Method of photocuring acrylate compositions
View Patent ↗Acrylate-containing compositions are photocured by mixing at least one N-oxyazinium salt photoinitiator, a photosensitizer for the N-oxyazinium salt, an N-oxyazinium salt efficiency amplifier, an aromatic heterocyclic, nitrogen-containing base, and one or more photocurable acrylates to form a photocurable composition. This photocurable composition is then irradiated to effect polymerization of the one or more acrylates. This method can be carried out in oxygen-containing environments.
1. A method of photocuring an acrylate-containing composition comprising:
mixing at least one N-oxyazinium salt photoinitiator, a photosensitizer for the N-oxyazinium salt, an N-oxyazinium salt efficiency amplifier, an aromatic heterocyclic, nitrogen-containing base, one or more photocurable acrylates, and optionally, one or more inert organic solvents, to form a photocurable composition,
wherein:
the aromatic heterocyclic, nitrogen-containing base has a pK a of at least 10 and up to and including 22 in acetonitrile,
the aromatic heterocyclic, nitrogen-containing base is present in the photocurable composition in an amount equal to or greater than the amount of the N-oxyazinium salt photoinitiator,
the photosensitizer is present in the photocurable composition in an amount of at least 10 −7 and up to and including 5×10 −5 moles per gram of one or more photocurable acrylates,
the N-oxyazinium salt photoinitiator is present in the photocurable composition in an amount of at least 6×10 −4 and up to and including 60×10 −2 moles per gram of one or more photocurable acrylates, and
the efficiency amplifier is present in the photocurable composition in an amount of at least 5×10 −7 and up to and including 1×10 −2 moles per gram of N-oxyazinium salt photoinitiator, and
irradiating the photocurable composition to effect polymerization of the one or more photocurable acrylates,
wherein the N-oxyazinium salt efficiency amplifier is an organic phosphite having the formula:
(R′O) 3 P
wherein the multiple R′ groups are the same or different alkyl groups having 1 to 20 carbon atoms, or the organic phosphite is chosen from trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, triisobutyl phosphite, triamyl phosphite, trihexyl phosphite, trinonyl phosphite, tri-(ethylene glycol) phosphite, tri-(propylene glycol) phosphite, tri(isopropylene glycol) phosphite, tri-(butylene glycol) phosphite, tri-(isobutylene glycol) phosphite, tri-(pentylene glycol) phosphite, tri-(hexylene glycol) phosphite, tri-(nonylene glycol) phosphite, tri-(diethylene glycol) phosphite, tri-(triethylene glycol) phosphite, tri-(polyethylene glycol) phosphite, tri-(polypropylene glycol) phosphite, and tri-(polybutylene glycol) phosphite.
2. The method of claim 1 , wherein the aromatic heterocyclic, nitrogen-containing base is a non-polymeric pyridine, quinoline, isoquinoline, imidazole, benzimidazole, benzthiazole, thiazole, oxazole, benzoxazole, 4,4′-bipyridine, pyrazine, triazine, pyrimidine, nicotinic acid, or isonicotinic acid, or it is a polymer having a backbone and non-polymeric pyridine, quinoline, imidazole, benzimidazole, benzthiazole, thiazole, oxazole, benzoxazole, 4,4′-bipyridine, pyrazine, triazine, pyrimidine, nicotinic acid, or isonicotinic acid moieties distributed along the backbone.
3. The method of claim 1 , wherein the aromatic heterocyclic, nitrogen-containing base is a pyridine, imidazole, or thiazole.
4. The method of claim 1 , wherein the irradiating step is carried out in the presence of oxygen.
5. The method of claim 1 , wherein the photocurable composition is partially cured during the irradiating step.
6. The method of claim 1 , wherein the photocurable composition is applied to a substrate in a patternwise fashion after mixing but before irradiation, using a flexographic printing member.
7. The method of claim 1 , wherein the N-oxyazinium salt photoinitiator is represented by either of the following Structures (I) and (II):
wherein A and B in Structure (I) independently represent a carbon, C—R 5 , C—R 6 or nitrogen, X is O, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently hydrogen, or alkyl or aryl groups, any of the A, B, and R groups where chemically feasible can be joined to form a ring, and Y is a charge balancing anion that can be a separate moiety or part of an A, B, or R,
wherein A in Structure (II) represents a carbon, C—R 5 , nitrogen, sulfur or oxygen atom with sufficient bonds and substituents to form a heteroaromatic ring, X is O, R 1 , R 2 , R 3 , R 4 , and R 5 are independently hydrogen, or alkyl or aryl groups, or any two R groups may form a ring, and Y is a charge balancing anion that can be a separate moiety or part of an R group.
8. The method of claim 1 , wherein the photosensitizer for the N-oxyazinium salt photoinitiator has a triplet energy of at least 20 kcal/mole of N-oxyazinium salt.
9. The method of claim 1 , wherein the one or more photocurable acrylates include the photosensitizer for the N-oxyazinium salt photoinitiator in the same molecule.
10. The method of claim 1 , wherein the photocurable composition further comprises metal-containing particles or carbon particles.