3.80 mol), 1,2-propylene glycol (362.2 g; 4.76 mol) and trimethylol propane (45.1 g; 0.34 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 no water was released. Subsequently, the reaction mixture was cooled down to 180° C.; once the temperature reached 180° C. fumaric acid (114.0 g; 0.98 mol) together with a small amount of t-butyl hydroquinone (0.1 g; 0.0006 mol) was added at a temperature of 180° C. followed by esterification at 205° C. (second step). When an acid value of less than 15 mg KOH/g resin was reached and water stopped being released, the third step of the polyester preparation was carried out under reduced pressure at 205° C. till an acid value of 6 mg KOH/g was reached. In order to lower the acid value of the resin below 5 mgKOH/g resin, 2,3-epoxy propyl neodecanoate (21.5 g; 0.09 mol) was added to the resin in order to react with the acid groups of the resin; upon the addition of 2,3-epoxy propyl neodecanoate the reaction continued for at least 30 minutes. Subsequently, the polyester resin was discharged onto an aluminum foil kept at room temperature. The polyester resin obtained had an acid value of 1 mgKOH/g resin and a hydroxyl value of 52.6 mgKOH/g resin.

(72) UR3

(73) A reactor 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 g) and the monomers for the first step (terephthalic acid (553.7 g; 3.33 mol), trimethylol propane (44.1 g; 0.33 mol) and neopentyl glycol (443.4 g; 4.26 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 no water was released. Subsequently, the reaction mixture was cooled down to 180° C.; once the temperature reached 180° C. fumaric acid (112.5 g; 0.92 mol) together with a small amount t-butyl hydroquinone (0.1 g; 0.0006 mol) was added at a temperature of 180° C. followed by esterification at 205° C. (second step). When an acid value of less than 15 mg KOH/g resin was reached and water stopped being released, the third step of the polyester preparation was carried out under reduced pressure at 205° C. till an acid value of 6.5 mg KOH/g was reached. In order to lower the acid value of the resin below 5 mgKOH/g resin, ethylene carbonate (5.6 g; 0.06 mol) was added to the resin in order to react with the acid groups of the resin; upon the addition of ethylene carbonate the reaction continued for at least 30 minutes. Subsequently, the polyester resin was discharged onto an aluminum foil kept at room temperature. The polyester resin obtained had an acid value of 3.1 mgKOH/g resin and a hydroxyl value of 42.7 mgKOH/g resin.

(74) 17.6 Synthesis of Vinyl Functionalized Urethane Resins Said Resins being Vinyl Ether Functionalized Urethane Resins

(75) Vinyl functionalized urethane resins (VFUR) were prepared and they were used as curing agents in the thermosetting powder coating compositions prepared herein.

(76) Table 2 presents the monomers used for the preparation of VFUR1-VFUR3 and the properties of said resins.

(77) VFUR1, VFUR2 and VFUR3 were crystalline vinyl functionalized urethane resins.

(78) VFUR1, VFUR2 and VFUR3

(79) A reaction vessel fitted with a thermometer and a stirrer, was filled with the monomers for the first step 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, for the second step an isocyanate as listed in table 2 was dosed such that the reaction mixture was kept below 120° C. during addition. After all 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 for at least half an hour to remove all volatiles. After vacuum the content of the vessel was discharged.

(80) 17.7 Preparation of Thermosetting Powder Coating Compositions: General Procedure

(81) Tables 3-10 present the compositions of the thermosetting powder coating compositions InvPCC1-41 and CompPCC1-25 along with their properties and the properties of their corresponding powder coatings which were derived upon curing of these compositions.

(82) Table A presents the chemicals used to prepare the unsaturated resins, copolymerizable agents, InvPCC1-41 and CompPCC1-25.

(83) Perkadox® L-W75 (supplied by AkzoNobel Polymer Chemicals) is a solid mixture of benzoyl peroxide and water wherein the amount of benzoyl peroxide is 75% w/w on the solid mixture; water is the carrier material for the benzoyl peroxide. Perkadox® L-W75 is viewed as a peranhydride.

(84) TC-R 3020 (supplied by AkzoNobel Polymer Chemicals; name of the product corresponds to experimental sample provided by AKZO), is a solid mixture of bis(4-methylbenzoyl) peroxide and water wherein the amount of bis(4-methylbenzoyl) peroxide is 62% w/w on the solid mixture; water is the carrier material for bis(4-methylbenzoyl) peroxide. TC-R 3020 is viewed as a peranhydride.

(85) Perkadox® CH50 (supplied by AkzoNobel Polymer Chemicals) is a solid mixture of BPO and 50% with dicyclohexyl phthalate wherein the amount of BPO is 50% w/w on the solid mixture; dicyclohexyl phthalate is the carrier material for the BPO. Perkadox® CH50 is viewed as a peranhydride.

(86) Trigonox® C-50D (supplied by AkzoNobel Polymer Chemicals) is a solid mixture of t-butyl peroxybenzoate and siliciumoxide wherein the amount of t-butyl peroxybenzoate is 50% w/w on the solid mixture; Trigonox® C-50D is viewed as a perester.

(87) Trigonox® 42S (supplied by AkzoNobel Polymer Chemicals) is a liquid mixture of t-butyl peroxy-3,5,5-trimethylhexanoate and water wherein the amount of t-butyl peroxy-3,5,5-trimethylhexanoate is 97% w/w on the liquid mixture; Trigonox® 42S is viewed as a peresters.

(88) Trigonox® 27 (supplied by AkzoNobel Polymer Chemicals) is a liquid mixture of t-butyl peroxydiethylacetate and water wherein the amount of t-butyl peroxydiethylacetate is 96% w/w on the liquid mixture; Trigonox® 27 is viewed as a perester.

(89) Trigonox® 141 (supplied by AkzoNobel Polymer Chemicals) is a liquid mixture of 2,5-Dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane and water wherein the amount of 2,5-Dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane is 90% w/w on the liquid mixture; Trigonox® 141 is viewed as a perester.

(90) Trigonox® 117 (supplied by AkzoNobel Polymer Chemicals) is a liquid mixture of t-butylperoxy 2-ethylhexyl carbonate and water wherein the amount of t-butylperoxy 2-ethylhexyl carbonate is 95% w/w on the liquid mixture; Trigonox® 117 is viewed as a monopercarbonate.

(91) Trigonox® 17 (supplied by AkzoNobel Polymer Chemicals) is a liquid mixture of Butyl 4,4-di(t-butylperoxy)valerate and water wherein the amount of butyl 4,4-di(t-butylperoxy)valerate 95% w/w on the liquid mixture; Trigonox® 17 is viewed as a perether.

(92) Trigonox® A80 (supplied by AkzoNobel Polymer Chemicals) is a liquid mixture of t-butyl hydroperoxide and water with di-t-butylperoxide wherein the amount t-butyl hydroperoxide 80% w/w on the liquid mixture; Trigonox® 17 is viewed as a hydroperoxide.

(93) Triallyl cyanurate (supplied by Sigma-Aldrich) is a crystalline unsaturated component with a theoretical WPU of 83 g/mol and a M.sub.n of 249 g/mol; triallyl cyanurate is viewed as a crystalline unsaturated monomer.

(94) Diacetone acrylamide (supplied by Alfa Aesar) is a crystalline unsaturated monomer with a theoretical WPU of 169 g/mol and a M.sub.n of 169 g/mol; diacetone acrylamide is viewed as a crystalline unsaturated monomer.

(95) Daiso DAP®-A (supplied by Daiso) is an amorphous diallyl phthalate resin with a WPU of 315 g/mol; the latter being calculated from the iodine value reported in the technical data sheet of this resin; Daiso DAP®-A is viewed as an amorphous copolymerizable resin.

(96) Uracross® P3307P is a crystalline vinyl functionalized urethane resin with a WPU of 204 g/mol and a M.sub.n of 400 g/mol; Uracross® P3307P is the commercial grade of the DSM ZW3307P shown in EP 0957 141 A1 (equivalent to U.S. Pat. No. 6,194,525 B1); Uracross® P3307P is viewed as a crystalline copolymerizable resin.

(97) Cobalt stearate (supplied by Alfa aesar) is an cobalt salt solution containing 8% w/w of cobalt; cobalt stearate is viewed as a transition metal compound.

(98) Cobalt Hex-Cem (supplied by OMG) is a mixture of cobalt 2-ethylhexanoate and white spirits, containing 10% w/w of cobalt; cobalt Hex-Cem is viewed as a transition metal compound.

(99) Manganese acetate (supplied by Sigma-Aldrich) is an manganese salt containing 23% w/w of manganese; manganese acetate is viewed as a transition metal compound.

(100) Nuodex® drycoat (supplied by Rockwood) is solution of manganese carboxylate in de-aromatized kerosene, containing 1% w/w of manganese; Nuodex® drycoat is viewed as a transition metal compound.

(101) Nuodex® Cu 8 (supplied by Rockwood) is a mixture of copper naphtenate in aliphatic hydrocarbons containing 8% w/w of copper; Nuodex® Cu 8 is viewed as a transition metal compound.

(102) Kronos® 2360 (supplied by Kronos Titan GmbH) is titanium dioxide and was used as a white pigment.

(103) t-Butyl hydroquinone (supplied by Sigma-Aldrich) was used as an inhibitor.

(104) t-Butyl catechol (supplied by Sigma-Aldrich) was used as an inhibitor.

(105) Resiflow® PV-5 (supplied by Worlée-Chemie GmbH) was used as a flow control agent.

(106) Byk0-361 (supplied by Byk) was used as a flow control agent.

(107) Martinal® ON310 (supplied by Martinswerk GmbH) is aluminum hydroxide [Al(OH).sub.3] and it was used as a filler.

(108) Benzoin (supplied by Alfa Aesar) was used as a degassing agent

(109) The thermosetting powder coating compositions PA and PB used for the Comp PCC, were prepared separately from each other.

(110) The thermosetting powder coating compositions PA and PB used for the InvPCC, were prepared separately from each other.

(111) The preparation of each of the thermosetting powder coating compositions PA and PB used for either the CompPCC or InvPCC was carried out as follows:

(112) i) the entire amount of all the unsaturated resins comprising ethylenic unsaturations (UR);

(113) ii) the entire amount of all unsaturated monomers—if present—;

(114) iii) an amount of all the copolymerizing agents (CA)—if present—, said amount being equal to 1/9 of the entire amount of all UR, and said amount observing the relevant weight ratios among the CA and among the components of each CA—if CA is a mixture itself—,

(115) were mixed in, in a blender; 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 obtained extrudate was allowed to cool to room temperature and it was broken into chips. Subsequently, the extrudate was placed in a blender, together with all the rest of the components of the thermosetting powder coating composition, including any remaining amount of CA, making the formulations as listed in Tables 3-10; subsequently, the mixture obtained was extruded in a PRISM TSE16 PC twin screw extruder at 80° C. with a screw speed of 200 rpm and a torque higher than 90%. The temperature of the extrudate exiting the extruder was approximately 85° C. The extrudate was allowed to cool at room temperature and broken into chips. After approximately 12-16 hours these chips were then ground in an ultra-centrifugal mill at 14000 rpm and sieved in a Retsch ZM100 sieve. The sieve fraction with particle size below 90 μm 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 in the Examples.

(116) Powders PA and PB prepared as mentioned herein above were mixed in a weight ratio R=1, for example 25 g of powder A and 25 g of powder B in a blender for 60 seconds to obtain CompPCC1-25, InvPCC1-31, InvPCC34-41.

(117) In the case of InvPCC32 (Table 8), powders PA and PB prepared as mentioned herein above were mixed in a weight ratio R=3, for example 37.5 g of powder A and 12.5 g of powder B in a blender for 60 seconds to obtain InvPCC32.

(118) In the case of InvPCC33 (Table 8), powders PA and PB prepared as mentioned herein above were mixed in a weight ratio R=0.33, for example 12.5 g of powder A and 37.5 g of powder B in a blender for 60 seconds to obtain InvPCC33.

(119) In the case of InvPCC30 (Table 8), in powder PA the K.sub.A=0.82 and in powder PB the K.sub.B=0.82.

(120) In the case of InvPCC31 (Table 8), in powder PA the K.sub.A=1.36 and in powder PB the K.sub.B=1.36.

(121) In the case of InvPCC34 (Table 8), in powder PA the M=0.11 and in powder PB the M=0.11.

(122) In the case of InvPCC35 (Table 8), in powder PA the M=0.33 and in powder PB the M=0.33.

(123) In the case of InvPCC36 (Table 8), in powder PA the M=0.11 and in powder PB the M=1.

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

(125) 17.8 Preparation of Powder Coatings on Aluminium Substrates

(126) The thermosetting powder coating compositions CompPCC and InvPCC alike, prepared herein, were electrostatically sprayed (corona spray gun, 60 kV) onto aluminium test panels (type AL36 test panels) at room temperature; subsequently, the coated panels were cured at 130° C. for 10 minutes in an air-circulation oven (Heraeus Instruments UT6120) affording clearcoats (non-pigmented powder coatings) or white powder coatings depending on the composition.

(127) The smoothness, chemical resistance and yellowness of powder coatings shown in the Examples were measured on the aforementioned coated aluminum substrates.

(128) The curing conditions (130° C. for 10 minutes in an air-circulation oven) were those at which the smoothness, chemical resistance and yellowness of the powder coatings were assessed.

(129) 17.9 Preparation of Powder Coatings on MDF Substrates

(130) MDF substrates (type Medite MR) was preheated at 60-70° C. using a gas catalytic IR oven from Vulcan. The thermosetting powder coating compositions CompPCC and InvPCC alike, prepared herein, were electrostatically sprayed (corona spray gun, 60 kV) onto the preheated MDF substrates at 50-60° C. Subsequently, the coated substrates were cured at at 130° C. for 3 minutes in a catalytic IR oven (Vulcan), affording clearcoats (non-pigmented powder coatings) or white powder coatings depending on the composition.

(131) The resistance to swelling and gloss 60° of powder coatings shown in the Examples were measured on the aforementioned coated MDF substrates.

(132) The curing conditions (130° C. for 3 minutes in a catalytic IR oven) were those at which the resistance to swelling and gloss 60° of the powder coatings were assessed.

(133) 17.10 Methods for the Measurement of Properties of the Powder Coatings Derived Upon Heat-Curing of the Thermosetting Powder Coating Compositions Prepared Herein

(134) The physical storage stability (PSS) of the comparative and inventive thermosetting powder coating compositions (CompPCC1-25 and InvPCC1-41) was tested at 23° C. for 7 weeks. Prior to assessing the PSS the thermosetting powder coating composition was left to cool down to room temperature for about 2-3 hours. The greater the extend of agglomeration or sintering the poorer the PSS, thus the lower its ranking according to the following scale. The extent of agglomeration was visually assessed and ranked according to the following rating on a 1-10 scale (1 representing the worst PSS and 10 the best PSS):

(135) 10: No change.

(136) 9: No agglomeration, very good fluidity.

(137) 8: No agglomeration, good fluidity.

(138) 7: Very low agglomeration; agglomeration can be dispersed by one light tap into a fine powder.

(139) 6: Very low agglomeration; agglomeration can be dispersed by several taps into a fine powder.

(140) 5: Low agglomeration; agglomeration can be dispersed by hand pressure into a fine powder.

(141) 4: Low agglomeration; agglomeration cannot be dispersed by hand pressure in a fine powder.

(142) 3: Severe agglomeration into several large lumps, material is pourable.

(143) 2: Severe agglomeration into several large lumps, material is not pourable.

(144) 1: product sintered to one lump, volume reduced.

(145) According to the invention, PSS equal or higher to 5 is desired.

(146) The coating (film) thickness of the powder coatings derived upon heat curing of the corresponding thermosetting powder coating compositions, on AL36 test panels was measured with a PosiTector 6000 coating thickness gauge from DeFelsko Corporation according to EN ISO 2808:2007. The measurement was carried out on a coated surface of the coated AL36 test panel. The film thickness of the relevant powder coatings of the Examples was 80±5 μm.

(147) The coating (film) thickness of the powder coatings derived upon heat curing of the corresponding thermosetting powder coating compositions, on MDF was measured with a Elcometer 195 Saberg Drill from Elcometer according to EN ISO 2808-5B:2007; the measurement was carried out on a coated surface of the coated MDF panel. The film thickness of the relevant powder coatings of the Examples was 100±20 micrometers.

(148) Smoothness (or also known in the art as flow) of clearcoats, or white powder coatings derived upon heat curing of the corresponding thermosetting powder coating compositions was determined by comparing the smoothness of the coating with PCI Powder Coating Smoothness panels (ACT Test Panels Inc., APR22163 (A) Batch: 50708816). The rating of smoothness is from 1 to 10, with 1 representing the roughest coating and 10 representing the smoothest coating. In addition, a ranking of <1 corresponds to a textured surface, in other words a poorer surface than available on the reference panels. According to the invention, smoothness equal or higher to 3 is desired.

(149) Gloss measurements of clearcoats, or white powder coatings—derived upon heat of the corresponding heat-curable thermosetting powder coating compositions—on MDF were accomplished according to ASTM-D-523/70 at 60° with a haze-gloss meter (Byk-Gardner). According to the invention, gloss at 60° equal to or lower than 45 (low gloss), more preferably equal to or lower than 40 (very low gloss) is desired.

(150) The yellowness (b*: chromatic value for yellow) of white powder coatings derived upon heat curing of the corresponding thermosetting powder coating compositions, was measured with the help of a colorimeter (Sheen Spectromatch Gloss Sphere) and according to ISO11664-4. The higher the b* value, the yellower the coating is. According to the invention, a b* value equal to or lower than 3 (low yellowness) is desired, preferably a b* value equal to or lower than 2,2 (very low yellowness) is desired.

(151) The chemical resistance of clearcoats or white powder coatings derived upon heat curing of the corresponding thermosetting powder coating compositions, was assessed with acetone (10 sec) and it was carried out according to DIN 68861 1B. The results were reported according to the following assessment/ranking on a scale 0-5, 5=best: 1: very poor cure: large damage of the surface, large part of the coating is dissolved, resulting in a clear difference in layer thickness between a treated spot and untreated spot on the coating 2: poor cure: small damage of the surface: this can be seen that part of the coating surface is washed away by the acetone, resulting in a feel able edge of the treated spot (in surface structure or coating thickness), or part of the coating is dissolved, resulting in small craters where one part of the dry-blended coating is dissolved. 3: cure ok: the coating is not damaged, but the treated spot is visible under several angles as a large gloss difference. 4: good cure: the spot which was in contact with acetone is only visible under a specific angle as a gloss difference. 5: perfect cure: The spot which was in contact with acetone is not visible
According to the invention, chemical resistance equal or higher than 3 is desired.

(152) The resistance to swelling of clearcoats, or white powder coatings derived upon heat curing of the corresponding thermosetting powder coating compositions, was assessed according to the following test: MDF panels having coated and cured thereon the relevant compositions of the Examples were prepared with an R2 radius on the 90° edges and coated with a powder coating and cured for 3 minutes at 130° C. A hole of Ø35 mm is drilled at a distance of 5 mm to the edge and a drill depth down to 5 mm remaining MDF thickness. (e.g. for 19 mm MDF drill depth is 14 mm). The dust is removed and the hole is completely filled with tap water at the start of test). Once the panel was prepared it was stored in an air-conditioned chamber at 6±2° C./70±5% relative humidity; refilling the hole with tapped water might be necessary after 24 hours testing. Visual inspections for cracks on the coatings due to the swelling of the MDF were carried out for up to 48 h and at the following points in time: after 2, 4, 6, 8, 24 and 48 hours from the initiation of the test. If cracks were observed at any point in time prior to any 48 h when inspections were carried out, the test was stopped. If no cracks were visible after 48 hours the test was stopped. The results were reported according to the following assessment/ranking on a scale 0-48, 48=best:

(153) 0: cracks on coating were spotted after 2 h (no resistance to swelling);

(154) 2: cracks on coating were spotted after 4 h (extremely poor resistance to swelling);

(155) 3: cracks on coating were spotted after 6 h (very poor resistance to swelling);

(156) 4: cracks on coating were spotted after 8 h (poor resistance to swelling);

(157) 12: cracks on coating were spotted after 24 h (some resistance to swelling);

(158) 24: cracks on coating were spotted after 48 h (good resistance to swelling);

(159) 48: no cracks on coating were spotted after 48 h (excellent resistance to swelling).

(160) According to the invention, excellent resistance to swelling is desired.

(161) TABLE-US-00001 TABLE A Chemicals used for the preparation of the Examples shown in Tables 1-10. Chemical name Trademark Comments Isophthalic acid n.a. dicarboxylic acid Terephthalic acid n.a. dicarboxylic acid Neopentylglycol n.a. diol Trimethylol propane n.a. triol 1,2-propylene glycol n.a. diol Hydrogenated bisphenol A n.a. diol Fumaric acid n.a. unsaturated dicarboxylic acid Hexanediol n.a. diol 4-Hydroxylbutyl vinylether n.a. hydroxylbutyl vinylether 1,6-Hexamethylene diisocyanate n.a. diisocyanate Triallyl cyanurate n.a. crystalline unsaturated monomer (Mn = 249 Da, theoretical WPU = 83); not according to the invention Diallyl phtalate resin Daiso DAP ®-A amorphous copolymerizable resin (WPU = 315) diacetone acryl amide n.a. crystalline unsaturated monomer (Mn = 169 Da, theoretical WPU = 169 g/mol); not according to the invention Vinyl functionalized urethane resin Uracross ® P3307 crystaline copolymerizable resin (Mn = 400 Da, WPU = 204 g/mol) t-butyl hydroquinone n.a. inhibitor t-butyl catechol n.a. inhibitor Titanium dioxide Kronos ® 2360 white pigment Aluminum hydroxide Martinal ® ON310 filler Polyacrylate Resiflow ® PV-5 flow control agent Acrylic copolymer Modarez ®MFP flow control agent Benzoin n.a. degassing agent bis(4-methylbenzoyl) peroxide n.a. peranhydride (abbreviated as TC-R 3020) Benzoyl peroxide Perkadox ® LW75 peranhydride Benzoyl peroxide Perkadox ® CH peranhydride Dilauroyl peroxide Laurox ® S peranhydride t-Butyl peroxy-3,5,5-trimethylhexanoate Trigonox ® 42S perester 2,5-Dimethyl-2,5- Trigonox ® 141 perester di(2-ethylhexanoylperoxy)hexane t-Butyl peroxybenzoate Trigonox ® C 50D perester t-Butyl peroxydiethylacetate Trigonox ® 27 perester t-Butylperoxy 2-ethylhexyl carbonate Trigonox ® 117 percarbonate Butyl 4,4-di(tert-butylperoxy)valerate Trigonox ® 17 perether t-butyl hydroperoxide Trigonox ® A80 hydroperoxide Cobalt stearate n.a. transition metal compound Cobalt 2-ethylhexanoate n.a. transition metal compound (known as Cobalt Hex-Cem) Manganese acetate n.a transition metal compound Copper naphtalate Nuodex ® Cu 8 transition metal compound Manganese carboxylate Nuodex ® drycoat transition metal compound

(162) TABLE-US-00002 TABLE 1 Composition and characterization of the unsaturated resins comprising ethylenic unsaturations UR1-UR3, each of which is an unsaturated polyester resin comprising 2-butenedioic acid ethylenic unsaturations. UR1 UR2 UR3 Monomers first step Isophthalic acid (mol) 1.93 Terephthalic acid (mol) 3.8 3.33 Neopentylglycol (mol) 3.02 4.26 Trimethylol propane (mol) 0.34 0.33 1,2-propylene glycol (mol) 4.76 Hydrogenated bisphenol A (mol) 1.12 Monomers second step Fumaric acid (mol) 2 0.98 0.97 Total (mol) 8.07 9.88 8.89 Monomers first step Isophthalic acid (g) 320.1 Terephthalic acid (g) 631.6 553.7 Neopentylglycol (g) 314.5 443.4 Trimethylol propane (g) 45.1 44.1 1,2-propylene glycol (g) 362.2 Hydrogenated bisphenol A (g) 270.1 Monomers second step Fumaric acid (g) 231.6 114 112.5 Total weight (g) 1136.3 1152.9 1153.7 Water formed during synthesis (g) 136.3 152.9 153.7 Weight (g) of resin produced 1000 1000 1000 Characterisation of UR Amorphous or crystalline amor- amor- amor- phous phous phous Theoretical values AV (mg KOH/g UR) 5 5 5 OHV (mg KOH/g UR) 29.9 59.9 55.3 Functionality (f) 2.0 2.8 2.9 M.sub.n (Da) 3214 2458 2723 WPU (g/mol) 500 1000 1028 Measured values WPU (g/mol) 536 1116 1130 T.sub.g (° C.) 53 55 47 Viscosity (Pa .Math. s) @ 160° C. 41.1 45.1 21.2 AV (mg KOH/g UR) 4.7 1 3.1 OHV (mg KOH/g UR) 35.7 52.6 42.7

(163) TABLE-US-00003 TABLE 2 Composition and characterization of the crystalline vinyl functionalized urethane resins VFUR1-VFUR3 used as crystalline copolymerizable resins in the Examples shown in Tables 3-10. VFUR1 VFUR2 VFUR3 Monomers first step Hexane diol (mol) 0.32 0.53 4-Hydroxylbutyl vinyl ether (mol) 5.00 4.53 4.25 Monomers second step 1,6-Hexamethylene diisocyanate (mol) 2.50 2.58 2.64 Total (mol) 7.50 7.43 7.42 Total weight of reactants (g) 1000 1000 1000 Weight (g) of VFUR produced 1000 1000 1000 Characterisation of VFUR Amorphous or crystalline crystalline crystaline crystalline Theoretical values M.sub.n (Da) 400 440 470 WPU (g/mol) 200 221 237 Measured values WPU (g/mol) 202 229 242 Tg (° C.) n.r. n.r. n.r. Tc (° C.) 77 84 81 ΔH.sub.c (J/g) 166 175 162 T.sub.m (° C.) 100 98 98 ΔH.sub.m (J/g) 165 170 165 Viscosity (Pa .Math. s) @ 160° C. <0.1 <0.1 <0.1 AV (mg KOH/g VFUR) 0 0 0 OHV (mg KOH/g VFUR) 0 0 0

(164) TABLE-US-00004 TABLE 3 Composition and properties of comparative thermosetting powder coating compositions CompPCC1-12 and of their corresponding powder coatings. CompPCC1 CompPCC2 CompPCC3 PA PB PA PB PA PB UR1 (g) 82.2 127.9 82.2 82.2 127.9 UR2 (g) 45.7 45.7 127.9 45.7 UR3 (g) VFUR1 (g) Uracross ® P3307 (g) Triallyl cyanurate (g) 9.14 9.14 9.14 9.14 9.14 9.14 Daiso DAP ®-A (g) 53 53 53 53 53 53 diacetone acrylamide (g) t-butyl hydroquinone (g) 0.04 0.04 benzoin (g) t-butyl catechol (g) Resiflow ® PV-5 (g) 3.5 3.5 perkadox CH50 (g) (peranhydride) Perkadox ® LW75 (g) (peranhydride) 1.14 1.14 1.14 1.14 1.14 1.14 Trigonox ® C 50D (g) (perester) 8 8 8 Trigonox ® 27 (g) (perester) 8 8 8 Cobalt stearate (g) 2.51 2.51 2.51 Cobalt Hex-Cem (g) Amounts (units as described in the application) of certain components in the language of the invention amount of perester and/or alkylperoxy carbonate 337 0 337 0 337 0 amount of peranhydride 20 20 20 20 20 20 amount of transition metal compound 0 22 0 22 0 22 amount of inhibitor 12 14 12 7 233 235 total amount of thermal radical initiator 188.5 188.5 188.5 Properties of the CompPCC Extrudable No No No No Yes Yes Physical storage stabillity (0-10, 10 = best) n.p.m n.p.m 1 Tg of CompPCC (° C.) 17 Properties of the CompPC Resistance to swelling (scale 0-48, 48 = best) n.p.m n.p.m 2 Smoothness (1-10 PCI, 10 = best) <1 Chemical resistance (0-5, 5 = best) 2 Gloss 60° n.p.m Yellowness (b*) n.a. CompPCC4 CompPCC5 CompPCC6 PA PB PA PB PA PB UR1 (g) 82.2 127.9 127.9 127.9 127.9 UR2 (g) 45.7 127.9 UR3 (g) VFUR1 (g) Uracross ® P3307 (g) Triallyl cyanurate (g) 9.14 9.14 9.14 9.14 Daiso DAP ®-A (g) 53 53 53 53 diacetone acrylamide (g) t-butyl hydroquinone (g) 0.04 0.04 0.04 0.04 0.04 0.04 benzoin (g) t-butyl catechol (g) Resiflow ® PV-5 (g) 3.5 3.5 3.5 3.5 3.5 3.5 perkadox CH50 (g) (peranhydride) Perkadox ® LW75 (g) (peranhydride) 1.14 1.14 1.14 1.14 1.14 1.14 Trigonox ® C 50D (g) (perester) 8 8 8 Trigonox ® 27 (g) (perester) 8 8 8 Cobalt stearate (g) 2.51 2.51 2.51 Cobalt Hex-Cem (g) Amounts (units as described in the application) of certain components in the language of the invention amount of perester and/or alkylperoxy carbonate 337 0 337 0 477 0 amount of peranhydride 20 20 20 20 28 28 amount of transition metal compound 0 22 0 22 0 31 amount of inhibitor 233 228 235 235 333 333 total amount of thermal radical initiator 188.5 188.5 266.5 Properties of the CompPCC Extrudable Yes Yes Yes Yes Yes Yes Physical storage stabillity (0-10, 10 = best) 1 1 3 Tg of CompPCC (° C.) 18 18 36 Properties of the CompPC Resistance to swelling (scale 0-48, 48 = best) 4 2 2 Smoothness (1-10 PCI, 10 = best) <1 <1 <1 Chemical resistance (0-5, 5 = best) 3 3 2 Gloss 60° n.p.m n.p.m n.p.m Yellowness (b*) n.a. n.a. n.a. CompPCC7 CompPCC8 CompPCC9 PA PB PA PB PA PB UR1 (g) 127.9 127.9 127.9 127.9 UR2 (g) UR3 (g) 127 127 VFUR1 (g) Uracross ® P3307 (g) 6.7 6.7 Triallyl cyanurate (g) 9.14 9.14 Daiso DAP ®-A (g) 53 53 diacetone acrylamide (g) t-butyl hydroquinone (g) 0.04 0.04 0.04 0.04 benzoin (g) 0.7 0.7 t-butyl catechol (g) 0.015 0.015 Resiflow ® PV-5 (g) 3.5 3.5 3.5 3.5 perkadox CH50 (g) (peranhydride) Perkadox ® LW75 (g) (peranhydride) 1.14 1.14 1.14 1.14 Trigonox ® C 50D (g) (perester) 8 8 5 Trigonox ® 27 (g) (perester) 8 8 Cobalt stearate (g) 2.51 2.51 Cobalt Hex-Cem (g) 0.28 Amounts (units as described in the application) of certain components in the language of the invention amount of perester and/or alkylperoxy carbonate 477 0 337 0 96 0 amount of peranhydride 28 28 20 20 0 0 amount of transition metal compound 0 31 0 22 0 4 amount of inhibitor 333 333 235 235 128 128 total amount of thermal radical initiator 266.5 188.5 48 Properties of the CompPCC Extrudable Yes Yes Yes Yes Yes Yes Physical storage stabillity (0-10, 10 = best) 1 3 7 Tg of CompPCC (° C.) 18 31 36 Properties of the CompPC Resistance to swelling (scale 0-48, 48 = best) 2 4 4 Smoothness (1-10 PCI, 10 = best) <1 <1 1 Chemical resistance (0-5, 5 = best) 2 2 2 Gloss 60° n.p.m n.p.m 27 Yellowness (b*) n.a. n.a. n.a. CompPCC10 CompPCC11 CompPCC12 PA PB PA PB PA PB UR1 (g) 82.2 127.9 82.2 UR2 (g) 45.7 45.7 127.9 42.7 42.7 UR3 (g) 127.9 127.9 VFUR1 (g) 52.5 52.5 52.5 52.5 Uracross ® P3307 (g) Triallyl cyanurate (g) Daiso DAP ®-A (g) 77.4 77.4 diacetone acrylamide (g) 90.3 90.3 t-butyl hydroquinone (g) 0.04 0.04 0.04 0.04 benzoin (g) t-butyl catechol (g) 0.027 0.027 Resiflow ® PV-5 (g) 3.5 3.5 3.5 3.5 perkadox CH50 (g) (peranhydride) 1.9 1.9 Perkadox ® LW75 (g) (peranhydride) 1.14 1.14 1.14 1.14 Trigonox ® C 50D (g) (perester) 8 8 15.9 Trigonox ® 27 (g) (perester) 8 8 Cobalt stearate (g) 2.51 2.51 Cobalt Hex-Cem (g) 2.38 Amounts (units as described in the application) of certain components in the language of the invention amount of perester and/or alkylperoxy carbonate 338 0 338 0 165 0 amount of peranhydride 20 20 20 20 16 16 amount of transition metal compound 0 22 0 22 0 16 amount of inhibitor 233 236 233 229 116 116 total amount of thermal radical initiator 189 189 98.5 Properties of the CompPCC Extrudable Yes Yes Yes Yes Yes yes Physical storage stabillity (0-10, 10 = best) 2 2 1 Tg of CompPCC (° C.) 35 35 9 Properties of the CompPC Resistance to swelling (scale 0-48, 48 = best) 48 48 4 Smoothness (1-10 PCI, 10 = best) 2 3 <1 Chemical resistance (0-5, 5 = best) 4 5 2 Gloss 60° 35 21 n.p.m Yellowness (b*) n.a n.a. n.a.

(165) TABLE-US-00005 TABLE 4 Composition and properties of comparative thermosetting powder coating compositions CompPCC13-22 and of their corresponding powder coatings. CompPCC13 CompPCC14 CompPCC15 CompPCC16 CompPCC17 PA PB PA PB PA PB PA PB PA PB UR1 (g) 127.9 127.9 127.9 127.9 127.9 127.9 127.9 127.9 127.9 127.9 VFUR1 (g) 46.5 46.5 46.5 46.5 46.5 46.5 46.5 46.5 46.5 46.5 Kronos ® 2360 (g) 52.3 52.3 52.3 52.3 52.3 52.3 52.3 52.3 52.3 52.3 Martinal ® ON310 (g) 69.8 69.8 69.8 69.8 69.8 69.8 69.8 69.8 69.8 69.8 Resiflow ® PV-5 (g) 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 t-butyl hydroquinone (g) 0.044 0.044 0.044 0.044 0.044 0.044 0.044 0.044 Trigonox ® C 50D (g) (perester) 10.33 1.7 6.8 3.4 Trigonox ® 141 (g) (perester) 10.4 TC-R3020 (g) (peranhydride) 11.9 1.4 7.8 Perkadox LW75 (g) (peranhydride) 5.74 3.05 Trigonox ® 17 (g) (perether) Trigonox ® A80 (g) (hydroperoxide) Cobalt stearate (g) 0.55 0.56 0.56 Manganese acetate (g) 0.42 0.2 Amounts (units as described in the application) of certain components in the language of the invention amount of perester and/or alkylperoxy carbonate 152 0 25 0 249 0 100 0 50 0 amount of peranhydride 0 157 0 18 0 103 0 102 50 0 amount of transition metal compound 0 5 0 5 0 10 5 0 0 5 amount of inhibitor 15 15 267 267 267 267 267 267 267 267 total amount of thermal radical initiator 154.5 21.5 176 101 50 Properties of the CompPCC Extrudable Yes No Yes Yes Yes Yes Yes Yes Yes Yes Physical storage stabillity (0-10, 10 = best) n.p.m 8 2 8 9 Tg of CompPCC (° C.) n.p.m 43 42 44 41 Properties of the CompPC Resistance to swelling (scale 0-48, 48 = best) n.p.m 12 48 24 12 Smoothness (1-10 PCI, 10 = best) n.p.m 4 2 1 8 Chemical resistance (0-5, 5 = best) n.p.m 2 3 3 2 Gloss 60° n.p.m 25 30 23 15 Yellowness (b*) n.p.m 1.3 1.4 1.6 1.3 CompPCC18 CompPCC19 CompPCC20 CompPCC21 CompPCC22 PA PB PA PB PA PB PA PB PA PB UR1 (g) 127.9 127.9 127.9 127.9 127.9 127.9 127.9 127.9 127.9 127.9 VFUR1 (g) 46.5 46.5 46.5 46.5 46.5 46.5 46.5 46.5 46.5 46.5 Kronos ® 2360 (g) 52.3 52.3 52.3 52.3 52.3 52.3 52.3 52.3 52.3 52.3 Martinal ® ON310 (g) 69.8 69.8 69.8 69.8 69.8 69.8 69.8 69.8 69.8 69.8 Resiflow ® PV-5 (g) 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 t-butyl hydroquinone (g) 0.044 0.044 0.044 0.044 0.044 0.044 0.044 0.044 0.044 0.044 Trigonox ® C 50D (g) (perester) 6.8 Trigonox ® 141 (g) (perester) 4.2 4.2 TC-R3020 (g) (peranhydride) 7.8 7.8 Perkadox LW75 (g) (peranhydride) 5.74 5.74 Trigonox ® 17 (g) (perether) 3.12 Trigonox ® A80 (g) (hydroperoxide) 2.28 Cobalt stearate (g) 0.54 0.94 0.94 Manganese acetate (g) 2.17 Amounts (units as described in the application) of certain components in the language of the invention language of the invention amount of perester and/or alkylperoxy carbonate 100 0 101 0 101 0 0 0 0 0 amount of peranhydride 0 0 0 103 0 103 0 102 0 102 amount of transition metal compound 0 5 0 0 0 51 0 9 0 9 amount of inhibitor 267 267 267 267 267 267 267 267 267 267 total amount of thermal radical initiator 50 102 102 101 101 Properties of the CompPCC Extrudable Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Physical storage stabillity (0-10, 10 = best) 8 8 8 8 8 Tg of CompPCC (° C.) 41 41 41 42 43 Properties of the CompPC Resistance to swelling (scale 0-48, 48 = best) 12 4 48 12 24 Smoothness (1-10 PCI, 10 = best) 3 3 2 4 5 Chemical resistance (0-5, 5 = best) 2 2 4 2 2 Gloss 60° 25 45 28 43 43 Yellowness (b*) 1.1 1.2 3.3 1.2 1.2

(166) TABLE-US-00006 TABLE 5 Composition and properties of inventive thermosetting powder coating compositions InvPCC1-5 and of their corresponding powder coatings. InvPCC1 InvPCC2 InvPCC3 InvPCC4 InvPCC5 PA PB PA PB PA PB PA PB PA PB UR1 (g) 127.9 127.9 82.2 127.9 123 123 UR2 (g) 45.7 158.5 158.5 UR3 (g) 200 200 VFUR1 (g) 52.5 52.5 52.5 52.5 40.8 40.8 VFUR2 (g) 49.9 49.9 VFUR3 (g) 15.9 15.9 t-butyl hydroquinone (g) 0.04 0.04 0.04 0.04 0.044 0.044 0.044 0.044 t-butyl cathechol (g) 0.12 0.12 Byke ® 361N (g) 1.2 1.2 Kronos ® 2360 (g) 52.3 52.3 52.3 52.3 Martinal ® ON310 (g) 69.8 69.8 69.8 69.8 Resiflow ® PV-5 (g) 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 Perkadox ® LW75 (g) (peranhydride) 1.14 1.14 1.14 1.14 7.5 2.8 1.5 2.8 1.5 Trigonox ® C 50D (g) (perester) 2.25 2.25 9.6 3.3 3.3 Trigonox ® 27 (perester) 2.25 2.25 Cobalt stearate (g) 2.51 2.51 1.1 1.1 Cobalt Hex-Cem (g) 0.85 Amounts (units as described in the application) of certain components in the language of the invention amount of perester and/or alkylperoxy carbonate 95 0 95 0 102 0 49 0 49 0 amount of peranhydride 20 20 20 20 0 96 50 27 50 27 amount of transition metal compound 0 22 0 22 0 6 0 10 0 10 amount of inhibitor 236 236 233 236 507 507 261 261 269 269 total amount of thermal radical initiator 67.5 67.5 99 63 63 Properties of the InvPCC Extrudable Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Physical storage stability (0-10, 10 = best) 8 7 6 8 8 Tg of PCC (° C.) 39 38 28 44 42 Properties of the InvPC Resistance to swelling (scale 0-48, 48 = best) 48 48 48 48 48 Smoothness (1-10 PCI, 10 = best) 5 5 3 5 5 Chemical resistance (0-5, 5 = best) 5 4 3 5 3 Gloss 60° 25 28 24 25 27 Yellowness (b*) n.a. n.a. n.a. 1.3 1.6

(167) TABLE-US-00007 TABLE 6 Composition and properties of inventive thermosetting powder coating compositions InvPCC6-17 and of their corresponding powder coatings. InvPCC6 InvPCC7 InvPCC8 PA PB PA PB PA PB UR1 (g) 127.9 127.9 127.9 127.9 127.9 127.9 VFUR1 (g) 46.5 46.5 46.5 46.5 46.5 46.5 Kronos ® 2360 (g) 52.3 52.3 52.3 52.3 52.3 52.3 Martinal ® ON310 (g) 69.8 69.8 69.8 69.8 69.8 69.8 Resiflow ® PV-5 (g) 3.5 3.5 3.5 3.5 3.5 3.5 t-butylhydroquinone (g) 0.044 0.044 0.044 0.044 0.044 0.044 Trigonox ® C 50D (g) (perester) 6.89 TC-R 3020 (g) (peranhydride) Trigonox ® 141 (g) (perester) Perkadox ® LW75 (g) (peranhydride) 5.74 5.74 5.74 Trigonox ® 27 (g) (perester) 3.48 Trigonox ® 42S (g) (perester) 4.6 Trigonox ® 117 (g) (percarbonate) Manganese acetate (g) Cobalt stearate (g) 0.94 0.94 0.94 Amounts (units as described in the application) of certain components in the language of the invention amount of perester and/or alkylperoxy carbonate 102 0 101 0 106 0 amount of peranhydride 0 102 0 102 0 102 amount of transition metal compound 0 9 0 9 0 9 amount of inhibitor 267 267 267 267 267 267 total amount of thermal radical initiator 102 101.5 104 Properties of the InvPCC Extrudable Yes Yes Yes Yes Yes Yes Physical storage stabillity (0-10, 10 = best) 8 8 8 Tg of PCC (° C.) 40 41 39 Properties of the InvPC Resistance to swelling (scale 0-48, 48 = best) 48 48 48 Smoothness (1-10 PCI, 10 = best) 3 3 3 Chemical resistance (0-5, 5 = best) 4 3 3 Gloss 60° 19 22 21 Yellowness (b*) 0.9 0.8 1.1 InvPCC9 InvPCC10 InvPCC11 PA PB PA PB PA PB UR1 (g) 127.9 127.9 127.9 127.9 127.9 127.9 VFUR1 (g) 46.5 46.5 46.5 46.5 46.5 46.5 Kronos ® 2360 (g) 52.3 52.3 52.3 52.3 52.3 52.3 Martinal ® ON310 (g) 69.8 69.8 69.8 69.8 69.8 69.8 Resiflow ® PV-5 (g) 3.5 3.5 3.5 3.5 3.5 3.5 t-butylhydroquinone (g) 0.044 0.044 0.044 0.044 0.044 0.044 Trigonox ® C 50D (g) (perester) 10.33 TC-R 3020 (g) (peranhydride) 11.9 Trigonox ® 141 (g) (perester) 4.21 Perkadox ® LW75 (g) (peranhydride) 5.74 5.74 Trigonox ® 27 (g) (perester) Trigonox ® 42S (g) (perester) Trigonox ® 117 (g) (percarbonate) 4.25 Manganese acetate (g) Cobalt stearate (g) 0.94 0.94 0.55 Amounts (units as described in the application) of certain components in the language of the invention amount of perester and/or alkylperoxy carbonate 101 0 94 0 152 0 amount of peranhydride 0 102 0 102 0 157 amount of transition metal compound 0 9 0 9 0 5 amount of inhibitor 267 267 267 267 267 267 total amount of thermal radical initiator 101.5 98 154.5 Properties of the InvPCC Extrudable Yes Yes Yes Yes Yes Yes Physical storage stabillity (0-10, 10 = best) 8 8 6 Tg of PCC (° C.) 40 40 43 Properties of the InvPC Resistance to swelling (scale 0-48, 48 = best) 48 48 48 Smoothness (1-10 PCI, 10 = best) 3 3 4 Chemical resistance (0-5, 5 = best) 4 4 3 Gloss 60° 18 23 33 Yellowness (b*) 1.4 1.2 1.6 InvPCC12 InvPCC13 InvPCC14 PA PB PA PB PA PB UR1 (g) 127.9 127.9 127.9 127.9 127.9 127.9 VFUR1 (g) 46.5 46.5 46.5 46.5 46.5 46.5 Kronos ® 2360 (g) 52.3 52.3 52.3 52.3 52.3 52.3 Martinal ® ON310 (g) 69.8 69.8 69.8 69.8 69.8 69.8 Resiflow ® PV-5 (g) 3.5 3.5 3.5 3.5 3.5 3.5 t-butylhydroquinone (g) 0.265 0.265 0.044 0.044 0.044 0.044 Trigonox ® C 50D (g) (perester) 10.33 3.4 TC-R 3020 (g) (peranhydride) 11.9 7.8 1.4 Trigonox ® 141 (g) (perester) 1.05 Perkadox ® LW75 (g) (peranhydride) Trigonox ® 27 (g) (perester) Trigonox ® 42S (g) (perester) Trigonox ® 117 (g) (percarbonate) Manganese acetate (g) 0.42 Cobalt stearate (g) 0.55 0.56 Amounts (units as described in the application) of certain components in the language of the invention amount of perester and/or alkylperoxy carbonate 152 0 25 0 50 0 amount of peranhydride 0 157 0 103 0 18 amount of transition metal compound 0 5 0 10 0 5 amount of inhibitor 1534 1534 267 267 267 267 total amount of thermal radical initiator 154.5 64 34 Properties of the InvPCC Extrudable Yes Yes Yes Yes Yes Yes Physical storage stabillity (0-10, 10 = best) 6 8 8 Tg of PCC (° C.) 39 42 41 Properties of the InvPC Resistance to swelling (scale 0-48, 48 = best) 48 48 48 Smoothness (1-10 PCl, 10 = best) 6 3 3 Chemical resistance (0-5, 5 = best) 3 3 3 Gloss 60° 33 38 22 Yellowness (b*) 1.9 1.6 1.2 InvPCC15 InvPCC16 InvPCC17 PA PB PA PB PA PB UR1 (g) 127.9 127.9 127.9 127.9 127.9 127.9 VFUR1 (g) 46.5 46.5 46.5 46.5 46.5 46.5 Kronos ® 2360 (g) 52.3 52.3 52.3 52.3 52.3 52.3 Martinal ® ON310 (g) 69.8 69.8 69.8 69.8 69.8 69.8 Resiflow ® PV-5 (g) 3.5 3.5 3.5 t-butylhydroquinone (g) 0.044 0.044 0.044 0.044 0.044 0.044 Trigonox ® C 50D (g) (perester) 6.8 10.2 TC-R 3020 (g) (peranhydride) 1.4 1.4 7.8 Trigonox ® 141 (g) (perester) 2.1 Perkadox ® LW75 (g) (peranhydride) Trigonox ® 27 (g) (perester) Trigonox ® 42S (g) (perester) Trigonox ® 117 (g) (percarbonate) Manganese acetate (g) 0.42 Cobalt stearate (g) 0.56 0.56 Amounts (units as described in the application) of certain components in the language of the invention amount of perester and/or alkylperoxy carbonate 100 0 150 0 50 0 amount of peranhydride 0 18 0 18 0 103 amount of transition metal compound 0 5 0 5 0 10 amount of inhibitor 267 267 267 267 267 267 total amount of thermal radical initiator 59 84 76.5 Properties of the InvPCC Extrudable Yes Yes Yes Yes Yes Yes Physical storage stabillity (0-10, 10 = best) 8 7 7 Tg of PCC (° C.) 41 41 42 Properties of the InvPC Resistance to swelling (scale 0-48, 48 = best) 48 48 48 Smoothness (1-10 PCl, 10 = best) 4 3 3 Chemical resistance (0-5, 5 = best) 4 4 3 Gloss 60° 23 33 36 Yellowness (b*) 1.3 1.3 0.6

(168) TABLE-US-00008 TABLE 7 Composition and properties of inventive thermosetting powder coating compositions InvPCC18-29 and of their corresponding powder coatings. InvPCC18 InvPCC19 InvPCC20 PA PB PA PB PA PB UR1 (g) 127.9 127.9 127.9 127.9 127.9 127.9 VFUR1 (g) 46.5 46.5 46.5 46.5 46.5 46.5 Kronos ® 2360 (g) 52.3 52.3 52.3 52.3 52.3 52.3 Martinal ® ON310 (g) 69.8 69.8 69.8 69.8 69.8 69.8 Resiflow ® PV-5 (g) 3.5 3.5 3.5 3.5 3.5 3.5 t-butylhydroquinone (g) 0.044 0.044 0.044 0.044 0.044 0.044 Trigonox ® C 50D (g) (perester) 3.4 3.4 TC-R 3020 (g) (peranhydride) 7.8 0.78 2.1 Laurox ® S (g) (peranhydride) Trigonox ® 141 (g) (perester) 4.2 Perkadox ® LW75 (g) (peranhydride) 3.05 3.05 Manganese acetate (g) 0.42 0.2 0.2 Cobalt stearate (g) Nuodex ® Cu 8 (g) Nuodex ® drycoat (g) Amounts (units as described in the application) of certain components in the language of the invention amount of perester and/or alkylperoxy carbonate 101 0 50 0 50 0 amount of peranhydride 0 103 54 10 54 28 amount of transition metal compound 0 10 0 5 0 5 amount of inhibitor 267 267 267 267 267 267 total amount of thermal radical initiator 102 57 66 Properties of the InvPCC Extrudable Yes Yes Yes Yes Yes Yes Physical storage stabillity (0-10, 10 = best) 7 8 8 Tg of PCC (° C.) 41 42 43 Properties of the InvPC Resistance to swelling (scale 0-48, 48 = best) 48 8 48 Smoothness (1-10 PCl, 10 = best) 3 7 4 Chemical resistance (0-5, 5 = best) 3 3 3 Gloss 60° 34 14 24 Yellowness (b*) 0.8 1.6 1.3 InvPCC21 InvPCC22 InvPCC23 PA PB PA PB PA PB UR1 (g) 127.9 127.9 127.9 127.9 127.9 127.9 VFUR1 (g) 46.5 46.5 46.5 46.5 46.5 46.5 Kronos ® 2360 (g) 52.3 52.3 52.3 52.3 52.3 52.3 Martinal ® ON310 (g) 69.8 69.8 69.8 69.8 69.8 69.8 Resiflow ® PV-5 (g) 3.5 3.5 3.5 3.5 3.5 3.5 t-butylhydroquinone (g) 0.044 0.044 0.044 0.044 0.044 0.044 Trigonox ® C 50D (g) (perester) 3.4 3.4 6.8 TC-R 3020 (g) (peranhydride) 8.2 11.9 Laurox ® S (g) (peranhydride) 7.15 Trigonox ® 141 (g) (perester) Perkadox ® LW75 (g) (peranhydride) 3.05 3.05 Manganese acetate (g) 0.2 0.2 Cobalt stearate (g) 0.54 Nuodex ® Cu 8 (g) Nuodex ® drycoat (g) Amounts (units as described in the application) of certain components in the language of the invention amount of perester and/or alkylperoxy carbonate 50 0 50 0 100 0 amount of peranhydride 54 108 54 157 0 103 amount of transition metal compound 0 5 0 5 0 5 amount of inhibitor 267 267 267 267 267 267 total amount of thermal radical initiator 106 130.5 101.5 Properties of the InvPCC Extrudable Yes Yes Yes Yes Yes Yes Physical storage stabillity (0-10, 10 = best) 8 7 8 Tg of PCC (° C.) 42 42 41 Properties of the InvPC Resistance to swelling (scale 0-48, 48 = best) 48 48 48 Smoothness (1-10 PCl, 10 = best) 3 3 3 Chemical resistance (0-5, 5 = best) 3 3 3 Gloss 60° 39 39 19 Yellowness (b*) 1.2 1.5 1 InvPCC24 InvPCC25 InvPCC26 PA PB PA PB PA PB UR1 (g) 127.9 127.9 127.9 127.9 127.9 127.9 VFUR1 (g) 46.5 46.5 46.5 46.5 46.5 46.5 Kronos ® 2360 (g) 52.3 52.3 52.3 52.3 52.3 52.3 Martinal ® ON310 (g) 69.8 69.8 69.8 69.8 69.8 69.8 Resiflow ® PV-5 (g) 3.5 3.5 3.5 3.5 3.5 3.5 t-butylhydroquinone (g) 0.044 0.044 0.044 0.044 0.044 0.044 Trigonox ® C 50D (g) (perester) 6.8 TC-R 3020 (g) (peranhydride) 7.8 7.8 Laurox ® S (g) (peranhydride) Trigonox ® 141 (g) (perester) 4.2 4.2 Perkadox ® LW75 (g) (peranhydride) 5.74 Manganese acetate (g) 0.11 0.22 Cobalt stearate (g) 0.54 Nuodex ® Cu 8 (g) Nuodex ® drycoat (g) Amounts (units as described in the application) of certain components in the language of the invention amount of perester and/or alkylperoxy carbonate 100 0 101 0 101 0 amount of peranhydride 0 102 0 103 0 103 amount of transition metal compound 0 5 0 2.6 0 5 amount of inhibitor 267 267 267 267 267 267 total amount of thermal radical initiator 101 102 102 Properties of the InvPCC Extrudable Yes Yes Yes Yes Yes Yes Physical storage stabillity (0-10, 10 = best) 8 8 8 Tg of PCC (° C.) 41 43 41 Properties of the InvPC Resistance to swelling (scale 0-48, 48 = best) 48 48 48 Smoothness (1-10 PCl, 10 = best) 3 3 3 Chemical resistance (0-5, 5 = best) 3 3 3 Gloss 60° 20 39 34 Yellowness (b*) 1.2 1.2 1.2 InvPCC27 InvPCC28 InvPCC29 PA PB PA PB PA PB UR1 (g) 127.9 127.9 127.9 127.9 127.9 127.9 VFUR1 (g) 46.5 46.5 46.5 46.5 46.5 46.5 Kronos ® 2360 (g) 52.3 52.3 52.3 52.3 52.3 52.3 Martinal ® ON310 (g) 69.8 69.8 69.8 69.8 69.8 69.8 Resiflow ® PV-5 (g) 3.5 3.5 3.5 3.5 3.5 3.5 t-butylhydroquinone (g) 0.044 0.044 0.044 0.044 0.044 0.044 Trigonox ® C 50D (g) (perester) 6.8 6.8 TC-R 3020 (g) (peranhydride) 7.8 7.8 7.8 Laurox ® S (g) (peranhydride) Trigonox ® 141 (g) (perester) 4.2 Perkadox ® LW75 (g) (peranhydride) Manganese acetate (g) 0.44 Cobalt stearate (g) Nuodex ® Cu 8 (g) 0.7 Nuodex ® drycoat (g) 4.87 Amounts (units as described in the application) of certain components in the language of the invention amount of perester and/or alkylperoxy carbonate 101 0 100 0 100 0 amount of peranhydride 0 103 0 103 0 103 amount of transition metal compound 0 10 0 5 0 5 amount of inhibitor 267 267 267 267 267 267 total amount of thermal radical initiator 102 101.5 101.5 Properties of the InvPCC Extrudable Yes Yes Yes Yes Yes Yes Physical storage stabillity (0-10, 10 = best) 8 8 6 Tg of PCC (° C.) 42 40 40 Properties of the InvPC Resistance to swelling (scale 0-48, 48 = best) 48 48 48 Smoothness (1-10 PCl, 10 = best) 3 3 3 Chemical resistance (0-5, 5 = best) 3 3 3 Gloss 60° 32 26 24 Yellowness (b*) 1.5 1 1.8

(169) TABLE-US-00009 TABLE 8 Composition and properties of inventive thermosetting powder coating compositions InvPCC30-36 and of their corresponding powder coatings. InvPCC30 InvPCC31 InvPCC32 InvPCC33 PA PB PA PB PA PB PA PB UR1 (g) 127.9 127.9 127.9 127.9 191.85 63.95 63.95 191.85 VFUR1 (g) 34.9 34.9 58.1 58.1 69.75 23.25 23.25 69.75 Daiso DAP ®-A (g) Kronos ® 2360 (g) 48.84 52.3 55.8 52.3 78.45 26.15 26.15 78.45 Martinal ® ON310 (g) 65.12 69.8 74.4 69.8 104.7 34.9 34.9 104.7 Resiflow ® PV-5 (g) 3.2 3.5 3.72 3.5 5.25 1.75 1.75 5.25 t-butylhydroguinone (g) 0.041 0.041 0.044 0.044 0.066 0.022 0.022 0.066 Trigonox ® C 50D (g) (perester) 6.5 7.2 5.1 1.7 TC-R 3020 (g) (peranhydride) 1.9 2.2 5.95 17.85 Perkadox ® LW75 (g) (peranhydride) 4.575 1.525 Manganese acetate (g) 0.1 0.3 Cobalt stearate (g) 1.05 1.2 Amounts (units as described in the application) of certain components in the language of the invention amount of perester and/or alkylperoxy carbonate 103 0 100 0 50 0 50 0 amount of peranhydride 0 27 0 27 54 157 54 157 amount of transition metal compound 0 10 0 10 0 5 0 5 amount of inhibitor 268 268 250 250 267 267 267 267 total amount of thermal radical initiator 65 63.5 117.25 143.75 Properties of the InvPCC Extrudable Yes Yes Yes Yes Yes Yes Yes Yes Physical storage stabillity (0-10, 10 = best) 8 8 8 8 Tg of PCC (° C.) 45 41 42 42 Properties of the InvPC Resistance to swelling (scale 0-48, 48 = best) 48 48 48 48 Smoothness (1-10 PCl, 10 = best) 4 7 4 4 Chemical resistance (0-5, 5 = best) 3 3 3 3 Gloss 60° 15 18 15 33 Yellowness (b*) 0.8 0.9 1.2 1.1 InvPCC34 InvPCC35 InvPCC36 PA PB PA PB PA PB UR1 (g) 127.9 127.9 127.9 127.9 127.9 127.9 VFUR1 (g) 41.9 41.9 34.9 34.9 41.9 23.3 Daiso DAP ®-A (g) 4.7 4.7 11.6 11.6 4.7 23.3 Kronos ® 2360 (g) 52.3 52.3 52.3 52.3 52.3 52.3 Martinal ® ON310 (g) 69.8 69.8 69.8 69.8 69.8 69.8 Resiflow ® PV-5 (g) 3.5 3.5 3.5 3.5 3.5 3.5 t-butylhydroguinone (g) 0.044 0.044 0.044 0.044 0.044 0.044 Trigonox ® C 50D (g) (perester) 7.2 7.2 7.2 TC-R 3020 (g) (peranhydride) 11.9 11.9 11.9 Perkadox ® LW75 (g) (peranhydride) Manganese acetate (g) Cobalt stearate (g) 0.54 0.54 0.54 Amounts (units as described in the application) of certain components in the language of the invention amount of perester and/or alkylperoxy carbonate 106 0 106 0 106 0 amount of peranhydride 0 156 0 157 0 156 amount of transition metal compound 0 5 0 5 0 5 amount of inhibitor 267 267 267 267 267 267 total amount of thermal radical initiator 131 131.5 131 Properties of the InvPCC Extrudable Yes Yes Yes Yes Yes Yes Physical storage stabillity (0-10, 10 = best) 8 8 9 Tg of PCC (° C.) 35 36 36 Properties of the InvPC Resistance to swelling (scale 0-48, 48 = best) 48 48 48 Smoothness (1-10 PCl, 10 = best) 4 3 3 Chemical resistance (0-5, 5 = best) 4 3 3 Gloss 60° 35 32 32 Yellowness (b*) 1.3 1.2 1.3

(170) TABLE-US-00010 TABLE 9 Composition and properties of: i) inventive thermosetting powder coating compositions InvPCC37-38 and of their corresponding powder coating as well as of ii) comparative thermosetting powder coatings compositions CompPCC23-24 and of their corresponding powder coatings. CompPCC23 CompPCC24 InvPCC37 InvPCC38 PA PB PA PB PA PB PA PB UR3 (g) 200 200 200 200 200 200 200 200 Uracross ® P3307 (g) 40.8 40.8 40.8 40.8 40.8 40.8 40.8 40.8 t-butyl hydroquinone (g) 0.12 0.12 0.12 0.12 t-butyl cathechol (g) 0.12 0.12 0.12 0.12 Byk ® 361N (g) 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 Perkadox ® LW75 (g) (peranhydride) 7.5 7.5 Trigonox ® C 50D (g) (perester) 14.5 14.5 14.5 14.5 Cobalt Hex-Cem (g) 0.85 0.85 0.85 0.85 Amounts (units as described in the application) of certain components in the language of the invention amount of perester and/or alkylperoxy carbonate 155 0 155 0 155 0 155 0 amount of peranhydride 0 0 0 0 0 96 0 96 amount of transition metal compound 0 6 0 6 0 6 0 6 amount of inhibitor 500 500 500 500 500 500 500 500 total amount of thermal radical initiator 77.5 77.5 125.5 125.5 Properties of the InvPCC & CompPCC Extrudable Yes Yes Yes Yes Yes Yes Yes Yes Physical storage stability (0-10, 10 = best) 6 6 6 6 Tg of PCC (° C.) 28 28 28 28 Properties of the InvPC & CompPC Resistance to swelling (scale 0-48, 48 = best) 24 24 48 48 Smoothness (1-10 PCl, 10 = best) 3 3 3 3 Chemical resistance (0-5, 5 = best) 1 1 3 3 Gloss 60° 25 25 23 24 Yellowness (b*) n.a. n.a. n.a. n.a.

(171) TABLE-US-00011 TABLE 10 Composition and properties of: i) inventive thermosetting powder coating compositions InvPCC39-41 and of their corresponding powder coatings as well as of ii) comparative thermosetting powder coating composition CompPCC25 and of its corresponding powder coating. CompPCC25 InvPCC39 InvPCC40 InvPCC41 PA PB PA PB PA PB PA PB UR1 (g) 127.9 127.9 127.9 127.9 127.9 127.9 127.9 127.9 VFUR1 (g) 46.5 46.5 46.5 46.5 46.5 46.5 46.5 46.5 Daiso DAP ®-A Kronos ® 2360 (g) 52.3 52.3 52.3 52.3 52.3 52.3 52.3 52.3 Martinal ® ON310 (g) 69.8 69.8 69.8 69.8 69.8 69.8 69.8 69.8 Resiflow ® PV-5 (g) 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 t-butylhydroquinone (g) 0.88 0.88 0.44 0.44 0.45 0.45 0.44 0.44 Trigonox ® C 50D (g) (perester) 6.8 6.8 6.8 13.6 TC-R 3020 (g) (peranhydride) 11.9 11.9 11.9 15.4 Trigonox ® 17 (g) (perether) 24.8 18.3 Cobalt stearate (g) 0.54 0.54 0.54 2.2 Amounts (units as described in the application) of certain components in the language of the invention amount of perester and/or alkylperoxy carbonate 100 0 100 0 100 0 200 0 amount of peranhydride 0 157 0 157 0 157 0 203 amount of transition metal compound 0 5 0 5 0 5 0 20 amount of inhibitor 5061 5061 2538 2538 2595 2595 2538 2538 total amount of thermal radical initiator 128.5 128.5 303.7 201.5 Properties of the InvPCC & CompPCC Extrudable Yes Yes Yes Yes Yes Yes Yes Yes Physical storage stabillity (0-10, 10 = best) 7 7 5 5 Tg of PCC (° C.) 41 41 36 34 Properties of the InvPC & CompPC Resistance to swelling (scale 0-48, 48 = best) 12 48 48 48 Smoothness (1-10 PCl, 10 = best) 7 7 6 4 Chemical resistance (0-5, 5 = best) 1 3 3 4 Gloss 60° 25 25 23 36 Yellowness (b*) 1.3 1.2 1.3 1.9

(172) Only the Inventive Examples (thermosetting powder coating compositions according to the invention of claim 1) had in combination all features of claim 1.

(173) It was surprisingly found (see results shown in Tables 3-10 that only the Inventive Examples were able to provide for a unique combination of very desired properties such as: i) each of the thermosetting powder coating compositions A and B, was extrudable; and ii) thermosetting powder coating compositions C were heat curable, and in particular they were heat curable at low temperatures; and iii) thermosetting powder coating compositions C had good physical storage stability; and iv) thermosetting powder coating compositions C provided powder coatings that had excellent resistance to swelling; and v) thermosetting powder coating compositions C provided powder coatings that had good smoothness; and vi) thermosetting powder coating compositions C provided powder coatings that had good chemical resistance; and vii) thermosetting powder coating compositions C provided powder coatings that had low gloss; actually all of them had very low gloss.

(174) In addition to properties i)-vii), all Inventive Examples provided for a further desired property, that is: viii) thermosetting powder coating compositions C provided powder coatings that had low yellowness and certain compositions had very low yellowness.

(175) None of the Comparative Examples had in combination all features of claim 1. In view of the results shown in Tables 3-10 related to the composition and properties of Comparative Examples, all Comparative Examples failed even to provide for properties i)-vi), let alone the combination of further [with respect to properties i)-vi)] properties such as properties vii) and viii).

(176) The invention of claim 1 constitutes a noticeable progress over the prior art and it contributes a great deal to the advancement and progress of the technology of thermosetting powder coatings. The reason being the invention of claim 1 makes feasible the achievement of low temperature cure powders that are able at the same time to achieve a fantastic and unique array of very desirable properties as explained and shown in this application.