Curable coating compositions
This invention relates to a curable coating composition comprising: I. at least one acetoacetate functional polyester further comprising the residues of a. a hydroxyl component comprising: i. a diol in an amount ranging from 70 to 100 mole %, based on the total moles of (i) and (ii); and ii. a polyol in an amount ranging from 0 to 30 mole %, based on the total moles of (i) and (ii); b. a carboxyl component comprising a polycarboxylic acid compound, a derivative of polycarboxylic acid compound, or a combination thereof; and c. an alkyl acetoacetate, a diketene, or a combination thereof in an amount ranging from about 5 to about 50 weight %, based on the total weight of (a), (b), and (c). II. a curing agent having two or more aldehyde functional groups, and III. a basic catalyst.
1. A curable coating composition comprising:
I. a polyester having two or more beta-ketoester groups, wherein said polyester (I) is an acetoacetate functional polyester comprising the residues of
a. a hydroxyl component comprising:
i. a diol in an amount ranging from 70 to 97 mole %, based on the total moles of (i) and (ii); and
ii. a polyol in an amount ranging from 3 to 30 mole %, based on the total moles of (i) and (ii), wherein the polyol is one or more of 1,1,1-trimethylol propane, 1,1,1-trimethylolethane, glycerin, and pentaerythritol;
b. a carboxyl component comprising a polycarboxylic acid compound, a derivative of polycarboxylic acid compound, or a combination thereof; and
c. an alkyl acetoacetate, a diketene, or a combination thereof in an amount ranging from about 5 to about 50 weight %, based on the total weight of (a), (b), and (c)
II. a curing agent having two or more aldehyde functional groups, wherein the curing agent is selected from the group consisting of 1,3-cyclohexanedicarboxaldehyde, 1,4-cyclohexanedicarboxaldehyde, mixtures of 1,3-and 1,4-cyclohexanedicarboxaldehyde, 2,6-norbornanedicarboxaldehyde, 2,5-norbornane-dicarboxaldehyde, cyclododecane-1,4,8-tricarbaldehyde, and 3, (4-formylcyclohexyl) propanal, and
III. a basic catalyst, wherein the basic catalyst is one or more selected from the group consisting of 1,8-diazabicyclo-[5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7- triazabicyclo [4.4.0] dec-5-ene (MTBD), 1,1,3,3-tetramethylguanidine, and 1,4-diazabicyclo [2.2.2] octane.
2. The curable coating composition of claim 1 , wherein the diol component (a) (i) is in an amount ranging from about 85 to about 95 mole %, based on the total moles of (i) and (ii), and the polyol component (a) (ii) is in an amount ranging from about 5 to about 15 mole %, based on the total moles of (i) and (ii).
3. The curable coating composition of claim 1 , wherein said alkyl acetoacetate is an amount ranging from about 15 to about 30 weight %.
4. The curable coating composition of claim 1 , wherein the diol component (ai) is one or more selected from the group consisting of 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4- cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol, hydroxypivalyl hydroxypivalate, 2,2,4,4-tetramethylcyclobutane-1,3-diol, and polyethylene glycol.
5. The curable coating composition of claim 1 , wherein the diol (a) (i) comprises 2,2,4,4-tetramethylcyclobutane-1,3-diol.
6. The curable coating composition of claim 1 , wherein the carboxyl component (b) is one or more selected from the group consisting of adipic acid, isophthalic acid (or dimethyl isophthalate), 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, maleic anhydride, succinic anhydride, phthalic acid, and phthalic anhydride.
7. The curable coating composition of claim 1 , wherein the diol (a) (i) comprises 2,2,4,4-tetramethylcyclobutane-1,3-diol and the carboxyl component (b) comprises hexahydrophthalic anhydride.
8. The curable coating composition of claim 1 , wherein said alkyl acetoacetate is one or more selected from t-butyl acetoacetate, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, and n-butyl acetoacetate.
9. The curable coating composition of claim 1 , wherein said polyester (I) has a glass transition temperature (Tg) of about −20°° C. to about 60°° C.
10. The curable coating composition of claim 1 , further comprising one or more organic solvents selected from the group comprising ethyl acetate, butyl acetate, xylene, methyl amyl ketone, methyl ethyl ketone, and toluene.
11. The curable coating composition of claim 1 , wherein the basic catalyst is in an amount ranging from 0.5 to 5 weight % based on the total weight of (I) and (II).
12. The curable coating composition of claim 1 , wherein said polyester is an acetoacetate functional polyester comprising the residues of
a. said hydroxyl component comprising:
i. 2,2,4,4-tetramethylcyclobutane-1,3-diol in an amount ranging from 10 to 60 mole %, based on the total moles of (i), (ii), and (iii);
ii. a diol other than 2,2,4,4-tetramethylcyclobutane-1,3-diol in an amount ranging from 35 to 85 mole %, based on the total moles of (i), (ii), and (iii); and
iii. a polyol in an amount ranging from 5 to 15 mole %, based on the total moles of (i), (ii), and (iii);
b. said carboxyl component comprising:
iv. hexahydrophthalic anhydride in an amount ranging from 50 to 100 mole % based on the total moles of (iv) and (v), and
v. a polycarboxylic acid compound other than hexahydrophthalic anhydride in an amount ranging from 0 to 50 mole % based on the total moles of (iv) and (v); and
c. said alkyl acetoacetate, said diketene, or said combination thereof in an amount ranging from about 15 to about 30 weight %, based on the total weight of (a), (b), and (c).
13. The curable coating composition of claim 1 , wherein said polyester (I) is an acetoacetate functional polyester, the curing agent (II) is selected from 1,3-cyclohexanedicarboxaldehyde, 1,4-cyclohexane-dicarboxaldehyde, and mixtures of 1,3-and 1,4-cyclohexanedicarboxaldehyde.
14. The curable coating composition of claim 13 , wherein the equivalent ratio of the acetoacetate functionality in the polyester (I) to the aldehyde functionality in the curing agent (II) is from about 1.2 to 0.9.
15. The curable coating composition of claim 1 further comprising an adduct having two or more β-ketoacetate functional groups selected from 2-methyl-1,3-propanediol diacetoacetate, neopentyl glycol diacetoacetate, 2,2,4,4-tetramethylcyclobutane-1,3-diacetoacetate, and trimethylolpropane triacetoacetate.