Aqueous coating compositions containing acetoacetyl-functional polymers, coatings, and methods
An aqueous coating composition containing (i) a polymer having one or more acetoacetyl-functional groups; and (ii) an acid-functional polymer, which may be the same as or distinct from the polymer comprising acetoacetyl-functional groups, wherein a nitrogen-free base has been used to neutralize or partially neutralize the acid-functionality on the polymer.
1. A coating composition comprising:
water;
a polymer comprising one or more acetoacetyl-functional groups;
an acid-functional polymer, which may be the same as or distinct from the polymer comprising acetoacetyl-functional groups, wherein a nitrogen-free base has been used to neutralize or partially neutralize the acid-functionality of the polymer;
an ethylenically unsaturated compound distinct from the acetoacetyl-functional polymer; wherein the ethylenically unsaturated compound is a monomer, oligomer, or mixture thereof; and
a hydrogen abstraction initiator in an amount of at least 0.1 wt-%, based on the total weight of the coating composition;
wherein the hydrogen abstraction initiator is selected to polymerize the acetoacetyl-functional polymer via a free radical UV cure mechanism through hydrogen abstraction of —C(O)—CH 2 —C(O)— hydrogens.
2. The coating composition of claim 1 , wherein the acetoacetyl-functional group is of the formula: —C(O)—R 1 —C(O)—R 2 , and wherein R 1 is a C1 to C22 alkylene group and R 2 is a C1 to C22 alkyl group.
3. The coating composition of claim 1 , wherein the base is selected from the group consisting of KOH, Ca(OH) 2 , NaOH, LiOH, and mixtures thereof.
4. The coating composition of claim 1 , wherein the polymer comprising one or more acetoacetyl-functional groups and the acid-functional polymer are the same polymer.
5. The coating composition of claim 1 , wherein the polymer comprising one or more acetoacetyl-functional groups and the acid-functional polymer are distinct polymers.
6. The coating composition of claim 1 , wherein the ethylenically unsaturated monomer, oligomer, or mixture thereof comprises a (meth)acrylate functional monomer, oligomer, or mixture thereof.
7. The coating composition of claim 1 , wherein the coating composition comprises latex polymer particles, each comprising the acetoacetyl-functional polymer, the acid-functional polymer, and the ethylenically unsaturated monomer, oligomer, or mixture thereof.
8. The coating composition of claim 6 , wherein the (meth)acrylate functional monomer, oligomer, or mixture thereof is a multifunctional monomer.
9. The coating composition of claim 8 , wherein the (meth)acrylate-functional monomer is selected from the group consisting of isobornyl (meth)acrylate, isodecyl (meth)acrylate, phenoxyethyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxylate tri(meth)acrylate, tripropylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, beta-carboxyethyl (meth)acrylate, bisphenol A ethoxylate di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, di-(trimethylolpropane tetra (meth)acrylate), pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and mixtures thereof.
10. The coating composition of claim 1 , comprising no more than 10 wt-% volatile organic compounds, based on the total weight of the composition.
11. The coating composition of claim 1 , wherein the acetoacetyl-functional polymer comprises an acetoacetyl-functional polyurethane, epoxy, polyamide, chlorinated polyolefin, acrylic, oil-modified polymer, polyester, or mixtures or copolymers thereof.
12. The coating composition of claim 1 , wherein the acetoacetyl-functional polymer comprises an acetoacetyl-functional latex polymer prepared from ethylenically unsaturated monomers.
13. The coating composition of claim 1 , wherein the acetoacetyl-functional polymer is present in an amount of at least 10 wt-% and no more than 95 wt-%, and the ethylenically unsaturated monomer, oligomer, or mixture thereof is present in an amount of at least 5 wt-% and no more than 70 wt-%, based on the combined weight of any monomers, oligomers, and polymers in the composition.
14. The coating composition of claim 1 , wherein the hydrogen abstraction initiator is a photoinitiator and comprises benzophenone, 4-methylbenzophenone, or combinations thereof.
15. The coating composition of claim 1 wherein the ethylenically unsaturated monomer, oligomer, or mixture thereof is present in an amount of at least 5 wt-%, based on the combined weight of any monomers, oligomers, and polymers in the composition.
16. The coating composition of claim 15 wherein the ethylenically unsaturated monomer, oligomer, or mixture thereof is present in an amount of at least 7.5 wt-%, based on the combined weight of any monomers, oligomers, and polymers in the composition.
17. The coating composition of claim 16 wherein the ethylenically unsaturated monomer, oligomer, or mixture thereof is present in an amount of at least 10 wt-%, based on the combined weight of any monomers, oligomers, and polymers in the composition.
18. A method of coating a substrate, the method comprising:
applying the coating composition of claim 1 to a substrate; and
applying UV radiation and allowing the coating composition to harden.
19. A coating on a substrate preparable by the method of claim 18 .
20. The coating of claim 19 , wherein the coating is in the form of a clear coating having an appearance with reduced luminescence relative to a coating wherein a nitrogen-containing base is used in absence of a nitrogen-free base to neutralize or partially neutralize the acid functionality of the polymer.
21. A method of preparing a coating composition, the method comprising:
preparing an acid-functional polymer in water, wherein the acid-functional polymer may or may not include acetoacetyl-functional groups;
in the presence of the acid-functional polymer, polymerizing a polymer, which may be the same as or distinct from the acid-functional polymer, comprising one or more acetoacetyl-functional groups of the formula:
wherein R 1 is a C1 to C22 alkylene group and R 2 is a C1 to C22 alkyl group, wherein a nitrogen-free base has been used to neutralize or partially neutralize the acid-functionality of the acid-functional polymer;
adding to the stabilized acetoacetyl-functional polymer an ethylenically unsaturated compound distinct from the polymer comprising acetoacetyl functionality; wherein the ethylenically unsaturated compound is a monomer, oligomer, or mixture thereof; and
adding a hydrogen abstraction initiator during or after the preparing step, wherein the hydrogen abstraction initiator is added in an amount of at least 0.1 wt-% based on the total weight of the coating composition;
wherein the hydrogen abstraction initiator is selected to polymerize the acetoacetyl-functional polymer via a free radical UV cure mechanism through hydrogen abstraction of —C(O)—CH 2 —C(O)— hydrogens.
22. A method of preparing a coating composition, the method comprising:
receiving a polymer prepared by a method comprising:
preparing an acid-functional polymer in water, wherein the acid-functional polymer may or may not include acetoacetyl-functional groups;
in the presence of the acid-functional polymer, polymerizing a polymer, which may be the same as or distinct from the acid-functional polymer, comprising one or more acetoacetyl-functional groups of the formula:
wherein R 1 is a C1 to C22 alkylene group and R 2 is a C1 to C22 alkyl group, wherein a nitrogen-free base has been used to neutralize or partially neutralize the acid-functionality of the acid-functional polymer; and
adding to the stabilized acetoacetyl-functional polymer an ethylenically unsaturated compound distinct from the polymer comprising acetoacetyl functionality; wherein the ethylenically unsaturated compound is a monomer, oligomer, or mixture thereof; and
adding a hydrogen abstraction initiator during or after the preparing step, wherein the hydrogen abstraction initiator is added in an amount of at least 0.1 wt-% based on the total weight of the coating composition;
wherein the hydrogen abstraction initiator is selected to polymerize the acetoacetyl-functional polymer via a free radical UV cure mechanism through hydrogen abstraction of —C(O)—CH 2 —C(O)— hydrogens.
23. A method of using a coating composition comprising:
hardening a coating composition via a free radical UV cure mechanism through hydrogen abstraction of —C(O)—CH 2 —C(O)— hydrogens, wherein the coating composition comprises:
water;
a polymer comprising one or more acetoacetyl-functional groups;
an acid-functional polymer, which may be the same as or distinct from the polymer comprising acetoacetyl-functional groups, wherein a nitrogen-free base has been used to neutralize or partially neutralize the acid-functionality of the acid-functional polymer;
an ethylenically unsaturated compound distinct from the acetoacetyl-functional polymer; wherein the ethylenically unsaturated compound is a monomer, oligomer, or mixture thereof; and
a hydrogen abstraction initiator in an amount of at least 0.1 wt-%, based on the total weight of the coating composition;
wherein the hydrogen abstraction initiator is selected to polymerize the acetoacetyl-functional polymer via a free radical UV cure mechanism through hydrogen abstraction of —C(O)—CH 2 —C(O)— hydrogens.